Professional Documents
Culture Documents
Testing Manual
Fourteenth Edition of the
Gardner-Sward Handbook
Copyright 9 1995 AMERICAN SOCIETY FOR TESTING AND MATERIALS, Philadelphia, PA.
All rights reserved. This material may not be reproduced or copied, in whole or in part, in any
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NOTE: This manual does not purport to address (all of) the safety problems associated with its
use. It is the responsibility of the user of this manual to establish appropriate safety and health
practices and determine the applicability of regulatory limitations prior to use.
Foreword
THIS PUBLICATION, Paint and Coating Testing Manual: Fourteenth Edition of the
Gardner-Sward Handbook, was sponsored by Committee D- 1 on Paint and Related
Coatings, Materials, and Applications. The editor was Joseph V. Koleske. This is
Manual 17 in ASTM's manual series.
III
Acknowledgments
ASTM WOULDLIKE TO EXPRESS its gratitude to the authors of the previous 13
editions of this publication. These publications made significant .contributions to
the technology; therefore, ASTM, in its goal to publish books of technical significance, called upon current experts in the field to revise and update this important
publication to reflect the changes and advancements that have taken place since
the last edition, which was published in 1972.
iv
Contents
xi
Preface
xiii
Introduction
PART 1: REGULATIONS
Chapter 1--Regulation of Volatile Organic Compound
Emissions from Paints and Coatings
by John J. Brezinski
15
23
26
30
39
53
60
68
CONTENTS
Chapter 10mEpoxy Resins in Coatings
by Ronald S. Bauer, Edward J. Marx, and Michael
J. Watkins
74
Chapter 11 ~Phenolics
by John S. Fry
79
Chapter 12~Polyamides
by Robert W. Kight
85
89
95
99
108
PART 4: PLASTICIZERS
Chapter 17~Plasticizers
by Peter Tan and Leonard G. Krauskopf
115
PART 5: SOLVENTS
Chapter 18--Solvents
by Stephen A. Yuhas, Jr.
125
PART 6: PIGMENTS
Chapter 19--White Pigments
by Juergen H. Braun
159
179
190
209
214
CONTENTS vii
Chapter 24mExtender Pigments
by Henry P. Ralston
2t7
223
229
238
252
PART 7: ADDITIVES
Chapter 29~Bactericides, Fungicides, and Algicides
by Vanja M. King
261
268
289
305
333
369
383
407
415
viii CONTENTS
424
439
447
Chapter 41~Gloss
by Harry K. Hammond III and Gabriele KigleBoeckler
470
481
507
513
525
534
547
Chapter 48mHardness
by Paul R. Guevin, Jr.
555
585
600
609
CONTENTS
619
643
654
662
667
677
683
696
706
711
717
Chapter 63--Masonry
by Frances Gale and Thomas Sliva
725
731
Chapter 65--Sealants
by Saul Spindel
735
741
748
x CONTENTS
753
767
783
Chapter 71--Chromatography
by Rolando C. Domingo
789
815
826
835
841
865
871
891
Appendix
895
Index
899
Preface
AT A JANUARY1967 MEETINGOF ASTM COMMITTEED-1 held in Washington, DC, ASTM
(American Society for Testing and Materials) accepted ownership of the Gardner-Sward
Handbook from the Gardner Laboratory. It was through this laboratory that Dr. Henry
A. Gardner published the previous twelve editions of the manual. Acceptance of this
ownership gave ASTM an assumed responsibility for revising, editing, and publishing
future editions of this well-known, respected manual. The undertaking was assigned to
Committee D-1 on Paint and Related Coatings, Materials, and Applications. This committee established a permanent subcommittee, D01.19 on Gardner-Sward Handbook,
chaired by John C. Weaver, to provide technical, editorial, and general policy guidance
for preparation of the 13th and subsequent editions of the Gardner-Sward Handbook.
The 13th edition was published in 1972 as the Paint Testing Manual (STP 500) with Mr.
G. G. Sward as editor. The manual has served the industry well for the past two decades;
it contains useful information that cannot be found elsewhere. However, the passage of
more than 20 years since its publication is readily apparent in many and perhaps most
chapters of the manual.
Although updating the manual was discussed through the years, a variety of reasons
prevented this task from being accomplished. Feasibility of updating the manual was
not realized until mid-1989 when Dr. John J. Brezinski, Union Carbide (retired), and
Mrs. Kathleen A. Dernoga, Manager of Acquisitions and Review of ASTM Technical
Books and Journals, discussed the matter and the 14th edition was conceived. Between
then and the spring of 1990 an outline for the 14th edition was developed and was
approved by members of Subcommittee DO1.19. Almost five years later the manual was
completed--no wonder such a long period elapsed between editions!
The scope of the new edition is in keeping with the stated scope of Subcommittee
D01.19:
"To provide technical, editorial, and general policy guidance for preparation of the
Fourteenth and subsequent editions of the Gardner-Sward Handbook. The handbook is intended for review of both new and experienced paint technologists and
the past, present, and foreseeable trends in all kinds of testing within the scope of
Committee D-1. It supplements, but does not replace, the pertinent parts of the
Society's Book of Standards. It describes briefly and critically all Test Methods
believed to have significance in the world of paint technology, whether or not these
tests have been adopted officially by the society."
In this new edition, ASTM standard methods are described by minimal detail with the
various volumes of the ASTM Book of Standards remaining the primary source of such
information. An effort was made to include references in the absence of ASTM information concerning industrial, other society, national, and international test methods. For
the most part, the manual contains either new chapters or the old topics/chapters in
rewritten form. In a few cases, the old manual was merely updated, attesting to either
the quality of the earlier writing, the lack of development in the area, or the apparent
waning of interest in the topic. A variety of modern topics has been included. Individual
authors, experts in their various fields, were given a great deal of freedom in expressing
information about their topics.
Many things have changed through the years. The chemical emphasis has shifted
from natural products to synthetic products, so this edition of the manual contains
chapters that deal with a large number of synthetic polymers used in the coating
industry. Instrumentation has undergone a marked change with innovative electronics
providing the key to many changes. An effort was made to include chapters dealing with
a broad variety of instruments.
xi
xii
PREFACE
To the authors, a warm, heart-felt "thank you." You put your talents to work and
sacrificed much personal time to make the manual a success. A "thank you" is also due
the reviewers, who are a special lot. They must be critical, yet carry out their task in a
constructive manner. Because of the customary anonymity accorded reviewers, they
should know that some authors made a special effort to express their appreciation for
the review comments that they felt strengthened their manuscripts. Those organizations who permitted authors' time, use of support staff, and supplies are truly appreciated. Works such as this manual could not be completed without their generosity--may
they prosper. The staff at ASTM is distinctive--they were interested and smilingly
helpful to the authors, reviewers, Subcommittee DO1.19, and the editor as they guided
us through the maze of the publication assembly process (though they may have gritted
their teeth at times). A very special thanks to Monica Siperko of ASTM, who worked
closely with the editor in dealing with authors, reviewers, ASTM staff, and manuscripts.
Her invaluable, cheerful assistance is appreciated. And last, but certainly not least, the
contributions of Maureen Quinn and David Jones of the ASTM editing staff are acknowledged. Their able assistance ensured that the manual was uniform in style and
grammar.
Joseph K Koleske
Editor
Introduction
P A S T TO P R E S E N T
More than a score of years has passed since the previous edition of this manual was
published, and many changes have taken place in the coating industry and elsewhere
since that time. In 1972, the previous publication date, over 90% of all industrial
coatings were low-solids, solvent-borne coatings. Total solids ranged from about 5 to
20% by weight. In the early 1970s, solvents were inexpensive, convenient carriers for the
binder polymers used in coatings, and there appeared to be little knowledge in the
scientific community about the consequences of breathing them, absorbing them
through the skin, or placing them either in the atmosphere or in the environment in
general. There were exceptions, as when a particular compound was known to be highly
toxic. The specific effect of certain solvents as well as other chemicals on certain
segments of the population was unknown in the scientific community. Large quantities
of solvent were needed to dilute the high-molecular-weight binders to an appropriate
application viscosity. High-molecular-weight binders imparted high-quality characteristics to the final coating. In addition, very dilute solutions allowed application of very
thin, but continuous, films. These factors coupled with the low cost of energy used to
drive the large ovens associated with coating manufacture were major reasons that kept
coating systems low in solids and solvent-borne in nature. Even a large percentage of
architectual coatings was oil-based, solvent-borne formulations. In an overall sense,
products of the coatings industry worked and did a satisfactory job.
However, new technologies were being talked about, worked on, and even commercialized, albeit in a small way. Terms such as "powder coatings," "radiation-cure coatings," and "water-borne coatings" were beginning to creep into the language of the
coating industry. The technologies promised a great deal, were considered mainly by
the innovative, and had many difficulties associated with their introduction. Abbreviations such as EPA, MSDS, OSHA, SARA, TSCA, and similar others that are familiar
to us today weren't yet in the industry's jargon. In fact, less than two pages (pp. 418-419)
in the previous edition of this manual were dedicated to the topic of atmospheric
pollution, and therein basically only Rule 66 was briefly discussed. No criticism is
m e a n t - - s u c h was the nature of the topic in the pre-1972 world. As stated previously,
"Times have changed," and this new edition devotes a significantly sized chapter to
acquaint readers briefly with the topic of regulation of volatile organic compounds
emitted from coatings. This topic and the related topics of health and safety are
mentioned a number of times in the manual.
POWDER COATINGS
Changes other than those of regulation, though related, have taken place in our
industry. In 1972, coating journals had discussions about the "powder explosion."
Powder coatings were to take over the industry since they were clean, 100% solids
systems that could be applied on any substrate that could be either heated for fluid-bed
application or made conductive for electrostatic spray application. Although powder
coatings had been used in Europe as early as the 1950s, not many powder-coating
systems existed in the United States in the 1970s. There was little incentive for largecompany, raw-material suppliers who sold solvents to get into the powder coating
business. A prime obstacle was the fact that there was little one could do to alter a
Xlll
xiv INTRODUCTION
powder coating once it was made. If a fully formulated product such as a powder
coating were to be sold by a raw-material supplier, there was a feeling that customers
for solvents and other raw materials would be alienated. Also, from the end-user point of
view, conversion from in-place, existing application equipment to powder coating
equipment required a capital expenditure. This is a factor that always was and still can
be a hindrance to conversion from existing to new technology.
It did not take long for the fuse of the powder keg to fizzle--but, more importantly, it
did not go out. Epoxide powders were in vogue for pipeline coatings and were used on
the Alaskan pipeline. In the early days of powder coatings, small amounts of vinyl
chloride homopolymer and copolymer, polyester, and nylon powders were used. Fluidbed application methods were first to be commercialized. It was relatively easy to meltmix and grind mixtures of polymers, pigments, plasticizers, and other formulating
ingredients to obtain the relatively large particle-size powders used by this method.
Electrostatic spray took longer to develop since procedures for manufacture of the fine
particle-size powders as well as the sophisticated spray equipment needed for effectively
and efficiently handling charged powder particles had to be developed.
Powder coatings not only had problems in manufacture and application, but also in
other areas such as: changeover from one color, availability and storage of a number of
colored powders, flow and leveling, in developing thermoset coatings that would flow
and level before cross-linking at an elevated temperature, in blocking during storage
and as the powder flowed through the spray-system hoses and gun, in cost coupled with
concerns about handling overspray and recovery and disposal. But, something new had
been born, and a new industry within the coating industry was going through the throes
of growing up in a competitive environment. Today the powder industry segment is
strong and is growing. It has developed to the point where it now has its own organization, The Powder Coating Institute, located in Alexandria, VA. Journals such as the
Journal of Coatings Technology, Industrial Paint and Powder, etc. now devote entire
issues to the topic. Local, national, and international meetings are held to discuss the
topic. The biennial trade show Powder Coating '92, held in Cincinnati, attracted over
4000 people, and 163 companies displayed their products. Powder coatings probably
will not take over the coating industry, but they now are and continue to be important
factors in the industry for the foreseeable future.
RADIATION C U R I N G
Another new technology born in the late 1960s was radiation curing. It also showed
great early promise and many problems--there were even unrealized problems at the
beginning since no one really understood that some of the chemicals used were human
sensitizers and strong irritants. Lack of knowledge in the scientific community about
the hazards of acrylates resulted in some people becoming sensitized to these compounds. However, the idea of taking a liquid, low-viscosity, coating formulation, applying it to a substrate with conventional equipment, and having the coating essentially
instantly converted into a solid, cross-linked film with very little or nil loss to the
atmosphere was attractive.
Radiation curing involved the use of electron-beam or ultraviolet-light radiation. Free
radicals were generated with ultraviolet light (photocure), and electrons were generated
with electron beams. Acrylates and maleate polyesters/styrene were very rapidly polymerized in the presence of these active species. Because the reaction took place in thin
films, the heat of reaction was readily dissipated and was not a problem to the technology. In the mid-to-late 1970s it was felt that this technology might capture only a
percentage or two of the industrial coatings market.
Proponents of these essentially 100% solids systems refined the technology. Adaptation of existing equipment to the technology involved relatively simple, low-cost improvement when ultraviolet-light radiation was involved, and many conventional application techniques could be used. Most potential users insisted on the formulated
products having low viscosity so that conventional equipment could be used. Such users
were the driving force toward low-molecular-weight, reactive products. Innovators
developed products that were quite safe to handle. A new branch of the technology that
involved cycloaliphatic epoxides and photoinitiators that generated cationic species
when photolyzed was begun at the end of decade.
INTRODUCTION
O T H E R N E W COATING T E C H N O L O G I E S
Adjuncts to high-solids coating technology are the water-borne systems (though they
may have predated organic-based systems) that require minimal cosolvent to achieve
good appearance and properties, two-package coating systems that have relatively short
pot lives, and water-borne emulsion or latex systems. The latter coatings are important
xv
xvi
INTRODUCTION
to the architectural coatings market, and today oil-base paints represent only a small
fraction of the huge market for these commodity items. Latex-based paints have increased their solids, decreased volatile organic components, and are formulated with
new thickening agents that have excellent flow characteristics. Even when the paint is
applied by amateurs, spattering is almost unknown. This industry segment also is
included in the above-mentioned symposium as well as at Lehigh University, which is
well known for its efforts in the field of water-borne coating technology.
SOLVENTS
The area of solvent technology has undergone a number of changes during the past
quarter of a century. The changes for the most part are associated with reduction of
their health-hazard profiles and characteristics. Knowledge was developed or "rediscovered" about many solvents since the previous edition was published. This knowledge
has led either to the demise or to "sharply" curtailed o r restricted usage of what had
been many commonly used solvents.
This same information was also responsible for innovation and has played an important role in development of new solvents that are less harmful to humans, animals, and
the environment. The abbreviation MSDS (Material Safety Data Sheet) became well
known for solvents and for other chemicals. Today these information sheets with safety
data about materials are not only required for chemicals, they are used by people in
laboratories and plants. It goes without saying that they should be required reading for
anyone handling chemical compounds.
OTHER INNOVATIONS
The advent of new technology to produce functional and decorative coatings involved
more than innovative organic chemistry. It also required innovative physical chemistry,
material science, polymer science, and engineering. In addition to new chemicals and
ways to use them, development of new application equipment and cure equipment was
required. Conventional suction-feed spray guns and roll coaters could not be used for
many of the new technologies. Powder coatings required development of methods of
manufacture, of handling systems that could be quickly cleaned during a color changeover, of methods for placing a charge on the powder, of understanding and elimination
of cage effects, of getting good wrap-around on other than flat substrates, of ways to
remove fused powder from hangers and conveyors, and so on. Radiation-cure coatings
required development of electron beam systems with improved safety features, of efficient ultraviolet light systems that could cure in other than line of sight, of low-viscosity
chemicals with improved safety and health characteristics, and more. Water-borne
systems had to deal with flash rusting, with minimizing cosolvents, with developing
latexes that would quickly dry and fuse while maintaining qualities such as hardness,
high gloss, and toughness. High solids required balances between molecular-weight,
functional groups and their effects and viscosity, as well as between reactivity and shelf
or pot life. It also required coating scientists to obtain high-quality finishes from the
small molecules needed to achieve the low viscosity used for reasonable application
characteristics at high-solids content.
Electronics also played an important role in the changes in coating technology and in
the testing of coatings. During the period we are discussing, there has been a "Buck
Rogerish" explosion in this industry. Many concepts and products related to such
concepts that were considered amazing and with little likelihood of success in 1970 are
realities today. Miniaturization technology has made printed circuit assemblies and
semiconductors possible. Today, hand-held calculators are almost as powerful as the
room-filling computers were in the early 1970s. Personal computers weren't even
thought about in 1972. Robots and various forms of robotics have become useful tools
in the 1990s. Application of electronics technology to a host of instruments, some of
which are described in this manual, has vastly improved our ability to probe and
otherwise examine and understand materials that are currently used, new materials as
they are being developed, and final coatings in both an as-made and an aged condition.
Both reliability and precision of tesing have been improved through new instruments.
INTRODUCTION
Yet within this array of new test equipment that has been enabled through electronics
and that allows quantitative results to be obtained in a reliable manner, there is still
room for and a need for some of the simple, homey tests used for many years. Tests that
are easy to apply and that require no elegant or complicated equipment are still
desirable. Quickly drawing a nickel over a coating while applying downward pressure to
the stroke almost immediately gives one a feeling for how well the coating is adhering to
the substrate and to its toughness and formability. Such a test can he performed "on
line" and by essentially anyone. Even interpretation of results is not difficult and is
largely intuitive. Pencil hardness testing may vary from operator to operator, but one
does not need to be a coatings scientist to quickly grasp what the test is measuring and
to have a "feel" for a coating's hardness from the test. Solvent double rubs are easy to do.
While the exact number of double rubs obtained may vary from individual to individual,
the test still gives a quick understanding of the coating's thermoset character as well as
the degree of cross-linking. Sharp impacts on the face or reverse side of a coated metal
panel can quickly give an understanding about the impact and adhesion characteristics
of the coating. These are four simple tests, but they can yield a great deal of understanding about a particular coating in a very short time. Other simple tests also exist.
Lest one get the wrong impression from the last few sentences, while these tests are
useful, they certainly do not lead to the fundamental understanding that is very important to development of knowledge so necessary for new products. Sophisticated testing
puts numbers on test results, probes deep into molecular achitecture, and allows both
comparison of competitive products and the development of improved products. Sophisticated analyses also provide the understanding necessary to develop new chemicals and technology that will lead to improvements in existing products and to new
products.
SUMMARY
Within the changed environment that has been described, the 13th edition of the
Paint Testing Manual has, for the most part, become outdated--as was expected when it
was compiled. Many of the methods described have changed, and the needs of the
industry have also changed. The 14th edition reflects these changes. Even its title has
been changed--to Paint and Coating Testing Manual. The collective effort of the many
authors has resulted in a manual that has deemphasized, though certainly not eliminated, natural products, that provides a description of the regulations currently in force
for the industry, and that discusses the main polymeric species, colorants, special
pigments, extenders, and additives used in the industry today. The manual also deals
with the analyses used to dissect and analyze a coating, the instruments used in the
industry, and the products of the industry as well as how they are used and tested.
Testing procedures for the most part are not detailed in the manual. Rather, the manual
is a guide that will lead a coatings scientist to more in-depth treatises about the various
topics and to test methods, procedures, and standards of ASTM and other national and
international organizations.
Joseph V. Koleske
Editor
xvii
Part I: Regulations
MNL17-EB/Jun. 1995
by J. John Brezinski I
Abbreviation
CAA
CAAA-77
CAAA-90
CWA
SDWA
TSCA
RCRA
CERCLA
(Superfund)
SARA
SARA, Title
III
www.astm.org
Sources of NOx: Flame of almost any kind, volcanoes, internal combustion engines, forest fires, cigarettes, boilers, space heaters.
Processes that Produce Hydrocarbons
9 Petroleum production, refining, transport
9 Internal combustion engines
9 Natural processes--forests and plants (isoprene and terpenes)
9 Surface coatings
A 1962 estimate of the contaminants discharged into the
Los Angeles air during the summer period revealed that motor vehicles accounted for about 60%, while the use of organic solvents (for all purposes) accounted for about 18% of
the organic gases. About one half of the organic solvent
emitted was attributed to the coatings industry, chiefly to the
use in paint and coatings. Approximately 66% of the NOx
released was assigned to gasoline (motor vehicle) combustion, while the combustion of fuels (energy supply) accounted
for about 26% [1].
Based on the results of laboratory studies in "smog chambers," in which a mixture of a solvent and nitrogen oxide was
exposed for 6 h to light approximately the intensity of noon
sunlight, the solvents could be classified as "low" or "high" in
photochemical reactivity related to the amount of peroxides
and ozone produced. These studies formed the basis for the
well-known Rule 66, an air pollution control regulation
passed by the Los Angeles Air Pollution Control District. Rule
66 identifies an "approved" solvent as one that contains less
than 20% by volume of specific chemicals and is further
limited to certain combinations of these chemicals. Thus,
approved solvents can contain no more than designated
amounts of the combinations shown in Table 2.
In effect, Rule 66 promoted the use of specific solvents such
as aliphatic and naphthenic hydrocarbons, alcohols, esters,
normal ketones, chlorinated hydrocarbons (except trichloroethylene), and nitroparaffins. Rule 66, superseded in 1976 by
Rule 442, Usage of Solvents, by the California South Coast Air
Quality Management District, was subsequently adopted by
various other state jurisdictions. Renewed interest has developed recently in the consideration of solvent photochemical
8%
Aromatic
hydrocarbons
(W/8 C
atoms)
20%
Ethylbenzene,
branched
ketones,
toluene, or
trichloroethane
reactivity in state, federal, and international programs related to air quality control.
VOC Definition
The United States Environmental Protection Agency (EPA)
was created in 1970 by Congress as part of a plan to consolidate several federal environmental activities. Studies directed
by the EPA laboratories in Research Triangle Park, NC of the
photochemical reactivity of materials in a laboratory smog
chamber revealed that when organic materials and nitrogen
oxide were irradiated for periods of up to 36 h, even those
solvents considered acceptable under Rule 66 reacted to form
peroxides and ozone. Only a few materials showed negligible
photochemical reactivity, among which were: methane, ethane, methylene chloride, 1,1,1-trichloroethane, and fluorinated compounds. These studies, which were prompted in part
by the passage of the Clean Air Act of 1970, led to the conclusion that most organic compounds emitted to the atmosphere
contribute to the formation of ozone. On this basis, EPA
adopted as a regulatory objective the limit of essentially all
volatile organic compounds emitted to the atmosphere from
all sources, including paint and coatings applications [3].
CHAPTER 1--REGULATION
OF VOC EMISSIONS
D E T E R M I N A T I O N OF VOC C O N T E N T
CONTROL OF VOC E M I S S I O N S F R O M
COATINGS
The Clean Air Act addressed air pollution eminating from
both existing sources and that from future new plant construction or significant modification of existing sources.
States with areas that did not comply with the ozone standard
were given primary responsibility to develop appropriate regulations for existing sources to meet the time schedule for
compliance specified by Congress. The Federal EPA was assigned oversight responsibility for the state programs that
were described in "State Implementation Plans" (SIP).
Kg VOC/L
Minus H20
2.8
1.2
1.9
2.8
2.8
4.8
2.8
4.2
5.5
3.7
2.8
3.8
0.34
0.14
0.23
0.34
0.34
0.58
0.34
0.51
0.66
0.44
0.34
0.45
1.7
2.6
3.0
3.5
0.20
0.31
0.36
0.42
Clear coat
Extreme performance
Powder coatings
All others
4.3
3.5
0.4
3.0
2.9
0.52
0.42
0.05
0.36
0.35
Vinyl
3.8
0.45
Lb VOC/Gal
Coatings Operation
CTG Date"
Appliances, large
Auto and light duty trucks
Dec., 1977
May, 1977
Cans
May, 1977
Fabric
May, 1977
Dec., 1978
May, 1977
None
None; may be
considered
fabric coating
See Paper coating
Fabric: May 1977
and/or Graphic
Arts Packaging
Rotogravure,
Dec. 1978
June, 1978
Primer, electrodeposit
Prime coat
Guidecoat (surfacer)
Topcoat
Final repair
Sheet basecoat
Interior body spray
Side seam
End seal compound
Fabric coating
Vinyl coating
(Consult CTG or state regulations)
(Based on the use of an incinerator)
Prime and topcoat or single coat
Air dry
NOTE:The information presented in this table is not complete. Persons subject to emission control for any of the operations are advisedto consult the state/local
regulations for details.
aCTG documents are available from the National Technical Information Service, 5285 Port Royal Road, Springfield,VA 22161.
bReasonably available control technology (RACT)limits recommended in CTG and, in most cases, adopted in state/local regulations.
Reference M e t h o d 24 is also included in the ASTM Manual on
Determination o f Volatile Organic Compound (VOC) Content
in Paints, Inks, and Related Coating Products, 2nd ed., 1993
[7].
Substantial revisions during 1989-1991 were also m a d e in
ASTM D 3960, Practice for D e t e r m i n i n g Volatile Organic
C o m p o u n d (VOC) Content of Paints and Related Coatings, a
standard developed in ASTM S u b c o m m i t t e e D01.21 to provide a guide for the calculation of VOC and to establish a base
for the investigation in ASTM of the precision of VOC co n t en t
determination. The definitions a n d symbols used in D 3960
are those ad o p t ed by the EPA and included in the Agency
d o c u m e n t "Procedures for Certifying Quantity of Volatile Organic C o m p o u n d s E m i t t e d by Paint, Ink a n d Other Coatings"
that was published in 1984 [8].
The general expression for calculating VOC c o n t e n t in
gr a m s p er liter of coating less w a t e r and e x e m p t solvent
specified in the EPA Control T e c h n i q u e Guidelines issued
t h r o u g h 1991 is:
voc
(Wo)(Oc)
100%
Vw -
vex
(W~ - W~ - W~x)(Dr
100%-
(1)
(Ww)(Dc/D~)- (W~)(D~/Dr
where
VOC = VOC co n t en t in g/L of coating less w a t e r and exe m p t solvent,
141o = weight % of organic volatiles = Wv - Ww - Wex,
Wu = weight % of total volatiles = (100% - weight %
nonvolatiles), (ASTM D 2369),
Ww = weight % of w at er (ASTM D 3792 or ASTM D
4017),
14~x = weight % of e x e m p t solvent (ASTM D 4457),
TABLE 4 - - V O C limits in New Source Performance (NSPS) for surface coatings operations.
Allowable Limitsb
Coatings Operation
Appliances, large
Auto and light duty trucks
Fabric (coating)
NSPS Date~
Oct.,1982
Dec., 1980
Graphic a r t s - - r o t o g r a v u r e and
flexography
Magnetic tape
Magnet wire
Metal coil
None
Nov., 1982
Kg VOC/L
Applied Solids
7.5
Prime coat
1.3
Guide coat
11.7
Top coat
12.2
Exterior base
2.4
Clear base coat
3.8
Inside spray
7.4
Aug.,1983
See Polymeric
coating of
supporting
substrate
Rotogravure only
Nov., 1982
Oct,, 1988
Metal furniture
Miscellaneous metal parts and
products
Plastic parts for business machines
Lb VOC/Gal
Applied Solids
0.90
0.16
1.40
1.47
0.29
0.46
0.89
Consult NSPS d o c u m e n t
1.7
Consult NSPS
0.2
.
.
.
.
w/o emission control device
2.3
With emission control device
1.2
7.5
.
.
.
.
Sept., 1989
Oct., 1983
June, 1984
None
.
0.28
0.15
0.90
.
1.5
2.3
0.20
1.0
NOTE: The information presented in this table is not complete. Persons subject to emission control for any of the operations are adv/sed to consult the specific
language of the referenced documents and state and local regulations.
~NSPS documents are available from the National Technical Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161.
bBest demonstrated technology (BDT) emission limits established as NSPS standards. In the NSPS, the limits are expressed as kilograms of VOC per liter of
applied solids.
Test Method f o r -
D 2369-81
D 1475-60
D 3792-79
D 4017-81
D 4457-85
Vw
Vex
Dc
Dw
D,x
=
=
=
=
=
volume
volume
density
density
density
1475).
% o f w a t e r -- (Ww)(Dc/Dw),
% of e x e m p t s o l v e n t = (Wex)(Dc/Dex),
o f c o a t i n g a t 25~ i n g/L ( A S T M D 1475),
o f w a t e r a t 25~ i n g/L -- 0 . 9 9 7 103, a n d
of e x e m p t s o l v e n t a t 25~ i n g/L ( A S T M D
( W , - Ww - We~)Dc
v.
where
V O C m = V O C c o n t e n t i n g/L o f c o a t i n g solids, a n d
(2)
AND
ASTM development activity on other VOC-related standards has expanded significantly since 1980. Many of the
standards listed in this section have not been approved by the
Federal EPA for use in demonstration of compliance with
VOC emission control regulations. Use of any of these standards to demonstrate compliance should be coordinated with
appropriate regulatory agencies. Among the new standards
developed or in process of development are the following:
S t a n d a r d s Specific to t h e A u t o m o b i l e I n d u s t r y
9 D 5087 Test Method for Determining the Amount of Volatile Organic Compounds (VOC) Released from Solvent-Borne Automotive Coatings and Available for
Removal in a VOC Control Device (Abatement)
9 D 5066 Practice for the Determination of the Transfer Efficiency Under Production Conditions for Spray Application of Automotive Paints--Weight Basis
9 D 5009 Test Method for Evaluating and Comparing Transfer Efficiency Under Laboratory Conditions
These standards were developed with the cooperation of
representatives from automotive coating suppliers and the
Motor Vehicle Manufacturers Association. Method D 5009
was derived from a study of transfer efficiency conducted for
the U.S. Environmental Protection Agency [9].
Masonry Treatments
9 D 5095 Test Method for Determination of the Nonvolatile
Content in Silanes, Siloxanesl and Silane-Siloxane
3EPAReference Method 24 does not include an analytical method
for determining V~, but states that the value be calculated from the
coating manufacturer's formulation.
CHAPTER 1 - - R E G U L A T I O N OF VOC E M I S S I O N S
tion of volatile organic content of waterborne coatings [10].
The method involves collecting, on activated charcoal in
weighed tubes, the organic effluent evolved on heating a paint
specimen for 1 h at 110~ while purging the reaction vessel
with dry nitrogen. Methanol is not captured on the charcoal.
9 D 5403 Test Method for Volatile Content of Radiation Curable Materials
Inks
9
9
9
9
9
Supplementary Information
Further information about the development, significance,
and limitations of these VOC-related ASTM standards as well
as about the use of ASTM standards for the demonstration of
compliance with VOC emission control regulations is available in the ASTM Manual on Determination of Volatile Or-
autobody refinishing
plastic parts (business machines)
plastic parts (others)
offset lithography
wood furniture
Design Value
(Ozone Level)
Years to Achieve
Compliance,
year
0.121-0.138
0.138-0.160
0.160-0.180
0.180-0.280
0.280 and above
3 (1993)
6 (1996)
9 (1999)
15 (2005)
20 (2010)
Marginal or moderate
Serious
Severe
Extreme
100
50
25
10
CHAPTER 1 - - R E G U L A T I O N OF VOC E M I S S I O N S
TABLE 9--Code of federal regulations subchapter topics.
Subehapter
Subject
Parts
Air Programs
New Source Performance Standards
Water Programs
Solid Waste
Superfund/Right-to-Know
Effluent Guidelines and Standards
Toxic Substances Control Act
50-87
60
104-149
240-281
300- 372
401-471
700-799
D
I
J
N
R
Coating Operation
Vol. II
EPA-450/2-77-032
EPA-450/2-77-033
EPA-450/2-77-034
EPA-450/2-78-015
EPA-450/2-78-032
EPA-450/2-78-033
Title VI--Stratospheric
Ozone Protection
Title VII--Enforcement
EPA is g r a n t e d b r o a d n e w a u t h o r i t y to i m p o s e penalties
a n d substantial fines for various actions including: violations
of the State I m p l e m e n t a t i o n Plan; violation of s o m e of the
o p e r a t i n g p e r m i t provisions; a n d false s t a t e m e n t s in records,
m o n i t o r i n g data, a n d reports. Also i n c l u d e d are provisions
for field citations b y inspectors.
States
Connecticut, Maine, Massachusetts,
New Hampshire, Rhode Island,
Vermont
New Jersey, New York, Puerto Rico,
Virgin Islands
Delaware, Maryland, Pennsylvania, Virginia,
West Virginia, District of
Columbia
Alabama, Florida, Georgia, Kentucky,
Mississippi, North Carolina, South
Carolina, Tennessee
Illinois, Indiana, Michigan,
Minnesota, Ohio, Wisconsin
Arkansas, Louisiana, New Mexico,
Oklahoma, Texas
Iowa, Kansas, Missouri, Nebraska
Colorado, Montana, North Dakota,
South Dakota, Utah, Wyoming
American Somoa, Arizona, Nevada,
Hawaii, Guam, California
10
11
Address
J. F. Kennedy Federal Bldg.
Room 2203,
Boston, MA 02203
Phone (617) 565-3715
26 Federal Plaza
New York. NY 10278
Phone (212) 264-2515
841 Chestnut St,
Philadelphia, PA 19107
Phone (800) 438-2474
345 Courtland St. NE
Atlanta, GA 30365
Phone (800) 282-0239 in GA
(800) 241-1754 in other Region 4 states
230 S. Dearborn St.
Chicago, IL 60604
Phone (800) 572-2515 in IL
(800) 621-8431 in other Region 5 states
1445 Ross Ave.
12th Floor, Suite 1200
Dallas, TX 75202
Phone (214) 655-2200
726 Minnesota Ave.
Kansas City, KS 66101
Phone (913) 236-2803
999 18th St.
Suite 500
Denver, CO 80202
Phone (800) 759-4372
215 Fremont St.
San Francisco, CA 94105
Phone (415) 974-8076
1200 6th Ave.
Seattle, WA 98101
Phone (206) 442-5810
12
REGULATION INFORMATION
Published Sources
F e d e r a l e n v i r o n m e n t a l regulations, including those prom u l g a t e d u n d e r the Clean Air Act, are p u b l i s h e d in the Code
of Federal Regulations (CFR), a series of b o o k s that are generally available in m a j o r libraries a n d law libraries. These regulations as well as those of related state a n d local codes are
also o b t a i n a b l e from the associated r e g u l a t o r y offices.
Regulations of p a r t i c u l a r interest to the coatings i n d u s t r y
can be found in s u b c h a p t e r s of the Code of Federal Regulations (Table 9).
The F e d e r a l Control Technique Guidelines for coating operations are not included in the CFR, b u t are available from
the National Technical I n f o r m a t i o n Service (NTIS), 5285
Port Royal Road, Springfield, VA 22161. CTG d o c u m e n t s
t h r o u g h 1991 are i n c l u d e d in the EPA p u b l i c a t i o n s listed in
Table 10.
P r o p o s e d regulations are p u b l i s h e d by the EPA in the Federal Register. Typically, a p u b l i c (written) c o m m e n t p e r i o d of
30 to 90 days on the p r o p o s a l s is allowed, a n d often a public
h e a r i n g is s c h e d u l e d at w h i c h oral c o m m e n t s can be presented. The c o m m e n t s received are c o n s i d e r e d by the Agency
in the d e v e l o p m e n t of a final regulation that is p u b l i s h e d in
the Federal Register together with the r e g u l a t i o n c o m p l i a n c e
date.
Information S o u r c e s
Questions relating to the interpretation, applicability, a n d
c o m p l i a n c e to air quality regulations m a y be a d d r e s s e d to the
REFERENCES
[1] Scofield, F. in Paint Testing Manual, 13th ed., American Society
for Testing and Materials, Philadelphia, 1972, p. 413.
[2] Gordon, J., "Solvent Restriction, Problem or Opportunity," presentation to the Chicago Coatings Society, 13 Nov. 1978.
[3] EPA Policy Statement, Recommended Policy on Control of Volatile Organic Compounds, FederalRegister, 8 July 1977.
[4] "Glossary for Air Pollution Control of Industrial Coating
Operations," EPA-450/3-83-013R, Environmental Protection
Agency, Washington, DC, December 1983.
[5] Berry, J. C., U.S. EPA, "Control of Volatile Organic Compound
(VOC) Emissions from Painting Operations in the United
States," presentation at the International Symposium on Paint
and the Environment, Copenhagen, 12-14 Nov. 1990.
[6] Code of Federal Regulations, Vol. 40, Subchapter C., Part 60,
Appendix A; Amendments in a Rule published in the Federal
Register, Vol. 57, No. 133, 10 July 1992, pp. 30654-30656.
[7] Manual on Determination of Volatile Organic Compounds in
Paints, Inks, and Related Coating Products, ASTM Manual Series,
MNL4, 1989, 2nd ed., 1993.
[8] Procedures for Certifying Quantity of Volatile Organic Compounds Emitted by Paint, Ink and Other Coatings, EPA-450/3-84019, Environmental Protection Agency, Washington, DC, December 1984.
[9] Development of Proposed Standard Test Method for Spray Painting TransferEfficiency, Vols. I and II, EPA Publication Nos. EPA600/2-88-026a and EPA-600/2-88-026b, Environmental Protection Agency, Research Triangle Park, NC.
[10] Method Development for Measuring the VOC Content of WaterBased Coatings, EPA Contract No. 68D90055, Work Assignments No. 28 and 40, Environmental Protection Agency, Research Triangle Park, NC.
MNL17-EB/Jun. 1995
Bituminous Coatings
by Ben J. Carlozzo 1
INTRODUCTION
General Overview
IN THE UNITED STATES,the terms "bituminous" and "asphaltic" are often used interchangeably. In Europe, bitumen refers to the mixture of heavy hydrocarbons, free of inorganic
impurities. Asphalt is often considered the impure form of
the generic material [1]. For our purposes, the ASTM definitions will be used.
ASTM Definitions of Terms Relating to Roofing, Waterproofing, and Bituminous Materials (D 1079-87a) [2] defines
bitumen as either "...(1) a class of amorphous black or dark
colored (solid, semi-solid, or viscous) cementitious substances, natural or manufactured, composed principally of
high molecular weight hydrocarbons, soluble in carbon disulfide, and found in asphalts, tars, pitches and asphaltites; or,
(2) a generic term used to denote any material composed
principally of bitumen."
Asphalt is similarly defined as " . . . a dark brown to black
cementitious material in which the predominating constituents are bitumens which occur in nature or are obtained in
petroleum processing." While the term has historically implied the natural deposits (the Trinidad Lake asphalts on the
Island of Trinidad or the Bermudez Lake, Venezuela asphalts), most asphalt used in the United States today for
coatings applications i s from petroleum processing [3].
15
www.astm.org
Coating Types
The types of asphaltic or bituminous coatings available can
be classified, in a large part, by the industry of use. Industries
considered are:
1. The paints and coatings industry, where bituminous coatings have been used to protect metal from the effects of
water and oxygen degradation.
2. The roofing industry, where asphalt coatings are used extensively to weatherproof buildings.
3. The construction industries, where concrete and mortar
are waterproofed.
4. The paving industry; where the adhesive properties of asphalt as binder is put to good use in roads.
Roof Coatings
In roof coatings, bitumens have been important raw materials since the turn of the century. Today, many commercial
roofing systems use some form of asphalt or chemically mod-
CHAPTER 2 - - B I T U M I N O U S COATINGS
ified asphalt in their construction. The application of an asphalt or polymer-modified hot melt asphaltic material, followed by the application of a reinforcing membrane, is the
basic construction of a modern built-up-roof (BUR).
In some markets, the current industry trend has been away
from the use of hot melt coatings, where a roofing kettle that
heats the materials up to 450~ (232~ to reach their application viscosity is required, and toward cold-applied systems.
Here, the asphalt is usually modified with solvents, fillers, and
thixotropes as well as various additives to result in a formulation that can be applied at ambient temperatures with good
flow properties and that which will subsequently dry or cure
into a weatherproofing membrane.
In these coatings, volatile solvents are varied to control
cure times. In general, the solvents are either mineral spirits
or naphthas. While asbestos was long a preferred additive for
thixotropy and reinforcement, the hazards of working with
and removing old installations with asbestos-containing materials have driven the products toward asbestos-free roofing
materials. This has led to the use of cellulose, synthetic, and
glass fibers as a partial replacement for asbestos. Bentonite
and attapulgite clays are then used to obtain the required
thixotropy. Today, there are still a significant number of manufacturers that continue to use asbestos in their formulations.
The asphalt portion of these coatings usually consists of
materials referred to as cutbacks. Various solvents are used to
cut (solubilize) the asphalt, depending on the cure times
required. The solvent predominantly used today is mineral
spirits, with a flash point (tag closed cup) of 104~ (40~
Faster evaporating versions of these cutbacks have been used
as primers for better substrate adhesion. These materials
generally use faster aromatic solvents, including toluene, xylene, and the aromatic naphthas. The asphalt content varies
from 30 to 70% by weight.
The preceding materials, while they can, in the strictest
sense, be considered coatings, are actually closer to adhesives
in performance; that is, these coatings are applied to hold the
reinforcing membranes together. Although the last coat applied may be a flood coat of the adhesive coating, the roof is
usually not left this way. Weathering characteristics are significantly improved when these roofs are gravel surfaced.
This graveled surface blocks harmful ultraviolet (UV) radiation and serves to improve the fire resistance. The most
common roof gravels are river-washed gravel, crushed stone,
granite, and blast-furnace slag recovered from the iron ore
reduction process and composed of silicates and aluminosilicates of lime [6]. Other materials, also available for this
purpose, include a variety of small, colored roofing granules,
similar to those used on shingles.
From 400 to 600 lb (181 to 272 kg) of river-washed gravel
per 100 ft2 (9.29 m 2) of roof is used, or, if weight considerations are important, 50 to 60 lb (22.68 to 27.2 kg) of the
smaller roofing granules can be used. The bituminous coating
is then an adhesive for these gravels.
Due to weight limitations on existing roofs and costs associated with roof tear-offs and subsequent reroofing, current
philosophy is to maintain the existing roof. When physically
possible, restoration instead of replacement is very cost effective. This requires the use of coatings whose purpose is to
repair damage to the roof and re-establish or maintain the
17
18
Waterproofing Membranes
Bitumen-modified waterproofing membranes are used extensively in the construction industry. The most common
substrate is poured or cast concrete or mortared "cinder
block." Prestressed concrete in the foundations, walls, and
roof decks of high-rise buildings is also a suitable candidate
for these membranes. In the home construction and repair
industries, cinder block foundations and concrete footers are
commonly waterproofed with bitumen-modified polymeric
coatings.
The bitumen of interest in these markets has predominately been coal tar pitch and petroleum asphalts. Waterproofing membranes are generally composed of bitumen in
an elastomeric polymer matrix. The aromatic polyurethanes
are frequently used for this purpose.
In coating structural steel and steel reinforcement bars,
coal tar epoxies have been extensively used. Their composition and purpose is similar to that of pipe coatings used for
the prevention of underground corrosion. Their composition
can be modified to conform to a particular steel coatings
application.
As in other markets, the use of aromatic coal tars is slowly
being replaced by safer soft petroleum asphalts. Environmental issues aside, higher tech systems are beginning to be seen.
Other types of coatings for rebar in the last five years have
included fused epoxy powder coatings systems and polyethylene dip coated systems. While much more expensive than
bitumen-modified systems, their improved performance have
made them of interest.
nature. The anionic and cationic emulsifiers form an emulsion in which the dispersed phase shows a definite charge.
These emulsions are said to "break" upon contact with a
charged aggregate, yielding the exclusion of one phase from
the other. The speed of break can be modified, yielding rapid,
medium, or slow setting emulsions. The cationic versions are
preferred because the coating formed does not re-emulsify.
With anionic emulsifiers, break occurs when emulsions destabilize due to water loss on drying. One disadvantage of this
is the possibility of re-emulsification in the early stages of
cure. Once the coating has dried, water is no longer a problem.
Paving sealers are used to protect new or old asphalt driveways or parking lots. The sealers are generally coal tar in
nature due to good resistance to gas and oil. Asphalt sealers
can also be used, but they must be latex or polymer modified
to improve solvent resistance.
Other types of bituminous coatings used in the paving
industry include slurry seals and micro surfacing, which uses
latex or polymer-modified asphalts with fine aggregate filler
as a surface treatment for repair of minor damage to roads.
Coal tar is not used in this application because the resulting
coating is too slippery. Tack coats consisting of asphalt
cutbacks are also used when one layer of asphalt needs to be
adhered to another.
I D E N T I F I C A T I O N OF B I T U M I N O U S
MATERIALS
This section will catalogue several test methods currently
available through ASTM for characterization of bituminous
paints and coatings. Many of these methods are familiar to
the coatings chemist as standard paint-related tests found in
Volumes 6.01 through 6.04 of the Annual Book of ASTM Standards. Several others are under the jurisdiction of Committee
D 8 on Roofing, Waterproofing, and Bituminous Materials.
These methods appear in Volume 4.04 of the Annual Book of
ASTM Standards.
Tests on Bituminous
Materials
General
D 4-86
D 5-86
D 36-86
D 70-82
D 88-81
D 92-90
D 95-83
in Trichloroethylene
D 2521-76 Specification for Asphalt Used in Canal, Ditch,
and Pond Lining
20
Paving Sealers
D 3320-90 Specification for Emulsified Coal Tar Pitch
(Mineral Colloid Type)
D 3423-84 Practice for Application of Emulsified Coal Tar
Pitch (Mineral Colloid Type)
D 4866-88 Performance Specification for Coal Tar Pitch
Emulsion Pavement Sealer Mix Formulations
Containing Mineral Aggregates and Optional
Polymeric Admixtures
General
Specialty Coatings
D 41-85
D 43-73
Emulsion Coatings
Roof Coatings
D 41-85
D 43-73
Waterproofing Membranes
D 41-85
D 43-73
General
D 466-42 Method of Testing Films Deposited from
Bituminous Emulsions
D 529-90 Practice for Accelerated Weathering Test
Conditions and Procedures for Bituminous
Materials (Carbon-Arc Method)
D 1187-82 Test Method for Asphalt-Base Emulsions for Use
as Protective Coatings for Metal
D 2939-78 Method for Testing Emulsified Bitumens Used as
Protective Coatings
Anionic Emulsions
D 1227-87 Specification for Emulsified Asphalt Used as a
Protective Coating For Built-Up Roofing
Non-Ionic Emulsions
D 1227-87 Specification for Emulsified Asphalt Used as a
Protective Coating For Built-Up Roofing
Cationic Emulsions
D 1227-87 Specification for Emulsified Asphalt Used as a
Protective Coating For Built-Up Roofing
22
CONCLUSION
B i t u m i n o u s coatings are still used extensively today. The
waterproofing a n d adhesive properties, coupled with the relatively inexpensive costs for m o s t b i t u m i n o u s materials, continue to drive their use in m a n y diverse industrial applications. The p r e c e d i n g i n f o r m a t i o n will give the r e a d e r an
u n d e r s t a n d i n g of the c h e m i s t r y a n d uses of b i t u m i n o u s coatings in i n d u s t r y a n d a realization that even several t h o u s a n d
years after t h e i r discovery a n d first use the usage of these
b i t u m i n o u s r a w m a t e r i a l s as an engineering r a w m a t e r i a l is
still growing.
REFERENCES
[1] Barth, E.J., Asphalt: Science and Technology, Gordon and
Breach Science Publishers, New York, 1962.
MNL17-EB/Jun. 1995
Cellulose Esters
by L. G. Curtis 1
possible. Hydroxyl content and molecular weight possibilities expand this range even further.
FACTORS A F F E C T I N G P E R F O R M A N C E OF
CELLULOSE E S T E R S IN COATINGS
Performance properties of cellulose acetate buytrate are
affected by the chemical composition and the viscosity of the
ester. As butyryl increases, solubility, compatibility, flexibility, diluent tolerance, and moisture resistance are increased.
Lower butyryl levels are associated with decreased water
tolerance, grease resistance, hardness, and increased melting
range. As the hydroxyl content of cellulose acetate butyrate
varies, several characteristics are also affected. Below 1%
hydroxyl, solubility in common coatings type solvents is limited but improves as the hydroxyl increases. At levels around
5%, solubility in lower molecular weight alcohols occurs. At
higher hydroxyl levels, reactivity increases, providing crosslinking capability with amino and isocyanate resins. However, in noncross-linking systems, higher levels decrease
moisture resistance due to increased hydrophilicity.
The viscosity of cellulose esters also influences physical
properties of the ester as well as coatings formulated with
them. Increasing the viscosity of a particular ester by increasing the molecular weight slightly lowers its solubility and
compatibility with other resins, but does not affect hardness
and density. Generally, toughness and flexibility are improved with increased molecular weight and viscosity.
P R O D U C T I O N OF CELLULOSE E S T E R S
For the production of coating-grade cellulose esters, three
organic acids and anhydrides are used, either separately or in
combination with each other. Cellulose acetate is the simplest cellulose ester since only acetic acid and acetic anhydride are used in the esterification reaction. If two different
organic acids and anhydrides are used simultaneously, the
resultant product is referred to as a mixed ester. Examples of
mixed cellulose esters are cellulose acetate butyrate and cellulose acetate propionate.
In addition to esterification and hydrolysis, several subsequent processing steps are required in the manufacture of
cellulose esters including filtration, precipitation, washing,
dewatering, drying, and screening. The final product is a dry,
free-flowing powder in most instances, although other physical forms can be produced. Unlike cellulose nitrate, organic
esters of cellulose are low in flammability and present no
handling hazards.
APPLICATIONS F O R CELLULOSE E S T E R S
IN COATINGS
T Y P E S OF CELLULOSE E S T E R S
Protective and decorative coatings for various substrates
can be formulated either as air-dry lacquer systems or as
converting or curing types often referred to as cross-linked
enamels. In many such coatings, cellulose esters are included
as either a modifying resin to impart a specific property to the
coating or to function as the primary film-forming resin in
the formulation. Both types of coatings can be applied over a
variety of substrates ranging from paper products to automobiles. Some areas in which cellulose esters are used include
automotive OEM and refinish, wood furniture coatings, leather coatings, printing inks, plastic coatings, aircraft coatings, cable lacquers, and various fabric coatings. Cellulose
esters are used in coatings to impart such properties as rapid-
23
Copyright9 1995 by ASTMInternational
www.astm.org
24
Viscosity,~ s
Acetyl,b %
CA-394-608
CA-398-3
CA-398-6
CA-398-10
CA-398-30
60.00
3.00
6.00
10.00
30.00
39.5
39.8
39.8
39.8
39.8
CAP-482-0.5
CAP-482-20
CAP-504-0.2
0.50
20.00
0.20
2.5
2.5
0.6
CAB- 171-158
CAB-321-0.1
CAB-381-0.1
CAB-381-0.5
CAB-381-2
CAB-381-20BP
CAB-381-20
CAB-381-20BP
CAB-500-5
CAB-531-1
CAB-551-0.01
CAB-551-0.2
CAB-553-0.4
15.00
0.10
0.10
0.50
2.00
2.20
20.00
16.00
5.00
1.90
0.01
0.20
0.40
29.5
18.5
13.5
13.5
13.5
14.5
13.5
15.5
4.0
3.0
2.0
2.0
2.0
Propionyl, %
Butyryl, %
Hydroxyl, %
Melting Range, ~
4.0
3.5
3.5
240-260
230-250
230-250
230-250
230-250
...
-..
--.
2.6
1.8
5.0
188-210
188-210
188-210
16.0
31.2
37.0
37.0
37.0
36.0
36.0
36.0
51.0
50.0
52.0
52.0
46.0
1.1
1.3
1.3
1.3
1.3
1.8
1.8
0.8
1.0
1.7
1.8
1.5
4.8
230-240
165-175
155-165
155-165
175-185
175-185
195-205
185-195
165-175
135-150
130-140
127-142
150-160
Celhtlose Acetate
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
~ASTMTest Method for Cellulose Acetate Proprionate and Cellulose Acetate Butyrate (Formula A) (D 817) and Test Methods for Viscosity of Cellulose Derivatives
by Ball-Drop Method (D 1343).
bASTM D 817.
d r y i n g , p i g m e n t c o n t r o l , v i s c o s i t y c o n t r o l , film t o u g h n e s s ,
and polishability.
Viscosity
V i s c o s i t y m e a s u r e m e n t o f c e l l u l o s e a c e t a t e is c a r r i e d o u t in
a c c o r d a n c e w i t h A S T M T e s t M e t h o d s f o r V i s c o s i t y o f Cellul o s e D e r i v a t i v e s b y B a l l - D r o p M e t h o d (D 1343) b a s e d o n t h e
ball d r o p o r f a l l i n g ball p r i n c i p l e . A p r e c i s i o n H o e p p l e r visc o m e t e r is u s e d i n m o s t v i s c o s i t y d e t e r m i n a t i o n s w i t h r e s u l t s
r e p o r t e d in ASTM seconds. F o r m u l a t i o n s for viscosity determ i n a t i o n a r e s h o w n in T a b l e 2.
20~
70
. . .
8
. . .
......
20 ~
20 b
80
. . .
. . . . . . . .
-..
8
. . . . . . .
72
15c
20~
l(F
. . . . . . . . .
.
80
...
8.5
......
. . . . .
9
76.5
.-.
81
1.24
aFor cellulose acetate having a max of 40.5% acetyl and for most mixed
esters having less than about 40% acetyl and more than about 8% propionyl or
butyryl.
bFor cellulose acetate having 40.5 to 42.7% acetyl and for most of the
commercial cellulose acetate propionate and acetate butyrates.
CFor cellulose acetate having 42.7 to 44.8% acetyl and for most of the
commercial cellulose acetate propionate and acetate butyrates; particularly
good for esters containing more than 40% acetyl.
aAcetone (99.4 -+ 0.1%) containing 0.3 to 0.5% water and under 0.3% ethyl
alcohol.
eEthyl alcohol (95% by volume). Formulas 2B, 3A, or 30 denatured ethyl
alcohol may be used.
fMethyl alcohol (sp gr 20/20~ = 0.785 to 0.795).
gMethylene chloride having a boiling range of 39.2 to 40.0~ and less than
0.001% acidity calculated as HCL
T E S T I N G OF CELLULOSE ACETATE
P R O P I O N A T E A N D CELLULOSE ACETATE
BUTYRATE
ASTM Test Method for Cellulose Acetate Propionate and
Cellulose Acetate Butyrate (D 817) contains the following
25
tests: acetyl and propionyl or butyryl contents; apparent acetyl content; free acidity; ash; color and haze, heat stability,
hydroxyl content; moisture content; sulfur content; and viscosity. Usually color and haze and viscosity are the only tests
run by the coatings manufacturer. The test methods are the
same as those used in the testing of cellulose acetate.
MNL17-EB/Jun. 1995
Drying Oils
by Joseph V. K o l e s k e I
HOCH2--CH(OH)--CH2OH + 3 RxCOOH
Glycerol
Fatty Acid
RxCOOCH2--CH(OOCRx)--CH2OOCRx + 3 H20
Triglyceride or Drying Oil
Water
CH~--O--OC--Ra
CH--O--OC--Rb
CH2--O--OC--R c
Generalized Triglyceride
where R a, Rb, and R~ are the same or different and represent
the hydrocarbon chain residues of fatty acids. In simple
terms, this means that most oils are mixed triglycerides. The
triglycerides are produced by the condensation reaction that
occurs between a glycerol molecule and three fatty acid molecules:
www.astm.org
Oil Class
Iodine Value
Drying oil
Semidrying
Nondrying
> 140
125- 140
< 125
C H A P T E R 4 - - D R Y I N G OILS
27
No.
Carbon
Atoms
No.
Double
Bonds
Structural Formula
Linolenic
Linoleic
Oleic
Eleostearic
Licanic
Ricinoleic
18
18
18
18
18
18
3
2
1
3
3
1
HOOC(CH2)7CH=CHCHECH~CHCH2CH=CHCH2CH 3
HOOC(CH2)7CH~CHCH2CH~CH(CH2)4CH3
HOOC(CH2)7CH~---CH(CH2)TCH3
HOOC(CH2)7CH~CHCH~--~-CHCH~---CH(CH2)aCH3
HOOC(CH2)ECH(O)(CH2)4CH--~CHCH--~CHCH--~CH(CH2)3CH3
HOOC(CH2)7CH~---CHCH2CH(OH)(CH2)5CH 3
drying oils a n d the ASTM m e t h o d t h a t contains o t h e r specification p r o p e r t i e s are d e l i n e a t e d in Table 5. The ASTM methods cited in Table 5 c o n t a i n references to o t h e r ASTM methods a p p r o p r i a t e for o b t a i n i n g the i n d i c a t e d p r o p e r t i e s a n d
for o t h e r p e r t i n e n t properties. The following drying oils are
the m o s t i m p o r t a n t m e m b e r s of this class of coating r a w
materials.
Castor oil is o b t a i n e d from b e a n s of the p l a n t Ricinus
communis. The oil differs f r o m the o t h e r oils in t h a t it is
m a d e u p of a very high p e r c e n t a g e of the hydroxyl-containing
ricinoleic acid residue. Although the fatty a c i d residues in this
oil c o n t a i n on the average only a single d o u b l e b o n d a n d for
this r e a s o n c a s t o r oil is essentially a n o n d r y i n g oil, it can b e
converted into a drying oil b y a d e h y d r a t i o n process in w h i c h
its hydroxyl group a n d a n a d j a c e n t h y d r o g e n a t o m are rem o v e d as w a t e r to form a double b o n d conjugate to the previously existing double bond. The resultant p r o d u c t is k n o w n
as d e h y d r a t e d castor oil, w h i c h has g o o d drying characteristics.
Cottonseed oil is o b t a i n e d from the p l a n t Gossypium
malvaceae. Although it is a drying oil, cottonseed oil is s e l d o m
u s e d as a n oil in the p a i n t a n d coating industry. Its m a i n use
is as a source of fatty acids that are used in the m a n u f a c t u r e
of alkyd resins.
Linseed oil, w h i c h is o b t a i n e d f r o m seed of the flax p l a n t
Linum usitatissimum, is the m o s t c o m m o n a n d widely used
oil. It has a high degree of u n s a t u r a t i o n , w h i c h i m p a r t s a
short drying time, due to its large percentages of linolenic a n d
linoleic triglycerides. It is m a r k e t e d in a n u m b e r of modifications including alkali-refined, acid-refined, boiled, blown,
a n d p o l y m e r i z e d linseed oil [2]. P o l y m e r i z e d linseed oils of
various acid values a n d viscosities are available.
Oiticica oil is o b t a i n e d f r o m the nuts of the tree Licana
rigida. It has a very high licanic acid content, a n d the three
c o n j u g a t e d d o u b l e b o n d s of this acid result in r a p i d drying
TABLE 3--Weight percentage of major unsaturated fatty acid residues in selected drying oils [2,3] (remainder of
oils is essentially all saturated fatty acid residues).
Drying Oil
Cottonseed
Castor
Linseed
Oiticica
Safflower
Soybean
Sunfloweff
Tall Oil Fatty Acids
Tung
Linolenic
Linoleic
.-.
40
...
3
52
16
. . . . . .
1
75
9
51
2
75-52
3
41
3
4
. . .
. . . .
. . .
.-. . .
. . .
. . .
. . .
80
Licanic
. .
. .
. .
.
.
.
.
.
.
.
.
Ricinoleic
.
.
.
.
.
.
.
.
.
. . .
87
. .
78
. .
. .
. .
. .
. . .
-..
28
Oil
Specific
Gravity,
25.5/25.5~
Cottonseed
Dehydrated castor
Fish
Linseed
Oiticica
Safflower
Soybean
Sunflower
Tall oil
Tung
0.919
0.931
0.925
0.926
0.967
0.922
0.920
0.917
.-.
0.915
Iodine
Value,
Wijs
105
135
158
180
150
145
135
135
133
170
Saponification
Value
Acid
Value
Refractive
Index,
25~
192
190
187
190
190
192
190
192
196
192
1.0
5.0
4.0
3.0
4.0
2.0
2.5
2.0
194.0
0.2
1.465
1.481
1.485
1.478
1.510
1.474
1.473
1.473
-..
1.517
TABLE 5--Selected property requirements for drying oils (indicated ASTM method has other requirements).
Oil
Specific
Gravity,
25/25~
Castor, raw
Dehydrated castor
Linseed, raw
Oiticica
Safflower
Soybean, refined
Tung, raw
0.957-0.961
0.926-0.937
0.926-0.931
0.972 (min)
0.922-0.927
0.917-0.924
0.933-0.938
Iodine
Value,
Wijs
83-88
125-145
177 (min)
135 (min)
140-150
126 (min)
163
Saponification
Value
Acid
Value,
max
ASTM
Method
176-184
188-195
189.0-195.0
None
189-195
189-195
I89-195
2.0
6
4.0
8.0
3.0
0.3
5.0
D 960
D 961
D 234
D 601
D 1392
D 1462
D 12
CHAPTER 4 - - D R Y I N G OILS
t h a t have c o n j u g a t e d double b o n d or o t h e r gelling characteristics. ASTM S t a n d a r d G u i d e for Testing Drying Oils (D 555)
is an overall guide to selection a n d use of p r o c e d u r e s for
testing drying oils that are c o m m o n l y u s e d in coatings.
REFERENCES
[1] "Fats and Oils Industry Overview," Chemical Economics Handbook, SRI International, Nov. 1990.
[2] Rheineck, A. E. and Austin, R. O., Film Forming Compositions,
R.R. Myers and J. S. Long, Eds., Marcel Dekker, Inc., New
York, Vol. 1, No. 2, 1968.
[3] Gunstone, F. D., Chemistry and Biochemistry of Fatty Acids and
Their Glycerides, 2nd Ed., Chapman and Hall, Ltd., 1967.
29
MNL17-EB/Jun. 1995
Applications
M E T A L L I C S O A P S AS B O D Y I N G A N D
FLATTING AGENTS
Aluminum stearates, aluminum octoates, and calcium
linoleate pulp were at one time widely used as bodying and
pigment-suspending agents in solvent-based coatings. Their
advantages include fairly high efficiency and ease of incorporation. However, they have a number of deficiencies, including sensitivity to variations in the formulation and in the
processing of paints, as well as adverse effects on film hardness and resistance properties. As a result, they have been
replaced to a considerable extent by the bentonite clay and
organic wax derivatives [2].
Zinc and calcium stearates are used on occasion as flatting
additives in clear solvent-based coatings. However, precipitated and fumed silicas are now more commonly used for this
purpose. Zinc stearate is also used to facilitate sanding of
primers and sealers for wood furniture finishing [2].
Acids
Catalysts
Potassium, lithium,
cobalt, copper, tin,
zinc, manganese
Octoates, naphthenates,
laurates,
neodecanoates
Stabilizers
Proprietary, sulfates,
carbonates, stearates
Biocides
Naphthenates, octoates,
phenyl acetates,
phenyl oleates,
laurates, butyl oxides
Bodying
agents
Aluminum, calcium
Stearates, octoates,
linoleates
Stearates
The induction period occurs because most drying oils contain natural antioxidants, the effects of which must be overcome before the drying process can begin. Oxygen is then
absorbed from the air at the unsaturated sites on the oil
molecule, and, as the absorption continues, forms peroxides.
These peroxides then decompose to form free radicals which
act as catalysts to promote cross-linking of the oil or resin
molecules at the unsaturated sites, resulting in dried films.
These steps will occur in the absence of driers, but driers
accelerate the process by means of the following mechanisms
[1,5]:
T H E O R Y OF O X I D A T I V E D R Y I N G A N D
F U N C T I O N OF D R I E R S [1,5]
Metals
Driers
www.astm.org
Active
Lead
1
Calcium
Zirconium
Zinc
Iron
Rare Earth
Cerium
Aluminum
31
Water-dispersible driers may be prepared by adding nonionic surfactants to naphthenate or synthetic acid driers.
However, proprietary cobalt and manganese drier compounds are available that are purported to be more suitable
for water-based coatings.
Trade names of the various commercial drier types available are listed in Table 2.
MISCELLANEOUS DRIERS
Auxiliary
D E S C R I P T I O N OF D R I E R ACIDS
Restrictions on solvent emissions have stimulated the development of both higher-solids and water-reducible coatings. In the process of formulating these coatings, chemists
are experiencing difficulty obtaining satisfactory drying
properties with the conventional metallic soap driers. Alternative drier compounds, including both organics and proprietary metallic complexes, are currently being offered [6].
Some typical examples are shown in Table 3. They are usually
recommended in combination with conventional metallic
soap driers for improved drying efficiency.
Another class of metallic compounds closely related to
driers are loss of dry inhibitors or "feeder" driers. These are
compounds designed to prevent loss of drying efficiency of
paints on aging resulting from the adsorption of driers by
pigments, particularly carbon black and organic red pigments. They function by dissolving gradually into the coating
vehicle so that the metals are available over a period of time
rather than immediately. In this manner, they replace the
drier metals that have been adsorbed by the pigments,
TABLE
Type of Drier
Synthetic acid
Octoate
Hex-Cem
Octoate
Mooney Chemical,
division of OMG
Huls America
Troy Corp.
Mooney Chemical,
division of OMG
Huls America
Neodecanoate
Ten-Cem
Mooney Chemical,
division of OMG
Naphthenate
Nap-All
Mooney Chemical,
division of OMG
Huls America
Troy Corp.
Nuodex
Troykyd
Tallates
Lin-All
Mooney Chemical,
division of OMG
Water dispersible
Hydro-Cem
Mooney Chemical,
division of OMG
Mooney Chemical,
division of OMG
Huls America
Troy Corp.
Ultra adhesives
Ultra adhesives
Ultra adhesives
Ultra adhesives
Hydro-Cure
Nuocure
Troykyd WD
Calcicat
Aquacat
Magnacat
Zircat
32
Trade Name
Company
Activ-8
Drymax
Nutra ADR 10%
R.T. Vanderbilt
Co.
Mooney
Chemicals Inc.
Huls America
Huls America
Huls America
Dri-RX
Composition
1,10-phenanthroline
2,2'-dipyridyl
2,2'-dipyridyl
proprietary metal
complex
proprietary metal
complex
thereby maintaining satisfactory drying on prolonged storage. Lead compounds, including litharge, were used formerly
but have been replaced by lead-free compounds based primarily on less soluble forms of cobalt and other drier metals.
Commercially available feeder driers are listed in Table 4.
All are lead-free metal complexes except for the last item [3].
D R I E R L E V E L S IN COATINGS
Drier requirements for coatings are usually expressed in
terms of percent drier metal based on oxidizable vehicle nonvolatile content. A typical calculation is as follows [1]:
Assume:
1. In a 1000-g paint formulation, there are 300 g of vehicle
nonvolatile.
2. Cobalt drier used is 12% metal by weight.
3. Calcium drier used is 10% metal by weight.
4. Required for optimum drying: 0.05% cobalt plus 0.2% calcium (percent metal based on vehicle nonvolatile).
per 1000 g of paint:
Cobalt metal required = 0.0005 x 300 g = 0.15 g
Calcium metal required = 0.002 x 300 g = 0.6 g
(10% calcium drier required) = (0.6 g calcium metal) = (6 g
(0.10 g metal/g drier)
drier as supplied)
(12% cobalt drier required) = (0.15 g cobalt metal) = (1.25 g
(0.12 g metal/g drier)
drier as supplied)
The optimum levels of drier metal required will vary depending on the type of resin system employed and the conditions of drying. Typical metal concentrations for a number of
common vehicles are indicated in Table 5.
Company
Mooney Chemical,
division of OMG
Mooney Chemical,
division of OMG
Troy Corporation
Huls America
Huls America
Huls America
T E S T I N G OF D R Y I N G E F F I C I E N C Y
Trade Name
Hex-Cem LFD
Hydroxy Ten-Cem
Cobalt
Troykyd Perma Dry
Nuact Cobalt 254
Nuact NOPB
Nuact Paste (lead-based)
The procedures used to determine the stages of film formation during the drying of coatings are described in ASTM Test
Methods for Drying, Curing, or Film Formation of Organic
Coatings at Room Temperature (D 1640) [4]. With coatings
containing metallic driers, it is recommended that the paint
samples age overnight following the drier additions before
drying tests. The drying conditions, shown in Table 6, are
usually specified but are subject to agreement between the
purchaser and the seller.
The methods used to determine the various stages of drying
may be summarized as follows:
1. Set-To-Touch-Time--no
33
Chain-stopped alkyd
Manganese
0.04-0.06
0.04-0.06
0.04-0.06
Zirconium
Calcium
0,1-0.2
0.1-0.3
0.1-0.3
0.1-0.2
0.04-0.06
0.04-0.06
0.04-0.06
0.1-0.3
0.04-0.06
0.04-0.06
0.04-0.06
0.1-0.3
0.1-0.2
0.1-0.2
0.05-0.08
0.05-0.08
0,0 I-0.03
Oil-modified urethane
0.02-0.04
0.02-0.04
0,1
Zinc
0.02
Epoxy Ester
0.02-0.03
0.02-0.03
0.02-0.04
0.1-0.3
0.1-0.2
0.2
0.1
O.I-0.5
0.1-0.3
0.1-0.3
0.02
0,02-0.04
0.02-0.04
0.02-0.03
0.02-0.03
0.02-0.04
0.03-0.05
0.03-0.05
0.04-0.08
Oleoresinous varnish
0.02-0.06
Vinyltoluene alkyd
0.02-0.04
0.02-0.04
0.2
0.1-0.2
0.1-0.3
0.1-0.2
0.1-0.15
0.1-0.3
0.2-0.3
0.2-0.3
0.1-0.2
0.1-0.2
0.1-0.15
0, I-0.2
0.1-0.2
0.1
0,1
0.2
0.1
0.1
0.04-0.06
0.5-0.9
0.04-0.06
Water-based alkyds
(water dispersible
driers)
2,2'-Dipyridyl,
30%
0.1-0.3
0.1-0.2
0.02-0.04
Linseed oil
1,10-Phenantbroline
0.5-0.9
0.04-0.06
0.2-0.4
0.04-0.06
0.04-0.06
0.05-0.1
0.1-0.3
0.15-0.3
Typical Value
Ambient temperature
Relative humidity
Film thickness (dry)
Substrate
Lighting
Applicators
Coating viscosity
23 + 2~
50 + 5%
12.5 to 45 ~m
Clean glass
No direct sunlight
Doctor blades
Close to normal application
0.2
0.2
0.2-0.4
0.1-0.3
0.15-0.2
0.1-0.3
S P E C I F I C A T I O N S F O R LIQUID P A I N T
DRIER
Drier specifications as described in ASTM Specification for
Liquid Paint Driers (D 600) involve the following classes:
Class A
2-ethyl hexanoic acids in p e t r o l e u m spirits.
Class B
N a p h t h e n i c acids in p e t r o l e u m spirits.
Class C
N e o d e c a n o i c acids in p e t r o l e u m spirits.
Class D
Tall oil fatty acids in p e t r o l e u m spirits.
Class E
Any of the above, plus additives to m a k e the
driers w a t e r dispersible.
Class F
Other unidentified acids a n d acid blends.
A c o m p r e h e n s i v e table of liquid p a i n t driers of the above
classes is given in ASTM D 600 [4]. The typical p r o p e r t i e s of
the driers listed a n d r e p r o d u c e d in Table 7 include p e r c e n t
m e t a l concentration, p e r c e n t nonvolatile content, specific
gravity, G a r d n e r Color, a n d G a r d n e r - H o l d t viscosity.
34
Class
Metal
A
A
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Calcium
Cerium
Cerium
Cobalt
Cobalt
Cobalt
Cobalt
Cobalt
Cobalt
Cobalt
Cobalt
Cobalt
Iron
Iron
Iron
Iron
Iron
Lead
Lead
Lead
Lead
Lead
Lead
Lead
Manganese
Manganese
B
B
C
D
E
E
F
F
F
F
F
A
B
A
A
B
C
D
E
E
F
F
A
B
F
F
F
A
B
C
D
E
F
F
A
B
Metal
Concentration, %
Min
Max
3.9
4.9
3.9
4.9
4.9
3.9
3.9
5.9
3.9
4.9
5.9
7.9
9.9
5.9
5.9
5.9
11.8
5.9
11.8
5.9
4.9
5.9
5.9
11.8
5.9
5.9
5.9
8.9
11.8
23.8
23.8
23.8
23.8
23.8
23.8
35.8
5.9
5.9
4.1
5.1
4.1
5.1
5.1
4.1
4.1
6.1
4.1
4.1
6.1
8.1
10.1
6.1
6.1
6.1
12.2
6.1
12.2
6.1
5.1
6.1
6.1
12.2
6.1
6.1
6.1
9.1
12.2
24.2
24.2
24.2
24.2
24.2
24.2
36.2
6.1
6.1
Nonvolative
Matter, %, Max
50
60
70
85
46
66
63
76
50
60
74
70
65
30
57
45
90
67
65
72
60
71
70
80
50
67
50
78
75
65
67
61
66
71
67
81
50
66
Typical Specific
Gravity, 25/25~
Min
Max
0.884 C
0.894
0.902
0.932
0.888
0.890
0.905
0.922
0.850
0.900
0.873
0.958
1.000
0.856
0.925
0.875
1.008
0.918
0.984
0.912
0.926
0.945
0.870
1.014
0.900
0.960
0.905
0.950
1.068
1.090
1.125
1.100
1.100
1.125
1.080
1.350
0.888
0.930
.-0.912
0.937
0.970
..0.918
0.930
0.960
0.884
0.936
0.948
--.
1.030
...
..0.900
1.060
0.970
...
0.956
-..
0.960
0.958
1.040
0.930
0.990
0.930
0.985
..1.110
1.160
...
1.125
1.150
1.140
1.393
0.920
0.965
Colorb Gardner
(Test Method
D 1544)
G-H Viscosity
(Test Method
D 1545)
3
5
10
11
2
9
A
C
D
T
A
B
5
3
4
6
5
7-8
N
A
B
N
B
K
17
Blue/purple
Blue/purple
Blue/purple
Blue
Purple
Red/purple
Blue/purple
Blue/violet
Blue/violet
Dark brown
Dark brown
Brown
Brown
Brown
3
11
2
10
7
10
8
Red/brown
17
A1
A
J
B
A
C
A
I
A
J
A
M
A
A
A
A
B
B
A2
A
A
H
A
D
Continued
T E S T I N G OF LIQUID P A I N T D R I E R S
7. Viscosity--According to A S T M T e s t M e t h o d for V i s c o s i t y
ing of D r y i n g Efficiency."
3.
4.
5.
o f T r a n s p a r e n t L i q u i d b y B u b b l e T i m e M e t h o d (D 1545).
This involves c o m p a r i n g t h e t i m e of travel of b u b b l e s in
t u b e s of t h e s a m p l e v e r s u s G a r d n e r - H o l d t s t a n d a r d tubes.
T h e s t a n d a r d s w e r e f o r m e r l y d e s i g n a t e d by l e t t e r b u t are
n o w i n d i c a t e d d i r e c t l y in stokes. A table in D 1545 indicates t h e c o n v e r s i o n f r o m letters to stokes.
C h e m i c a l analysis is u s e d to d e t e r m i n e t h e m e t a l c o n t e n t of
l i q u i d p a i n t driers. T h e E D T A m e t h o d is u s e d for m o s t d r i e r
m e t a l s (Table 8). T h e l i q u i d d r i e r is d i s s o l v e d o r d i g e s t e d in
solvents a n d t h e n t r e a t e d w i t h a n excess of s t a n d a r d E D T A
s o l u t i o n ( d i s o d i u m salt of e t h y l e n e d i a m i n e t e t r a c e t i c a c i d dihydrate). T h e excess of E D T A is t h e n t i t r a t e d to a n e n d p o i n t
d e t e r m i n e d b y a specified i n d i c a t o r . This m e t h o d is a p p l i c a ble to single m e t a l d r i e r s only, n o t to d r i e r blends. An E D T A
m e t h o d is n o t yet a v a i l a b l e for c e r i u m , a n d a n o x i d i m e t r i c
d e t e r m i n a t i o n is specified [ASTM Test M e t h o d for C e r i u m in
P a i n t D r i e r s by O x i d i m e t r i c D e t e r m i n a t i o n (D 3970)]. T a b l e 8
o u t l i n e s t h e A S T M d e s i g n a t i o n s , i n d i c a t o r s , a n d t i t r a t i n g sol u t i o n s for analysis o f d r i e r m e t a l s by E D T A titration.
35
TABLE 7--Continued
Class
Metal
C
D
E
E
F
F
F
A
A
A
B
C
A
A
B
B
D
E
F
F
A
A
A
A
C
C
E
E
F
F
F
F
Manganese
Manganese
Manganese
Manganese
Manganese
Manganese
Manganese
Nickel
Rare earth a
Rare earth
Rare earth
Rare earth
Zinc
Zinc
Zinc
Zinc
Zinc
Zinc
Zinc
Zinc
Zirconium
Zirconium
Zirconium
Zirconium
Zirconium
Zirconium
Zirconium
Zirconmm
Zirconmm
Zirconium
Zirconium
Zirconium
Metal
Concentration, %
Min
Max
5.9
5.9
4.9
5.9
5.9
8.9
11.8
9.9
5.9
11.8
3.9
5.9
7.9
17.8
7.9
9.9
7.9
7.9
7.9
15.8
5.9
11.8
17.8
23.8
5.9
11.8
5.9
11.8
5.9
11.8
17.8
23.8
6.1
6.1
5.1
6.1
6.1
9.1
12.2
10.1
6.1
12.2
4.1
6.1
8.1
18.2
8.1
10.1
8.1
8.1
8.1
16.2
6.1
12.2
18.2
24.2
6.1
12.2
6.1
12.2
6.1
12.2
18.2
24.2
Typical Specific
Gravity, 25/25~
Min
Max
Nonvolative
Matter, %, Max
50
72
42
69
55
80
75
70
30
55
35
35
50
90
70
75
70
42
60
80
30
56
55
77
23
46
31
55
28
55
80
93
0,870
0.942
0.911
0.942
0.870
0.950
1.044
1.032
0.630
0.977
0.840
0.876
0.880
1.068
0.915
0.980
1.008
0.946
0.855
1.020
0.860
0.960
1.070
1.240
0.864
0.976
0.864
0.975
0.855
.
.
1.090
1.240
.-.
0.972
...
0.965
1.020
1.020
...
.-.
0.880
-..
0.855
...
0.906
1.130
0.960
1.044
...
...
0.963
1.100
0.864
0.992
1.074
-..
.-...
...
1.020
0.870
.
.
1.130
1.260
Colorb Gardner
(Test Method
D 1544)
G-H Viscosity
(Test Method
D 1545)
10
Brown
Brown
Brown
18
18
16
Green
6
Yellow/green
10
8
6
7
9
8
11
2
7
3
2
4
3
2
2
2
4
4
2
.
.
.
.
4
6
A
E
E
E
A
H
C
A
E
C
A
A5
G
Z
A
L
D
A
C
B
A
A
A
J
A5
A
A
A
A5
.
.
Z
J
"Source: National Paint and Coatings Association, Chemical Specialties Section, Raw Material Index, April 1978 edition per Gardner Method D 1544.
blf off the scale, as observed by the unaided eye.
~'Only one drier was listed in this category.
aThe metal content represents total rare earth metals calculated as cerium, but the drier contains cerium and lanthanum, as well as minor amounts of other rare
earth metals.
TABLE 8 - - M e t a l analysis by EDTA titration.
Metal
Cobalt
Lead
Manganese
Calcium or zinc
Iron
Zirc
Vanadium
Total rare earth
ASTM
Method
D
D
D
D
D
D
D
D
2373
2374
2375
2613
3804
3969
3988
3989
Solvent
Indicator
Titrating
Solution
PANa
PAN~
E r i o c h r o m e hlack-T
E r i o c h r o m e black-T
E r i o c h r o m e black-T
Xylenol orange
Xylenol orange
Xylenol orange
Cupric sulfate
Cupric sulfate
Zinc chloride
Zinc chloride
Zinc chloride
B i s m u t h nitrate
Zinc chloride
Zinc chloride
a1(2-Pyridylazo)-2-Naphthenol.
REFERENCES
[1] Hurley, R., "Metal Soaps: Drier Stabilizers a n d Related Compounds," Handbook of Coatings Additives, Chap. 13, Marcel Dekker, Inc., New York, 1987, pp. 485-509.
[2] Schnall, M., "Thickeners for Solvent-Based Coatings," Handbook
of Coatings Additives, Chap. 3, Marcel Dekker, Inc., New York,
1987, pp. 33-34.
[3] Raw Materials Index, Chemical Specialties Section, National Paint
& Coatings Association, W a s h i n g t o n , DC, March 1989, pp. 2-11
a n d pp. 22-27.
MNL17-EB/Jun. 1995
CH 3
I
(--CH2--C - - ) - -
I
--(--CH2--C--)--
I
C ~0
OR
An acrylate
I
C=0
OR
A methacrylate
Methyl
Ethyl
Butyl
4
7
230
1000
33
3
750
1800
2000
Polyacrylates
Methyl
Ethyl
Butyl
1Group leader and research fellow, Architectural Coatings Research, Rohm and Haas Co., Research Laboratories, 727 Norristown
Road, Spring House, PA 19477.
NOTE:Psi + 14.22 = k g / c m 2.
(Reprinted with permissionof Modem Paint and Coatings. Copyright1973).
39
9000
5000
1000
www.astm.org
40
solvent-based systems because of the industry's need to control organic emissions. Over the past 20 years, acrylic emulsion manufacturers have made great strides in improving the
properties of acrylic emulsions so that they now offer performance similar to the solvent-based coatings they are replacing.
When the first acrylic emulsion designed for use in house
paints was introduced in 1953, it had the low-odor, quickdrying, and easy cleanup features of its water-based competitors, styrene-butadiene and poly(vinyl acetate) emulsions;
but, in addition, it offered excellent exterior durability that
allowed use in exterior paints. During the past 40 years, it has
been good exterior durability that enabled acrylic emulsions
to replace solvent alkyds as the dominant binder in the exterior house paint market.
W 1
W2
(1)
Tgl and
Tg 2 =
1.22
1.21
1.1~
1.1"
,, -""
""
11"111"1~.""
09 ,..,"/", . / ' ~ j
,, ""
.,
C18
0
-
/ " "
1.05
...,. ,.
1.o3
1.01 , *
'12
./
.,.//
f/
" -
.-"
0.97
0.05
0.93
0.91
C ~ ~ ~ ~ +
~
0.89
0.87
0.85
0.83
~ t t t t t t t f t
-80 -60 -40 -20 0 20 40 60 80 100 120 140
Temperature, ~
where
W1
FIG. 1 -Specific volume-temperature relations for the poly-(nalkyl methacrylates). (Reprinted with permission from the
American Chemical Society. Copyright 1957,)
Polymer
n = K(MW) a
(2)
where
91 = solution viscosity
K and a = constants derived experimentally for a specific
polymer/solvent combination (for polymethyl
methacrylate in toluene, K l0 s = 7.1 and a
-- 0.73). The type molecular weight used in
determining the constants should be specified.
As molecular weight increases, the solution viscosity also
increases, thereby posing handling and application problems
if the molecular weight becomes too high. For example, high
spray solids are desirable for acrylic lacquers because of
e c o n o m y and emissions concerns. The lower the molecular
weight of the polymer, the lower the viscosity at a given solids
content, or conversely, the higher the spray solids at spray
viscosity. Consequently, low molecular weight is beneficial to
solids and application concerns, whereas high molecular
weight is needed for good film properties.
The obvious answer to the viscosity versus film property
dilemma is to reach an o p t i m u m balance by producing an
intermediate molecular weight polymer. For this reason,
most thermoplastic acrylic solution polymers have weightaverage molecular weights in the 75 000 to 100 000 range. It is
also helpful to narrow the molecular weight distribution,
reducing the a m o u n t of low-molecular-weight fractions,
which have a deleterious effect on resistance and strength
properties, while also minimizing high-molecular-weight
portions, which increase viscosity and cause application
problems such as cobwebbing of spray-applied acrylic automotive lacquers.
Since the application and drying properties of an acrylic
resin are largely controlled by the physical characteristics of
the solvent contained in the resin, as well as by the interaction
of the polymer and solvent, it is essential to carefully select
poly(methyl methacrylate)
poly(ethyl methacrylate)
poly(n-propyl methacrylate)
poly(isopropyl methacrylate)
poly(n-butyl methacrylate)
poly(sec-butyl methacrylate)
poly(isobutyl methacrylate)
poly(t-butyl methacrylate)
poly(n-hexyl methacrylate)
po]y(2-ethylbutyl methacrylate)
poly(n-octyl methacrylate)
poly(2-ethylhexyl methacrylate)
poly(n-decyl methacrylate)
poly(lauryl methacrylate)
poly(tetradecyl methacrylate)
poly(hexadecyl methacrylate)
poly(octadecyl methacrylate)
poly(stearyl methacrylate)
poly(cyclohexyl methacrylate)
poly(isobornyl methacrylate)
poly(phenyl methacrylate)
poly(benzyl methacrylate)
poly(ethylthioethyl methacrylate)
poly(3,3,5-trimethylcyclohexylmethacrylate)
41
105
65
35
81
20
60
53
107
- 5
11
- 20
- 10
- 60
- 65
- 72
- 100
104
170(110)
110
54
-20
poly(methyl acrylate)
poly(ethyl acrylate)
poly(propyl acrylate)
poly(isopropyl acrylate)
poly(n-butyl acrylate)
poly(sec-butyl acrylate)
poly(isobutyl acrylate)
poly(t-butyl acrylate)
poly(hexyl acrylate)
(brittle pt)
poly(heptyl acrylate)
poly(2-heptyl acrylate)
poly(2-ethylhexyl acrylate)
poly(2-ethylbutyl acrylate)
poly(dodecyl acrylate)
(brittle pt)
poly(hexadecyl acrylate)
poly(2-ethoxyethyl acrylate)
poly(isobornyl acrylate)
poly(cyclohexyl acrylate)
Tg, ~
6
- 24
-45
- 3
- 55
- 20
- 43
43
-
57
60
38
50
50
- 30
35
- 50
94
16
79
42
H
I
CH2--C--CH2-\0 /
~----~
~H~
,--,
--O--(z
&,--,
x)--C--(/
/
\~/
&
\ ) - - O - - C H 2 - - C H - - C H2
\/
CH~ \ ~ /
The acrylic solution polymer is made acid functional simply by incorporating acrylic or methacrylic acid into the
backbone; when cured under suitable conditions, it reacts
with the epoxide to form ester linkages between the two
polymers:
E P O X Y - - C H - - C H 2 + ACRYLIC--COOH
\/
O
EPOXY--CH--CH2
I
OH
I
OCO--ACRYLIC
43
44
Tukon hardness
16.2
Pencil hardness
2H
6B
6B
5B
Mustard, 30 min
Ink, 30 min
Print resistance, cold-rolled steel
82~
light print
30 min, 2 psi
Detergent resistancea
1% detergent, 74~
200 h
Few--6
95.5
95.4
9.2
13.0
22.8
0-0-0
0-0-0
22 (2.48)
15 (1.70)
35 + (3.96 + )
50 + (5.65 +)
AMINO R E S I N - - N H C H 2 O R + A C R Y L I C - - O H
)
AMINO R E S I N - - N H C H 2 O--ACRYLIC + ROH
Reactions with a m i n o resins containing an -NH-CH2OH
group are possible b e c a u s e this group differs from a simple
alcohol in that it is far m o r e acidic a n d reactive. Likewise, the
methylol e t h e r (when c a p p e d with alcohol) is m o r e reactive
t h a n a conventional dialkyl ether. The curing c o n d i t i o n required for acid functional acrylics cross-linked with a m i n o
resins is a p p r o x i m a t e l y 30 m i n at 150~ while for an analogous hydroxyl functional acrylic, the r e a c t i o n is m o r e facile,
requiring 30 m i n at 125~ with an acid catalyst [15]. Since the
acid-methylol r e a c t i o n is relatively slow, it allows significant
self-condensation of the a m i n o resin [16]. This detracts from
the overall toughness a n d resistance properties.
The hydroxyl-functional acrylics are, therefore, favored
over acid-functional p o l y m e r s a n d are m o s t often used in
[18]:
P O L Y M E R - - C O - - N H 2 + HCHO
POLYMER--CO--NH--CH2OH
P O L Y M E R - - C O - - N H - - C H a O H + ROH
P O L Y M E R - - C O - - N H - - C H 2 O R + H20
As an alternative process, the AM m o n o m e r can be methylolated before being polymerized. The finalized methylolated a m i d e acrylic p o l y m e r s condense readily w h e n acid
catalyzed at bake conditions of 30 m i n at 150~ The condensation process is a two-stage r e a c t i o n [19]:
2 POLYMER--CO--NH--CHzOH
)
POLYMER--CO--NH--CH2--O--CH2-N H - - C O - - P O L Y M E R + H20
45
TABLE 4--Compositions, viscosities, and film properties of HEMA-based copolymers containing a variety of other monomers a [17].
Acrylate
Styrene
HEMA
BA
BMA
St
MeSt
EtSt
Viscosity in 1/1 xylenefoutanol
Solids content, % by wt
Cross-linking agent, % by wtb
27.5
22.5
.-.
50.0
. . .
.
.
U-V
47.8
30
Methacrylate
Styrene
Methacrylate
Methyl Styrene
Copolymer Composition,
27.5
.
.
.
.
.
22.5
50.0
.
.
.
.
.
W+
49.4
30
% by wt
27.5
.
.
.
22.5
.
.
.
.
50.0
Methacrylate
Ethyl Styrene
27.5
.
22.5
.
X+
49.4
30
...
50.0
X+
48.3
30
Film Properties
Color or yellowness factorb
Initial
After 4 h/219~
Gloss (60~ initial
After 4 h/219~
Front impact, in./lb to fail
Flexibility, l/s-in, mandrel
Knife scratch
Resistance to:
20% NaOH, 12-day exposure
50% HAc, 7-h exposure
Butyl acetate, 4-h exposure
0.5% Rinso at 74~ blisters
after 4 days of immersion
- 2.4
6.2
98
84
2
0
7+
- 4.6
- 0.9
98
92
0
0
7
- 5.2
0.6
94
84
0
0
7
- 3.0
10.1
98
74
0
0
7
10
10
6
9-
10
10
10
9
10
10
10
9
10
10
3
9
~Allcopolymers were <1 in Gardner Holdt color. Films baked for 30 rain. at 149~ Ratings: 10 = best or no failure; 0 = complete failure.
bButylatedbenzoguanamine formaldehyde.
(Reprinted with permission of the Journalof Coatings Technology.Copyright 1961.)
further h e a t
>
POLYMER--CO--NH--CH2--NH--CO-POLYMER + H20
If the m e t h y l o l a t e d a m i d e has b e e n etherified b y b u t a n o l
capping, i n s t e a d of w a t e r as a by-product, a mixture of b u t a nol a n d dibutyl ether w o u l d be obtained. These types of selfcondensing acrylic resins will also react with a m i n o resins,
b u t usually there is no justification for so doing (i.e., no
i m p r o v e m e n t s in performance). The strength of the methylol
a m i d e acrylics is that they have no glaring weaknesses a n d
m a k e very g o o d g e n e r a l - p u r p o s e resins.
Isocyanate-Reactive Acrylics
Acrylic solution p o l y m e r s t h a t are cross-linked with isocyanates (often referred to as acrylic urethanes) are u n i q u e
a m o n g the various cross-linking systems b e c a u s e they cure
u n d e r a m b i e n t c o n d i t i o n s - - t h e y don't require baking. The
isocyanate g r o u p ( - - N = C = O) is extremely reactive a n d will
cross-link with any type of functionality having a labile hyd r o g e n atom. This includes amines, alcohols, ureas, urethanes, carboxylic acids, a n d amides. Acrylic p o l y m e r s
designed to be cross-linked with isocyanate resins generally
contain hydroxyl functionality i n c o r p o r a t e d b y p o l y m e r i z i n g
hydroxyethyl acrylate (HEA) o r hydroxyethyl m e t h a c r y l a t e
(HEMA) into the acrylic backbone.
There are six basic types of curing m e c h a n i s m s for uret h a n e coatings [see ASTM T e r m i n o l o g y Relating to Paint,
Varnish, Lacquer, a n d Related Products (D 16-75)]. The
two-package polyisocyanate/polyhydroxyl coatings m a k e up
"Type V." Of this class, acrylic u r e t h a n e s b a s e d on weatherresistant hydroxyl functional acrylics p r e d o m i n a t e . The hydroxyl functional acrylic reacts with isocyanate resin as follows:
ACRYLIC--OH + R--N = C = O
R--NH--COO--ACRYLIC
(a urethane)
>
46
the solids of the acrylic r e d u c e s solvent levels in the form u l a t e d coating. To c o m p e n s a t e for lower m o l e c u l a r weight,
one w a y to i m p r o v e p e r f o r m a n c e is to increase hydroxyl
content, w h i c h in t u r n requires higher levels of isocyanate.
An alternative a p p r o a c h to r e d u c e d solvent o r higher solids
is to m o d i f y the acrylic u r e t h a n e with a reactive diluent w h i c h
is fluid a n d acts like a solvent b u t t h e n reacts to form p a r t of
the cross-linked n e t w o r k [21]. One such diluent is a lowmolecular-weight, difunctional oxazolidine w h i c h is nonreactive with isocyanates until a m b i e n t m o i s t u r e opens the
ring, releasing b o t h hydroxyl a n d a m i n e functionality [22].
Deionized Water
Surfactant
Ethyl acrylate (15 ppm MEHQ)
Methyl methacrylate (25 ppm MEHQ)
Glacial methacrylic acid (100 ppm MEHQ)
Ferrous sulfate solution (0.15%)
Ammonium persulfate in 5 mL of water
Sodium formaldehyde sulfoxylate in 5 mL of
water
t-butyl hydroperoxide (70%)
Procedure:
R"
\
O/C
H2C
~N--R--N/C
R"
~O
CH2 H2C
+ 2H20
>
CH2
HO
H2C
HN--R--NH
CH 2
H2C
OH
+ 2R'CHO
CH 2
Sodium Salt
Free Acid
35.0
34.3
5.6
7.9~
22.8 b
22~
36.0
35.6
1.8
10.5a
12.3r
3tY
47
pigment volume concentration (PVC) to obtain gloss, the pigment does not contribute significantly to film hardness; it
must all come from the polymer.
Since these gloss and semigloss latexes are often used over
old oil-based enamels, adhesion to aged oil-based paints is
required. This may be accomplished by copolymerizing adhesion promoting functional monomers into the acrylic polymer backbone. A major breakthrough in latex adhesion
technology came about with the development of ureide functional acrylic monomers [24]. The adhesion promoter particularly is needed to improve adhesion and blister resistance
when the paint film becomes wet, as it might in a bathroom.
Since the gloss paints are often used in wet areas such as a
bathroom, the water resistance of the dry film is also an
important property. To ensure good water resistance, acrylic
emulsions used in this market often contain hydrophobic
monomers such as styrene.
Since interior trim paints are so highly visible, overall appearance properties are critical to the success of the paint job,
and features such as flow and levelling, gloss, and film build
are expected to be similar to oil-based enamels. This level of
outstanding appearance has been possible in recent years
with the introduction of associative thickeners. The traditional thickener for latex paints has been hydroxyethyl cellulose (HEC), which thickens by a flocculation mechanism and
usually produces poor flow and gloss. Associative thickeners
loosely bind to the surface of the latex particles through
hydrophobic interactions, forming a network structure
which accounts for their thickening action. The degree of
interaction between the thickener and the latex particle is
largely a result of the surface chemistry of the emulsion particles. Smaller particle-size emulsions have greater surface
area and therefore have more interaction with associative
thickeners. More hydrophobic latexes have stronger association with the new thickeners. Consequently, small-particlesize, hydrophobic acrylic emulsions have been designed specifically for use with associative thickeners. These newer
acrylic emulsions optimize thickener interaction and produce exceptional flow and gloss. In fact, before these new
emulsion/thickener systems, truly high-gloss latex paints
were out of the question. They also improve brushability and
film build, while eliminating the problem of roller spatter.
Overall, the appearance properties of the newer small particle-size hydrophobic acrylics, when used in combination
with associative thickeners, rivals that of oil-based enamels.
In an effort to further improve the performance of acrylic
emulsions, the morphology of emulsion particles has become
an additional important variable. In the past few years, new
composite acrylic emulsions have been introduced, particularly into the interior gloss area, which are made up of two or
more nonhomogeneous phases. They are prepared by a twostage polymerization process sometimes referred to as a sequential emulsion polymerization that results in various
types of core-shef structures. The goal of this type of polymerization is to incorporate the best characteristics of the
different phases.
The hard acrylic emulsions typically used in interior gloss
paints provide excellent performance but require considerable amounts of coalescent to achieve film formation (i.e., 10
to 20% by weight on polymer solids). This is undesirable both
48
[25].
Small-particle-size, large-surface-area emulsions, when
thickened with HEC, have poorer flow and film build than
larger particle-size emulsions, which are less aggregated by
49
alkyd paints along with expected advantages in chalk resistance, color retention, and other decorative qualities. However, to the surprise of some segments of the maintenance
industry, acrylic maintenance emulsions often outperformed
solvent alkyds for corrosion resistance and overall metal protection. This is partly because the alkyds continue to harden
and eventually crack, leaving the substrate exposed and subject to the elements. Acrylic emulsions do not continue to
harden once the paint film is dry, and they remain sufficiently
pliable to expand and contract with the substrate.
The one weakness of the acrylic latexes in the area of
maintenance coatings was their low Tg, which reflected a
lower hardness than the alkyd paints. This limitation was
removed by the development of aqueous gloss enamel
binders. These hard latex binders used in interior and exterior gloss paints were fine tuned to maximize corrosion resistance and overall protection. Commercialized in the mid1980s, this new generation of maintenance vehicles has
proved very successful in extensive field tests, particularly on
bridges in the southeastern United States. The small particle
size of these binders fits perfectly with associative thickener
technology to give tight water-resistant films, which are an
improvement over HEC-thickened paints that can have microscopic defects as a result of the flocculating mechanism of
HEC [27].
50
factants, additives, a n d c o m p o s i t i o n s to i m p r o v e r a t h e r t h a n
d e t r a c t from c o r r o s i o n resistance.
N e w e r heterogeneous acrylic e m u l s i o n s c o m p r i s e d of two
o r m o r e phases have recently b e c o m e i m p o r t a n t in the industrial coatings industry. One such type of h e t e r o p o l y m e r , the
core-shell polymer, is being used to achieve r a p i d h a r d n e s s
d e v e l o p m e n t with i m p r o v e d block a n d p r i n t resistance at low
VOC. These p r o p e r t i e s allow the m a n u f a c t u r e r to stack, pack,
a n d ship coated parts m o r e quickly [28]. Using core-shell
technology, acrylic e m u l s i o n s have been able to rival the
p e r f o r m a n c e of traditional, high-solvent-content nitrocellulose lacquers in w o o d coatings a n d furniture finishes. The
m a j o r deficiency of acrylic emulsions in these areas is the
"warmth" of w a t e r - b a s e d coatings c o m p a r e d to solvent-based
materials. " W a r m t h " is a quality w h i c h refers to the feel a n d
a p p e a r a n c e of the coated wood.
Thermosetting Emulsions
Just as is the case with solution acrylics, functional groups
can be i n c o r p o r a t e d into the p o l y m e r b a c k b o n e of an acrylic
e m u l s i o n so that it can react with a n o t h e r functional m a t e r i a l
after a p p l i c a t i o n to the substrate, f o r m i n g a cross-linked
polymer. Typically hydroxyl o r hydroxyl/acid functional
acrylic emulsions are cross-linked with u r e a o r m e l a m i n e resins. Acid functional acrylic e m u l s i o n s can be cross-linked
with emulsified epoxy resins. The c h e m i s t r y of these systems
is identical to the cross-linking c h e m i s t r y discussed earlier
for solvent-based acrylic resins. After the e m u l s i o n is cross-
TABLE 6--Properties for an aqueous acrylic/melamine coil coatings enamel over aluminum
and galvanized steel [29].
Substrate
Aluminuma
Primer thickness
Topcoat film thickness
Gloss 20~ ~
Image clarity
Tukon hardness (KHN)
Pencil hardness
Initial
Wet 16 h, 38~ H20
Flexibility--X30 microscope
Direct impact, in.-lbs
Reverse impact, in.-lbs
Metal mark resistance
Rheology
MEK rubs
Cleveland condensing cabinet,
200 h at 60~
After 1000 h Salt Spray Exposure
X-scribed area
Tape adhesion, % removed
Lifting
Undercutting
Blistering~
Exposed edge
Undercutting
Blistering~
1/8-in. mandrel bend
Blistering~
White rust
Flat
Blistering~
0
0.9 to 1.0
65/89
Very good
9
Mini-Spangle
Galvanized Steel~
0.2
0.8
-/80 b
Good
9
B
2-3T
20 to 25
15
Excellent
Excellent
200
Pass
B
3T
35
10
Excellent
Excellent
200
Pass
0
None
1/16 in.
None
0
None
1/16in.
Mod-Dense, No. 6, No. 8
...
...
4/16 in.
Mod, No. 2, No. 4
...
...
None
None
None
None
51
Solvent Resistance
>300
Mod. soft
Mod. soft
Lt. soft
Lt. soft
Lt. soft
Epoxy/
Polyamide
Alkyd
>300
120
Lifted
Mod. soft
Mod. soft
Lt. soft
Lt. soft
Mod. soft
Lifted
Lt. soft
Lt, soft
Lt. soft
Mod. soft
Lt. stain
OK
Lt. stain
OK
OK
Med. stain
OK
Hvy. stain
OK
OK
No effect
No effect
No effect
Dissolved
Stain Resistance
Spot tests, 24 h
Mustard
Coffee
Red ink
Cola
Grape juice
OK
OK
OK
OK
OK
Acid/Base Resistance
No effect
No effect
4
Poor
10
REFERENCES
[1] Chemicals for
The Lakeside
1959, p. 20.
[2] Chemicals for
The Lakeside
1959, p. 21.
[3] Brendley, W. H. Jr., "Fundamentals of Acrylic Polymers," Paint
and Varnish Production, July 1973.
[4] Fox, T. G., Bulletin of the American Physics Society, Vol. 1, 1956,
p. 123.
[5] Fox, T. G., Jr. and Flory, P. J., Journal of Applied Physics, Vol. 21,
1950, p. 581.
[6] Rogers, S. and Mandelkern, L., Journal of Physical Chemistry,
Vol. 61, 1957, p. 985.
[7] Simha, R. and Boyer, R. F., Journal of Chemical Physics, Vol. 37,
No. 5, t 962, p. 1003.
[8] Kine, B. B. and Novak, R. W., "Acrylic and Methacrylic Ester
Polymers," Encyclopedia of Polymer Science and Engineering,
2nd ed., H. F. Mark, N. M. Bikales, C. G. Overberger, G. Menges,
and J. I. Krosckwitz, Eds,, Vol. I, John Wiley and Sons, New
York, 1985, pp, 257-258.
52
[30] Mercurio, A., American Paint & Coatings Journal, 20 Jan. 1992,
p. 43.
MNL17-EB/Jun. 1995
Pellowe 2
HISTORY
Although condensation products of dihydric alcohols and
dicarboxylic acids were known at the start of the 20th Century, alkyds modified with drying oils were developed in the
late 1920s by Kienle et al. [1-5]. The early condensation
products were not soluble in common solvents and did not air
dry until monofunctional acid or fatty acids were incorporated into the polymeric material. Kienle coined the term
"alkyd" from the alcohols ("al") and acids ("cid") used in their
preparation. The early spelling of"alcid" was later changed to
the current form, "alkyd." Air-dry films were the result of
iMcWhorter Technologies, 1028 South Third Street, Minneapolis,
55415.
2Retired, formerly employed by Frost Paint.
53
Copyright9 1995 by ASTM International
www.astm.org
54
An alkyd resin can be modified with a number of intermediates. Some of the more common types are:
9 Acrylates
9 Benzoic acid
9 Epoxides
9 Isocyanates
9 Paramethyl styrene
9 Phenolics
9 Polyamides
9 Rosin
9 Silicone
9 Styrene
9 Vinyl toluene
Solvent Reflux P r o c e s s
Fusion P r o c e s s
In this method of manufacture, the alkyd intermediates are
charged into the reaction vessel. Then an inert gas, such as
MOTOR g~ i'~
THERMOMETER
~'.:"~;'J
GLASS BEARING
MM O.D. TUBING
NIUM FOIL
RS ALL CORKS
HEATING MANTLE
FIG. 1-Apparatus for fusion cooking of alkyds. (Diagram courtesy of ICI Hercules
Alkyd Reports.)
CHAPTER 7 - - A L K Y D AND P O L Y E S T E R S
55
ALLEQUIPMENTHAS29/42JOINTS
,EDRICH'S
NDENSER
MOTOR
TRUBORESTIRRER4
THERMOMETER II
L E T ~
CO2IN
SOLVENT
LAYER
WATEF
SEPARATORY
TRAP
,. SAMPLE
HEMISPHERICALGLAS-COL
HEATINGMANTLE
FIG. 2-Laboratory apparatus for solvent cooking of alkyds. (Diagram courtesy of ICI
Hercules Alkyd Reports.)
reached. Then the alkyd is thinned with the desired type and
amount of organic solvent. Only a small amount, usually less
than 3% by typically 1% of the total weight, of the reflux or
azeotrope solvent remains in the alkyd. The solvent reflux
process advantages are less emission of by-products to the
atmosphere and faster processing time. Also, a greater variety
of alkyds can be made by this process. The final alkyd solution properties are measured at 25~ Typical tests include
color, acid number, hydroxyl number, hardness, viscosity,
and percent nonvolatiles.
PHYSICAL PROPERTIES
The most common physical properties used to identify
characteristics of alkyd resins are determined by ASTM
methods.
Viscosity
The viscosity of alkyds covers a wide range and must be
compared to the nonvolatile content and type organic solvent
used, ASTM D 1545: Test Method for Viscosity of Transparent Liquids by Bubble Time Method [6]. The bubble tubes
and measured times in seconds are easy to run with proper
testing equipment and a constant temperature set at 25~
Viscosity is important in reflecting alkyd molecular weight
and the final coating application properties, thickness, and
minimizing batch-to-batch variation of each specific alkyd.
Relatively high-molecular-weight alkyds need to be reduced
to application viscosity with a greater amount of solvent or
solvent mixture or with solvents that have a particular solvency for the specific alkyd.
NONVOLATILE CONTENT
The nonvolatile content of alkyd solutions is determined
with ASTM D 1259: Test Method for Nonvolatile Content of
Resin Solutions. Alkyd specifications are designed to show a 1
or 2% variation from an agreed on nonvolatile by weight
requirement. This method is sometimes varied to a higher
oven temperature of 150~ and a shorter dwell time in resin
processing use.
56
POLYFUNCTIONAL
Adipic acid
Azelaic acid
Chlorendic anhydride
Fumaric acid
~Isophthalic acid
~Maleic anhydride
aphthalic anhydride
Succinic acid
Sebacic acid
Citric acid
aTrimelletic anhydride
MONOFUNCTIONAL
Abiatic acid
~Benzoic acid
Caproic acid
Caprylic acid
Capric acid
Castor oil acids
Coconut oil acids
Cottonseed fatty acids
Lauric fatty acids
Linoleic acid
Linolenic acid
Oleic acid
Tallow acids
aTall oil fatty acids
Tertiary-butyl benzoic acid
Special blended fatty acids
aMost commonlyused in commercialalkyds.
Alkyd resin solutions vary from 30% nonvolatile (flat wall,
medium-oil alkyds) to 100% nonvolatile content by weight
(very long oil alkyds for exterior paints, stains, latex modifiers, and similar products).
Color
The color of alkyd solutions is determined by comparison
with a range of color standards referred to as the GardnerHoldt color standards, ASTM D 1544: Test Method for Color
of Transparent Liquids (Gardner-Holdt Scale) [8]. The color
or degree of yellowness of the alkyd solution may or may not
have an effect on the color of the final coating films.
TABLE 2--Polyhydric alcohols used in alkyd manufacture.
POLYHYDRICALCOHOLS
aGlycerin
aEthylene glycol
Propylene glycol
Trimethylol propane
aNeopentyl glycol
Hexylene glycol
Pentanediol
1,3-Butylene glycol
Diethylene glycol
Triethylene glycol
~Pentaerythritol
Methyl glucoside
Dipentaerythritol
Sorbitol
aTrimethylpentanediol
Trimethylol ethane
~Mostcommonlyused in commercialalkyds.
Castor oil
aCoconut oil
Corn oil
Cottonseed oil
Dehydrated castor oil
~Linseed oil
Safflower oil
aSoybean oil
Tung oil
Walnut oil
Sunflower oil
Menhadden oilb
Palm oil
aMostcommonlyused in commercialalkyds.
bAnonvegetableoil derived from fish.
Density
The density or specific gravity of alkyds is also referred to
as the weight per gallon or density and can be determined by
following ASTM D 1475: Test Method for Density of Paint,
Varnish, Lacquer, and Related Products [9].
Flash Point
The flash point of alkyds is mainly of importance as it
pertains to shipping the products and formulated paints, i.e.,
to bill of lading and other regulations. ASTM D 3278: Test
Methods for Flash Point of Liquids by Setaflash-Closed-Cup
Apparatus [10] is the most common test that will provide
conformance with Department of Transportation regulations. However, other ASTM methods are utilized. The
method utilized depends on flash cup availability and other
specified requirements.
Neat alkyds have low vapor pressure. Therefore, the flash
point of an alkyd solution reflects the flash point of the
solvent used to dissolve the alkyd. It is recommended that
flash points on alkyd solutions actually be measured by laboratory determination. The flash point of an alkyd solution is
different from that of the actual solvent or solvents incorporated into the solution.
Drying Properties
The drying properties of alkyds are of importance when
describing the product. Metallic driers are based on cobalt,
manganese, iron, lead, calcium, and rare earths reacted with
synthetic organic acids, such as vegetable fatty acids, to form
soaps. When these driers are added to the alkyd-based coating, they act as catalysts and accelerate the rate of air drying
and cross-linking. Driers are formulated in combinations or
blends to maximize desired dry film surface and interior
characteristics. In recent years, synthetic acid-based metallic
driers have gained popularity for two main reasons: (1)
higher metal concentration in the drier, and (2) greater uniformity of drier performance. Methods associated with determining drying are given in ASTM D 1640: Test Methods for
Drying, Curing, or Film Formation of Organic Coatings at
Room Temperature [11].
CHAPTER 7 - - A L K Y D AND P O L Y E S T E R S
Acid Value
H I G H E R S O L I D S ALKYD R E S I N S
Hydroxyl Value
The hydroxyl value or number is a measurement of the free
hydroxyl groups remaining in the alkyd that have not been
reacted with carboxyl groups during the condensation stage
of the alkyd resin preparation process. Hydroxyl value determinations are more difficult to perform than acid number
determinations. There are several reasons for this. First, the
hydroxyl group can be sterically hindered or less available
within the polymer and thus difficult to reach with the reactants. Second, hydroxyl groups on primary carbon atoms are
more reactive than those on secondary carbon atoms, and
these are more reactive than those located on a tertiary carbon atom. Tertiary-positioned hydroxyl groups are the most
difficult to esterify in this determination. Manufacturers can
often specify methods that can be used for secondary hydroxyl groups.
Hydroxyl numbers are important in determining equivalent weight, which in turn is important to determining the
amount of urea formaldehyde, melamine formaldehyde, or
urethane prepolymer to react with the alkyd. In the case of
oil-modified urethanes, also called uralkyds, the hydroxyl
groups coreact with free isocyanate functionality. Although
theoretical equivalency based on hydroxyl numbers is a good
guideline to establishing performance characteristics, a ladder of co-reactant ratios is important to optimizing particular
performance characteristics.
ALKYD R E S I N CLASSIFICATION
Unmodified alkyds are classified into four types that depend on oil content--very long-oil, long-oil, medium, and
short-oil alkyds. Properties such as speed of drying, ease of
brushing, film flexibility, chemical resistance, and exterior
gloss retention are all dependent on the oil content. These
properties are summarized in Table 4.
A summary of alkyd resins comparing types of oil/fatty
acids, nonvolatile, solvent, and typical application is given in
Table 5.
57
Highest
Slowest
Best
Highest
Worst
Worst
(
<
<
<
<
(
)
)
)
>
)
)
Lowest
Fastest
Worst
Lowest
Best
Best
W A T E R - B O R N E ALKYD R E S I N S
Water-borne alkyds obtain their water reducibility by the
use of coupling solvents and amine-neutralized carboxyl
groups on the polymer. Typical coupling solvents are ethylene glycol monobutyether, propylene glycol monoethylether,
propylene glycol monopropylether, and four-carbon alcohols
such as s-butyl alcohol. Water-borne alkyds are available in
most classes of "conventional alkyds" such as those shown in
Table 7.
SATURATED P O L Y E S T E R S
Saturated polyesters are also called oil-free alkyds. The oil
or fatty acid modification is zero percent, and this factor
results in a polymer that cannot be air dried to a cross-linked
coating. Rather, these polymers are formulated with a curing
agent or cross-linker and baked. The curing agent can be a
urea-formaldehyde or a melamine formaldehyde resin, both
of which require baking. Polyurethane prepolymers can be
coreacted with polyester resins for air-dry or low-bake coatings in two-component systems. In such systems, the saturated polyester provides the hydroxyl groups for cure with
free isocyanate groups on the polyurethane prepolymer.
The physical properties of these coatings are outstanding
due to the absence of fatty acids, and they afford coatings
with excellent color retention, flexibility, exterior durability,
and hardness.
The type of resins can be adapted to provide higher solids
saturated polyesters by redesigning the polymer and using
organic solvents with appropriate solvency rather than the
customary blends of aromatic hydrocarbons with ketones,
alcohols, and glycolethers.
Water-borne polyesters are available through design of
polymers having acid numbers in the range of 40 to 60. When
these products are neutralized with an amine, they become
Oil or
Fatty A c i d
Nonvolatiles
Typical
Applications
Solvent
Very long
Linseed
Soya
Tall oil
85-100%
Aliphatic hydrocarbon
Exterior latex
modifier
House paint modifier
Oil-based stain and
ink vehicles and
modifiers
Long
Linseed
Safflower
Soya
Sunflower
Tall oil acids
60-70%
Aliphatic hydrocarbon
Architectural coatings
Maintenance coatings
One-coat enamels
Exterior enamels
Primers
Topcoats
Medium
Linseed
Safflower
Soya
Sunflower
Tall oil acids
Blends
45-50%
Aliphatic hydrocarbon
Aromatic hydrocarbon
Farm implements
Railway equipment
Maintenance
Short
Castor
Dehydrated
castor
Coconut
Linseed
Soya
Tall oil acids
Blends
50%
Aromatic hydrocarbon
or Rule 66-type
solvent blenda
Industrial coatings
SILICONE-MODIFIED POLYESTERS
Conventional Types
Silicone modification of polyesters is accomplished by use
of a silicone intermediate incorporated t h r o u g h reaction at a
30 a n d 50% level. The silicone intermediates are of either
hydroxy or methoxy functionality, a n d w h e n they are reacted
with the polyester, water or m e t h a n o l is eliminated. This
modification improves the weatherability and/or heat resistance of the alkyd a n d resulting organic coating. The siliconemodified polyesters are available in both self-curing a n d baking ( m e l a m i n e formaldehyde resin cross-linked) types. They
are used as coil coatings for prefabricated building panels,
prefabricated architectural products, metal advertising sign
stock, a n d other applications requiring excellent exterior durability and/or good heat resistance.
59
[12] ASTM D 1639: Test Method for Acid Value of Organic Coating
Materials," Annual Book of ASTM Standards, Section 6, Vol.
6.01, 1992, pp. 192-193.
REFERENCES
[1] Kienle, R. H. and Ferguson, C. S., Industrial and Engineering
Chemistry, Vol. 21, 1929, p. 349.
[2] Kienle, R. H. and Hovey, A. G., Journal of the American Chemical Society, Vol. 51, 1929, p. 509.
[3] Kienle, R. H. and Hovey, A. G., Journal of the American Chemical Society, Vol. 52, 1930, p. 3636.
[4] Kienle, R. H., Industrial and Engineering Chemistry, Vol. 22,
1930, p. 590.
[5] Kienle, R. H., U.S. Patent 1,893,873, 10 Jan. 1933.
[6] ASTM D 1545: Test Method for Viscosity of Transparent Liquids
by Bubble Time Method, Annual Book of ASTM Standards, Section 6, Vol. 06.03, 1992, pp. 214-215.
[7] ASTM D 1259: Test Methods for Nonvolatile Content of Resin
Solutions," Annual Book of ASTM Standards, Section 6, Vol.
06.03, 1992, pp. 212-214.
[8] ASTM D 1544: Test Method for Color of Transparent Liquids
(Gardner-Holdt Scale)," Annual Book of ASTM Standards, Sec-,
tion 6, Vol. 06.02, 1992, pp. 267-268.
[9] ASTM D 1475: Test Method for Density of Paint, Varnish, Lacquer, and Related Products," Annual Book of ASTM Standards,
Section 6, Vol. 06.01, 1992, pp. 178-180.
[10] ASTM D 3278: Test Methods for Flash Point of Liquids by
Setaflash-Closed-Cup Apparatus," Annual Book of ASTM Standards, Section 6, Vol. 6.03, 1992, pp. 406-412.
[11] ASTM D 1640: Test Methods for Drying, Curing, or Film Formation of Organic Coatings at Room Temperature," Annual Book of
ASTM Standards, Section 6, Vol. 6.01, 1992, pp. 194-197.
BIBLIOGRAPHY
Blegen, J. R. and Fuller, W. P., Alkyd Resins, Unit 5 of the Federation
Series of Coatings Technology, Philadelphia, PA, 1967.
Holmberg, K., High Solids Alkyd Resins, Marcel Dekker, Inc., New
York, 1987.
Oldring, P., Resins for Surface Coatings, SITA Technology, London,
1987.
Keane, J., et al., Systems and Specifications, Vol. 2, 4th ed., Steel
Structures Painting Council, Pittsburgh, PA, 1985.
Kask, T. and Lesek, F., Processes and Equipment for Alkyd and Unsat-
MNL17-EB/Jun. 1995
INTRODUCTION
Definition and Description
FIG. 1-Urea.
NH 2
FIG. 2-Melamine.
ways m a d e with m e t h a n o l or c o m b i n a t i o n s of m e t h a n o l a n d
butanol, a l t h o u g h a small n u m b e r of high-solids resins are
available which are m a d e exclusively with butanol.
Where Used
Amino resins are used in coatings to cross-link the p r i m a r y
film-former, usually a n acrylic, polyester, o r alkyd resin
carrying p r i m a r y o r s e c o n d a r y hydroxyl groups. The crosslinking r e a c t i o n ("cure") is p r i n c i p a l l y one of trans-etherification between hydroxyl groups on the p r i m a r y film-former
a n d alkoxymethyl groups on the a m i n o resin. In a d d i t i o n to
the trans-etherification reaction, the a m i n o resin a l m o s t always u n d e r g o e s self-condensation reactions.
The m a j o r b y - p r o d u c t s of the cure r e a c t i o n include m e t h a nol a n d / o r butanol, formaldehyde, a n d water. Cure t e m p e r a tures are in the range of 180 to 400~ (82 to 204~ for t i m e s
w h i c h vary from 20 to 30 m i n at the lower end of the t e m p e r a ture range to p e r h a p s only 30 s at the u p p e r end. An a c i d
catalyst m a y be used to accelerate cure, d e p e n d i n g on the
cure t e m p e r a t u r e a n d the p a r t i c u l a r a m i n o used. Claims have
been m a d e for a m i n o resin f o r m u l a t i o n s w h i c h cure at r o o m
t e m p e r a t u r e , but as far as is known, no such f o r m u l a t i o n s are
presently c o m m e r c i a l l y available.
Urea resins are less expensive t h a n m e l a m i n e resins, w h i c h
is u n d e r s t a n d a b l e given that m e l a m i n e is m a d e f r o m urea.
Urea resins are also faster curing t h a n m e l a m i n e resins, b u t
are m o i s t u r e sensitive a n d therefore not suitable for use outdoors. They are used widely for w o o d finishing, e.g., furniture, kitchen cabinets, a n d in paper, film, a n d foil applica-
History
Historically, the first a m i n o resins used in coatings were
the r e a c t i o n p r o d u c t s of u r e a o r m e l a m i n e with formaldehyde a n d b u t a n o l (either n- or iso-). They were substantially
p o l y m e r i c a n d were f o r m u l a t e d at a b o u t 50 to 60% solids in
butanol/xylene mixtures. They have been c o m m e r c i a l l y available for a b o u t 60 years. Parenthetically, it should be noted
that resins m a d e by reacting u r e a o r m e l a m i n e with formald e h y d e w i t h o u t subsequent r e a c t i o n with an alcohol have
b e e n available for 70 years o r more. These resins are used as
m o l d i n g p o w d e r s a n d adhesives a n d are generally unsuitable
for coatings applications.
High-solids coating resins, usually m a d e with higher ratios
of r e a c t e d f o r m a l d e h y d e t h a n the older, conventional resins,
have been available for a b o u t 35 years. They are a l m o s t al1Principal technologist, Monsanto Chemical Co., 730 Worcester
Street, Springfield, MA 01151.
60
9
C=O
www.astm.org
CHAPTER 8 - - A M I N O R E S I N S
tions. Wood and paper applications capitalize on the
relatively rapid cure of the urea resin since lower temperatures must be used to avoid damage to the substrate. In some
wood applications, cure temperature is at or near ambient.
Melamine resins, on the other hand, find much b r o a d e r
application since they are not nearly as water sensitive as the
ureas. Perhaps the largest single use for melamine resins is in
automotive OEM (original equipment manufacture), where
the finished paint must stand up to extremes of temperature,
humidity, and the degradative effects of sunlight, etc, Melamine resins are used also in coil coatings, metal containers,
etc. (see E n d U s e s o f A m i n o R e s i n s ) .
) H2NCONHCH2OH
monomethylolurea
(1)
HOCH2NHCONHCH20R + ROH
)
ROCH2NHCONHCH2OR + H20
bis(alkoxymethyl)urea
~ >NCH2N< + ROH
R = H, alkyl
>NCH2OH + HOCH2N<
(5)
Structure/Property Variations
The difference between conventional solids and high-solids
a m i n o resins represents not so much a difference in solids
)
HOCH2NHCONHCH20H (2)
dimethylolurea
HOCH2NHCONHCH20H + ROH
)
HOCH2NHCONHCH2OR + H20
61
(3)
(4)
ROCH2\
/CH2OH
ROCH2./N"'~NI~N'H
N. N
N
ROCH2/
62
Analysis/Analytical Methods
Structural analysis of amino resins has been reviewed by
Christensen [8 ]. Methods discussed include 1H NMR and 13C
NMR for determining levels of combined formaldehyde and
alcohol, analysis of alkoxy groups by Zeisel cleavage, and by
trans-etherification followed by gas chromatography. Christensen [8] and Kambanis and Rybicky [9] also describe nondestructive methods for removing solvent from amino resin
solutions in order to determine nonvolatile content.
Classically, amino resins for coatings have been characterized by three test procedures. These procedures, which tell
the coating formulator most of what he needs to know with
regard to formulation and cure conditions, are measurement
of (1) solids content, (2) viscosity, and (3) solvent tolerance.
These are discussed below.
Viscosity Measurement
Amino resin viscosities are most commonly measured by
the Gardner bubble viscometer method. This method is similar to the Test Method for Viscosity of Transparent Liquids by
Bubble Time Method (ASTM D 1545). A tube containing the
resin under test is placed in a rack containing reference tubes
of known viscosity. The tubes are equilibrated to 25~ in a
constant temperature bath. The rack is quickly inverted, and
the rate of rise of an air bubble in the sample tube is compared against similar bubbles in the reference tubes. The
reference tubes are letter graded A through Z and Z1 through
Z6.
Solids Content
The most common methods used to determine solids content are gravimetric. Solvent is allowed to evaporate from a
weighed sample under carefully controlled conditions of time
and temperature. The sample is then reweighed. The loss in
weight gives a measure of solvent content, and the solids
content is obtained by difference. One difficulty with this test
is the tendency of amino resins to deformylate and/or selfcondense when heated, with evolution of formaldehyde, alcohol, and water. To the extent that this occurs, the measured
solids content will be lower than the "true" value. Frequently,
however, the paint formulator is interested in the "contributed solids," i.e., what fraction of the amino resin solution
remains in the cured film. In that case, a solids test method
which approximates the time and temperature of cure might
be more appropriate.
For these reasons, solids test methods fall into two groups:
(1) methods which reflect the solids content in the absence of
self-condensation, etc., and (2) other methods, which reflect
varying degrees of self-condensation in addition to loss of
formaldehyde and solvent(s).
The most common of the first methods is the so-called foil
solids test, which is used almost universally for high-solids
amino resins. Essentially, a 1-g sample of resin solution is
weighed onto a piece of preweighed aluminum foil. The foil is
folded over on itself and the sample compressed between the
two foil surfaces to provide a thin film about 3 to 4 in. (7 to 10
cm) in diameter. The foil is then opened up to give a thin film
on each foil surface. The foil is placed in a 45~ oven for 45
min, at the end of which time it is removed, reweighed, and
the solids content calculated. These conditions are known to
be sufficiently mild that no resin condensation occurs; nor
does the resin lose formaldehyde via demethylolation. Surprisingly, the foil solids test may on occasion overestimate
the solids content, particularly when (1) the resin is relatively
Solvent Tolerance
There are a number of different solvent tolerance tests. All
involve titrating a weighed sample of the amino resin with a
standard reagent (solvent). The object of the test is to measure how much of the reagent the amino resin can accept
before the solution turns cloudy/milky. Results are typically
reported in milliliters of reagent per gram of sample. Typical
reagents used include xylene, iso-octane, and the iso-octane/
decahydronaphthalene/toluene mixture described in ASTM
Test Method for Solvent Tolerance of Amine Resins (D 1198).
While the immediate objective of the solvent tolerance test
is to determine the amount of reagent which the amino resin
can accept before solution clouding occurs, the real purpose
of the test is to gain insight into the structure and composition of the resin and hence have a better understanding of
how it will perform in a given coating application. In general,
amino resins of high molecular weight, or having high levels
of polar functional groups, i.e., >NH, >NCH2OH, will have
limited compatibility with the typical hydrocarbons used and
hence will give low tolerance test results. Experience shows
that a low tolerance value means a faster curing resin and vice
versa, especially in the absence of acid catalyst. However,
although the tolerance test represents a quick and easy way to
measure potential cure response, it does not uniquely define
the resin structure. Thus, a low tolerance reading can be
caused by either high polarity or high molecular weight or
both.
Combining Ratios
Amino resins may also be characterized by measurement
of the amounts of formaldehyde and alcohol which have re-
400 -
Monomer
mV
350 -
300 -
250"~
200 -
Dimer
150 ~
100-
50 20
35
30
25
40
45
Minutes
FIG. 4-Size exclusion chromatogram of a typical high-solids methylated melamine resin.
600"mV
Hexamethoxy
500-
Pentamethoxy
400 350200 -
Tetra-
1000
20
25
30
63
35
40
45
50
Minutes
FIG. 5-High-performance liquid chromatogram of a typical high-solids methylated
melamine resin.
64
Viscosity
N(CH2OCH3)2
FIG. 6-Hexa(methoxymethyl)melamine.
synthesis. They are therefore present in many high-solids
amino resins.
Determination of combining ratios may be done most easily by either IH or 13C NMR techniques [8]. Older methods
involve complete hydrolysis of the resin to the starting materials, followed by wet-chemical analysis for formaldehyde
and gas chromatographic determination of alcohol (methanol or butanol).
Free Formaldehyde
Amino resins always contain some unreacted formaldehyde, usually referred to in product specifications as "free"
formaldehyde. Free formaldehyde may be analyzed quantitatively by a number of methods. One of the most commonly
used is the sodium sutfite method [10]. Formaldehyde reacts
rapidly and completely with aqueous sodium sulfite to form a
bisulfite addition complex. Sodium hydroxide is liberated
quantitatively on a mole-for-mole basis
CH20 + Na2SO3 + HaO
) >NH + CHaO
(8)
PHYSICAL PROPERTIES
General
Amino resins are typically viscous liquids, with an aminelike odor. Depending on composition, they may also smell of
formaldehyde and/or solvent. They are readily soluble in alcohols, ketones, hydroxy-functional glycol ethers, esters, etc.,
but have limited solubility in hydrocarbons. Some resins,
especially methylol-rich resins with low levels of both combined formaldehyde and combined methanol, are water soluble. Many more are water reducible in the presence of other
solvents, e.g., alcohols and glycol ethers.
Because of their resinous nature, aminos have neither a
well-defined freezing point nor boiling point. Uncured resins
typically have glass transition temperatures around -40~
When heated, they undergo decomposition, with release of
formaldehyde and alcohol, at temperatures above about
140~ This tendency to decompose causes difficulties in determining the solids content of resin solutions, as described
Surface Tension
The surface tension of amino resins is quite strongly related to the nature of the etherifying alcohol and is much less
affected by the level of combined formaldehyde and alcohol.
In the author's laboratory, surface tension measurements on
high-solids, solvent-free resins using a DeNouy tensiometer
have given values ranging from about 45 dynes/cm for methylated resins to about 28 dynes/cm for butylated resins. Mixed
methyl/butyl resins give intermediate values, depending on
the methyl and butyl content. The reduction in surface tension vghen butanol is the etherifying alcohol may be one reason that high-solids butyl and methyl/butyl resins provide
improved flow and leveling in high-solids formulations compared to their fully methylated counterparts.
~ >NCH20--A + ROH
(9)
where
R = alkyl, and
A = primary film-former.
Additionally, direct etherification may take place, the end
result being the same
CHAPTER 8 - - A M I N O R E S I N S
>NCH2OH + HO--A
>NCH20--A + H20
(10)
where
A = primary film-former.
These two reactions both result in chemical bond formation between the amino and the primary film-former (cocondensation). Two other reactions may also take place, both
of which involve reaction of the amino resin with itself (selfcondensation). These are
>NH + ROCHzN<
>NCH2N< + ROH
(11)
where
R = H, alkyl.
>NCH2OH + HOCH2N<
Besides the co-condensation and self-condensation reactions, hydrolysis and deformylation reactions may also occur
>NCH2OR + H20
>NCH2OCH2OR + H20
>NCHzOH
) >NCHzOH + ROH
(13)
(14)
~ >NH + CH20
(15)
65
) --I~ICH2OR + BH
) - - N = CH2 + OR-
- - N = CH2 + H20
OR- + BH +
) --NHCH2OH
) ROH + B
(16)
(17)
(18)
(19)
>NCH2--OR + H +
>NCH2OHR +
> N C H f + H20
(20)
) >NCH~- + ROH
(21)
) >NCH2OH + H +
(22)
) >NCH2OHR + + A-
(23)
) >N
- - N = CH 2 + H20
= CH 2 +
ROH + HA (24)
) --NHCHEOH
(25)
66
ENVIRONMENTAL/TOXICITY
The past 20 years have seen increased emphasis on the
quality of the environment both in the workplace and beyond.
In the coatings industry, this has meant strict controls on
exposure of workers to hazardous ingredients in the coating
formulation when applied, as well as on the nature and
.2.yN.yN.2
E n d Uses o f A m i n o R e s i n s
Amino-based surface coatings protect and decorate the
substrate to which they are applied. Their technology and use
has developed over many years. As already mentioned, resins
based on urea and melamine dominate the field. Urea resins
are traditionally used in clear coatings for wood, e.g., furniture, kitchen cabinets, in paper, film, and foil applications,
and in some appliance and general industrial coatings. They
are also used to some extent in automotive primers. They
cannot be used in automotive topcoats because of their sensitivity to hydrolysis.
Melamine resins are much more widely used. They give
better chemical resistance, as well as resistance to weathering
FIG. 7-Benzoguanamine.
"N~ ~'N ~
H
H
FIG. 8-Glycoluril.
CHAPTER 8 - - A M I N O R E S I N S
a m o u n t s of volatile organics (the so-called VOCs) released to
the e n v i r o n m e n t w h e n the f o r m u l a t i o n is cured.
Amino resin suppliers have r e s p o n d e d to these environm e n t a l challenges in a n u m b e r of ways. Chief a m o n g these
has been a progressive shift t o w a r d s higher-solids, lowermolecular-weight aminos, w h i c h are n o w the resins of choice
of coatings formulators. M a n y a m i n o resins are supplied at
100% nonvolatiles, especially for the a u t o m o t i v e industry.
W h e r e solvents are needed, those presenting the least h a z a r d
to w o r k e r a n d e n v i r o n m e n t are selected. F o r their part, p a i n t
p r o d u c e r s have i n c r e a s e d the functionality of the c o r e a c t a n t
resin while lowering its m o l e c u l a r weight to m i n i m i z e solvent
use with the object of b u i l d i n g m o l e c u l a r weight to the maxim u m possible extent d u r i n g cure. This has m e a n t using
h i g h e r levels of a m i n o resin, as m u c h as 40 to 50% of total
b i n d e r weight in s o m e cases.
Perhaps the m o s t i n t r a c t a b l e e n v i r o n m e n t a l p r o b l e m with
a m i n o resins is the use of f o r m a l d e h y d e in t h e i r m a n u f a c t u r e .
F o r m a l d e h y d e is r e c o g n i z e d b y the I n t e r n a t i o n a l Agency for
R e s e a r c h on Cancer (IARC) as a carcinogen. The A m e r i c a n
Conference of G o v e r n m e n t a l I n d u s t r i a l Hygienists (ACGIH)
lists f o r m a l d e h y d e as an "A2" substance, i.e., one suspected of
carcinogenic potential for m a n , a n d the O c c u p a t i o n a l Safety
a n d Health A d m i n i s t r a t i o n (OSHA) has set w o r k p l a c e exposure limits of 0.75 p p m (8-h t i m e w e i g h t e d average) a n d 2
p p m (15-min s h o r t - t e r m exposure limit).
The f o r m a l d e h y d e content of a m i n o resins is p r e d o m i n a n t l y "combined," i.e., chemically reacted, a n d r e p r e s e n t s
a b o u t 30 to 50% by weight of the resin. A small a m o u n t ,
ranging from a b o u t 0.1 to a b o u t 3% is present free, o r unr e a c t e d (see the section entitled A n a l y s i s / A n a l y t i c a l Methods). Amino resin suppliers have m a d e c o n s i d e r a b l e progress
over the p a s t several years in lowering the level of free formald e h y d e in their products, w h i c h is i m p o r t a n t b e c a u s e of
OSHA labelling requirements.
In an ideal situation, all of the c o m b i n e d f o r m a l d e h y d e
w o u l d r e m a i n in the coating after cure as p a r t of the p o l y m e r
network, In practice, however, some of the c o m b i n e d formaldehyde a n d all of the free f o r m a l d e h y d e is released d u r i n g
cure a n d m a y r e a c h the environment, d e p e n d i n g on the mechanics of the coating a n d curing operation. It is the p a r t i a l
release of c o m b i n e d f o r m a l d e h y d e d u r i n g cure w h i c h is of
m o s t concern, since the a m o u n t released c a n easily be several
times t h a t of the free formaldehyde. I n c i n e r a t i o n of off gases,
w h e r e possible, is the best solution.
REFERENCES
[1] DeJong, J. I. and DeJonge, J., Recueil de Travail Chimie Pay-Bas,
Vol. 71, 1952, p. 643.
67
[2] Gordon, M., Halliwell, A., and Wilson, T., Journal of Applied
Polymer Science, Vol. 10, 1966, p. 1153.
[3] Gordon, M., et al., "The Chemistry of Polymerization Processes,"
SCI Monograph No. 20, Society of Chemical Industry, London,
1966, p. 187ff.
[4] Aldersley, J. W. et al., Polymer, Vol. 9, 1968, p. 345.
[5] Okano, M. and Ogata, Y., Journal of the American Chemical
Society, Vol. 74, 1952, p. 5728.
[6] Braun, D. and Legradic, V., Angewaudte Makromolekular
Chemie, Vol. 35, 1974, p. 101.
[7] Tomita, B., Journal of Polymer Science, Vol. 15, 1977, p. 2347.
[8] Christensen, G., "Analysis of Functional Groups in Amino Resins," Progress in Organic Coatings, Vol. 8, 1980, pp. 211-239.
[9] Kambanis, S. M. and Rybicki, J., Journal of Coatings Technology,
Vol. 52, No. 667, 1980, p. 61.
[10] Walker, J. F., Formaldehyde, 3rd ed., Robert E. Krieger Publishing Co., Huntington, NY, 1975, p. 486.
[11] Hill, L. W. and Wicks, Z., Progress in Organic Coatings, Vol. 10,
1982, p. 55.
[12] Yamamoto, T., Nakamichi, T., and Ohe, O., Journal of Coatings
Technology, Vol. 60, No. 762, 1988, p. 51.
[13] Blank, W., Journal of Coatings Technology, Vol. 51, No. 656,
1979, p. 61.
[14] Blank, W., Journal of Coatings Technology, Vol. 54, No. 687,
1982, p. 26.
[15] Santer, J. O. and Anderson, G. J., Journal of Coatings Technology,
Vol. 52, No. 667, 1980, p. 33.
[16] Santer, J. O., Progress in Organic Coatings, Vol. 12, 1984, p. 309.
[17] Lazzara, M. G., Journal of Coatings Technology, Vol. 56, No. 710,
1984, p. 19.
[18] Nakamichi, T., Progress in Organic Coatings, Vol. 14, 1986, p. 23.
[19] Hill, L. W. and Kozlowski, K., Journal of Coatings Technology,
Vol. 59, No. 751, 1987, p. 63.
[20] Bauer, D. R., Progress in Organic Coatings, Vol. 14, 1986, p. 45.
[21] Bauer, D. R., Progress in Organic Coatings, Vol. 14, 1986, p. 193.
[22] Berge, A., Kvaeven, B., and Ugelstad, J., European Polymer Journal, Vol. 6, 1970, p. 981.
[23] Berge, A., Advances in Organic Coatings Science and Technology,
Vol. 1, 1979, p. 23.
[24] Berge, A., Gudmundsen, S., and Ugelstad, J., European Polymer
Journal, Vol. 5, 1969, p. 171.
[25] English, A. D., Chase, D. B., and Spinelli, H. J., MacromoIecules,
Vol. 16, 1983, p. 1422.
[26] English, A. D. and Spinelli, H. J., Journal of Coatings Technology,
Vol. 56, No. 711, 1984, p. 43.
[27] Bauer, D. R., Journal of Applied Polymer Science, Vol. 27, 1982, p.
3651.
[28] Bauer, D. R. and Briggs, L. M., "Characterization of Highly
Crosslinked Polymers," American Chemical Society Symposium
Series No. 243, Washington, DC, 1984.
[29] Parekh, G. G., Journal of Coatings Technology, Vol. 51, No. 658,
1979, p. 101.
[30] McGuire, J. M. and Nahm, S. H., Journal of High-Resolution
Chromatography, Vol. 14, 1991, p. 241.
MNLI7-EB/Jun.
1995
Ceramic Coatings
by Richard A. Eppler ~
GLAZES
Leadless Glazes
Glazes are essentially mixtures of silica with other oxides
added to permit the glaze to form at a readily achievable
temperature. In a leadless glaze, the alkali and alkaline earth
oxides, together with magnesia (MgO), zinc oxide (ZnO), and
boron oxide (B203), are used to provide the fluxing action.
Table 1 gives the formulas of a few typical ceramic glazes.
Glaze 1 is a feldspathic glaze suitable for use on soft paste
porcelains or hard stoneware [4]. This glaze is typical of that
used on medieval Chinese porcelains.
Glaze 2 is a sanitary-ware glaze [5]. It is derived from the
soft paste porcelain glaze by the addition of ZnO in large
quantity. Increasing the melting rate by increasing the per-
www.astm.org
69
Na20
KzO
CaO
MgO
ZnO
SrO
BaO
PbO
B203
A1203
SiO2
ZrO2
1
2
3
4
5
6
7
8
2.24
2.05
6.54
1.81
3.06
2,46
0.00
0.85
3.24
3.12
1.47
2.71
1.72
0.00
0.00
1.91
9.71
11.15
7.67
9.16
7.65
3.09
0.00
10.08
0.44
0.00
0.16
0.62
0.00
0,00
0.00
0.00
0.00
5.39
10.18
10.94
0.00
0.00
0.00
0,00
0.00
0.00
0.00
3.07
0.00
0.00
0~00
0.00
0.00
0.00
0.00
2.50
0.00
0.00
0,00
0,00
0.00
0.00
0.00
0.00
16.08
35.30
88.14
28.87
0.00
0.00
1.36
5.47
6.04
8.93
0.00
4.20
14.44
18.58
10.36
7.37
9.57
7.04
0.00
9.17
69.90
59.71
62.25
55.79
55.88
42.45
11.86
35,99
0.00
0.00
0.00
0,57
0,00
0,72
0,00
8.92
Title
C 1027
C 650
C 609
Lead-Containing Glazes
Litharge (PbO) is used in glazes for several reasons [8], the
most i m p o r t a n t of which is the strong fluxing action of PbO,
which allows the f o r m u l a t i o n of glazes that m a t u r e at temperatures lower t h a n their leadless counterparts, leading to
greater flexibility in the f o r m u l a t i o n of the glaze to o b t a i n
desired properties, .Glazes for electronic substrates, artware,
a n d some dinnerware, a n d tiles c o n t a i n lead oxide. However,
PbO is highly toxic. Therefore, use of lead-containing glazes
requires special care in processing a n d in testing the ware
produced.
Glaze 5 i n Table 1 is a n example of a lead-containing dinnerware glaze [9]. Glaze 6 is a n example of a clear glaze
suitable for use o n artware a n d hobbyware bodies [10]. Glaze
7 is an example of a coating used on integrated circuit packages to seal t h e m [11].
C 554
C 424
C 556
C 539
C 372
C 584
C 1034
C 738
C 895
Testing o f Glazes
ASTM Committee C-21 on Ceramic Whitewares a n d Related Products has developed several test methods to evaluate
the physical properties of ceramic glazes. These are listed in
Table 2 [12]. These tests form the basis for most quality
control testing programs.
There are several m e t h o d s concerned with the fit of the
glaze to the substrate. These include: C 5 5 4 - - T e s t Method for
Crazing Resistance of Fired Glazed Ceramic Whitewares by a
Thermal Shock Method; C 4 2 4 - - T e s t Method for Crazing
Resistance of Fired Glazed Whitewares by Autoclave Treatment; C 5 3 9 - - T e s t Method for Linear T h e r m a l E x p a n s i o n of
Porcelain E n a m e l a n d Glaze Frits a n d Ceramic Whiteware
Materials by the Interferometric Method; and C 3 7 2 - - T e s t
Method for Linear T h e r m a l Expansion of Porcelain E n a m e l
PORCELAIN ENAMELS
Porcelain e n a m e l coatings are ceramic coatings designed
for application to metals. Conventional porcelain e n a m e l
coatings are prepared in a n aqueous system a n d applied to
the substrate by spray, dip, or flow coating. The coating is
70
P A I N T A N D COATING T E S T I N G M A N U A L
dried before firing. Newer technology involves dry application of powdered porcelain e n a m e l by electrostatic spray.
The total market for porcelain-enameled products was reported to be $5486 billion i n 1989 [13]. About 86% of the
products are appliances, such as ranges, water heaters, h o m e
laundry, a n d dishwashers. About 6% are cast-iron sanitary
ware, a n d 8% are architectural, cookware, a n d miscellaneous
items.
A porcelain e n a m e l m u s t be formulated such that it will
b o n d to the metal substrate. For proper adherance of the
e n a m e l to the metal, it is necessary to develop a c o n t i n u o u s
electronic structure across the interface [14]. This structure is
developed by saturating the e n a m e l coating a n d the substrate
metal with a n oxide of the metal [15], which for iron a n d steel
substrates is ferrous oxide (FeO).
Certain t r a n s i t i o n metal oxides, such as cobalt oxide (COO),
nickel oxide (NiO), a n d cupric oxide (CuO), can be added to
a n e n a m e l f o r m u l a t i o n to improve the adherence between the
metal a n d the substrate. G r o u n d coat enamels c o n t a i n
adherance oxides, while cover coat enamels do not.
G r o u n d Coat E n a m e l s
A general-purpose g r o u n d coat e n a m e l like E n a m e l 1 in
Table 3 is a n alkali borosilicate c o n t a i n i n g small a m o u n t s of
adherance oxides to promote the b o n d i n g process. E n a m e l 2
is a h o m e l a u n d r y enamel that has been formulated for outstanding alkali resistance t h r o u g h the addition of large q u a n tities of zirconia (ZrO2) [16]. Hot water t a n k coatings like
E n a m e l 3 have very stringent thermal- a n d corrosion-resistance requirements.
E n a m e l 4 is a c o n t i n u o u s clean coating. This is a porous
coating which provides a m e a n s of volatilizing a n d removing
food soils from the i n t e r n a l surfaces of ovens during n o r m a l
operation [17].
Cover Coat E n a m e l s
Cover coat porcelain enamels are formulated to provide
specific color a n d appearance characteristics, a b r a s i o n resistance, surface hardness, a n d resistance to corrosion, heat, a n d
t h e r m a l shock. They c a n be clear, semiopaque, or opaque.
Opaque enamels such as E n a m e l 5 are used for white a n d
pastel coatings [18]. They c o n t a i n high c o n c e n t r a t i o n s of
titania (TiO2) to provide the opacification. S e m i o p a q u e
enamels like E n a m e l 6 are used for most m e d i u m - s t r e n g t h
colors. Clear enamels like E n a m e l 7 are used to produce
strong, bright colors. They are similar to g r o u n d coat formulations without the adherance oxides.
Testing o f Porcelain E n a m e l s
Test m e t h o d s for porcelain e n a m e l coatings are u n d e r the
jurisdiction of ASTM Committee B-8 o n Metallic a n d Inorganic Coatings. The methods are listed in Table 4. Again, they
form the basis for most quality control test programs.
Several of these test methods are c o n c e r n e d with the chemical durability of porcelain enamels. They include: C 2 8 2 - Test Method for Acid Resistance of Porcelain E n a m e l s (Citric
Acid Spot Test); C 6 1 4 - - T e s t Method for Alkali Resistance of
Porcelain Enamels; C 7 5 6 - - T e s t Method for Cleanability of
Surface Finishes; C 5 3 8 - - T e s t Method for Color Retention of
Red, Orange, a n d Yellow Porcelain Enamels; C 8 7 2 - - T e s t
Method for Lead a n d C a d m i u m Release from Porcelain
E n a m e l Surfaces; a n d C 2 8 3 - - T e s t Method for Resistance of
Porcelain E n a m e l e d Utensils to Boiling Acid. A related issue
is the possibility of defects providing a pathway from the
surface to the substrate, usually called c o n t i n u i t y of coating.
Methods in this area include: C 5 3 6 - - T e s t Method for Continuity of Coatings in Glassed Steel E q u i p m e n t by Electrical
Testing; C 7 4 3 - - T e s t Method for Continuity of Porcelain
Enamel1
Enamel2
Enamel3
Enamel4
Enamel5
Enamel6
Enamel7
Li20
Na20
K20
CaO
MgO
ZnO
BaO
CoO
NiO
CuO
0.88
13.15
2.30
6.18
0.00
0.00
7.27
0.47
0.29
0.20
0.81
12.60
1.56
2.80
0.18
0.26
0.73
0.36
0.31
0.00
1.33
13.92
0.00
2.04
0.00
1.27
0.56
0.47
0.00
0.00
0.52
7.30
1.47
0.65
0.00
0.00
0.00
0.03
0.03
13.99
0.89
9.41
6.13
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.10
8.58
9.15
0.00
0.00
1.04
0.00
0.00
0.00
0.00
1.76
12.23
3.83
0.00
0.00
0.00
0.00
0.00
0.00
0.00
B203
A]203
Cr20 s
Sb203
15.37
6.35
0.00
0.00
15.99
11.50
0.00
0.00
7.60
2.02
0.00
0.00
1.18
41.38
1.24
0.30
16.13
2.25
0.00
0.00
16.53
1.34
0.00
0.00
7.11
2.72
0.00
0.00
SiO2
ZrO2
TiO2
MnO2
P205
Nb205
WOs
MoOs
44.01
0.00
0.00
0.20
0.70
0.00
0.00
0.00
41.55
6.36
2.55
0.66
0.45
0.00
0.00
0.00
56.05
11.66
0.00
1.81
0.00
0.00
0.00
0.00
24.20
7.24
0.03
0.03
0.00
0.00
0.00
0.00
40.97
0.00
20.97
0.00
1.30
0.06
0.05
0.00
46.74
0.00
13.25
0.00
0.00
0.00
0.00
0.00
59.07
7.86
3.58
0.00
0.00
0.00
0.00
0.47
2.71
2.31
2.19
0.72
3.17
3.93
2.35
CHAPTER 9 - - C E R A M I C COATINGS
E n a m e l Coatings; a n d C 5 3 7 - - T e s t M e t h o d for Reliability of
Glass Coatings on Glassed Steel R e a c t i o n E q u i p m e n t by H i g h
Voltage.
ASTM
Method
C 724
C 735
GLASS ENAMELS
C 675
Glass e n a m e l s are vitreous coatings a p p l i e d on glass. They
provide a m e a n s of decoration, not an i m p r o v e m e n t in c h e m ical d u r a b i l i t y or in cleanability. These coatings m u s t be mat u r e d at t e m p e r a t u r e s b e l o w the d e f o r m a t i o n p o i n t of glass
(1000 to 1200~ o r 538 to 649~
Hence, they require large
quantities of fluxing elements so t h a t c h e m i c a l d u r a b i l i t y is
difficult to achieve.
Glass e n a m e l s are p r o d u c e d in ready-to-use form (paste,
t h e r m o p l a s t i c s , s p r a y m e d i u m s , ultraviolet curable med i u m s ) b y a few select m a n u f a c t u r e r s . They r e p r e s e n t a specialty p r o d u c t that is m o r e a k i n to organic p a i n t s t h a n to
o t h e r c e r a m i c coatings. The m a r k e t s for this specialty product are c a t e g o r i z e d as tableware, glass containers, architectural, lighting, a n d automotive. As s u p p l i e d to the user, glass
e n a m e l s are m e c h a n i c a l mixtures of pigments, fluxes, a n d
organic s u s p e n d i n g media. The r e q u i r e m e n t for low maturing t e m p e r a t u r e s necessitates the use of very high lead
oxide c o n t a i n i n g borosilicates for the flux. Leadless fluxes are
u n d e r development, b u t have n o t yet achieved c o m m e r c i a l l y
acceptable properties. The organic s u s p e n d i n g m e d i a are
similar to m a t e r i a l s u s e d to m a k e organic paints.
TABLE 4--Test methods for porcelain enamels
Number
C 448
C 282
C 614
C 756
C 538
C 839
C 536
C 743
C 374
C 346
C 872
C 539
C 537
C 283
C 285
C 703
C 385
[19].
Title
Test Methods for Abrasion Resistance of Porcelain
Enamels
Test Method for Acid Resistance of Porcelain Enamels
(Citric Acid Spot Test)
Test Method for Alkali Resistance of Porcelain Enamels
Test Method for Cleanability of Surface Finishes
Test Method for Color Retention of Red, Orange, and
Yellow Porcelain Enamels
Test Method for Compressive Stress of Porcelain
Enamels by Loaded-Beam Method
Test Method for Continuity of Coatings in Glassed
Steel Equipment by Electrical Testing
Test Method for Continuity of Porcelain Enamel
Coatings
Test Methods for Fusion Flow of Porcelain Enamel
Frits (Flow-Button Methods)
Test Method for 45-degree Specular Gloss of Ceramic
Materials
Test Method for Lead and Cadmium Release from
Porcelain Enamel Surfaces
Test Method for Linear Thermal Expansion of
Porcelain Enamel and Glaze Frits and Ceramic
Whiteware Materials by the Interferometric Method
Test Method for Reliability of Glass Coatings on
Glassed Steel Reaction Equipment by High Voltage
Test Method for Resistance of Porcelain Enameled
Utensils to Boiling Acid
Test Method for Sieve Analysis of Wet-Milled and DryMilled Porcelain Enamel
Test Methods for Spalling Resistance of PorcelainEnameled Aluminum
Test Method for Thermal Shock Resistance of
Porcelain-Enameled Utensils
C 676
C 824
C 927
C 978
C 777
71
[12].
Subject
Test Methods for Acid Resistance of Ceramic
Decorations on Architectural-Type Glass
Test Method for Acid Resistance of Ceramic
Decorations on Returnable Beer and Beverage Glass
Containers
Test Methods for Alkali Resistance of Ceramic
Decorations on Returnable Beverage Glass
Containers
Test Method for Detergent Resistance of Ceramic
Decorations on Glass Tableware
Practice for Specimen Preparation for Determination of
Linear Thermal Expansion of Vitreous Glass
Enamels and Glass Color Frits by the Dilatometer
Method
Test Method for Lead and Cadmium Extracted from
the Lip and Rim Area of Glass Tumblers Externally
Decorated with Ceramic Glass Enamels
Test Method for Photoelastic Determination of
Residual Stress in a Transparent Glass Matrix Using
a Polarizing Microscope and Optical Retardation
Compensation Procedures
Test Method for Sulfide Resistance of Ceramic
Decorations on Glass
REFRACTORY COATINGS
F l a m e s p r a y techniques can be used to a p p l y c e r a m i c coatings in the m o l t e n state to heat-sensitive o r massive substrates that c a n n o t themselves be h e a t e d to high temperatures. Most c e r a m i c coating m a t e r i a l s u s e d currently c a n
be a p p l i e d b y flame spraying [20]. Silicates, silicides, carbides, oxides, a n d nitrides have all been d e p o s i t e d by this
process.
I n these processes, the coating m a t e r i a l is m e l t e d a n d p r o jected as h e a t e d particles onto the suhstrate, w h e r e it instant a n e o u s l y solidifies as a coating. Three m e t h o d s of h e a t i n g
a n d propelling the particles in a plastic c o n d i t i o n to the
s u b s t r a t e surface include: (1) c o m b u s t i o n flame spraying, (2)
p l a s m a arc flame spraying, a n d (3) d e t o n a t i o n gun spraying.
C o m b u s t i o n flame spraying is used for c o a t i n g m a t e r i a l s t h a t
melt readily. P l a s m a arc flame spraying is used for very re-
72
COATING APPLICATION
Ceramic coatings are applied to their substrates by one of
several powder-processing techniques. In wet processes the
raw materials are dispersed in a slip. Slip preparation involves mixing the ingredients, particle-size reduction, dispersion in water, and the addition of minor amounts of additives
to modify the rheological properties of the slip [21-22]. These
processes are carried out together in a ball mill comprising a
rotating cylinder partly filled with freely moving, impactresistant shapes.
The application process for a ceramic coating must be
straightforward and foolproof, reproducible, economical,
and flexible [21]. Selection of the application technique is one
of the most important decisions the coatings engineer makes.
Criteria for this selection are type of ware, shape and size of
ware, throughput required, energy and labor costs, and space
available. All of these factors affect the quality and the cost of
a coating process, so that the best solution must be determined on an individual basis.
Dipping is a simple, efficient, rapid technique requiring no
capital equipment. The ware is immersed in the coating slip,
moved around in a controlled way, removed from the slip,
shaken to remove excess slip, and set down to drain and dry.
Any bare spots are touched up with a finger wet with coating
material. Its limitations are extreme sensitivity to operator
skill and difficulty in automating volume production.
Spraying is a process whereby a coating slip is broken
down into a cloud of fine particles that are transferred to the
substrate by either pneumatic, mechanical, or electrical
forces. The method requires a gun, a container or feed mechanism, an impelling agency, and a properly designed hood or
booth maintained under negative pressure [23]. Spraying
lends itself to high-volume automated systems [24]. The articles are continuously fed under a battery of angled spray
guns. Coating reclaim is an essential part of automated systems.
Slip can also be applied mechanically with a rotating atomizer. Slip is passed onto a set of closely spaced rotating disks
which throw the coating into a fan of droplets. Costs are
similar to spraying. The primary use of this technique is in
producing textured coatings on tile.
If the substrate is conductive (that is, a metal), the surface
quality and uniformity of a ceramic coating can be improved
by using the electrostatic spray coating technique [25,26]. In
REFERENCES
[1] Eppler, R. A., "Glazes and Enamels," Chap. 4, Glass Science and
Technology, Vol. 1, Academic Press, New York, 1983, pp.
301-337.
[2] Eppler, R. A., "Corrosion of Glazes and Enamels," Chap. 12,
Corrosion of Glass, Ceramics, and Ceramic Superconductors,
D. E. Clark and B. K. Zoitos, Eds., Noyes Publications, Park
Ridge, NJ, 1992.
[3] Ceramic Industries, August 1990, p. 36.
CHAPTER 9--CERAMIC
[4] Tichane, R., "Ching-te-Chen; Views of a Porcelain City," N.Y.
State Institute for Glaze Research, Painted Post, NY, 1983.
[5] Singer, F. and German, W. L., "Ceramic Glazes," Borax Consolidated, 1964.
[6] Orth, W. H., "Effect of Firing Rate on Physical Properties of
Wall Tile," American Ceramic Society Bulletin, Vol. 46, No. 9,
1967, pp. 841-844.
[7] O'Conor, E. F., Gill, L. D., and Eppler, R. A., "Recent Developments in Leadless Glazes," Ceramic Engineering Society Proceeding& Vol. 5, Nos. 11-17, 1984, pp. 923-932.
[8] Eppler, R. A., "Formulation and Processing of Ceramic Glazes
for Low Lead Release," Chap. 10, Proceedings, International
Conference of Ceramic Foodware Safety, J. F. Smith and M. H.
McLaren, Eds., Lead Industries Association, New York, 1976,
pp. 74-96.
[9] Marquis, J. E., "Lead in Glazes--Benefits and Safety Precautions,"American Ceramic Society Bulletin, Vol. 50, No. 11, 1971,
pp. 921-923.
[10] Eppler, R. A., "Formulation of Glazes for Low Pb Release,"
American Ceramic Society Bulletin, Vol. 54, No. 5, 1975, pp.
496-499.
[11] Tummala, R. R. and Shaw, R. R., "Glasses in Microelectronics
in the Information-ProcessingIndustry," "Commercial Glasses,"
Advances in Ceramics, Vol. 18, American Ceramic Society, Columbus, OH, 1986, pp. 87-102.
[12] ASTM Annual Book of Standards, Part 15.02: Glass, Ceramic
Whitewares.
[13] Ceramic Industries, August 1990, p. 49.
[14] Pask, J. A., "Chemical Reaction and Adherance at Glass-Metal
Interfaces," Proceedings, PEI Technical Forum, Vol. 22, 1971, pp.
1-16.
[15] King, B. W., Tripp, H. P., and Duckworth, W. H., "Nature of
Adherance of Porcelain Enamels to Metals," Journal of the American Ceramic Society, Vol. 42, No. 1t, 1959, pp. 504-525.
[16] Eppler, R. A., Hyde, R. L., and Smalley, H. F., "Resistance of
Porcelain Enamels to Attack by Aqueous Media: I--Tests for
COATINGS
73
Enamel Resistance and Experimental Results Obtained," American Ceramic Society Bulletin, Vol. 56, No. 12, 1977, pp. 10641067.
[17] Monteith, P. G., Linhart, O. C., and Slaga, J. S., "Performance
Tests for Properties of Low Temperature Thermal Cleaning
Oven Coatings," Proceedings, PEI Technical Forum, Vol. 32,
1970, pp. 73-79.
[18] Shannon, R. D. and Friedberg, A. L., "Titania-Opacified Porcelain Enamels," Illinois University Engineering Experimental Station Bulletin, Vol. 456, 1960.
[19] ASTM Annual Book of Standards, Part 2.05: Metallic and Inorganic Coatings.
[20] Taylor, T.A., Bergeron, C.G., and Eppler, R.A., "Ceramic
Coating," Metals Handbook, 9th ed., Vol. V, ASM International,
Metals Park, OH, 1982, pp. 532-547.
[21] Taylor, J. R. and Bull, A. C., Ceramics Glaze Technology, Pergamon Press, Oxford, England, 1986.
[22] Reed, J. S., Introduction to the Principles of Ceramic Processing,
John Wiley & Sons, New York, 1988.
[23] Bloor, W. A. and Eardley, R. E., "Environmental Conditions in
Sanitary Whiteware Shops, II. Glaze Spraying Shops," Transactions, Journal of the British Ceramic Society, Vol. 77, No. 2, 1978,
pp. 65-69.
[24] Whitmore, M., "Spraying of Earthenware Flatware," Transactions, Journal of the British Ceramic Society, Vol. 73, No. 4, 1974,
pp. 125-129.
[25] Hebberlein, K., "Electrostatic Glazing of Tableware," Berichte
der Deutschen Keramischen Gesellschaft, Vol, 53, No. 2, 1976, pp.
51-55.
[26] Lambert, M., "Industrial Application of Electrostatic Enamelling to Parts in Sheet Steel and Cooking Equipment," Vitreous
Enameller, Vol. 24, No. 4, 1973, pp. 107-109.
[27J ASM Committee on Porcelain Enameling, "Porcelain Enameling," Metals Handbook, 9th ed., Vol. 5, ASM International,
Metals Park, OH, 1982.
MNL17-EB/Jun. 1995
10
EPoxy RESINSHAVEBECOMEtechnologically important materials that find extensive application in high-performance coatings, adhesives, and reinforced plastics. Almost since their
commercial introduction in 1950, epoxy resin systems have
been used in protective coatings. Historically, protective
coatings were the largest single end use for epoxy resins.
Although in recent years the noncoating applications of epoxy resin have been growing, coatings still represent about
half of the annual epoxy resin usage.
Epoxy resin coatings offer a unique combination of adhesion, chemical resistance, and physical properties that provide outstanding protection against severe corrosive environments. They are used extensively in coatings for refineries,
chemical plants, and marine equipment such as offshore
drilling platforms and merchant ships. Other important applications where epoxy resin coatings are used almost exclusively because of the corrosion protection they afford include
automotive, aircraft, and appliance primers as well as to
protect both the inside and outside of pipe. Epoxy resins are
the predominant thermosetting resin used for the interior
linings of beer and beverage cans, cans for hard-to-contain
food products such as sauerkraut, tomato juice, and meat
products, and for chemical-resistant linings of pails and
drums. These coatings are used not only to protect the metal
of the container from corrosion, but also to protect the flavor
of the contents, which can be affected by direct contact with
metal.
The principal components of any epoxy resin coating system are the epoxy resin and the curing agent or hardener.
Epoxy resins are reactive intermediates that can be liquid or
solid, and they are converted into the final coating by reaction
with curing agents (hardeners). Curing agents function by
reacting with specific groups in the epoxy resin molecule to
give a three-dimensional, infusible polymer network. Although the resin and curing agent are common to all epoxy
coatings, other materials are incorporated to achieve the
desired rheological characteristics, cure speed, and film performance.
CURING AGENTS
Epoxy resins are reactive intermediates composed of mixtures of oligomeric materials containing one or more epoxy
groups per molecule. To convert epoxy resins into useful
products, they must be cross-linked or "cured" into a threedimensional polymer network. Cross-linking agents, or
curing agents as they are generally called, function by reaction with or cause the reaction of epoxide or hydroxyl groups
in the epoxy resin. The number of curing agents that have
been developed over the years for epoxy resins is overwhelming. Selection of the curing agent is as important as that of the
base resin; it is dependent on the performance requirements
of the film and the constraints dictated by the specific method
of application.
The most important types of curing agents used in epoxy
resin coatings are the amine-functional materials for ambient-cure coatings and the amino- and phenoplast resins for
heat-cured systems. The principal amine-functional curing
agents used in ambient-cure coatings are aliphatic amine adducts of epoxy resins, polyamides, and ketimines. Aminefunctional materials cure epoxy resins by polyaddition
RESIN TYPES
Generically, epoxy resins can be characterized as a group
of commercially available oligomeric materials which con1Research adviser and 2senior research chemist, Shell Development Co., Westhollow Research Center, P.O. Box 1380, Houston, TX
77521-1380.
74
Copyright9 1995 by ASTMInternational
www.astm.org
75
--I
CH2CHCH2Jn --
O- CH2CH-CH 2
CH3
Average
EEW~
Approximate
Average
Value of n
Viscosity,
P, 25~
Softenin~
Point, ~ v
350
182
...
80
..-
380
600
900
1400
2900
188
310
475
900
1850
0.2
1
2
4
10
140
Semisolid
Solid
Solid
Solid
...
40
70
100
130
3750
3050
13
Solid
150
Applications
Solventless and solvent-borne ambient cure
coatings, electrical encapsulation, flooring, and
filament winding
Solvent-borne, ambient cure coatings
Powder coatings
Heat cure, solvent-borne coatings for cans, drums,
primers, etc.
aEEW = epoxideequivalent weight, i.e., grams of resins needed to provide 1 M equivalent of epoxide. Alsoreferred to as WPE (weight per epoxide) and EMM
(epoxy molar mass). All three terms are interchangeable.
bSoftening point by Durran's mercury method [ASTMSpecification for Epoxy Resins (D 1763)].
t h r o u g h reaction of the amine with the epoxy groups. Aminoand phenoplast cross-linking resins are generally etherified
urea-formaldehyde, melamine-formaldehyde, and phenolformaldehyde condensates. The amino- and phenoplast resins cure by condensation with the backbone hydroxyls of the
epoxy resin with elimination of water or an alcohol.
Aliphatic amines such as ethylene diamine (EDA), diethylene triamine (DETA), and triethylene tetramine (TETA) have
always been popular curing agents for epoxy resins because
of their ability to readily cure at r o o m temperature. However,
aliphatic amines present certain handling hazards because of
their high basicity and relatively high vapor pressure. Epoxy/
amine adducts, amine-terminated polyamides, ketimines,
and other modified polyamines are less hazardous derivatives
of aliphatic amines and often provide performance and handling advantages.
TWO-PACKAGE, AMBIENT-CURE
COATINGS
By far the largest volume of ambient-cure epoxy resin coatings are the "two-package" type, which are typically manufactured from liquid or low-molecular-weight solid epoxy resins
cured with a polyamine, amine adduct, or polyamide. A twopackage coating, as the n a m e implies, is a two-part system:
76
the epoxy component and the curing agent, which are packaged separately and often in volume ratios of 2 to 1 or 4 to 1 of
epoxy component to curing agent. Two-package epoxy coatings are mixed just prior to application and are characterized
by a limited working life or pot life after the resin and curing
agent components are mixed. Commercial systems will have
pot lives of a few hours to a couple of days, with typical
working times of about 8 to 12 h.
Two-package epoxy resin coatings include a broad range of
products and properties. Specific film properties depend on
selection among many epoxy resins, curing agents, pigments,
and modifiers, as well as the ratios of these materials. Resins
differ primarily in molecular weight. As the molecular weight
of the resin increases, the flexibility, flexibility retention, filmleveling properties, and pot life of the coating increase. However, cross-link density decreases with increasing molecular
weight, resulting in reduced solvent and chemical resistance
as well as nonvolatile content of the paint at application
viscosity.
Although aliphatic polyamines are less expensive and have
been used extensively as curing agents, polyamine adducts,
amine-terminated polyamides, and ketimines are generally
preferred. Among the advantages provided by aliphatic
amine adducts are:
9 Milder odor.
9 Lower volatility.
9 Less tendency to produce blush when coatings are applied
under conditions of high humidity.
9 Greater suitability for application at low temperature.
9 Less tendency to corrode metal containers.
Two general types of polyamine adducts are available, i.e.,
those based on a low-molecular-weight liquid epoxy resin and
those based on a high-molecular-weight solid epoxy resin.
The performance properties of amine-cured coatings are not
significantly different from those of aliphatic polyamine
cured systems. Like polyamines, amine adducts offer maxim u m resistance to solvents, acids, and other highly corrosive
chemicals. Initial flexibility and impact resistance are excellent, and retention of these properties is adequate for most
uses over rigid or semi-rigid substrates.
More pounds of polyamide curing agents are consumed
annually in the United States than any other type of epoxy
resin curing agent. Polyamides are obtained from the condensation of dimerized and/or trimerized fatty acids with aliphatic polyamines such as diethylene triamine and triethylene tetramine to give an amine-terminated polyamide.
Polyamide cured epoxy coatings develop superior adhesion
to moist and poorly prepared surfaces, and they provide a
high degree of corrosion resistance. Like epoxy resins, polyamides are also mixtures of oligomers. Thus, a range of polyamides which vary in viscosity, amine equivalent weight, and
reactivity is available. Polyamide cured coatings exhibit
somewhat better retention of flexibility and impact resistance
on aging than polyamine adducts. Although resistance to solvents and acids is not quite as good as with other types of
amine curing agents, polyamides are adequate for most
applications where amine cure epoxy coatings are used.
Ketones add reversibly to primary amines with the loss of
water to give ketimines. The ketimines obtained from the
typical polyamine curing agents have rather low volatility
compared to the precursor polyamine. Ketimine curing
CHAPTER I O - - E P O X Y R E S I N S IN COATINGS
cross-linking occurs principally through the hydroxyl functionality. Thermosetting resins such as urea-formaldehyde,
melamine-formaldehyde, and phenol-formaldehyde resins
are used as cross-linkers for the coatings of this type. This
cross-linking requires heat, and usually a strong acid catalyst
is used to accelerate the cure. Thus, these systems are supplied as "one-component" systems, i.e., the resin, curing
agent, and accelerator are packaged together.
Aminoplast (urea-formaldehyde or melamine-formaldehyde) cross-linking resins are used because of their good
color and relatively low cure temperature. They are typically
used in linings for beer and beverage containers and as clear
coatings for brass and jewelry. Pigmented aminoplast cured
coatings are used as coatings for industrial equipment, appliances, and hospital and laboratory furniture. Phenoplast
(phenol-formaldehyde) cured coatings are more chemically
resistant, and they find application in beer and beverage
containers (particularly in Europe), drum and pail linings,
internal coatings for pipe, wire coatings, and appliance
primers. Phenoplast resins, generally giving coatings of
poorer color than arninoplast resins, are used only when maxi m u m resistance to solvents and other chemicals is required.
ELECTRODEPOSITION COATINGS
Epoxy resin electrodeposition coatings are also waterborne
coatings formulated from either anionic or cationic epoxy
resin polymers. The part to be coated is dipped into the
electrodeposition bath, and an appropriate electrical charge
is applied, causing the coating to deposit onto the part. The
part is then removed from the bath, rinsed, and baked to cure
the coating. In the United States, epoxy-based electrodeposition coatings account for over 92% of all electrodeposition
coatings. Epoxy-based cathodic electrodeposition (CED) automotive primers dominate this application, accounting for
over 82% of all electrodeposition coatings. Over 40 million
pounds of epoxy resin are used in the United States in CED
automotive primers, making this one of the largest single end
uses for epoxy resins in coatings. Virtually every automobile
made in the United States, Europe, and Japan is primed with
a CED primer. CED primers are used because they afford
77
exceptional corrosion protection and because they are deposited uniformly to all areas of the automobile, even in areas
which would be inaccessible to other coating application
methods such as spray. Because of their major importance,
the remainder of this discussion will deal with CED automotive primers.
The preparation of CED coatings generally begins by reacting a bisphenol A based liquid epoxy with bisphenol A to give
an epoxy resin with an epoxy equivalent weight in the range
of 500 to 1000. This epoxy resin is then reacted with a flexibilizing diol. This diol can be an aliphatic diol or a polyether
diol. The principal requirement is that the diol contain primary hydroxyl functionality. These primary hydroxyls are reacted with the epoxy groups in the presence of a suitable
catalyst (e.g., a tertiary amine) to form ether linkages between the epoxy and the flexibilizing diol. At this point, the
resin will have an epoxy equivalent weight in the range of
1000 to 1500. The remaining epoxy functionality is then reacted with amines. Generally, secondary amines are chosen
to minimize further chain extension. One favored method to
accomplish this is to use a diketimine of diethylene triamine.
During coating preparation, the ketimine groups decompose
to give primary amines. These primary amines are fairly basic, resulting in stable dispersions at a relatively high bath pH
(pH > 6). At this point, the CED resin preparation is complete. In practice, specialized CED resins are used to make
the pigment grind pastes. These are developed to efficiently
make stable pigment dispersions, which retain good stability
in the CED coating bath.
Curing agents used are generally blocked isocyanates.
These are chosen to be stable and unreactive in the coatings
bath, but to unblock and cure the coating at baking temperature. An example of such a curing agent would be the reaction
product of 3 mol of toluene diisocyanate with 1 tool of trimethylolpropane. This is then reacted with 3 mol of a suitable
blocking agent, such as 2-ethyl-1-hexanol. Catalysts such as
tin or lead salts are generally used to facilitate unblocking
and coating cure. The coating is prepared by blending the
resin with pigment paste, curing agent, catalysts, additives,
and solvents. A low-molecular-weight organic acid, such as
lactic or acetic acid, is then added to the mixture to make
a m m o n i u m salts with the amine groups in the resin. This
mixture is then dispersed in water to make the CED coating.
Solvents may be required in the preparation of the CED resin
or other components. In order to reduce the volatile organic
compound content of the finished coating, it is usually subjected to a vacuum stripping step which can reduce VOC to
less than 0.7 lb/gal. When the automobile is dipped into the
CED bath, a negative charge is applied to it (making it the
cathode) relative to counter electrodes in the bath. Electrolysis of water occurs, forming hydroxide ions in the immediate
vicinity of the automobile surface. These hydroxide ions react
with the a m m o n i u m ion groups in the resin near the surface,
regenerating the neutral amine groups and causing the coating to be deposited onto the surface. In this way, a uniform
film is applied to the entire conductive surface of the automobile. The automobile is then removed from the bath, rinsed,
and baked.
78
E P O X Y R E S I N P O W D E R COATINGS
Powder coatings are produced by melt blending homogenous dispersions of nonvolatile solid resins, curing agents,
pigments, fillers, and various additives. The dispersion is
solidified by cooling, ground into a finely divided powder
form, and classified for subsequent use. The resultant powder
is normally electrostatically deposited onto grounded substrates and, through the application of heat, converted into
very high performance thermoset films. The process of applying coating powders allows nearly 100% powder utilization
and evolves almost no volatile organic compounds.
The 1970's volatiles regulations and energy concerns raised
interest in powder coating technology. The real sustaining
driving forces for growth, however, have been improvements
in powder coating raw materials, formulations, manufacturing technology, and application equipment. The advantages
for the use of powder coatings can best be summed up in the
"Four E's," used by The Powder Coating Institute: (1) excellence of finish, (2) economy in use, (3) energy efficiency, and
(4) environmental acceptability. The Clean Air Act, as
amended in 1990, has contributed to even greater interest in
the use of powder coatings to meet more stringent volatile
organic requirements. Powder coatings is the fastest growing
area of coatings technology. Growth rate for powder coatings
in the 1990 to 1995 time frame is projected to be at 10 to 12%
versus a conventional "wet" coatings rate of about 2%.
The unique characteristics of solid epoxy resins account for
their choice by formulators for use in powder coatings applications. Bisphenol-A based epoxides with equivalent weights
REFERENCES
[1] Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill
Book Co., New York, 1967.
[2] May, C. and Tanaka, Y., Epoxy Resins Chemistry and Technology,
Marcel Dekker, Inc., New York, 1973.
[3] Bauer, R. S., Epoxy Resin Chemistry, ACS Symposium Series 114,
American Chemical Society, Washington, DC, 1979.
MNL17-EB/Jun. 1995
ii
11
Phenolics
by John S. Fry 1
CHEMISTRY
HISTORY
Phenolic resins, initially commercialized in 1909, were the
first completely synthetic materials for the burgeoning plastics business. The expansion of several new technologies of
the time, namely the electrical, communications, and automotive industries, all required and depended on new materials that had better electrical insulating properties, higher
heat resistance, and improved resistance to chemicals, acids,
oils, and moisture. The heat-reactive resins, developed by Dr.
Leo H. Baekeland [1], were formulated into blends that were
convenient for mass production compression moldings and
satisfied the above-mentioned requirements. Improved and
new items such as coil supports, commutators, distributor
heads, telephone sets, vacuum tube bases, radio parts, and
electrical switches all blossomed onto the market within a
few years.
RAW M A T E R I A L S
The commercially important phenols used in coatings resins are shown in Fig. 1. While phenol is the most common,
the substituted phenols are also used to vary the solubility
and reactivity properties of resins. The cresols, butyl phenol
and bisphenol-A, are widely employed while the others have
limited or specialty uses.
Phenol has three aldehyde reactive ring positions; the 2 and
6 carbon atoms (ortho) and the 4 position (para). Phenols
with substituents in the above positions have lower functionalities and are frequently used to modify resin properties.
The aldehyde co-reactant of choice for the phenols is formaldehyde, the most reactive of those commercially available.
Formaldehyde, a gas, is conveniently handled as an aqueous
solution (formalin) or as a solid polymeric form known as
paraform. Formaldehyde in aqueous solutions exists as hydrated glycols or low-molecular-weight glycol ethers.
CH20 + H20
B A S E CATALYST
Strong base catalysts (pH above 8) produce initial reaction
products such as the methylol phenols shown in Fig. 2a.
Phenol can produce five different methylol-related species,
while the substituted phenols, with lower functionality, produce fewer methylol derivatives. Further reaction causes the
methylol groups to condense with other ring positions (meth-
) HOCH2OH- HOCH20[CH20]H
www.astm.org
80
~ ~H3~CH3~
OH
OH
Phenol
Orthocresol
OH
OH
Metacresol
CH3
Paracresol
OH
OH
OH
()
0
OH
CH3-C-CH3
I
cn3
CH3-C-CH3
I
CH 2
I
CH 3
OH
CH3
CH3
Xylenols
OH
CH3-C-CH3
I
CH2
I
CH3=C-CH 3
I
CH3
OH
2,2 Bis (4Hydroxylphenyl)
Propane
(Bisphenol-A)
p-Phenyl
Phenol
p-tert-Butyl
Phenol
p-tert
Amylphenol
p-tert-Octyl
Phenol
ylene link) or to etherify with other alcohol groups (methylene ether links) (Fig. 2b). Additional reaction raises the
molecular weight to branched, heat-reactive resin products
which are dehydrated, dissolved in solvents, or isolated as
grindable solids for later formulation.
ACID CATALYST
At a pH of 0.5 to 1.5, the acid-catalyzed phenol-formaldehyde reaction proceeds through an unstable addition intermediate to condensed, methylene-linked phenolic rings (Fig.
3). When phenol is used, highly branched "novolaks" are
obtained. However, when substituted phenols are used, the
functionality of the system is reduced to two and mostly
linear resins are formed.
INTERMEDIATE
pH
CATALYSIS
TESTING
OF PHENOLIC
RESIN
PRODUCTS
CHAPTER ll--PHENOLICS
OH
OH
OH
+ CH20
~ ~
Base
C
' H2OH
+
CH2OH
OH
<
OH
H2OH
HOCH2~
H2OH
,'H2OH
OH
HOCH2~
CH2OH
CH2OH
FIG. 2a-Base-catalyzed initial reaction products.
OH
OH
H2OH
Base y ~
OH
CH2
CH2OH+H20
METHYLENELINK
Or
OH
OH
METHYLENE ETHER
FIG. 2b-Methylol phenol reaction products.
+ H20
81
82
P A I N T A N D COATING T E S T I N G M A N U A L
OH
CH20
H+
~- HO
Acid
CH 2 ~
Q
CH2
H E A T REACTIVE R E S I N S IN COATINGS
Alcohol-Soluble Resins
The thermosetting, alcohol-soluble resins are based on
muhifunctional monomers such as phenol, cresols, xylenols,
and bisphenol-A. These resins are also soluble in ketones,
esters, and glycol ethers, but insoluble in aromatic and aliphatic hydrocarbons. They are compatible with amino resins,
epoxies, polyamides, and poly(vinyl butyral) and are, in many
cases, formulated with said resins as crosslinking agents. The
resins are commercially available as solvent solutions, solids,
or waterborne systems. Low-molecular-weight resins with a
high methylol content form water solutions, while higher molecular weight resins may be used in dispersion form [4,5].
Once formulated into vehicles, the resins may be applied by
spray, dip, brush, or roller coating methods. The films are
then baked at typical temperatures of 135 to 250~ for times
varying from several minutes to several hours. When used
alone, phenolic resins crosslink with the release of water to
form 0.2 to 1.0-mil films. Since volatiles are released during
cure, bubbles may develop in thicker films. Multiple coats
may be applied as long as the intermediate coats are given a
short bake.
Baked phenolic coatings are hard and glass-like with excellent resistance to organic solvents, boiling water, acids, and
acidic or neutral inorganic salts. They are not resistant to
alkalies unless combined with epoxides as will be discussed
later. These phenolic coatings have excellent electrical resistance and also resist dry heat to 370~ for short periods. As a
CHAPTER l l - - P H E N O L I C S
83
CH3
OH
CI-I3
CH2
A1
EPOXY
I
PHENOLIC
CH 3
OCH2-CH-CH2
I
CH3
+H20 I
CH2
OH
FIG. 4-Crosslink formation.
Nonheat-Reactive Resins--Unsubstituted
The acid-catalyzed reaction of formaldehyde with an excess of phenol and/or cresols produces the nonheat-reactive,
novolak-type resins. These resins do not form useful films by
themselves, but when formulated with polyfunctional epoxy
resins they act as co-reactants (hardeners) to produce thermoset systems. In this case, the chemistry involves the basecatalyzed reaction of an epoxy group with the phenolic by-
droxyl group to form ether-type crosslinks which are resistant to chemicals, moisture, and heat (Fig. 5). Since this reaction does not produce by-products, thick films may be
obtained via powder coatings or high solids solution coatings. Such coatings find application as pipe coatings, reinforcement bar, and electronic encapsulation coatings.
Varnish Resins
Substituted phenols containing the ten-butyl group or
higher alkyl groups are reacted with formaldehyde under
acidic conditions to produce "oil soluble" novolak resins.
O.CH2_CH_CH2
\o/
84
REFERENCES
[1] Baekeland, L. H., Industrial Engineering Chemistry, Vol. 1, No. 3,
1909.
[2] Megson, N. J. L., Phenolic Resin Chemistry, Academic, New York,
1958.
[3] Martin, R.W., The Chemistry of Phenolic Resins, Wiley, New
York, 1956.
[4] Harding, J., U.S. Patent 3,823,103, 1974 (to Union Carbide Corporation).
[5] Fry, J. S., U.S. Patent 4,124,554, 1978 (to Union Carbide Corporation).
[6] Richardson, S. H., Paint and Varnish Production, August 1955.
[7] Yee, A. and Fry, J. S., American Paint and Coatings Journal, 23
June 1986, p. 41.
MNL17-EB/Jun. 1995
Polyamides
by Robert W. Kight 1
Monocyclic
COOH
(I ~H2)8
<~
(CH2)s--COOH
CH~CH--(CH2)4--CH 3
(CH2)4
CH3
Polycyclic
COOH
(CH2)7--COOH
CH3--(CH2)4~~.~
ACIDS
(Ctt2)4
CH3
AMINES
The dimer acids are reacted with various polyamines to
form polyamides and a variety of other useful products.
The polyamines commonly used in industry are polyethylene polyamines of various chain lengths that are linear,
branched, or cyclic. The linear polyethylene polyamines are
characterized as secondary amine groups separated by ethylene chains, terminated on either end by primary amine
groups. Diethylenetriamine is an example of a simple linear
polyethylene polyamine.
HzN--CH2--CH2--NH--CH2--CH2--NH2
The cyclic and branched polyamine isomers contain tertiary amine groups in addition to the primary and secondary
amine groups. Aminoethylpiperazine is an example of a cyclic polyamine.
/CH2--C~H2
CH 3
CH3[
(~H2)8
CH
(~ H2)7
~H
H2N--CH2--CH2--N
NH
/
CH2--CH 2
The reaction between dimerized fatty acids and polyamines yield amide oligomers with amine group termination.
These amide oligomers are used as coreactants with epoxy
resins in high-performance coatings, as well as components
of a variety of other useful commercial compositions including two-component adhesives.
I
(~H2)7 (~H2)7
COOH
COOH
85
Copyright9 1995 by ASTM International
www.astm.org
86
EARLY H I S T O R Y
H2N--CH2--CH2--NI
~-C34
C~2/N
CH2
--C
II
N
\/
N - - C H 2 - - C H 2 - - N H2
CH 2
CH2
S Y N T H E S I S OF P O L Y A M I D E S
Polyamides are polycondensation products of difunctional
fatty acids and polyfunctional amines. In a typical commercial example, 1 mol of dimer acid is reacted with 2 mol of
diethylenetriamine. During this condensation reaction, 2 mol
of water are evolved. As the reaction proceeds, an interesting
side reaction occurs: an additional mol or so of water evolves
from a secondary reaction. One of the primary amine groups
reacts with the dimer acid to form an amide linkage, which is
a nitrogen bonded carbonyl. In addition, the ethylene chain
next to the amide function and the secondary amine nitrogen
are incorporated into a five-membered ring, known as an
imidazoline ring. This condensation reaction, which also
evolves water, eliminates an active hydrogen to yield a tertiary amine group. The degree of cyclization obtained is controlled to yield a product with specific useful properties, such
as improved solubility and compatibility and longer pot life.
Similar reactions occur at the other carboxylic acid group of
the dimer [2]. If 50% of the diethylenetriamine present in the
polyamide is cyclized to imidazoline, a total of 3 tool of water
of reaction is evolved. These products are shown in the following structures:
For the polyamide
O
H2N--CH2--CH2-- N, - C H 2 - C H 2 - N - C H
II
C2A
O
- - C - - N - - C H 2 - - C H 2 - - N - - C H 2 - - C H 2 - - N H2
CHEMICAL PROPERTIES
The total amine value of the polyamide is determined by
potentiometric titration using ASTM Test Method D 2073:
Test Methods for Total, Primary, Secondary, and Tertiary
Amine Values of Fatty Amines, Amidoamines, and Diamines
by Referee Potentiometric Method. Note, however, that the
methods specified therein for primary, secondary, and tertiary amine values are not applicable to polyamides. The total
amine value is commonly listed in the specification properties of commercial polyamides and is defined as the number
of milligrams of potassium hydroxide equivalent to the basicity in 1 g of sample.
The acid value, generally less than 5, that is also specified in
commercial polyamides is defined as the number of milligrams of potassium hydroxide required to neutralize 1 g of
sample. The acid value may be determined using ASTM Test
Method D 2076: Test Methods for Acid Value and Amine
Value of Fatty Quaternary Ammonium Chlorides. The procedure specified for determining the amine value in Method
D 2076 is not applicable to polyamides.
The imidazoline content is not specified in commercial
polyamides except in special cases where the level is deemed
critical. The level of imidazoline is usually controlled by the
polyamide manufacturer to provide products with specific
compatibility and/or solubility. Imidazoline level can best be
measured by scanning the polyamide with an infrared spectrophotometer and comparing the absorption at 6.25/zm to
the absorption at 6.05/~m. The imidazoline ring absorbs at
6.25 /zm, and the nitrogen-bonded carbonyl, or amide, absorbs at 6.05/~m. The result is reported as either a ratio of
imidazoline:amide (I/A) or as a percentage. In the example
CHAPTER 1 2 - - C H E M I C A L DESCRIPTIONS
reaction described previously, the imidazoline ratio would be
1.0 and the percentage would be 50%.
PHYSICAL PROPERTIES
Polyamides are supplied commercially in solution or as
100% reactive liquids depending on the handling and storage
requirements of the coatings manufacturer. For ease of handling, they may be supplied in various solvents. Most polyamides suitable for coatings applications are quite viscous, and
these polyamides are soluble in a variety of organic solvents
including alcohols, glycol ethers, ketones, and aromatic hydrocarbons. Thus the coatings manufacturer has considerable latitude in selecting specific solvents for optimum applications properties.
The percent nonvolatile content of polyamide solutions
may be determined in accordance with ASTM Test Method
D 1259: Test Method for Nonvolatile Content of Resin Solutions. Commercial polyamides are generally supplied in a
single organic solvent at between 60 and 80% solids, which
provides a handleable viscosity. The coatings formulator further dilutes the polyamide solution with more of the same
solvent, or with a solvent blend, to form one component of
the two-component system.
The polyamide component may be clear or may contain
pigments in colored coatings formulations. The color of the
polyamide or polyamide solution is determined in accordance with ASTM Test Method D 1544: Test Method for Color
of Transparent Liquids (Gardner Color Scale).
The viscosity of the polyamide may be measured at elevated temperature in accordance with ASTM Test Method
D 2196: Test Method for Rheological Properties of Non-Newtonian Materials by Rotational (Brookfield) Viscometer. The
viscosity of commercial polyamides is typically specified at 75
or 150~ The viscosity of polyamide solutions that may also
be measured by this method is generally specified at 25 or
40~ The viscosity of polyamide solutions may also be measured in accordance with ASTM Test Method D 1545: Test
Method for Viscosity of Transparent Liquids by Bubble Time
Method. A modification of this Method is usually used in
which the polyamide solution is placed in a sample tube, the
viscosity is compared to Gardner-Holdt Letter standard
tubes, and the observation is reported as the alphabetic letter
of the tube most closely matching the sample. A plus ( + ) or a
minus ( - ) is then used to indicate that the viscosity is greater
or less than the designated letter.
R E A C T I O N OF P O L Y A M I D E S IN C O A T I N G S
Polyamides react with epoxy resins in several stages to
form a complex insoluble cross-linked matrix. The initial reaction is between the terminal primary amine groups of the
polyamide and the oxirane ring of the epoxy resin. The active
hydrogen opens the ring and the oligomers join end to end.
This initial reaction can be represented by the following
simplified structure.
O
/\
OH
H2C--CH-- + H--N--
~--N--CH2--CH--
87
ENVIRONMENTAL/TOXICITY
CONSIDERATIONS
In response to environmental concerns over the emission
of organic compounds into the atmosphere, many coatings
manufacturers have begun to produce high solids coatings
that contain much lower levels of volatile organic compounds
(VOCs). These products do not contain polyamides; instead,
amidoamines are used, products formulated from m o n o m e r
fatty acid rather than dimer acid [6]. A significant volume of
polyamide/epoxy coatings continues to be used.
Though polyamides are less toxic than aliphatic amines
and amine adducts, direct contact exposure with the skin,
eyes, and the respiratory system must be avoided. Polyamide
solutions must also be handled with care to avoid exposure to
ignition sources as they contain flammable or combustible
solvents and the vapor level from polyamide solutions must
be monitored in the workplace to avoid overexposure to the
organic solvents present.
Polyamide manufacturers supply material safety data
sheets (MSDS), which should be consulted for hazard information and guidance on the safe use of the products. The
MSDS also contains information regarding procedures to follow if a spill occurs, as well as guidelines for hazardous waste
disposal. Those polyamide solutions that are classified as
hazardous waste due to the presence of organic solvents must
88
REFERENCES
[1] McMahon, D. and Crowell, E., "Characterization of Products
from Clay Catalyzed Polymerization of Tall Oil Fatty Acids,"
Journal of the American Oil Chemists Society, Vol. 51, 1974, p. 522.
[2] Lee, H. and Neville, K., "Amides and Miscellaneous Nitrogen
Compounds as Epoxy-Resin Curing Agents," Handbook of Epoxy
Resins, McGraw-Hill, New York, 1967, Chapter 10, pp. 2-12.
[3] "Epoxy Resins," Encyclopedia of PolymerScience and Engineering,
2nd ed., John Wiley & Sons, New York, 1988, Vol. 6, pp. 348-354.
[4] "Polyamides from Fatty Acids," Encyclopedia of Polymer Science
and Engineering, 2nd ed., John Wiley & Sons, New York, 1988,
Vol. 11, pp. 476-489.
[5] Allen, R., "Epoxy Resins in Coatings," Federation Series of Coatings Technology, 1972, Unit 20.
[6] Bozzi, E., "Epoxy Resins in High Solids Coatings," The Epoxy
Resin Formulators Training Manual, James Kaszyk, Ed., The Society of the Plastics Industry, Inc., New York, 1984, Chapter XIII,
pp. 149-162.
MNL17-EB/Jun. 1995
13
Polyurethane Coatings
by Joseph V. Koleske 1
INTRODUC~ON
THERMOPLASTIC POLYURETHANES WERE FIRST
developed by
Otto Bayer [1,2] in the Leverkusen laboratories of I. G. Farbenindustrie AG in 1937 [3,4] as they searched for a product
that would be competitive with the polyamides, now known
as nylons, that had been introducedby duPont. Shortly thereafter, Schollenberger and coworkers [5] used formula modification to prepare elastomeric polyurethane products from
Bayer's products that were like nylon or other engineering
plastics in physical characteristics.
Polyurethanes are widely used in coatings, flexible and
rigid foams, elastomers, and composites. In an overall sense,
the polyurethane business is huge and is concerned with rigid
foams, flexible foams prepared in both slab and molded
forms, elastomers, including reaction-injection-molded products, and coatings. Excluding coatings, the 1988 U.S. consumption of polyurethanes was about 2750 million lb (1.25
million metric tons) with the forecast for 1993 about 3150
million lb (1.43 million metric tons) [6]. In 1991, the national
market for polyurethane coatings was about 209 million lb
(95 000 metric tons) [7]. Although the market for polyurethane coatings is large and growing, it is readily apparent that
it represents only about 5 to 10% of the total domestic polyurethane market. In 1991 consumption of polyurethanes for
coatings in Western Europe and Japan was 301 and 100
million lb (137 000 and 46 000 metric tons), respectively [7].
Reasons for the use of polyurethane coatings include: highperformance characteristics such as flexibility, toughness,
strength, and abrasion resistance; chemical resistance such
as water, detergent, many industrial chemicals, and stain
resistance; good light stability when aliphatic isocyanates are
used; and low temperature-cure characteristics. The latter
factor is a major reason for use of polyurethanes on plastic
substrates.
DEFINITIONS
ASTM [8] defines polyurethane coatings as vehicles containing a minimum of 10% by weight on a nonvolatile vehicle
basis of a multifunctional isocyanate monomer reacted in
such a manner as to yield polymeric systems with urethane
linkages, active isocyanate groups, or multifunctional isocyahate monomers in any ratio, proportion, or combination.
JSenior consultant, Consolidated Research, Inc., 1513 Brentwood
Road, Charleston, WV 25314-2307.
Copyright9 1995 by ASTM International
89
www.astm.org
90
CHEMISTRY
As with many phases of chemistry, one can consider the
chemistry of urethane coatings in a simple or a complex
manner. Simplistically, urethane coatings contain urethane
linkages, - - N H C O - - , that are formed through a rearrangement reaction when an hydroxyl group reacts with an isocyanate group and that can be represented with monofunctional
materials as follows
ROH + R'NCO
~RO--C--NR'
II
Raw Materials
Isocyanates
Two types of isocyanates are used in coatings--aliphatic
and aromatic. Polyurethanes prepared from either type isocyanate have excellent chemical and physical properties. Aromatic isocyanates are used in products where weathering
resistance, particularly sunlight or ultraviolet light resistance, is not important because of discoloration, which almost
always manifests itself as yellowing. Yellowing in itself is a
loss of an aesthetic property, but its cause and result do not
deleteriously affect mechanical properties. Ultraviolet light
attacks the labile hydrogen atoms on the aromatic ring structure. Aliphatic isocyanates are less reactive and more costly
than aromatic isocyanates and, while these factors can be
cost considerations, aliphatic isocyanates are widely used for
both interior and exterior applications.
The two main aliphatic isocyanates currently used are 4,4'diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI), which is a mixture of the 2,4- and 2,6-isomers.
Moisture-cure urethanes and urethane alkyds usually employ
TDI, though MDI has some use due to its low vapor pressure.
Xytylene diisocyanate (XDI) is used to some extent, but
mainly in Japan. Recently tetramethylxylylene diisocyanate
(TMXDI) and isopropenyl dimethyholuene diisocyanate
(TMI) have been introduced by American Cyanamid. Naphthalene diisocyanate has also been used.
Aliphatic isocyanates are more costly, and they are used for
urethane coatings that require excellent sunlight resistance
and no discoloration. These coatings are used on plastics,
automobiles, signs, and similar outdoor end-use products.
The main aliphatic isocyanates are hydrogenated MDI
(4,4'dicyclohexylmethane diisocyanate, HMDI, or H12MDI),
hexamethylene diisocyanate (HDI), particularly in a biuret or
trimer form for improved vapor pressure, mixtures of 2,2,4and 2,4-4-trimethyl hexamethylene diisocyanate (TMHDI),
1,4-cyclohexane diisocyanate (CHDI), and isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate or IPDI) [9]. IPDI and HI2MDI are the isocyanates
most widely used in coating preparation.
Type III polyurethane coatings, including powder coatings,
employ blocked isocyanates that provide room-temperature
stable, one-package systems that are activated at elevated
temperatures. At elevated temperatures, the molecules dissociate and the blocking group leaves, freeing the isocyanate
functionality that then readily reacts due to its nature and the
kinetic effect of elevated temperature with available active
hydrogen groups. Blocking groups are proton donors such as
E-caprolactam, malonic, and acetoacetic esters as well as
other enolizable esters, ketoximes, phenol, etc. For example,
trimethylolpropane (TMP) can be reacted with TDI and then
blocked by reacting the free isocyanate groups with phenol:
C2HsC(CH2OH)3 + C6Ha(CHa)(NCO)2
TMP
TDI
C2HsC(CH2OCONH--C6H3(CH~)--NCO)3
ISOCYANATE-TERMINATED ADDUCT
C2HsC(CH2OCONH--C6Ha(CH3)--NCO) 3 + 3 C6Hs--OH
ISOCYANATE-TERMINATED ADDUCT
PHENOL
C2HsC(CH2OCONH--C6Ha(CH3)--NHOCOC6Hs)3
PHENOL-BLOCKED TRIISOCYANATE
91
Polyfunctional amines, which form urea linkages with isocyanates, are also used as chain extenders. Low-molecularweight compounds such as ethylenediamine are used as
chain extenders to make polymers for Type VI lacquers.
Amine-terminated oligomers based on the alkylene oxides are
available [14-16].
Catalysts
Catalysts are often used to promote the reaction between
isocyanates and hydroxyl-containing compounds. Only small
amounts, on the order of 10 to 100 parts per million, of
catalyst are needed to cause marked increases in reaction
rate. Popular catalysts include dibutyltin dilaurate, stannous octoate, and zinc octoate. Diaza(2.2.2)bicyclooctane
(DABCO), dibutyltin diacetate, bismuth stearate, and zirconium octoate have been used.
Reactions
As indicated above, hydroxyl groups react with isocyanates
to form polyurethanes. Multifunctional reactants are used to
link molecules as in Type I urethane alkyd [17] to cause molecular chain length increase in either a prereaction to form
the final polyurethane that could be used in a Type VI lacquer
coating or to form prepolymers that are later reacted in twopackage coatings as would be used in Type IV and Type V
coatings. In other instances, multifunctional (usually difunctional) isocyanates are used to end cap diols, triols, and
tetraols with isocyanate functionality as is needed for Type II,
IV, and V coatings. Both hydroxyl-functional and isocyanate
functional prepolymers are used. For example:
HO--R--OH + 20CN--R'--NCO
DIOL
DIISOCYANATE
OCN--R'NHCOO--R--OOCNHR'--NCO
ISOCYANATE-TERMINATED PREPOLYMER
2 HO--R--OH + OCN--R'--NCO
DIOL
DIISOCYANATE
HO--R--OOCNH--R'NHCOO--R--OH
HYDROXYL-TERMINATED PREPOLYMER
Other prepolymers can be prepared by reacting, for example,
an hydroxyl-terminated prepolymer with two molecules of
diisocyanate to produce an isocyanate-terminated prepolymer that contains urethane linkages in the central portion of
the prepolymer. It should be apparent that this method of
chain extension cannot be carried too far since viscosity will
increase very rapidly as chain extension takes place, which is
not a desirable result if materials for high-solids or other
energy-conserving formulations are produced.
Moisture-cure polyurethanes are molecules with free isocyanate end groups. Sufficient quantities of isocyanate are reacted with polyols such that there are more equivalents of
isocyanate groups compared to hydroxyl groups. For example, a trifunctional oligomer or polyol can be reacted with an
isocyanate under moisture-free conditions and then packaged under moisture-free conditions.
OLIGOMER(OH) 3 + 3 R'(NCO) 2
OLIGOMER(O--CONHR'NCO)3
92
II
2 --R'NCO
\/
O
URETIDINE DIONE
II
/%
3 --R'NCO
~ --R'NHCONHR'-UREA LINKAGE
--R'NCO + --R'NHCONHR'--
~ --R'NHCON(CONHR--)R'-BIURET LINKAGE
~ --R'N(CONHR'--)COOR'-AN ALLOPHANATELINKAGE
NR'--
~ [--R'NHCOOH]
> --R'NH2 + CO2 T
CARBAMICACID, AN
UNSTABLE INTERMEDIATE
--R'NCO + --R'NH2
R'NCO + RCOOH
--R'N
NR'--
--R'N
O~-~C C~-~O
\/
N
R-ISOCYANURATE
Thermoplastic Polyurethanes
Thermoplastic polyurethanes are used in Type VI lacquers
and in many industrial end uses that require solid products.
Their chemistry is similar to that of prepolymers except
short-chain extenders are used to connect the prepolymer
molecules and build them into long polymeric materials. In a
structural sense, they may be described as linear block copolymers of the ABn type. One of the blocks is a relatively
long, number-average molecular weight of about 300 to 3000,
polyether or polyester that forms the soft or flexible segment.
The other block is formed by the reaction of a diisocyanate
and a low-molecular-weight diol chain extender. The polar
nature of the urethane linkages in the hard segment results in
hard segment aggregation and domain segregation from the
soft segment. The hard segments act as pseudo cross-links,
and as a result tough, strong, elastomeric macromolecules
are formed.
In a mole sense, these polymers can be viewed as polyol/
diisocyanate/short-chain extender polymers that are formed
in an equivalents ratio of 1/X/(X - 1). The n u m b e r X c a n vary
from 1 or less to as much as 20 or more, though more
typically in coatings X has a value of one or less to about 3 or 4
[10,13]. Because of solubility characteristics, a ratio of about
1/2/1 is often used. A small excess of hydroxyl groups is used
to keep final free isocyanate content and storage reactivity at
a nil level. When the wide range of values of X, the types of
isocyanates, the types and functionalities of polyols, and the
range of polyol molecular weight available is considered, it is
readily apparent that a myriad of polyurethanes can be prepared and that a broad range of mechanical and chemical
properties can be achieved. The chemistry is basically isocyanates reacting with hydroxyl groups to form urethane linkages.
CHAPTER 1 3 - - P O L Y U R E T H A N E COATINGS
CH3
OCN--R'--NHCOOCH2~CHzOOCHN--R'--NCO
COOH
[ + (n + 1 ) H O - - P O L Y O L - - O H
ISOCYANATE-TERMINATEDPREPOLYMER
OCN--R'--NHCO--O--POLYOL--O--OCNH--R'--NCO+
CH2~-CHCOOCH2CH2--OH
93
CH3
HO--(POLYOL--OOCHN--R'--NHCOOCH2CCH2OOCHN-/
COOH
2-HYDROXYETHYL ACRYLATy
CH2~CHCOOCH2CH2--O--OCNH--R'--NHCO--O--POLYOL-O--OCNH--R'--NHCO--OCH2CH2OOCHC=CH2
A URETHANE ACRYLATE
The reactions as depicted above have been idealized. In all
commercial and most laboratory preparations there is a significant amount of reaction between the ingredients so that
chain extension occurs and molecular weight increases. This
causes the final product to have a markedly higher-thanexpected viscosity. Oligomeric compounds such as these are
formulated with triacrylates such as trimethylolpropane
triacrylate to provide cross-linking, monomeric acrylates,
N-vinyl pyrrolidone, or other compounds for viscosity reduction to provide low-viscosity, essentially 100% solids systems
that will cure when exposed to actinic radiation. In formulations, the urethane acrylate is considered as the main ingredient contributing to mechanical properties of the cured film.
When the actinic radiation source is ultraviolet light, a
photoinitiator (for example, 2,2-diethoxyacetophenone or
benzophenone in combination with an amine synergist, etc.)
is added as a free radical source. Electron beam curable
formulations do not require a photoinitiator.
Radiation-cured polyurethanes are often used on plastic
substrates that require only low or moderate curing temperatures such as clear overprint lacquers on vinyl decals, electronic circuit boards, "no wax" vinyl flooring, and tile. Although radiation-cured colored and pigmented inks and
coatings are used in the marketplace, the skill needed in
preparing such products, because of difficulty with light penetration or absorption, is readily apparent.
Water-Borne Polyurethanes
Water-borne polyurethanes are prepared in bulk or in a
solvent by first preparing an ionomer prepolymer that is
neutralized and then chain extended to a desired molecular
weight. The polymer then is dispersed into water. Both
cationic [21,22] and anionic [23,24] systems are known.
Cationic systems employ an amine-containing diol such
as diethanolamine, methyl diethanolamine, N,N-bis(hydroxyethyl)-a-aminopyridine, lysine, N-hydroxyethylpiperidine, and similar compounds. Anionic systems use a car-
R'--NHCOO),--POLYOL--OH
WATER DISPERSIBLE POLYURETHANE
Water-borne polyurethane laminating adhesives that are
completely free of volatile organic compounds are expected
to be the next developments in this area [25]. These adhesives
are expected to be for the low-to-medium demand product
area such as for snack food and similar packaged products.
Powder Coatings
Polyurethane powder coatings are usually urethane-modifled polyesters and polyacrylics that cure at high temperatures. High temperatures are needed for the powdered polymer to flow and level to the extent needed for a particular end
use. The key to successful powder coatings is related to a
balance between molecular weight and related viscosity and a
cross-linking mechanism that is stable under storage conditions and not effected to any significant degree until flow and
leveling takes place at the cure temperature. Another requirement is that the glass transition temperature should be sufficiently high that the powder does not block during storage.
The main end use for powdered polyurethanes is in the major
appliance market--refrigerators, dryer drums, range cabinets, etc.--coatings.
MARKETS
Polyurethanes of the various types are used in a number of
market areas and end uses. Many of these were mentioned
above. Two features of polyurethane coatings that have been
often looked on as disadvantages are high cost and special
handing of the potentially hazardous isocyanates that are
used in manufacture or as curing agents. However, the various industry segments have been able to develop safe handling and use methods that overcome one of the objections.
The very- high performance characteristics of polyurethanes,
their ability to cure at lower baking temperatures, and the
94
HOME FURNISHINGS
Drum dryers
Furniture
"No wax" flooring and tile
Range cabinets
Refrigerators
Wood floors
PLASTIC SUBSTRATES
Fascia
Electronic parts and
equipment
Optical fibers
Printed circuit boards
Sheet molding compound
INDUSTRIAL MAINTENANCE
Bridges
Industrial buildings
Marine coatings
Plant equipment
Public utility works
Roof coatings
Windows
RECREATIONAL PRODUCTS
Golf balls
Golf clubs
Gym floors
Toys
MISCELLANEOUS
Aerospace coatings
Luggage
Magnetic tape coatings
Mast and spar finishes
Medical equipment
Safety glass
Shoes
Vinyl decal overprints
Wire coatings
TEXTILES
Apparel
Leather
Tarpaulins
Upholstery
TRANSPORTATION
Aircraft
Automotive OEM
Automotive refinish
Golf carts
Motorcycles
Railroad cars
Trucks and buses
Vans
REFERENCES
[I] Bayer, 0., Modern Plastics, Vol. 24, 1947, p. 149.
[2] Wright, P. and Cumming, A. P. C., Solid Polyurethane Elastomers, Elsevier Publishing Company, Amsterdam, 1969.
[3] Bayer, O., Rinke, H., Siefken, W., Orthner, L., and Schild, H.,
German Patent 728,981 (1942).
[4] Bayer, O., Angewandt Chemie, Vol. A59, 1947, p. 275.
[5] Schollenberger, C.S., Scott, H., and Moore, G.R., Rubber
World, Vol. 137, No. 4, 1948, p. 549.
[6] Smith, R. M., "Polyurethanes," Supplement C, Report No. 10C,
SRI International, Menlo Park, CA, May 1991.
[7] Linak, E., Kalt, F., and Takei, N., "Urethane Surface Coatings,"
Chemical Economics Handbook, SRI International, Menlo Park,
CA, August 1992, p. 592.8000.
[8] ASTM D 16: Terminology Relating to Paint, Varnish, Lacquer,
and Related Products, Vol. 06.01, ASTM Book of Standards,
1992.
[9] "Chemical Products for Resins, Coatings, Sealants, Adhesives,
and Elastomers," Hill America Inc., Piscataway, NJ, 1992.
[10] Seefried, C. G., Jr., Koleske, J. V., and Critchfield, F. E., "Thermoplastic Urethane Elastomers. I. Effects of Soft Segment Variations," Journal of Applied Polymer Science, Vol. 19, 1975, p.
2493.
[11] Bailey, F. E. and Koleske, J. V., Alkylene Oxides and Their Polymers, Marcel Dekker, Inc., New York, 1991, p. 218.
[12] Critchfield, F. E., Koleske, J. V., Magnus, G., and Dodd, J. L.,
"Effect of Short Chain Diol on Properties of Polycaprolactone
Based Polyurethanes," Journal ofElastoplastics, Vol. 4, January
1972, p. 22.
[13] Seefried, C. G., Jr., Koleske, J. V., and Critchfield, F. E., "Thermoplastic Urethane Elastomers. II. Effects of Hard Segment
Variations," Journal of Applied Polymer Science, Vol. 19, 1975, p.
2503.
[14] Lee, J. M. and Winfrey, J. C., U.S. Patent No. 3,236,895 (1966).
[15] Yeakey, E. L., U.S. Patent No. 3,654,370 (1972).
[16] Bishop, T. E., Coady, C.J., Zimmerman, J. M., Noren, G. K.,
and Fisher, C. E., European Patent Publication 209,641 (1987).
[17] Christenson, R. M. and Erikson, J. A., U.S. Patent 4,222,911
(1980).
[18] Salim, M. S., Polymer, Paint, Colour Journal, Vol. 177, No.
4203,762 (1987).
[19] Martin, B., Radiation Curing, Vol. 13, No. 4, August 1986, p. 8.
[20] Hodakowski, L.E. and Carder, C.H., U.S. Patent 4,131,602
(1978).
[21] Scriven, R. L. and Chang, W. H., U.S. Patent 4,046,729 (1977).
[22] Scriven, R. L. and Chang, W. H., U.S. Patent 4,066,591 (1978).
[23] Scriven, R. L. and Chang, W. H., U.S. Patent 4,098,743 (1978).
[24] Milligan, C., U.S. Patent 3,412,054 (1968).
[25] Long, D. and Barush, J., "VOC-Free Adhesive Use Grows Due to
Increased Performance," Adhesive Age, Vol. 36, No. 10, September 1993, p. 42.
[26] Wojcik, R. T., "Super-Low-ViscosityAliphatic Isocyanate Crosslinkers for Polyurethane Coatings," Modern Paint and Coatings,
Vol. 83, No. 7, July 1993, p. 39.
[27] Gardon, J. L., "Polyurethane Polyols: Ester-Bond Free Resins
for High Solids Coatings," Journal of Coatings Technology, Vol.
65, No. 819, April 1993, p. 25.
MNL17-EB/Jun. 1995
Silicone Coatings
by D. J. Petraitis ~
Silicone based coatings are among the most useful materials for a wide variety of applications. Because the basic bond
energies of Si--C and Si--O bonds are so high, the chemical
processes usually associated with aging of coated surfaces are
often much slower and in many situations virtually eliminated for silicone coatings. Also, because the Si--O and
Si--C bonds are not present in the natural organic world,
biocompatibility and resistance to degradation via biochemical and biophysical processes are also significantly reduced.
In a similar manner, some silicone resinous coatings and
fluorosilicone based coatings, in particular, have excellent
solvent resistance.
Silicone coatings based on trifluoropropyl methyl polysiloxanes have resistance to swelling from such agents as
gasoline, jet fuel, solvents, and various other reagents. Highly
branched resinous silicone coatings chemically begin to approach the properties of silica surfaces as the organic pendant content is reduced. As the organic pendant groups are
reduced, the SiO4/2 content increases and the chemical resistance increases. Such resinous coatings can provide physical
scratch resistance as well as chemical resistance. Silicone
elastomeric coatings, however, do not provide good resistance to strong acids and/or bases. Strong acids or bases, in
particular at elevated temperatures, can cause depolymerization of the siloxane backbone, resulting in failure, or in the
case of silicone elastomeric coatings, dissolution of the coating itself.
In a similar manner, silicone coatings are resistant to virtually all frequencies of the electromagnetic spectrum. For
complaint coatings, silicones are unsurpassed in resistance to
hard radiation, such as that from a cobalt-60 source for doses
in excess of 20 Mrd, as well as the ultraviolet and infrared
frequencies. When combined with their hydrophobicity and
oxygen and ozone resistant properties, silicones provide excellent weatherability characteristics, and when these properties are combined with the resistance to atomic oxygen in
low earth orbit, silicone coatings provide protection for organic substrates in varied spacecraft applications.
Another family of applications which combine the chemical and biochemical characteristics of silicones are those
which are used to provide coatings for medical devices. Silicone coatings are used to encapsulate and seal permanent
F O R M S OF S I L I C O N E C O A T I N G S
Silicone coatings are available in various forms ranging
from a hard, rigid resin to a compliant elastomer to a soft,
almost gel-like character. The rigid resins are typically supplied in a solvent solution and are mixed with curing agents
prior to application. Among the most common curing agents
are lead and zinc octoate, which require approximately 1 h at
250~ to attain complete cure. The cross-linking mechanism
involves the condensation of silanol groups
~-~SiOH + H O S i ~
95
Copyright9 1995 by ASTMInternational
~ ~ S i O S i F + H20
www.astm.org
96
Type 00 = 10
Type A = 70
0.34 to 13.8 MPa
50 to 1500%
0.88 to 43.8 kN/m
The properties and the cure systems which are chosen for
these elastomeric coatings depend, to a large extent, on the
end use and the method of application. For instance, the
SiOH + HSi (No. 1) mechanism is often used to provide
release coatings for backing paper for pressure sensitive adhesives. The actual coating itself has poor strength but attains
its properties by simply impregnating the substrate.
The acetoxy cure system (No. 2) is used where one-part
convenience is desired, where relatively slow cure is acceptable, and where acetic acid given off during the cure is not a
problem.
The oxime (No. 5) cure system provides many of the properties of the acetoxy cure system, but results in an oxime
leaving group instead of an acetic acid leaving group. Among
the applications for the oxime cure systems are coatings for
electronic components and protection for organic composites to prevent atomic oxygen degradation, and coating of
quartz blankets to provide adequate emissivity and reflectivity characteristics for certain thermal protection surfaces on
the space shuttle. The alkoxy 2-part (No. 3) cure system, when
combined with certain thermal enhancing fillers such as iron
oxide, glass microballoons, and various fibers, is often used to
provide ablative and thermally insulating coatings. Various
products incorporating the alkoxy two-part cure system are
used to protect surfaces and components exposed to plume
radiation from various rocket motors and jet engines.
The addition cure system (No. 4) has characteristics which
permit rapid heat-accelerated cure, tough physical properties, virtually nil shrinkage, and, due to the platinum catalyst,
the best overall flame resistance. Applications include solar
cell protection, particularly for satellites, and burn-through
protection for the liners of solid rocket motors. The only
negative characteristic of the addition cure system is its susceptibility to inhibition. Because the system contains partsper-million levels of platinum catalyst, it can be readily
"poisoned." Among the most common inhibitors are sulfurcontaining organic rubbers and organo-tin compounds
CHAPTER 1 4 - - S I L I C O N E COATINGS
their low toxicity and nonflammability, are being phased out
because of Montreal Protocol Agreements. Similarly, hydrocarbon solvents are undesirable because of their flammability, toxicity, and environmental effects. Silicone-based conformal coatings have been developed without solvent
carriers. However, thin layer applications are difficult unless
the viscosity is low enough to permit proper coating. Unfortunately, the technology for high-strength, low-viscosity, 100%
solids, silicone coating does not exist. The current products,
therefore, when cured, are very low strength and do not
provide coatings that are resistant to handling. Research is
ongoing to develop water-based dispersions, but to date, the
demonstrated physical properties, although higher than the
100% solids coatings, are significantly less than the current
solvent-based silicone coatings.
Methods of Applications
The methods of applications for silicone coatings depend
on the device being coated and the specific type of silicone
being used. Dipping, spraying, and painting are the most
common types of application. The thinnest coatings result
from spraying of two solvent dispersion utilizing standard
aerosol spray guns. Needless to say, experience involving
aerosol spraying is critical for acceptable coatings. Among
the variables to consider are the following: viscosity, solvent,
percent solids, pot life, and cure system choices.
The most securely sealed surface layer is accomplished by
dip coating. Again, variables including solvent, bath life, and
cure systems must be optimized. Additionally, the evaporation of solvent during the dip processing needs to be compensated for by periodically or continuously adding make-up solvent to maintain optimal bath viscosity. If a one-part
humidity-actuated cure system is used, consideration must
be given to provide a dry blanket over the bath to prevent a
partially cross-linked elastomeric skin from forming. Dry argon is often utilized to prevent moisture in the air from
reacting with the silicone base coating. Another consideration for the dip coatings is the possibility of air bubble
inclusion. Again, several variables need to be considered.
Low viscosity, controlled immersion and withdrawal rates,
and vibration of the bath and/or object to be coated can be
used to minimize bubble entrapment. Similarly, the use of
two distinct solvents with different rates of evaporation are
often used to ensure uniform coating with minimal drip regions and minimal bubble formation.
Painting or brush coating substrates is yet another method
to apply a uniform silicone coating. Painting, however, is
usually not applicable for either large areas or mass production coatings. For painting application, virtually all of the
variables discussed in the above dipping and spraying also
apply.
Regardless of the methods of application, the cure parameters demand significant considerations. Vacuum exposure
may be used to remove air bubbles and to ensure flow under
surface irregularities or impregnation of porous substrates.
Vacuum treatment may also be used to enhance removal of
the solvents, but care should be taken to prevent evaporation
of the reactive volatile components which would prevent cure
even after removal from the vacuum. Of course, most commonly, the vacuum removal of solvent is unwarranted and
97
TESTING CONDITIONS
The test requirements for silicone coatings include MIL-I46058C for qualifying silicone coatings as insulating compounds for electrical coating applications of printed circuit
board assemblies. MIL-I-46058C includes the following tests:
Curing Time and Temperature
Appearance
Coating Thickness
Fungus Resistance
Insulation Resistance
Dielectric Withstanding Voltage
Leakage Current Testing
Q Resonance
Q Resonance after Immersion
Thermal Shock
Flexibility
Thermal Humidity Aging
Flammability
Materials which are used in applications for spacecraft are
tested via ASTM Test Method for Total Mass Loss and Collected Volatile Condensable Materials from Outgassing in a
Vacuum Environment (E 595). This test is used to determine
the amount of collected volatile condensable material and
total mass loss that eludes from a material when exposed to
125~ for 24 h at vacuum less than 5 10 .2 torr. Basically,
the maximum CVCM value for coatings intended for space
applications is 0.1% and the m a x i m u m TML is 1.0%. The
coatings intended for satellite applications require these high
levels of purity to prevent the contamination of solar cells,
optical surfaces, and other sensitive instrumentation. For
most silicone materials, extended devolatilization is required
for the polymeric components prior to compounding into the
finished product.
For silicone elastomeric coatings, the physical properties
of the cured elastomer are critical parameters. The tensile
strength, elongation, and modulus are defined in ASTM Test
Methods for Rubber Properties in Tension (D 412). Durometer and tear strength measurements are defined in ASTM
Test Method for Rubber Property--Durometer Hardness
(D 2240) and ASTM Test Method for Tear Strength of a
Convential Vulcanized Rubber and Thermoplastic Elastomer
(D 624) respectively. The viscosity, nonvolatile content, and
specific gravity tests are defined in ASTM Test Method for
Viscosity of Adhesives (D 1084), ASTM Test Method for
Weight Loss of Plasticizers on Heating (D 2288), and ASTM
Test Method for Specific Gravity (Relative Density) and Density of Plastics by Displacement (D 792), respectively.
98
MNL17-EB/Jun. 1995
15
by Richard J. Burns 1
History
Definition
About 1912 Ostromislenski pioneered the industrial investigation of vinyl polymers and made and fractionated
poly(vinyl chloride). E. W. Reid invented the copolymers of
vinyl chloride and vinyl acetate in 1928. In 1933, Davidson
and McClure described applications of vinyl resins including
their use as swimming pool coatings [1].
Commercial production of poly(vinyl chloride-vinyl acetate) resins was begun in 1936. Carboxyl-modified copolymers were introduced in 1939 and hydroxyl-modified resins
in 1945. The first commercial use of these vinyl resins was in
1936 as a coating for the inside of beer cans.
Organosol and plastisol coatings technology that permitted
the use of very-high-molecular-weight resins were developed
about 1943 [2,3].
Polymerization
Vinyl chloride monomer is a gas at standard conditions
with a boiling point of - 13.9~ Polymerization is carried out
in autoclaves under moderate to high pressure. The reaction
is typically initiated by free radical generating compounds
such as peroxides. The polymerization is exothermic, and
reaction temperature regulation is necessary to control the
growth (molecular weight) of the polymer. The use of high
pressure and low temperature generally favors the formation
of high-molecular-weight resins, and chain transfer agents
are commonly used to control molecular growth. The number average molecular weight (M,) of commercially available
solvent-soluble vinyl chloride homopolymers and copolymers ranges from a low of a few thousand to about 45 000.
The M, of vinyl resins used for plastisol and organosol coatings ranges between about 60 to 110 000 [4].
General
Important characteristic features of vinyl resins/coatings
are: (1) relatively high glass transition temperature; (2) excellent resistance to water, alcohols, aliphatic hydrocarbons,
vegetable oils, dilute acids, and alkali; and (3) inertness in
contact with foods (FDA-listed resins only).
Vinyl resin films can be degraded by exposure to high
temperatures or by long-term exposure to ultraviolet light,
with a resultant change in color from clear to amber, red, and
eventually black. Suitable heat stabilizers are employed that
allow the processing of vinyl coatings at high temperature,
while proper pigmentation helps to protect vinyl coatings
from attack by UV light. Some stabilizer systems can provide
limited protection to clear vinyl films.
Manufacture
Vinyl resins for coatings are made by several processes.
Polymerization by solution and suspension processes is used
to make the solvent-sofuble resins, while emulsion or dispersion polymerization is used to make the much higher molecular weight polymers for plastisols and organosols. Some solvent-soluble grades are also made by the emulsion process.
Post-polymerization processes are applied to some resins to
achieve special properties.
99
Copyright9 1995 by ASTM International
www.astm.org
Suspension Polymerization
Suspension polymerization is generally carried out in a
water medium. High-molecular-weight water-soluble colloidal polymers are used in small amounts to stabilize the droplets of suspended monomer(s) to control particle size. The
stabilizer used remains with the resin during and after polymerization and resin recovery. Normally the preparation of
solutions of suspension resins requires that mild heating be
employed to achieve m a x i m u m clarity of solutions at minim u m viscosity. Particles of suspension vinyl resins are characterized as spherical with a size between 100 to 300/~m.
Emulsion Polymerization
Like the suspension process, emulsion polymerization is
also carried out in water, but in place of water-soluble polymers, surfactants are normally used to stabilize the smaller
m o n o m e r droplets during polymerization. A special form of
emulsion polymerization called dispersion polymerization
uses an oil-soluble rather than water-soluble initiator and
produces resin of particles size ranging from about 0.2 to 2
/~m. These high-molecular-weight powdered products are
used in plastisol and organosol coatings.
Post-Polymerization Process
Some vinyl-alcohol modified resins are prepared in a twostep process. The first step consists of the preparation of a
poly(vinyl chloride-acetate) copolymer by either a solution or
suspension process. Next, the copolymer resin is dissolved in
a suitable solvent and a catalyst is added to partially hydrolyze the pendant acetoxy groups to yield a vinyl alcohol moiety. The modified resin is then precipitated from solution and
dried as described for the solution process. The resin thus
formed has only secondary hydroxyl groups, which accounts
for its unique solubility/compatibility properties.
These vinyl-alcohol-containing resins differ from those
prepared directly using other hydroxy-containing monomers
in their compatibility with alkyds and in the rate of reactivity
with coreactants such as isocyanate or amino-formaldehyde
cross-linkers.
FDA Status
Vinyl copolymer resins are listed by chemical identity in
several U.S. Food and Drug Administration regulations such
as 21CFR 175.300, 176.170, 176.180, and 177.1210 as components of coatings on metal and paper substrates for use as
food contact surfaces of articles used in processing, manufacturing packing, producing, heating, packaging, holding, or
transporting food, or as components of closures with sealing
gaskets for food containers. Vinyl chloride-acetate copolymers, hydroxyl-modified vinyl chloride-acetate copolymer,
and several other vinyl chloride copolymers made with
monomers having acid or ester functionality are described.
Vinyl Resins--Analysis
There are many references to chemical methods for identifying and characterizing vinyl resins [5,6]. However, the infrared spectra of vinyl resins are very useful for qualitative
and quantitative purposes. Spectra of neat vinyl resins can be
found in sources such as atlases, encyclopedia of plastics, or
specific papers dealing with the subject [7-9].
Also, several ASTM documents deal with the identification
and characterization of vinyl resins used in coatings materials. ASTM Guide for Testing Poly(Vinyl Chloride) Resins
(D 4368-89) describes methods for homo- and copolymer vinyl resins to determine important characteristics such as
total chlorine content for composition, dilute solution viscometry to assess polymer molecular weight, high and low
shear viscosity measurements to characterize vinyl dispersion resins for plastisols and organosols [10].
ASTM Test Method for Infrared Identification of Vehicle
Solids from Solvent-Reducible Paints (D 2621-87) covers the
qualitative characterization of separated paint vehicle solids
by infrared spectroscopy. A spectrum for an ortho-phthalic
alkyd, vinyl chloride-acetate modified vehicle is presented
[11].
ASTM D 2124-70 (Reapproved 1988), Test Method for
Analysis of Components in Poly(Vinyl Chloride) Compounds
Using an Infrared Spectrophotometric Technique, presents
methods whereby vinyl compounds can be separated into
components including resins, plasticizers, stabilizers, and
fillers. Each component can then be analyzed by infrared
technique [12].
101
Inherent
Viscosity,
ASTM
D 1243
Glass
Transition
Temperature
(Tg), ~
Average
Molecular
Wt, M.*
Solution
Viscosity ~'
at 25~
cP
0.74
0.50
0.40
79
72
72
44 000
27 000
22 000
1300 i
600
200
0,50
0.38
0.32
74
72
70
27 000
19 000
15 000
650
100
55
---
67
15 000
--.
2.3
2.3
0.53
0.44
79
77
27 000
22 000
1000
400
Hydroxyl
Hydroxyl
Hydroxyl
1.~ ~
1.9
2,0
0.56
0.44
0.30
70
65
65
33 000
24 000
15 000
930
275
70
Hydroxyl
3.0
0.15
54
5 5O0
2O
Reactive
UCAR|
Solution
Vinyl
Po/y(vinyl
chloride)
Poly(vinyl
acetate)
VYNS-3
VYHH
VYHD
90
86
86
10
14
14
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
VMCH
VMCC
VMCA
86
83
81
13
16
17
1a
1a
2a
Acid
Acid
Acid
1.0
1.0
2.0
VERR-40
82
9 b'c
Epoxy
1.8g~
VAGH
VAGD
90
90
4
4
6d
6d
Hydroxyl
Hydroxyl
VAGF
VAGC
VROH
81
81
81
4
4
4
15e
15e
152
VYES-4
67
11
22 e
Functionality
Other
Type
Wt%
Vinyl
Chloride
Vinyl
Acetate
1000A
1000AS
IO00C
1000CS
1000GKT
86
86
86
86
91
14
14
13
13
3
TABLE 3 - - S u s p e n s i o n
Composition, wt%
Grade
Vinyl
Chloride
Vinyl Isobutyl
Ether
Approximate Solution
Viscosity," MPa.s
MP-25
MP-35
MP-45
MP-60
75
75
75
75
25
25
25
25
35
35
45
60
Carboxylic
Acid
. . . . . .
. . . . . .
1
1
..-
Acrylic
Ester
Inherent
Viscosity
---..
6
0.5
0.4
0.5
0.4
0.5
s t r o n g a d h e s i o n is d e s i r e d , t h e r e a r e s p e c i a l c o a t i n g s s u c h as
s t r i p p a b l e o r p e e l a b l e c o a t i n g s w h e r e a d h e s i o n is n o t w a n t e d .
T a b l e 6 lists t h e r e l a t i v e a d h e s i o n o f s e v e r a l v i n y l r e s i n s t o
various polymers and substrates.
The resin selection may be made on the need for reactive
functionality to produce cross-linked coatings that change
the nature of the coating from thermoplastic to thermosetlike properties that are characterized by improved solvent or
stain resistance.
Solubility
Variation in the ratio of vinyl chloride to vinyl ester and the
d e g r e e o f p o l y m e r i z a t i o n p r o d u c e a w i d e r a n g e o f v i n y l polymers with different solubility characteristics. Highest solubility is f a v o r e d b y l o w v i n y l c h l o r i d e c o n t e n t a n d l o w m o l e c u l a r
w e i g h t . T h i s r e l a t i o n s h i p i n t e r m s of v i s c o s i t y o f r e s i n s o l u t i o n s is c o m p a r e d i n T a b l e 1.
102
Vinyl
Chloride
Grade
Acrylic
Ester
Inherent
Viscosity
E 15/45
H 15/45
H 15/50
85
85
85
15
15
15
9..
9..
9..
0.5
0.5
0.6
H 40/43
H 40/50
H 40/55
60
60
60
40
40
40
9..
9..
...
0.46
0.6
0.7
H 40/60
E 15/45M
H 15/45M
60
84
82
40
15
17
9-.
9..
9..
0.88
0.5
0.56
E 15/40A
E 20/55A
E 22/48A
85
80
78
.....
7
15
20
15
0.4
0.68
0.56
Grade
Vinyl
Chloride
MPR-TA
MPR-TS
MPR-TM
91
87
86
Composition,wt%
Vinyl
Vinyl
Acetate
Alcohol
3
13
13
Acid
6
...
. . . . . .
...
1
...
1
1
S o l u t i o n Characteristics
Vinyl solution resins are dissolved by ketones, esters, certain chlorinated solvents, a n d some nitroparaffins. As a class,
ketones are the best solvents i n terms of the ability to dissolve
higher solids at lower solution viscosity. Hydrocarbons are
chiefly used as diluents primarily to lower cost. Aromatic a n d
aliphatic h y d r o c a r b o n s c a n be usd as diluents. Aromatic hydrocarbons, chiefly toluene a n d xylene a n d higher boiling
fractions such as Aromatic 100 or 150, are preferred as they
can be used at high levels, in the range of 50 to 65% of the
solvent b l e n d depending on the resin composition, molecular
weight, a n d desired solids. The Aromatic 100 a n d 150 are
usually used only in baking finishes.
Aliphatic h y d r o c a r b o n s can be used in limited a m o u n t s , up
to a b o u t 30% of the solvent blend. Higher levels can lead to
viscosity instability, a n d only low boiling aliphatic hydrocarbons, those with boiling points up to 117~ are suitable. The
use of higher boiling aliphatic h y d r o c a r b o n s can cause precipitation of the resin d u r i n g drying.
Alcohols are strong precipitants for vinyls a n d are n o t
generally used in unmodified vinyl lacquers. However, in
some cases vinyls, usually hydroxyl-modified vinyls, are readily formulated with other resins that are carried in alcohol.
With these, up to 15 to 20% alcohol m a y be used in the solvent
blend. Careful attention m u s t be paid in vinyl coating formulations that c o n t a i n alcohols to be sure that problems do n o t
develop d u r i n g application a n d drying of the coatings. Glycol
ethers a n d glycol ether esters are sometimes used in vinyl
coatings to improve flowout of baked coatings.
I n response to regulations restricting the type a n d a m o u n t
of solvents used in coatings, such as Los Angeles Rule 66 a n d
later versions, vinyl coatings were reformulated as c o m p l i a n t
systems by reducing the a m o u n t of b r a n c h e d ketones a n d
Plasticizers
Plasticizers are often used with vinyl resin coatings to improve flexibility, formability, a n d impact resistance of the
coating. M o n o m e r i c as well as polymeric plasticizers or compatible polymers with low glass t r a n s i t i o n t e m p e r a t u r e (Tg)
m a y be used to plasticize a vinyl coating.
103
Substrate
Copolymer
VYHH
Carboxy
Modified
VMCH
Hydroxy
Modified
VAGH
VAGF
WB
Vinyl
AW-875
Steel
Galvanized
Paper (glassine)
Aluminum foil
Polyethylene, treated
Polypropylene, treated
Polysulfone
Acrylic
PVC plastic
ABS plastic
Polycarbonate
Polyphenylene oxide
Polyethylene terephtalate
Impact polystryene
Inked surface
0
0
10
0
0
0
7
10
I0
10
10
4
0
0
0
10
10
10
10
0
0
10
10
10
I0
10
I0
0
0
5
5
5
10
7
0
0
10
10
10
10
10
0
5
0
8-10
0
0
10
10
0
0
10
10
10
10
10
0
0
0
5
Memory
Effect
180
Non-Regulated
Rule 66 Compliant
MIBK
50 MEK
Toluene or Xylene _ 50
_
Butyl acetate
100% Cyclohexanone
Toluene
Xylene
VM&P naphtha
66/EPA
33/50 Initiative ~
14 MEK
7
46 Acetone
3
9 MIAK
15
12 Butyl acetate
40
7 Cyclohexanone 9
1___22Toluene
6
100 VM&P naphtha 20
.g
g
Cooled
~50% reduction of MEK and toluene, which are EPA 33/50 listed solvents.
Ambient
Heated
Resin
Maximum
Solids
Typical Solvent
Blend, wt%
15
25
MEK/toluene, 67/33
MIBK/toluene, 50/50
28
MIBK/toluene, 50/50
33
MIBK/toluene, 33/67
Pigmentation
60
MEK/toluene, 10/90
44
27-34
19-22
15
5.5
VYNS-3
VAGF, VAGH,
VMCH, VYHH
VAGC, VAGD,
VMCC, VYHD
VERR, VMCA,
VROH
VYES-4
Phthalate, phosphate, a n d glycol ester plasticizers are typically used. Plasticizers are selected to meet the r e q u i r e m e n t s
of the coating that m a y include low-temperature flexibility,
resistance to extraction by solvents, resistance to migration,
to humidity, etc. Blends of plasticizers m a y be required to
meet specific requirements. Table 9 presents a listing of plasticizers that are c o m m o n l y used with vinyl resins. Care m u s t
be exercised in choosing the level of plasticizer as excessive
a m o u n t s tend to make the film soft a n d p r o n e to dirt retention. Ordinarily, a level of 25 p h r (parts per h u n d r e d parts
resin) of plasticizer is considered a b o u t m a x i m u m for use
with coating resins.
Weeks
FIG. 1 - M e m o r y effect,
Citrates
Acetyl trim-butyl citrate
Epoxies
Epoxidized soybean oil (ESO)
2-Ethylhexyl epoxytallate
Flexible Packaging
Solvent-soluble carboxyl-modified vinyl chloride copolymers have good adhesion to most materials used in flexible or
semi-rigid packaging including aluminum foil, paper and
plastic films such as polyethylene terephthalate, polycarbonate, PVC, and cellophane. This type of resin is used for its
adhesion characteristic, ease of heat sealing, and resistance
to attack by the packaged product. The vinyl resin may be
used alone or modified with plasticizers or other resins and
polymers to formulate heat-sealable coatings for applications
requiring varying degrees of force needed to open the container. This could range from applications such as blister
packaging where the bond needs to be strong enough to cause
substrate failure when the package is opened, to items such
as jellies or cream containers found in restaurants where a
tight but readily peelable bond is required.
Vinyl coatings are also used to coat collapsible metal tubes
for packaging materials such as pharmaceutical preparations, toothpastes, and the like where the need is for a very
flexible coating that will not crack nor be attacked by the
contents of the package even though high stresses from collapsing and rolling up the tube are encountered.
Other applications include decorative coatings for the aluminum foil paper laminates for cigarette packaging, food
wrappers for fast food restaurant items, for butter, marga-
105
106
Wood Finishes
Reactive heavy duty vinyl finishes for wood have been developed consisting of a hydroxyl-modified vinyl resin crosslinked with amino/formaldehyde resins. Alkyd resins were
often added to improve film build. Such finishes became
established as the standard for kitchen cabinets because of
their retention of excellent adhesion and water resistance,
particularly when the coated wood becomes wet from high
humidity or water splashing. These finishes also have excellent resistance to a variety of household chemicals, solvents,
and stains and have been used as fine furniture finishes [19].
Powder Coatings
Vinyl powder coatings are formulated with vinyl chloride
homopolymers and copolymers for application by fluidized
bed, powder spray, or electrostatic powder spray. Powder
coatings are prepared by dry compounding resins, plasticizer, pigments, and additives in ribbon blenders followed by
attrition or dispersion to powder in mixers such as the
Henschel mixer. Some powder coatings are prepared by a
melt mix technique followed by cryogenic grinding. This latter technique produces powders of smaller particle size [21].
Powder coatings prepared by dry compounding are usually
applied by fluidized bed or by spray techniques. The metal
parts are heated for fluid bed application so that the powder
will adhere to the part and begin to flow to form a film. A bake
after the powder application is needed to complete the filmforming process by fusion or melting.
Cryogenically ground powder coatings are applied by electrostatic powder spray. With the electrostatic method, it is
not necessary to preheat the parts, but a bake is necessary
after application to fuse the powder to a film. The finer particle size allows the deposition of smoother and thinner films
than is attainable from fluidized bed or powder spray process. However, the high costs of cryogenic grinding made
these materials substantially more expensive than dry grinding and as a consequence, the cryogenic ground powders
account for only a small share of the PVC powder-coating
market.
PVC powder coatings are used to coat products such as
pipe, fencing, and metal furniture.
PVC Latex
Emulsion polymerized vinyl chloride homopolymers and
copolymers are used in the latex form not so much to make
finished coatings but rather as material coated on a base or
support to provide the substrate for items such as wall coverings, backing for carpeting, and the like. In a sense, such
use could be considered analogous to a waterborne version of
an organosol coating. The vinyl chloride homopolymers need
to be modified with a substantial loading of plasticizer, and
some grades are sold as preplasticized latexes. These waterbased materials require a high temperature bake to fuse the
resin plasticizer mix into a continuous film.
By varying the type and amount of comonomer used to
make emulsion polymerized copolymer latexes, lower Tg
products are available that can use lower temperature bakes
to form films.
Trends i n V i n y l Coatings
To meet the VOC requirements that are either in place or
proposed for the future, developments in vinyl coatings have
centered on high solids and waterborne systems.
For high solids vinyl coatings, substantially increased resin
solubility was achieved by reduction in the polymer molecular weight, so that viscosity stable solutions could be prepared at two to three times the level of solids content that was
possible with earlier vinyl resins. However, at the low molecular weights needed for high solubility, the performance of
coatings made from such resins was greatly reduced in terms
of chemical resistance and physical properties. As a result,
high solids vinyl resins are modified to contain hydroxyl functionality to allow for reaction with added coreactant materials to build molecular weight. Though the high solids resins
may be used alone for less demanding applications, they are
Composition, wt%
Solids
Water~
38
39
50
61
Cosolventb
pH
12
..-
7.0
7.0
REFERENCES
[1] Industrial and Engineering Chemistry, Vol. 25, No. 6, June 1933.
[2] Myers, R. and Long, J. S., Eds., Treatise on Coatings, Film Forming Compositions, Vol. 1, Part II, Dekker, New York, 1968.
[3] Powell, G. M., Federation Series on Coatings Technology, Unit 19,
Federation of Societies for Paint Technology, Philadelphia,
April 1972.
[4] Breziuski, J.J., Koleske, J.V., and Potter, G.H., "Hydrodynamic Properties of Vinyl Chloride-Vinyl Acetate Copolymers in
Dilute and Concentrated Solutions," Proceedings of X1 Congress
FATIPEC, Florence, Italy, 1972.
[5] Paint Testing Manual, ASTM STP 500, 13th ed., G. G. Sward, Ed.,
ASTM, Philadelphia, 1972.
[6] Crompton, T. R., Analysis of Plastics, Pergamon Press, New
York, 1984.
[7] Infrared Spectra Atlas of Monomers and Polymers, Sadtler Research Labs, Philadelphia, 1980.
[8] Burley, R. A. and Bennett, W. J., "Spectroscopic Analysis
of Poly(Vinyl Chloride) Compounds," Applied Spectroscopy,
APSPA, Vol. 14, 1960, p. 32.
107
[9] An Infrared Spectroscopy Atlas for the Coatings Industry, 4th ed.,
Vols. I and II, D. R. Brezinski, Ed., Federation of Societies for
Coating Technology, Philadelphia, 1991.
[10]ASTM Guide for Testing Poly(Vinyl Chloride) Resins
(D 4368-89), ASTM Book of Standards, Vol. 06.03, American
Society for Testing and Materials, Philadelphia, 1993.
[11] ASTM Test Method for Infrared Identification of Vehicle Solids
from Solvent-Reducible Paints (D 2621-87), ASTM Book of Standards, Vol. 06.01, American Society for Testing and Materials,
Philadelphia, 1993.
[12] ASTM Test Method for Analysis of Components in Poly(Vinyl
Chloride) Compounds Using an Infrared Spectrophotometric
Technique [D 2124-70 (1988)], ASTM Book of Standards, Vol.
08.01, American Society for Testing and Materials, Philadelphia, 1993.
[13] Burns, R. J. and McKenna, L. A., Paint and Varnish Production,
February 1972.
[14] Hardman, D. E. and Brezinski, J. J., "Pigmented Vinyl Copolymer Coatings: A Discussion of Factors Influencing Exterior
Durability," Official Digest, Vol. 36, No. 476, 1964, pp. 963-984.
[15] Good, R. H., ACS Symposium Series 365, American Chemical
Society, Washington, DC, 1988, pp. 203-216.
[16] Corps of Engineers CW-099040, U.S. Department of the Army,
August 1981.
[17] Steel Structures Painting Council, Pittsburgh, PA, Paint No.
SSPC-9.
[18] Martell, R. J. and Yee, A., Journal of Protective Coatings and
Linings, Vol. 5, No. 9, September 1988.
[19] Mayer, W. P., Journal of the Oil and Colour Chemists Association, Vol. 73, No. 4, April 1990.
[20] Kreiselmaier, K.W., "Pigmentation of Magnetic Tapes," Pigment Handbook, Vol. Ill: Applications and Markets, T. C. Patton,
Ed., John Wiley & Sons, New York, 1973.
[21] Ginsberg, T., "Vinyl-Modified Epoxy Coatings," Modern Paint
and Coatings, November 1988.
MNL17-EB/Jun. 1995
16
HO--[CH(CH3)--CH2~L - O - R - O - [ C H 2 - C H ( C H 3 ) ] b - O H
POLYOLS
Polyols, or polyalcohols as they are sometimes known, are
compounds containing one or more, but usually two or more,
free hydroxyl groups. Most definitions, and particularly those
over ten years old, list typical polyols as compounds such as
ethylene glycol, propylene glycol, neopentyl glycol, glycerol
or glycerin, trimethylolpropane, pentaerythritol, and sorbitol
that were used in the preparation of alkyds and polyesters.
Today the word "polyols" is far more encompassing and more
often than not refers to alkylene oxide [1 ] and E-caprolactone
[2] adducts of the above-mentioned and other monohydric or
polyhydric alcohols, low-molecular-weight polyesters prepared from the above mentioned as well as other polyhydroxyl compounds and dicarboxylic acids (particularly adipic
acid) [3-5], polytetrahydrofurans prepared by a cationic
ring-opening polymerization of tetrahydrofuran [6, 7], and
low-molecular-weight polycarbonates [8-10]. There are
other compounds that meet the above definition, but they are
not usually termed polyols. Compounds such as these are
certain vinyl chloride copolymers, hydroxyl-containing glycidyl ether compounds, vinyl alcohol copolymers, and so on.
This chapter will not be concerned with these latter compounds since they are dealt with elsewhere in the manual.
Polyols are important compounds used in the manufacture
of alkyds and polyurethane coatings, of intermediates used in
radiation curable formulations, as copolymerizable ingredients in high solids and cationic photocure systems, as well as
in a number of other end uses including elastomeric fibers,
dentistry, artifact preservation, and pharmaceutical preparations. The two main classes of polyols used in coatings are the
polyether polyols, which are typified by the poly(propylene
oxide) polyols (PPO), and the polyester polyols, which include both poly(glycol adipates) (PEA) and poly+caprolactone polyols (PCP). Both classes of polyols are available as
difunctional and
108
Copyright9 1995 by ASTM International
www.astm.org
CHAPTER 1 6 - - M I S C E L L A N E O U S
End capping polyols can provide adducts with different
properties. For example, poly(propylene oxide) polyols which
contain terminal secondary hydroxyl groups can be end capped with ethylene oxide to provide polyols with more reactive
primary hydroxyl groups [1, 7]. Ways to apply nuclear magnetic resonance to measure the ethylene oxide content of
these and other propylene oxide/ethylene oxide copolymers is
detailed in ASTM Test Methods of Polyurethane Raw Materials: Determination of the Polymerized Ethylene Oxide Content of Polyether Polyols (D 4875). Also described in the literature [1, 7] are polyols modified to have amine, allyl, carboxyl,
cyano, and vinyl ether end groups. Glycols that are solid
and/or that have subliming characteristics, as 2,2'-dimethyl3-hydroxypropyl 2,2'dimethyl-3-hydroxypropionate, can be
modified with a few ethylene or propylene oxide groups to
yield new polyols that are liquid, have low viscosity, and do
not sublime with even a few molecules of ethylene oxide
having nil or very little effect on moisture resistance [15].
Polyols can be end capped with an anhydride to form adducts
that have free carboxylic acid functionality or a mixture of it
and hydroxyl functionality as has been done with the poly-~caprolactone polyols [I 6] or the alkylene oxide capped glycols
[17]. In other instances, poly(propylene oxide) polyols have
had carboxyl groups grafted to their backbone with acrylic or
methacrylic acid. These grafted polyols retain their original
hydroxyl end groups and are used in coating formulations
[18].
Polyols can be incorporated into alkyds, made into moisture-curing urethanes, can be cross linked with aminoplasts,
and can be cross linked with cycloaliphatic epoxides when
terminated with carboxylic acid end groups. In using the
polyols, the hydroxyl number [19] is their most important
physical characteristic to be measured and used. Five wet
chemical methods and two nuclear magnetic resonance
methods for determining the hydroxyl number are given in
ASTM Method for Testing Polyurethane Polyol Raw Materials: Determination of Hydroxyl Numbers of Polyols (D 4274)
and in ASTM Method for Testing Polyurethane Raw Materials: Determination of Primary Hydroxyl Contents of Polyether Polyols (D 4273), respectively. The equivalent weight or
combining weight of a polyol is determined from the hydroxyl number by the following relationship
Equivalent Weight = 56 100/Hydroxyl Number
when potassium hydroxide is used as the titrating agent. Of
course, if functionality is known, polyol molecular weight can
be calculated by multiplying the equivalent weight by the
functionality. Manufacturers provide information about hydroxyl number and usually about methods for analytically
determining it.
Another important reactivity parameter is the acid number
described in ASTM Test Method for Polyurethane Raw Materials: Determination of Acid and Alkalinity Numbers of
Polyols (D 4662). Acidity and alkalinity in polyols can affect
reactivity, shelf life, color, and hydrolytic stability of coatings
prepared from polyols. Polyethers and poly-ecaprolactone
polyols usually have very low acid numbers. However, due to
the nature of the condensation reaction coupled with transesterification used to produce polyester polyols, these polyols
have relatively high acid numbers. Color, which has obvious
implications, can be determined with ASTM Test Method for
109
CYCLOALIPHATIC E P O X l D E S
Although the topic of epoxides in coatings is the subject of a
separate chapter in this manual, that chapter deals with glycidyl or 1,2-epoxides that are not attached to a ring structure.
Such epoxides are the largest volume products of all epoxides
used, and the main products in this class are the diglycidyl
ethers of bisphenol A. However, there is a special class of
epoxides, termed "cycloaliphatic epoxides," that are used in
specialty coatings and in cationic radiation-cure coatings.
These epoxides are characterized by a saturated ring structure that imparts a high degree of weatherability and excellent electrical properties such as dielectric constant, dissipation factor, dielectric breakdown voltage, etc., to coatings and
other products made from them. The good weatherability of
the cycloaliphatic epoxides is apparent from the fact that they
have been used for decades to make the large electrical insulators used in substations [20]. These compounds react well
with carboxylic acids, as evidenced by their time-honored use
as acid scavengers, and this reactivity often forms the basis
for their use in coating formulations.
The main commercial cycloaliphatic epoxide is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate that
has the structure
H
\/
H
O
/c\
H/
II
k/
/c\ /H
\/c\ / \ H
\/c\ /
H
110
Specific
Gravity,
25/25~
Color, 1933
Gardner
(max)
Epoxide
Equivalent
Weight
Boiling Point, ~
(mm Hg)
3,4-Epoxycyclohexylmethyl3,4epoxycyclohexane carboxylate
3"50-450
1.175
131-143
Bis(3,4-epoxycyclohexylmethyl)adipate
550-750
1.15
2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4epoxy)cyclohexane-m-dioxane
7000-17 000
at 38~
1.18
1-Vinyl-epoxy-3,4-epoxycyclohexane
<15
1.18-1.10
Chemical Name
COATING FILMS
Films of many different polymers are available in different
forms for use as functional and decorative coatings, adhesive
backings, and other uses. Some of these materials [27,28] are
listed in Table 2. A directory of film manufacturers that lists
the manufacturer product name or number and a short description of the product is available [29]. Full description of
these films and their uses is beyond the intent and scope of
this manual.
METALLIC COATINGS
[28,30,31]
Vapor Pressure
at 20~ m m Hg
Solidification or
Glass Point, ~
354 (760)
<0.1
-20
190-210
258 (10)
<0.1
133-154
>250 (760)
<0.01
70-74
227 (760)
<0
0.1
-55
Cellophane
Cellulose acetate
Cellulose acetate-butyrate
Cellulose triacetate
Ethylene/vinyl acetate
copolymer
Fluorocarbon
Ionomer
Nylon
Polycarbonate
Polyester
Polyethylene
Polyethylene linear low density
Polypropylene, nonoriented
Polypropylene, oriented
Polyurethane
Poly(vinyl alcohol)
Poly(vinyl chloride)
Polyvinylidine chloride
Conventional Film
shrink Film
Yes
Yes
Yes
Yes
Yes
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
Yes
No
Yes
Yes
No
No
Yes
No
No
Yes
Yes
ode sputtering, and ion plating of aluminum, copper, chromium, gold, silver, and silicon monoxide [32]. Many special
effects can be produced including multilayers for cost and
protection, iridescent effects by using compounds with high
(CeO2, ZnS) and low (MgF2, SiO) refractive index, dyeing-particularly of aluminum to achieve a gold color and other
colors, and glass coatings on plastic optical parts. Coatings
formed by such vacuum deposition processes are most often
applied to plastic substrates with end uses for the coated
parts including automotive parts, plastic and paper webs for
decorative and functional packaging of cosmetics, drugs,
clothing, foods, etc., household fixtures, data storage systems, optical components, semiconductor devices, and glass
for automotive and architectural applications. As indicated
above, the packaging industry has a very large use for thin
metallic films on paper and plastic substrates.
A new plasma technique [33] known as unbalanced magnetron sputtering (UBM) has advantages over conventional balanced magnetron sputtering (CBM), which is usually used to
metalize silicon wafers and architectural glass. In such techniques, an argon plasma is used to remove atoms from a
negatively charged target, and magnets are then placed at the
outer edges of the target, which is made the cathode. Each of
the magnets produces a field of the same strength, and because of this the system is termed "balanced." This conven-
CHAPTER 16--MISCELLANEOUS
tional system works well when the substrate is silicon and the
coating is thin. However, in certain end uses, thick, dense
coatings with excellent adhesion are required, and it is herein
that UBM has significant advantages for applying coatings of
hard, wear-resistant alloys such as TiN, NbN, TiC, CrN,
TiNbN, and the like to metal-cutting saw blades and other
tools, cams, and gears.
Metallic and ceramic coatings are also applied to metals by
a thermal spray technique in which a metallic or ceramic
wire, rod, or powder is melted and driven through air or a
vacuum at high velocities [34,35]. The molten material,
which can range from soft, abradable nickel-graphite to hard
ceramic zirconia, is deposited on a surface of base metal to
which it bonds through chemical and mechanical processes.
Thermally sprayed coatings are used as abrasion, corrosion,
and heat barriers for expensive machined components, castings, and other parts used in hostile chemical, mechanical,
and thermal environments encountered in automotive,
spacecraft including aerospace and aircraft, and industrial
applications. The special protection provided by these coatings is needed to improve reliability and durability.
Other metal deposition processes for protective, cost savings and/or decorative coating metal, glass, and plastics include electrodeposition by electroplafing (Cu, Ni, Cr) and
electroless plating (Cu) and galvanizing (Zn). Other than this
brief introduction, the metallic coatings mentioned in this
short chapter are beyond the scope and intent of the manual
and will not be treated further.
111
Phenoxy
Polyhydroxyethers which are commonly known as phenoxy polymers or merely phenoxy, are high-molecularweight, high-performance thermoplastic materials that are
similar in character to the diglycidyl ethers of bisphenol A
that are described in Fig. 1 of the manual chapter entitled
"Epoxy Resins in Coatings." However, there are significant
differences that make the phenoxy polymers separate and
unique polymers [37-39]. These polymers have the structure
--[O--C6H4--C(CH3)2--C6H4--O--CH(OH)--CH2]n where n is about 100, indicating a molecular weight of about
30 000 compared with a molecular weight of about 300 to
10 000 for the diglycidyl ethers of bisphenol A. In addition,
phenoxy polymers do not have active epoxide end groups and
are thermally stable materials with no limit on shelf life, are
tough and ductile, and can form useful, resistant films by
solvent evaporation without cross-linking. The hydroxyl
functionality associated with phenoxy polymers provides a
site for cross-linking with isocyanates, epoxides, or aminoplasts. Films from these polymers are considered to have
excellent physical and chemical resistance properties when
the polymer is in a thermoplastic form, but if improved resistance to certain solvents is needed, the polymers may be crosslinked. The high molecular weight of these polymers results
in relatively low solids (-20%) coating systems, and this
might be a restriction to their use in today's climate for high
solids. The excellent properties of these polymers has led
researchers into investigations of ways for advancing
molecular weight of the diglycidyl ethers of bisphenol A during the curing stages [40].
HS--(C2HaO--Ctf2OC2Ha--S--S)xC2H4OCH2OC2H4SH
from bis(2-chloroethyl)formal, 1,2,3-trichloropropane and
sodium polysulfide. The polymers are available in a molecular weight range of 1000 to 8000. The thiol or mercaptan end
groups of this polymer provide sites for curing in an oxidative
manner with manganese dioxide, dicumene hydroperoxide
and organic peroxides in general, p-quinonedioxime, by reaction with glycidyl epoxides in the presence of tertiary amines,
or by reaction with multifunctional isocyanates. The polymers are used as rubbery coatings and sealants in buildings
and civil engineering projects requiring excellent ultraviolet
light resistance and other general weatherability properties.
Polysulfide coatings have been commercially used for over 50
years. The most recent use of the polymers is to provide
chemically resistant barrier coatings on chemical-containment storage-tank dikes that protect the environment from
chemicals that could cause serious pollution problems.
REFERENCES
[I] Bailey, Jr., F. E. and Koleske, J. V., Alkylene Oxides and Their
Polymers, Marcel Dekker, Inc., New York, 1991.
[2] Hostettler, F. and Young, D. M., U.S. Patent 3,169,945 (1965).
[3] Dombrow, B. A., "Esterification Process," U.S. Patent 3,162,616
(1964).
1 12
[4] Le Bras, L. R. et al., "Oxides of Tin as Catalysts in the Preparation of Polyesters," U.S. Patent 3,157,618 (1964).
[5] Voss, H., "Process for Making Polyester Polyols Having a Low
Acid Number," U.S. Patent 3,907,863 (1975).
[6] Dreyfuss, P. and Dreyfuss, M. P., Advances in Polymer Science,
Vol. 4, 1967, p. 528.
[7] Bailey, F. E. and Koleske, J. V., "Polyoxyalkylenes," Ullmann's
Encyclopedia of Industrial Chemistry, Vol. A21, VCH Publishers,
Inc. Weinheim, Germany, 1992, pp. 579-589.
[8] Hostettler, F. and Cox, E. F., U.S. Patent 3,301,824 (1967).
[9] Harris, R. F., Joseph, M. D., Davidson, C., Deporter, C. D., and
Dais, V.A., "Polyurethane Eastomers Based on Molecular
Weight Advanced Poly(ethylene ether carbonate) Diols. I. Comparison to Commercial Diols," Journal of Applied Polymer Science, Vol. 41, 1990, pp. 487-507.
[10] Takata, T., Igarashi, M., and Endo, T., "Synthesis and Cationic
Ring-Opening Polymerization of a Cyclic Carbonate, 5-Methylene-l,3-dioxan-2-one," Journal of Polymer Science: Part A:
Polymer Chemistry, Vol. 29, 1991, pp. 781-784.
[11] Comstock, L. R., Milligan, C. L., and Monter, R. P., "Urethane
Coatings Derived from Caprolactone Polyols, I. Rigid Substrate
Coatings," Journal of Paint Technology, Vol. 44, No. 573, 1972,
pp. 63-70.
[12] Comstock, L. R., Gerkin, R. M., Milligan, C. L., and Monter,
R. P., "Urethane Coatings Derived from Caprolactone Polyols,
II. Flexible Substrate Coatings," Journal of Paint Technology,
Vol. 44, No. 574, 1972, pp. 75-83.
[13] Basque, D. E. and Rajangam, G. D., "Specialty Polyols Achieve
Improved Performance Traits," Adhesives Age, Vol. 34, No. 8,
July 1991, pp. 17-18.
[14] Monks, R., "New Additives and Polyols Surface at Urethane
Conference," Plastics Technology, Vol. 33, No. 6, June 1992, pp.
47-51.
[15] Koleske, J. V. and Knopf, R. J., U.S. Patent 4,163,114 (1979).
[16] Smith, O. W. and Koleske, J. V., U.S. Patent 4,096,125 (1978).
[17] Smith, O.W., Koleske, J.V., and Knopf, R.J., U.S. Patent
4,171,423 (1979).
[18] Barksby, N. and Gerkin, R. M., "Acid-Grafted Polyethers: Their
Use in Low-VOC Coatings," Modern Paint and Coatings, Vol. 80,
No. 6, June 1990, pp. 34-43.
[19] Wellons, S. L., Carey, M. A., and Elder, D. K., "Determination of
Hydroxyl Content of Polyurethane Polyols and Other Alcohols,"
Analytical Chemistry, Vol. 52, 1980, p. 1374.
[20] "Cycloaliphatic Epoxides for Electrical and Electronic Applications," Brochure F-50010, Union Carbide Corporation, Danburg, CT, August 1984, pp. 1-19.
[21] Union Carbide Corporation, "Cycloaliphatic Epoxide Systems,"
Brochure F-42953B, March 1978, pp. 1-18, and "ERL-4206:
Low Viscosity Reactive Diluent," Brochure F-50033, May 1985,
pp. 1-12.
[22] Koleske, J. V., "Cationic Radiation Curing," Federation Series
on Coatings Technology, June 1991, Federation of Societies for
Coatings Technology, Blue Bell, PA, pp. 1-27.
[23] "ENVIBAR UV1244 and UV1244T EnvironmentalBarrier Coatings," Specialty Coating Systems, Inc., Indianapolis, 1988.
[24] Koleske, J. V., "Conformal Coatings Cured with Actinic Radiation," U.S. Patent 5,043,221 (1991).
[25] Koleske, J. V., "Conformal Coatings Cured with Actinic Radiation," U.S. Patent 5,155,143 (1992).
[30] Winterhalter, H., "Vakuum-Bedampfen yon Kunststoff-Formteilen," Veredeln von Kunstoffe-Oberfldchen, K. Stoeckhert, Ed.,
Hanser Verlag, Miinchen, 1974, pp. 75-106.
[31] Hartwig, E., "High Vacuum Roll Coating," Web Processing and
Converting Technology and Equipment, D. Satas, Ed., Van Nostrand Reinhold, NY, 1984, pp. 182-212.
Part 4: Plasticizers
MNL17-EB/Jun. 1995
17
Plasticizers
by Peter Tan 1 and Leonard G. Krauskopf 2
PAINTANDCOATINGFORMULATIONSoften incorporate high boiling fluids as plasticizers where rigid or brittle resins fail to
meet toughness and flexibility requirements. The primary
function of the plasticizer is to impart flexibility to the resin,
thus minimizing film cracking. Depending on resin and other
ingredients used in the system, plasticizer choice may affect
compatibility, toughness, flammability, smoke generation,
heat and light stability, and other aging or permanence-related performances. Plasticizers are primarily employed in
heavy gage coatings and/or when improved toughness is required for industrial, automotive, and appliance applications.
Plasticizers function by reducing the glass transition temperature of the resin to a point below its application temperature. The chemical mechanism of plasticization involves a
strong polar association of polymer-plasticizer molecules,
but not a chemical reaction between them. Plasticizers fundamentally reduce Van Der Waals forces between polymerpolymer molecules in the amorphous regions and do not
penetrate crystallites [1-3]. The plasticized morphological
phase is then of a different nature than that of the neat
polymer and has unique mechanical properties.
The absence of a chemical bond between the plasticizer
and the polymer impairs permanence; plasticizer molecules
are free to leave the polymeric coating by means of extraction
and volatility. Plasticizer loss, however, is minimal in most
applications except for very low molecular weight plasticizers
and/or exposure to very severe thermal conditions. Thus,
plasticized coatings products have high durability and long
service life in most applications. Plasticizers are liquids of
molecular weight greater than that of solvents--to limit volat i l i t y - b u t are not solids, such as alloying polymers, etc. It
should be noted that cross-linked resinous coatings significantly reduce plasticizer loss due to diffusibility and volatility. Several thousand high boiling fluids are potential plasticizers for coatings applications. The choice of plasticizer is
dependent on compatibility with the resin in use, cost, and
other desired attributes.
Plasticizers may be classified by both chemical structure
and performance characteristics, as shown in Table 1 [4].
Typical plasticizers are liquid esters of molecular weight between about 200 to 800, with specific gravities between 0.75
tManager, Marketing Technical Services, Exxon Chemical Asia
PTE LTD, Intermediates Technology Center, Block 14 (Maxwell) No.
02-03, Science Park Drive, Singapore 0511.
2Research associate, Exxon Chemical Company, Intermediates
Technology, P.O. Box 241, Baton Rouge, LA 70821.
PHYSICAL A N D CHEMICAL P R O P E R T I E S
Acidity
Plasticizer acidity may be due to improper processing, degradation during storage, contamination, presence of by-products, or residual catalyst. ASTM Test Method for Acidity in
Volatile Solvents and Chemical Intermediates Used in Paint,
Varnish, Lacquer, and Related Products (D 1613) may be
used for determination of acidity. Either ethyl or isopropyl
alcohol may be used as diluent for the plasticizer, which is
titrated with aqueous sodium hydroxide or potassium hydroxide to the phenolphthalein end point. Results may be
expressed in weight percent, as weight equivalents of acetic
acid, acid number (milligrams potassium hydroxide consumed per gram of sample), or if the plasticizer is an ester, as
weight percent of the parent acid of the ester (see section
entitled "Ester Value").
Color
The majority of plasticizers are colorless. As a class, esters
are very stable chemical reagents. However, exposure to abnormal conditions such as high thermal or ultra-violet energy, moisture, or chemically active surfaces may induce development of color bodies and/or chemical decomposition of
the plasticizers. Higher molecular weight phthalates, polymeric plasticizers, and chlorinated paraffins may range in
color from light to bright yellow. ASTM Test Method for
Color of Clear Liquids (Platinum-Cobalt Scale) (D 1209) is
the standard color measurement method for plasticizers.
115
Copyright9 1995 by ASTM International
www.astm.org
116
Phthalates
Trimellitates
Aliphatic dibasic
esters
Phosphates
Epoxides
Polyesters
Extenders
General
Purpose
Strong
Solvating
X
. . . . . .
. . . . .
,/
...
. . . . . .
. . . . . .
X
,/
Low
Volatility
Low
Temperature
,/
X
~/
,/
X
~/
,/
. . . . . .
...
...
...
,/
~/
,/
,/
..~/
...
. . . . . .
X
. . . . . .
. . . . . .
Low
Diffusibility
Flame
Resistant
Stabilizer
X
-..
Copper Corrosion
ASTM Test Method for Detection of Copper Corrosion
from Petroleum Products by the Copper Strip Tarnish Test
(D 130), and ASTM Test Method for Copper Corrosion of
Industrial Aromatic Hydrocarbons (D 849), which is normally applied to hydrocarbon solvents, m a y be used to evaluate the copper corrosive tendencies if suspected to be sourced
in plasticizer. The appearance of a copper strip, which has
been immersed in the test fluid, under standard conditions, is
c o m p a r e d with twelve special standard strips classified as
follow:
1. Slight tarnish (la,b) light orange, dark orange.
2. Moderate tarnish (2a,b,c,d,e) claret red, brassy, or gold.
Distillation Range
Most plasticizers have high boiling points or boiling
ranges. This property can be used as a measure of its degree
of permanence or resistance to loss through volatilization.
Presence of lighter components can also be detected. The
measurement of vapor pressure is a costly and time-consuming procedure. Thus, commercial liquids of high molecular w e i g h t - - l o w vapor pressures--are typically characterized
by boiling ranges in which one determines initial, mid, and
final (or drypoint) boiling point temperatures. For fluids with
dry point > 140~ ASTM Test Method for Distillation of Petroleum Products (D 86) is used. Fluids with dry point
< 140~ are measured using ASTM Test Method for Distillation Range of Volatile Organic Liquids (D 1078). For very
high boiling fluids or where decomposition m a y occur, distillation m a y be done under v a c u u m regulated at 5 m m Hg. The
initial and final boiling points or the mid boiling point are
typically reported.
Gas chromatographic (GC) techniques are c o m m o n l y applied as a fundamental measure of plasticizer chemical purity
and isomer distribution. Direct relationships between GC
traces and boiling ranges have not yet been established for
plasticizers.
Both distillation range and GC analyses are means to relate
vaporization characteristics of plasticizers to practical needs.
The fundamental characteristic of vapor pressure m a y be
measured by ASTM Test Method for Vapor Pressure-Temperature Relationship and Initial Decomposition Temperature
of Liquids by Isoteniscope (D 2879). The log of plasticizer
vapor pressure varies linearly with the reciprocal absolute
temperature (degrees Kelvin) according to the ClausiusClapeyron equation [8]
In
1)
~22 - ~
(1)
CHAPTER 17--PLASTICIZERS
where
P1 and P2 = vapor pressure, g.cm2.s -2,
T1 and T2 = respective temperatures, K,
AH = molar heat of vaporization, cal.g- 1, and
R = gas constant, 1.99 cal ~
Vapor pressure values are useful to estimate normal boiling
points at 760 m m mercury and solubility parameters [1].
Sears and Darby have reported that the vapor pressure of
binary plasticizer blends may be expected to fall between the
values of the neat plasticizers, but cannot be predicted from a
knowledge of the blend ratio and the neat vapor pressures.
Ester Value
Esters are the largest group of materials that are commercially useful as plasticizers. This is a result of reasonable costs
and broad utility in a wide range of polymers having moderate to high polarity characteristics. Ester value can be used to
estimate the purity or ester content of the plasticizer. ASTM
Test Method for Ester Value of Lacquer Solvents and Thinners (D 1617) or ASTM Methods of Sampling and Testing
Plasticizers Used in Plastics (D 1045) may be used for this
determination. The methods involve saponification of the
ester in a known excess amount of KOH. The excess amount
of KOH is then determined by titration with standard sulfuric
acid. The amount o f / ( O H consumed in the saponification
process is a measure of the ester content of the plasticizer.
A gas chromatography method, ASTM Test Method for
Purity of Monomeric Plasticizers by Gas Chromatography
(D 3465), may also be used to determine the purity of monomerle plasticizers. The GC method does not provide "ester
values." It is useful to characterize major isomers present
versus known standards and to ascertain trace quantities of
nonparent organic compounds. GC instrumentation is costly
and requires comparison of output traces against a library of
known materials that have been characterized under a specific set of conditions using specific GC instruments and columns.
Flash P o i n t
Most plasticizers are high flash materials. Either ASTM
Test Method for Flash and Fire Points by Cleveland Open Cup
(D 92) or ASTM Test Method for Flash Point by PenskyMartens Closed Tester (D 93) may be used. Preference should
be for the dosed cup method; this yields a more conservative
number and is consistent with Department of Transportation
(DOT) regulations in the United States. DOT has revised the
definitions and classifications of hazardous materials, effective 1 Oct. 1993, as follows:
Flash Point
Not Regulated
Combustible
Flammable
>_93~ (200~
61 to 92.5~ (142 to 199~
<_60.5~ (141~
117
ods for Flash Point of Liquids by Setaflash Closed Cup Apparatus (D 3278).
Flash point values are reported for commercially significant monomeric plasticizers in E. J. Wickson's Handbook
on PVC Formulating [7]. While not a very good analytical tool,
flash points will reflect presence of nonparent, low-flashpoint contaminants.
P o u r Point
Due to the high molecular weight and isomeric mixtures of
plasticizers, few have distinct freezing points. The pour point
can be useful information for handling plasticizers during
cold seasons. Method of measurement is described in ASTM
Test Methods for Pour Point of Petroleum Oils (D 97). Plasticizer pour point temperatures may also be estimated from
viscosity/temperature plots as the temperature at which kinematic viscosity is 50 000 cSt. Most plasticizers have pour
points of less than - 30~ [7]; no known relationship exists
between pour point and plasticizer performance properties in
polymers under low-temperature conditions.
Refractive I n d e x
The refractive index of a plasticizer is measured using
ASTM Test Method for Refractive Index and Refractive Dispersion of Hydrocarbon Liquids (D 1218). Refractive index is
often thought of as a means of identifying the plasticizer. This
is an erroneous assumption. It may be used, however, to
differentiate between classes of plasticizers, as, for example,
between phthalates and adipates [10]. When used with other
physical measurements, refractive index may be used as a
supplemental test. Refractive index can also be used to check
for product contamination, but it is only useful to distinctify
commercial materials having very widely different refractive
indices.
R e s i d u a l Odor
Residual odor may be contributed by reaction by-products
from manufacturing or by residual raw ingredients which are
often more volatile and odorous than the plasticizer. When
ASTM Test Method for Odor of Volatile Solvents and Diluents
(D 1296) is used, tests at elevated temperatures (about 150~
can be considered to improve detection. Since odor is a
subjective characteristic, generalizations for plasticizers are
limited to terms such as "mild and characteristic."
Sampling
To obtain representative samples of plasticizers for evaluation, ASTM Methods for Sampling and Testing Plasticizers
Used in Plastics (D 1045) may be followed. ASTM Recommended Practice for Sampling of Industrial Chemicals
(E 300) can also be used.
118
at the specified temperature; it is generally used in the characterization of plasticizers or as a means to detect gross contamination. Specific gravity at 20/20~ is measured with
ASTM Test Methods for Specific Gravity of Liquid Industrial
Chemicals (D 891) and is commonly employed in industry.
Commercial plasticizers typically fall within the range of 0.92
to 1.50 sp gr at 20/20~ ASTM Test Method for Density and
Relative Density of Liquids by Digital Density Meter (D 4052)
is the recommended procedure to measure specific gravity of
fluids that lie between 0.68 and 0.97; this method is applicable to hydrocarbons that are commonly used as plasticizer
extenders.
Viscosity
Viscosity measures the fluid's resistance to flow; the thicker
the fluid, the higher its viscosity and the greater its resistance
to flow under gravity. In ASTM Test Method for Kinematic
Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity) (D 445), time is measured in
seconds for a fixed volume of the fluid to flow under gravity
through the capillary of a calibrated viscometer at constant
temperature. The kinematic viscosity of a plasticizer varies as
a log log function versus the log of absolute temperature
according to the following equation
log log ~ ---A - B log T
(2)
where
= kinematic viscosity, centistokes,
T = temperature, degrees Kelvin, and
A and B = constants.
This reflects the tremendous influence of temperature on
viscosity and allows one to interpolate viscosity values at
specified temperatures. The kinematic viscosity (centistokes)
can be converted to its dynamic viscosity (centipoise) by
multiplying by the true density of the fluid at the specified
temperature: dynamic viscosity, cP = kinematic viscosity,
cSt, times density.
Water
Residual water from manufacturing processes and moisture absorbed from the atmosphere can affect the quality and
clarity of coatings. Water content can be measured using
ASTM Test Method for Water in Volatile Solvents (Fischer
Reagent Titration Method) (D 1364). Plasticizers are hydrophobic liquids and typically have a limited capacity to take up
water and/or be dissolved into water. Higher-molecularweight phthalates are practically insoluble in water with solubilities in the 0.1 to 1.2 mg/L (ppm) range with even less
solubility in salt water [6].
Typical Properties
As shown in Table 1, commercial plasticizers fall into about
seven chemical family groups (eight if we were to add a
"miscellaneous" grouping). The major plasticizer types in use
are phthalates, trimellitates, and aliphatic dibasic esters such
as adipates. The families of esters are formed by reacting the
parent acid with monomeric alcohols ranging from C4H9OH
(butanol) to C13H27OH (tridecanol); the alcohol may also vary
METHODS OF IDENTIFICATION
A plasticizer may initially be characterized by its functional
groups. While absolute identification is complicated without
sophisticated chemical or instrumental methods, it is possible to identify the type of plasticizer by functional groups or
presence of elements associated only with the plasticizer by
the use of infrared analyses or wet chemistry. Most plasticizers are a member of one of the following families:
Isolation of Plasticizers
Plasticizers may be separated from a lacquer or dried film
by solvent extraction if it is to be analyzed. The lacquer is first
dried to remove all solvents present. The dried solid is then
solvent extracted (in an appropriate apparatus) with hot ethyl
ether or another appropriate solvent that will extract the
plasticizers while leaving most of the resins behind. The extractant is concentrated, and a small amount of methyl or
ethyl alcohol is added. This will cause some of the dissolved
resin to precipitate out. Next, filter and concentrate the extractant. ASTM Test Method for Acetone Extraction of Phenolic Molded or Laminated Products (D 494) may be applied.
Instrumental Methods
Modern instrumental analytical methods are able to
separate, identify, and quantify components in composite
mixtures. Rapidly falling costs of such instruments have enabled instrumental methods to be more widely available.
These include gas chromatography (GC), high-performance
liquid chromatography (HPLC), infrared spectroscopy
(FTIR), and other emerging analytical instruments like supercritical fluid chromatography (SFC), GC/FTIR, and
GC/MS (mass spectrometry).
Infrared Spectrophotometry
An infrared scan of the isolated plasticizer is by far the best
way to identify the functional groups in the molecule. Mixtures of plasticizers can present problems due to masking
effects. If one or more of the component plasticizers is known
and its IR scan available, subtracting it from the IR scan of
CHAPTER
17--PLASTICIZERS
119
TABLE 2--Typical physical properties of plasticizer esters made with isononyl and 2-ethylhexyl alcohols.
DOP
Alkyl
Molecular weight
Specific gravity at 20/20~ (68~
Refractive Index n2D~
Viscosity, cSt at 20~
Pour point, ~
Vapor pressure, mm Hg at 200~
Mid boiling point, ~ at 5 turn Hg
Flash point, ~
Color, Pt-Co
Phthalate
DINP
2EH
390
0.986
1.484
83
- 47
1.2
230
204
<25
INA
424
0.973
1.486
102
- 48
0.5
245
213
<25
Trimellitate
TOTM
TINTM
2EH
546
0.992
1.482
312
- 46
0.08
300
221
< 100
INA
596
0.979
1.484
430
- 40
0.03
331
241
< 100
Adipate
DOA
DINA
2EH
370
0.927
1.445
16
< - 60
2.5
215
193
<25
INA
404
0.924
1.449
26
- 59
1.5
233
199
<25
Source: Edenbaum, J., Plastics Additives and Modifiers Handbook, Van Nostrand Reinhold, New York, 1992, p. 362. Reprinted with
permission.
NOTE:DOP
di(2-ethylhexyl)
phthalate
DINP
di (isononyl) phthalate
TOTM
tris(2-ethylhexyl)
trirnellitate
TINTM tris(isononyl) trimellitate
DOA
di(2-ethylhexyl)
adipate
DINA
di(isononyl) adipate
Chromatography
Gas Chromatography
By c o m p a r i n g relative r e t e n t i o n t i m e s a n d p e a k s h a p e s
with k n o w n samples, a plasticizer o r mixture can often be
identified a n d quantified. W h e n coupled with IR (i.e.,
GC/FTIR), the IR s p e c t r u m of each c h r o m a t o g r a p h i c p e a k
can assist in the identification of functional groups a n d hence
plasticizer identity.
Qualitative Methods
F o r the detection of nitrogen, chlorine, sulphur, o r phosphorus, the s a m p l e needs to be fused with metallic sodium.
This p r e p a r a t i o n should be c a r r i e d out in a fume h o o d and
caution observed w h e n h a n d l i n g metallic sodium. A small
a m o u n t (about 3 m m 3) of metallic s o d i u m is p l a c e d in a d r y
6-in. (15.24-cm) test tube. The test t u b e should be held vertically by c l a m p i n g it at the o p e n end. The test t u b e is t h e n
h e a t e d until a cloud of s o d i u m v a p o r begins to form. Remove
the flame immediately. Add two to three d r o p s of the plasticizer s a m p l e directly to the s o d i u m vapor. W h e n the test tube
is cold, b r e a k off the end with the s o d i u m in a m o r t a r . Add
several milliliters of alcohol to d e s t r o y u n r e a c t e d sodium.
Add a b o u t 20 rnL of distilled o r deionized water, g r i n d u p the
sample, transfer to a beaker, b r i n g to boil, and filter. The
filtrate is t h e n used for the c h e m i c a l detection of the elements.
Sulfur
Add two to three d r o p s of 10% solution of lead acetate to
2 m L of a 10% solution of s o d i u m hydroxide. Add this mixture to 5 m L of the filtrate, A b l a c k p r e c i p i t a t e of l e a d
sulphide indicates the presence of sulphur, Positive identification suggests that the s a m p l e is either a s u l p h o n a m i d e o r
sulphate.
Nitrogen
Bring 2 mL of the filtrate to boil in a test tube. Add five
d r o p s of a 10% solution of N a O H a n d five d r o p s of 10%
ferrous sulphate solution. W h e n cold, add, dropwise, a 10%
solution of h y d r o c h l o r i c acid until the solution is acidic a n d
the precipitate of ferrous h y d r o x i d e has dissolved. Avoid using a n excessive a m o u n t of acid. A blue or green color o r blue
precipitate indicates p r e s e n c e of nitrogen. A positive test suggests that the plasticizer could be an amide.
Chlorine
Acidify 5 m L of the filtrate with several d r o p s of dilute
sulfuric acid a n d b r i n g it to boil. Cool a n d acidify with nitric
acid. Add several d r o p s of a 10% silver nitrate solution. A
white precipitate indicates the presence of a c h l o r i n a t e d compound.
Phosphorus
Boil 5 m L of the filtrate with 3 m L of c o n c e n t r a t e d nitric
acid for I rain. Cool and a d d twice the v o l u m e of 10% a m m o n i u m m o l y b d a t e solution. H e a t to a b o u t 60~ a n d set aside to
cool. A yellow precipitate indicates the presence of p h o s p h o rus. P h o s p h a t e plasticizers will result in a positive test.
Phthalates
Add a b o u t 0.05 g of resorcinol and 0.05 g of p h e n o l to separate 6-in. (15.24-cm) test tubes. Add to each test t u b e two to
three drops of the isolated plasticizer a n d a d r o p of concen-
120
PERFORMANCE PROPERTIES
Compatibility
Compatibility is the ability of two or more substances to
mix together without objectionable separation [12]. In the
case of plasticizers, it is primarily a measure of the solvency
or strength of positive interactions between the plasticizer
and the polymer which attract them together.
Solvency is the extent (or amount) of interaction of plasticizer or solvent molecules at the surface of a polymer particle;
a solid solution results when the polymer and plasticizer-and possibly additional reagents--become molecularly homogeneous. The degree to which a homogeneous solution, or
miscibility, is stable is a function of the plasticizer/polymer
interactions when in the presence of other reagents employed
in the coating formulation; it must be recognized that the
presence of these additional reagents can compete with the
polymer/plasticizer interactions. The rule of thumb "like dissolves like" applies, but more specific knowledge is required
to avoid results that appear to be anomalous.
Dried polymeric coatings may be considered as solid solutions; the limits of miscibility are impacted by all of the
reagents that become components of the coating--those intentionally added, as well as inadvertent contaminates and/or
degradation products formed in the coating process. When
plasticizers are employed, they have a major effect on compatibility, primarily due to the level, or concentration, used in
the polymer. If we accept the definition of a solution as a
homogeneous mixture of two or more types of molecules,
then "solvency" is a measure of a given solvent or plasticizer
to homogenize and interact with a given polymer. Quantification of this "interaction" has been elusive; scales which have
been devised are capable of measuring only gross differences.
Observations of phase separation of plasticizer/polymer have
been more finite than that predicted in many cases, while on
the other hand, observations of symptoms (compatibility) are
incapable of separating "solvency" from other interfering
mechanisms that are concurrent, such as diffusibility.
Hansen publications [13-14] define the total solubility parameters of polymers, solvents, and other reagents as a function of three component parameters:
)kT = (~t~ + ~tp2 -{- }~)1/2, ( c a l / c m 3 ) l / 2
(3)
where
hr = total solubility parameter,
hd = dispersion parameter,
hp = polarity parameter, and
hh = hydrogen bonding parameter.
The location of polymers and other non-ionic reagents may
be defined on this three-dimensional grid. Hansen states that
it may be assumed that the closer a plasticizer lies to the
center of the polymer solubility space of a polymer, the more
Permanence
"Reactive" plasticizers are specialty types designed to selfpolymerize or graft onto the polymeric resin during the
curing process. But, in most cases, plasticizers do not chemically react with the polymer. They function by an overall
solvating action that is less strong than that of a good solvent,
but stronger than that of incompatible reagents such as lubricants. This interaction imparts a slight effect on plasticizer
"permanence," or more properly "transience." One of two factors are generally the controlling influence over loss of plasticizer:
9 Rate of diffusion of plasticizer from the resin bulk to the
surface.
Low-Temperature Properties
Some applications require flexibility and impact resistance
at low temperatures. This property may be significantly improved at increased plasticizer levels, as well as being a function of the plasticizer type [1 ]. For example, at approximately
50 PHR, plasticizer in poly(vinyl chloride) phthalates of linear alcohols impart about - 10~ improvement in low-temperature brittleness over branched, DOP-type, phthalate
plasticizer. Dialkyl adipates, however, impart about -25~
improvement over the brittleness value of DOP-plasticized
PVC as measured by ASTM Test Method for Brittleness Temperature of Plastics and Elastomers by Impact (D 746).
CHAPTER 17---PLASTICIZERS
121
CA
CAB
CN
EC
PMMA
PS
VAc
VB
PVC
VC/VAc
Phthalates
DOP
DIOP
DINP
DIDP
I
I
P
P
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
P
C
C
C
C
I
C
C
P
P
P
P
P
C
C
C
C
C
C
C
C
Trimellitates
TOTM
TINTM
P
P
C
C
C
C
C
C
P
P
C
C
P
P
P
P
C
C
C
C
Phosphates
TCP
TOP
C
P
C
P
C
C
C
C
P
I
C
C
C
I
C
C
C
C
C
C
Acyclic esters
DOA
DINA
DOZ
DOS
P
P
P
P
C
C
C
C
C
C
C
C
C
C
C
C
P
P
P
P
C
C
C
C
P
P
P
P
P
P
P
P
C
C
C
C
C
C
C
C
Epoxidized
S o y b e a n oil
(2EH) tallate
I
I
P
C
C
C
C
C
I
I
I
I
I
I
I
C
C
C
C
C
Polyesters
Adipic/Diol
Phthalic/Diol
P
P
C
C
C
C
C
C
P
P
C
C
P
P
P
P
C
C
C
C
Phthalates
DOP = di(2-ethylhexyl)
DIOP = di(isooctyl)
DINP = di(isononyl)
DIDP = di(isodecyl)
Trimellitates
TOTM = tris(2-ethylhexyl)
TINTM = tfis(isononyl)
Acyclic Esters
DOA = di(2-ethylhexyl) adipate
DINA = di(isononyl) adipate
DOZ = di(2-ethylhexyl) azelate
DOS = di(2-ethylhexyl) sebacate
NOTE: Compatibility of plasticizers in specific polymers is a function of relative concentration (PHR), as well
as the presence of other formulating reagents and residuals present in polymers. The above ratings are
based on plasticizer levels typically used in coatings applications (<40 PHR).
Commercial coatings require the optimum choice of plasticizer type and concentration to meet required costs, hardness
or modulus, permanence, and low-temperature properties.
Acknowledgments
The authors would like to acknowledge the contributions,
consultation, and review given by their co-workers Arthur D.
Earlywine and Thomas M. Larson.
REFERENCES
[1] Sears, J. K. a n d Darby, J. R., The Technology of Plasticizers, J o h n
Wiley a n d S o n s , N e w York, 1982.
[2] K r a u s k o p f , L. G., N a s s , L. I., a n d Heiberger, C. A., Eds., "Plasticizers," Encyclopedia of PVC, 2 n d ed., Vol. 2, M a r c e l Dekker,
Inc., N e w York, 1988.
[3] Gould, R. F. Ed., Plasticization and Plasticizer Processes, A m e r i c a n C h e m i c a l Society, W a s h i n g t o n , DC, 1965.
[4] K r a u s k o p f , L. G., "Plasticizer S t r u c t u r e / P e r f o r m a n c e R e l a t i o n ships," Society of Plastics E n g i n e e r s , Brookfield, CT, Vinyl I
RETEC, 30 Sept.-1 Oct. 1992.
122
[12] Whittington, L. R., Whittington's Dictionary of Plastics, Technomics, Westport, CT, 1978, p. 66.
Part 5: Solvents
MNL17-EB/Jun. 1995
18
Solvents
by Stephen A. Yuhas, Jr.
CLASSIFICATION B Y CHEMICAL T Y P E
Solvents can be broadly classified by chemical type into
three categories:
1Chemical engineer, technical consultant, Solventures, Inc., 56
Wick Drive, Fords, NJ 08863.
Copyright9 1995 by ASTM International
Solvents
Aliphatic Hydrocarbons
Most aliphatic hydrocarbon solvents are manufactured by
distilling the appropriate boiling range fractions from crude
oil and subsequently treating them to improve odor and color
stability. These saturated organic molecules are generally
mixtures of straight chain or normal-paraffins and branched
chain or iso-paraffins, with perhaps some cycloparaffins [1].
Unique, distinguishing characteristics of commodity aliphatic hydrocarbons are: very weak solvency, low odor, specific gravity, and cost. Although they are active solvents for
some varnishes and alkyds, they are used primarily as lowcost diluents in solvent blends. Weak solvency is not necessarily a disadvantage of aliphatic hydrocarbons. They are preferred as carrier solvents in vinyl organosols and as reaction
125
www.astm.org
126
Aromatic Hydrocarbons
Aromatic hydrocarbons, which are cyclic, unsaturated
compounds, are also made from petroleum. However, their
manufacture requires additional processing steps. An ali-
Aromatic 100 consists mainly of C9 aromatics, while Aromatic 150 is a mixture of predominantly C~0 aromatics. Both
are slow evaporating and are used in baked industrial coatings.
Solvent
Hexanes
Heptane
Lacquer diluent
VM&P naphthas
Type I "Regular"
Type II "High Flash"
Type III "Odorless''a
Mineral spirits
Type I "Regular"
Type II "High Flash"
Type III "Odorless"a
Type IV "Low Dry Point,"
"Stoddard Solvent"
Deodorized kerosene
~Isoparaffinic hydrocarbon.
ASTM
Specification
Specific
Gravity,
60/60~
Distillation
Range, ~
Evaporation
Rate,
n-BuAc = 100
Flash
Point,
TCC, ~ (~
KauriButanol
Value
Aniline
Point,
~ (~
D 1836
.....
D 3735
0.68
0.73
0.75
64-70
94-99
93-115
1500
600
400
32
36
40
150 (66)
129 (54)
120 (49)
0.75
0.76
0.72
12ff-150
140-175
120-150
200
150
210
41 (5)
81 (27)
41 (5)
38
40
29
117 (47)
110 (43)
165 (74)
0.79
0.79
0.76
0.77
150-210
177-210
150-210
150-185
10
8
10
15
108 (42)
142 (61)
104 (40)
104 (40)
37
36
27
38
130 (54)
135 (57)
184 (84)
123 (51)
0.81
177-265
142 (61)
30
160 (71)
D 235
...
CHAPTER 18--SOLVENTS
127
Solvent
Toluene
Mixed xylenes
ortho-xylene
meta-xylene
para-xylene
Ethylbenzene
High flash aromatic naphthas
Type I "Aromatic 100"
Type II "Aromatic 150"
ASTM
Specification
D 841
D 843
D 4076
.-.
D 5136
D 3193
D 3734
Specific
Gravity,
60/60~
KauriButanol
Value
Mixed
Aniline
Point,
~ (~
137-142
143-145
139-140
138-139
136-137
180
70
65
70
70
74
45 (7)
83 (28)
90 (32)
81 (27)
81 (27)
70 (21)
105
98
106
97
93
95
48 (9)
51 (10)
51 (10)
51 (10)
52 (11)
52 (11)
0.874
0.895
150-175
180-215
20
5
108 (42)
150 (66)
91
95
56 (13)
60 (15)
Terpenes
Terpene solvents are obtained from pine trees and to a
much lesser extent as a by-product of the citrus industry.
They are the oldest solvents used in coatings, predating ancient Egyptian civilization [1,3]. The main solvents in this
group are turpentine, dipentene, and pine oil. Chemically,
they are mixtures of Cw unsaturated hydrocarbon compounds. A good review of terpenes may be found in ASTM
D 804, "Standard Definitions of Terms Relating to Naval
Stores and Related Products."
Terpene solvents have volatiles similar to mineral spirits.
However, they have only minor commercial significance today because they are more expensive than hydrocarbon solvents. Although their solvency is greater than that of aliphatic
hydrocarbons, they have a much narrower range of solvency
and evaporation rate and a stronger odor. Furthermore, because of their unsaturated structure, they are restricted in
some areas by air pollution regulations.
There are four kinds of turpentine, as specified in ASTM
D 13, Specification for Spirits of Turpentine, depending on
the source and method of production [1,4].
Gum turpentine or gum spirits is produced by distilling the
crude gum or oleoresin collected from living pine trees. It
TABLE 3--Typical properties of cyclohexane.
D 3055
0.782
174-178
1000 (estimated)
- 4 (-20)
52
93 (34)
110-111
Flash
Point,
TCC,~ (~
0.872
0.871
0.885
0.869
0.866
0.872
Naphthenic Hydrocarbons
ASTM specification
Specific gravity, 60/60~
Distillation range, ~
Evaporation rate, n-butyl acetate = 100
Flash point, ~ (~
Kauri-butanol value
Aniline point, ~ (~
Distillation
Range, ~
Evaporation
Rate,
n-BuAc = 100
Oxygenated Solvents
Oxygenated solvents contain oxygen functionality in the
molecules. Unlike hydrocarbon solvents, oxygenated solvents
128
Dipentene
D 13
D 233
0.865
150-170
40
. . .
D 801
0.853
170-190
18
95 (35)
56
70 (21)
120 (49)
62
32 (0)
Ketones
Ketones are c h a r a c t e r i z e d chemically by a c a r b o n y l g r o u p
b o n d e d to two c a r b o n a t o m s or alkyl groups in the molecule.
This versatile class of solvents has powerful solvency and a
wide range of e v a p o r a t i o n rates, from very fast-evaporating
acetone to slow-evaporating isophorone. Ketones are further
c h a r a c t e r i z e d by their strong, s h a r p odors. They have n a r r o w
distillation ranges b e c a u s e of t h e i r high purity. Acetone is
c o m p l e t e l y w a t e r miscible, while o t h e r ketones have varying
degrees of w a t e r solubility. Properties of selected ketones,
with their ASTM specification references, are s u m m a r i z e d in
Table 5. (Diacetone alcohol is included in this category since
this ketone alcohol functions m o r e as a ketone t h a n a n alcohol.)
Acetone is very fast-evaporating. It is often used in aerosols
a n d sprayed coatings, p a r t i c u l a r l y in nitrocellulose a n d
acrylic lacquers, to effectively reduce viscosity for s p r a y application a n d then quickly flash off d u r i n g the spraying process. Methyl ethyl ketone (MEK) has a fast e v a p o r a t i o n rate
a n d methyl isobutyl ketone (MIBK) a m o d e r a t e e v a p o r a t i o n
Pine Oil
.
.
D 802
0.923
200-225
5
130 (54)
>500
<-4 (<-20)
Esters
Esters used as solvents are alkyl acetates a n d p r o p i o n a t e s
a n d glycol e t h e r acetates. Several o t h e r types of ester solvents
are also c o m m e r c i a l l y available as specialty products. The
alkyl esters cover a wide range of volatilities, m a i n l y methyl
t h r o u g h hexyl esters. Glycol e t h e r acetates are slow-evaporating, a n d they are used as r e t a r d e r solvents in solvent-based
coatings a n d as coalescents in latex paints.
Esters have strong solvency, a l t h o u g h generally slightly
w e a k e r t h a n ketones of s i m i l a r volatility. They are characterized by their pleasant, sweet, fruity odors. All esters have
n a r r o w distillation ranges since they are relatively p u r e compounds.
Typical p r o p e r t i e s of the m o s t c o m m o n ester solvents are
s u m m a r i z e d in Table 6. As with ketones, their solvencies follow a general pattern, d i m i n i s h i n g with increasing m o l e c u l a r
weight a n d with increasing b r a n c h i n g of the molecule. Evapo r a t i o n rate also decreases with increasing m o l e c u l a r weight,
b u t increases with i n c r e a s e d branching, n-Butyl acetate, one
of the most i m p o r t a n t ester solvents, has a m e d i u m evaporation rate. It is used as a reference for expressing e v a p o r a t i o n
rates of o t h e r solvents.
Glycol Ethers
Glycol ethers are e t h e r alcohols, having b o t h ether a n d
alcohol functionality. The ethylene glycol ethers, derived
from ethylene oxide a n d alcohols, have been widely used in
coatings. However, b e c a u s e of health h a z a r d c o n c e r n s associated with certain ethylene glycol ethers, they are being rep l a c e d in m a n y a p p l i c a t i o n s b y p r o p y l e n e glycol ethers w h i c h
are derived from p r o p y l e n e oxide.
Glycol ethers have a truly unique c o m b i n a t i o n of p r o p e r ties: strong solvency, slow e v a p o r a t i o n rate, c o m p l e t e w a t e r
miscibility, high flash point, a n d m i l d odor. They are often
ASTM
Specification
Purity
Test,
ASTM
Specific
Gravity,
20/20~
Boiling
Point, ~
Evaporation
Rate,
n-BuAc = 100
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl isoamyl ketone
Methyl n-amyl ketone
Diacetone alcohol
Isophorone
D 329
D 740
D 1153
D 2917
D 4360
D 2627
D 2916
D 1363
D 2804
D 3329
D 3893
D 3893
...
D 2192
0.792
0.806
0.802
0.814
0.817
0.940
0.922
56
80
116
145
151
170
215
1160
570
165
50
40
12
3
Flash
Point,
TCC,~ (~
0
20
60
96
102
120
180
(-18)
( - 7)
(16)
(36)
(39)
(49)
(82)
Toluene
Dilution
Ratio
4.5
4.3
3.6
4.1
3.9
3.0
6.2
CHAPTER 18--SOLVENTS
129
Solvent
Methyl acetate
Ethyl acetate
Isopropyl acetate
n-propyl acetate
Isobutyl acetate
n-butyl acetate
n-amyl acetate
Methyl amyl acetate
n-hexyl acetate
n-butyl propionate
n-pentyl propionate
2-ethoxyethyl acetate b
PM acetatec
ASTM
Specification
Purity
Test,
ASTM
. . . . . .
D 4614~
D 3545
D 3131
D 3545
D 3130
D 3545
D 1718
D 3545
D 4615~
D 3545
D 3540
D 1617
D 2634
D 1617
D 5137
D 1617
. . . . . .
. . . . . .
D 3728
D 3545
D 4835
D 4773
Specific
Gravity,
20/20~
Boiling
Point, ~
Evaporation
Rate,
n-BuAc = 100
0.904
0.901
0.873
0.889
0.871
0.883
0.876
0.858
0.874
0.876
0.872
0.974
0.969
55
77
88
101
115
126
140
148
165
145
168
156
146
1180
410
360
230
145
100
40
20
17
45
18
20
34
Flash
Point,
TCC, ~ (~
0 ( - 18)
24 ( - 4 )
35 ( + 2)
55 (13)
62 (17)
81 (27)
101 (38)
96 (36)
134 (57)
100 (38)
135 (57)
126 (52)
114 (46)
Toluene
Dilution
Ratio
2.9
3.1
3.0
3.2
2.7
2.8
2.3
1.7
1.8
2.1
1.8
2.5
2.6
~Four grades.
bEthyleneglycol monoethylether acetate.
cPropylene glycolmonomethylether acetate.
Alcohols
Mcohols are chemically characterized as organic comp o u n d s having a single hydroxyl group. This structure imparts some degree of water solubility to alcohols, complete
for the lower members, methanol, ethanol, a n d propanol, a n d
partial for the higher m e m b e r s of the family. Alcohols are
further characterized physically as having mild, pleasant
odors. Typical properties of selected alcohols are s u m m a rized in Table 8.
By themselves, alcohols are very poor solvents or n o n solvents for most polymers. There are few exceptions; ethanol
is a solvent for shellac, poly(vinyl acetate), poly(vinyl butyrate), some phenolics, a n d n a t u r a l resins. Alcohols find applications as latent solvents or co-solvents for nitrocellulose
lacquers, m e l a m i n e - f o r m a l d e h y d e a n d urea formaldehyde
resins, a n d certain alkyds. They are also useful coupling solvents, with glycol ethers, to solubilize water-reducible resins.
I n addition to their use as solvents, latent solvents, a n d coupling solvents, alcohols are used as chemical raw materials
for the m a n u f a c t u r e of other solvents (e.g., ketones a n d esters), m o n o m e r s , a n d synthetic polymers.
Methanol is the fastest evaporating alcohol. It is the only
alcohol which has some solvency for nitrocellulose. Methanol, historically k n o w n as wood alcohol, is n o w rarely used as
a solvent because of its relative toxicity.
Pure ethyl alcohol (ethanol) is restricted in use by law to
beverages a n d to scientific a n d analytical purposes. It c a n n o t
be used without a federal g o v e r n m e n t permit. Commercial
ethyl alcohol, for solvent a n d chemical i n t e r m e d i a t e use, is
d e n a t u r e d with any of a large n u m b e r of government-approved substances to make it unfit for use in beverages. There
are close to 100 approved d e n a t u r e d f o r m u l a t i o n s available
in both 95 vol% (190 proof) a n d a n h y d r o u s (200 proof)
grades. Because of the large multiplicity of grades, ASTM
specifications have not been established for ethyl alcohol.
Isopropyl alcohol can replace ethyl alcohol in most coating
solvent applications.
Butyl alcohols (butanols) differ in volatility a n d solvency
a m o n g the four isomers, which are: normal, secondary, iso-,
a n d tertiary. All have moderate volatility. B r a n c h i n g increases volatility a n d decreases solvency, n - B u t a n o l is by far
the most widely used isomer, t-Butanol is a solid at r o o m
temperature.
Solvent
2-Methoxyethanol~
2-Ethoxyethanolb
2-ButoxyethanoF
Propylene glycol
monomethyl ether
Dipropylene glycol
monomethyl ether
ASTM
Specification
Purity
Test,
ASTM
Specific
Gravity,
20/20~
Boiling
Point, ~
Evaporation
Rate,
n-BuAc = 100
D 3128
D 331
D 330
D 4837
...
--.
...
D 4773
0.966
0.931
0.902
0.923
125
136
171
121
56
35
6
71
D 4836
D 4773
0.956
188
Flash
Point,
TCC, ~ (~
103
108
150
94
Toluene
Dilution
Ratio
(39)
(42)
(66)
(34)
4.0
4.9
3.5
5.2
167 (75)
4.2
130
Solvent
Methanol
Ethanol (anhydrous)
Isopropanol
n-Propanol
sec-butanol
Isobutanol
n-butanol
n-amyl alcohol
Methyl isobutyl
carbinol
2-ethyl hexanol
Purity
Test,
ASTM
Specific
Gravity,
20/20~
Boiling
Point, ~
Evaporation
Rate,
n-BuAc= 100
Flash
Point,
TCC, ~ (~
D 1152
E 346
. . . . . .
D 770
...a
D 3622
...4
D 1007
...a
D 1719
...a
D 304
...4
D 319
..-~
D 2635
...~
0.793
0.790
0.786
0.804
0.808
0.803
0.811
0.813
0.808
64
78
82
97
99
107
117
130
131
600
260
230
100
120
70
50
30
30
52
55
54
74
74
85
97
91
103
D 1969
0.834
182
<1
164 (73)
D 5008
(11)
(13)
(12)
(23)
(23)
(29)
(36)
(33)
(39)
Solubility, 20~
wt%
In Water
Water In
Complete
Complete
Complete
Complete
20.0
9.5
7.9
1.7
1.6
Complete
Complete
Complete
Complete
36.3
14.3
20.8
9.2
6.3
0.1
2.6
~Purityand identity of these pure compounds are determined by a combination of tests of specificgravity (ASTMD 268 or D 4052), boiling point, and distillation
range (ASTMD 1078).
Other Solvents
Chlorinated Hydrocarbons
Chlorinated solvents obviously c o n t a i n chlorine a t o m s in
the molecules. This gives t h e m u n i q u e features of non-flammability, i.e., no flash point, a n d very high specific gravity.
Several c h l o r i n a t e d solvents specified by ASTM s t a n d a r d s are
s u m m a r i z e d in Table 9.
Methylene chloride has long b e e n the active ingredient in
m o s t p a i n t removers. It has strong solvency to soften a n d
swell c u r e d p a i n t films a n d a very fast e v a p o r a t i o n rate.
1,1,1-trichloroethane ( m e t h y l c h l o r o f o r m ) has f o u n d solvent a p p l i c a t i o n s in coating f o r m u l a t i o n s b e c a u s e it is considered to be n o n - p h o t o c h e m i c a l l y reactive by m a n y regulatory agencies, a n d therefore it does not have to be i n c l u d e d in
m e a s u r i n g volatile organic c o m p o u n d (VOC) content [1].
Trichloroethylene is widely used for metal cleaning in vap o r degreasing operations. (See ASTM D 3698, Practice for
Solvent V a p o r Degreasing Operations.)
Use of c h l o r i n a t e d solvents is declining due to (a) global
c o n c e r n s a b o u t t h e i r d a m a g i n g effects on the earth's protective o z o n e layer a n d (b) c o n c e r n s a b o u t the toxicity a n d
carcinogenicity of m a n y c h l o r i n a t e d solvents.
Nitrated Hydrocarbons
N i t r o g e n - c o n t a i n i n g h y d r o c a r b o n solvents include nitroparaffins a n d N-methyl-2-pyrrolidone (NMP). These are not
currently specified b y ASTM s t a n d a r d s .
There are four nitroparaffinic solvents c o m m e r c i a l l y available: n i t r o m e t h a n e , nitroethane, 1-nitropropane, a n d 2-nit r o p r o p a n e (2NP). Of these, 2NP is of m o s t interest to the
coatings industry. It has an e v a p o r a t i o n rate s i m i l a r to t h a t of
n-butyl acetate, a n d it is r e p o r t e d to have fast solvent release
f r o m coating films.
NMP is a specialty solvent having strong solvency, high
flash point, c o m p l e t e w a t e r solubility, a n d high specific gravity. It is r e p o r t e d to be b i o d e g r a d a b l e a n d have a low o r d e r of
toxicity. Applications include p a i n t strippers, w a t e r - b a s e d
coatings, printing inks, a n d r e a c t i o n solvent for high-tempera t u r e resins.
ASTM
Specification
Grade or Application
D 3506
D 4079
D 4701
D 4126
D 4080
D 4081
Pentachlorophenol solutions
Vapor degreasing
Technical grade
General solvent; vapor degreasing
Vapor degrcasing
Dryclea-ning
Specific
Gravity,
20/20~
Boiling
Point, ~
Evaporation
Rate,
n-BuAc= 100
1.366
39
1450
1.327
1.465
1.625
72
86
121
600
450
210
CHAPTER 18--SOLVENTS
Supercritical Carbon Dioxide [7]
It has long been known that certain gases under supercritical temperature and pressure conditions can behave
as solvents. They have become useful in a variety of industrial
and analytical separation processes, such as extraction, polymer fractionation, chromatography, and catalyst regeneration, and as a reaction medium.
Supercritical fluids have properties intermediate to those
of normal liquids and gases. The supercritical fluid region on
a phase diagram corresponds to temperatures and pressures
near or above the critical point of the fluid where the properties of the liquid and gas are similar or identical, so that in
effect only one fluid phase, which is simultaneously liquidlike and gas-like, exists (Fig. 1).
Supercritical carbon dioxide has many useful attributes
which make it attractive as a diluent for spray-applied coatings. Carbon dioxide is environmentally compatible because
it is not regarded as a volatile organic compound (VOC). It
acts as a hydrocarbon diluent and replaces organic solvents
to the extent of 10 to 30 vol% of a formulation. Low VOC
coatings can be formulated with existing high-performance
polymer systems, and 70 to 80% reductions in VOC are
achievable. Using carbon dioxide as a coating solvent effects
a net reduction in the amount of "green house" carbon dioxide that is otherwise produced as a result of coating operations.
5000 _
1000
L,OUID
REGION/
/
_-
_
-
--
CRITICAL
POINT
SOLID
REGION
VAPOR
REGION
100
.,,.,,e
131
CLASSIFICATION
BY FUNCTION
Active Solvents
Active solvents are sometimes called "true solvents." They
are the ones that really do the work to dissolve resins and
other film formers. Active solvents are usually the more expensive ones with strong solvent power: ketones, esters, and
glycol ethers. They are essential for dissolving film-forming
resins and for effectively reducing viscosities of paints, varnishes, and lacquers for application.
Relative solvency of active solvents, particularly for lacquers, may be determined by ASTM method D 1720, Dilution
Ratio of Active Solvents in Cellulose Nitrate Solution, and
expressed in terms of toluene dilution ratio. Stronger solvents
will tolerate more hydrocarbon diluent and still keep resins in
solution. High toluene dilution ratio values indicate strong
solvency. Typical values for selected active solvents may be
compared in Tables 5 through 7.
Latent Solvents
By themselves, latent solvents are either poor solvents or
nonsolvents for most coating resins. However, they possess a
hidden or latent solvency which manifests itself when they
are used in combination with active solvents. Latent solvents
then behave as if they were strong active solvents. This synergism is used to advantage in formulating nitrocellulose lacquers in particular. Latent solvents are often alcohols, and
they are intermediate in cost.
RIPLE
POINT
==
Diluents
1
-160
-120 -80
-40
40
80
TEMPERATURE IN ~'F
120
Diluents are generally nonsolvents if used alone with synthetic resins. Their function is to participate in solvent blends
to provide viscosity reduction through dilution of lacquers
and paints and to reduce the cost of thinners and coating
2Union Carbide Chemicals and Plastics Co. Inc., 39 Old Ridgebury
Road, Danbury, CT 06817-0001.
132
Solvent Balance
In formulating coating solvents and thinners, careful attention must be paid to the proper balance of solvency and
evaporation rate. Generally, expensive active solvents are
kept to a minimum amount sufficient to provide adequate
solvency and viscosity reduction. Diluent content is usually
maximized to keep cost low.
Evaporation rate of each component must be considered in
selecting appropriate active solvents and diluents depending
on the method of coating application. As the applied coatings
dry, the balance of active solvents and diluents remaining in
the wet coating must be such that solvency for the coating
resin remains sufficiently strong throughout the drying process. Otherwise, resin blush, i.e., precipitation or separation
of the resin, can occur resulting in loss of gloss, incompatibility, haze, or other serious coating defects.
Kauri-Butanol Value
Kauri-butanol value (KBV) is one measure of the solvent
power of hydrocarbon solvents. High KBV indicates relatively strong solvency and often relatively high aromatics
content as well. Typical KBVs may be compared in Tables 1
through 4.
KBV is a continuous scale and is sometimes used as an
indicator of aromatics content; low aromatic (aliphatic) hydrocarbons have low KBVs and weak solvency, while highly
aromatic hydrocarbons have high KBVs and relatively strong
solvency. For example, odorless mineral spirits at the low end
of the scale has a KBV of about 27, regular mineral spirits
about 37, and aromatic hydrocarbons close to 100.
KBV is defined in ASTM Method D 1133, Kauri-Butanol
Value of Hydrocarbon Solvents, as the volume in milliliters of
the solvent at 25~ required to produce a defined degree of
turbidity when titrated into a specified quantity of a standard
clear solution of kauri resin in n-butyl alcohol. Kauri resin, a
natural product, now archaic, was once used as a coating
resin. However, standard test solutions are available from
chemical supply companies. The kauri resin solution is standardized against toluene, which has an assigned value of 105,
and a mixture of 75% n-heptane and 25% toluene on a volume
basis, which has an assigned value of 40.
The procedure is to accurately weigh 20 g of standardized
kauri-butanol solution into an Erlenmeyer flask and bring the
flask and its contents to 25~ in a water bath. It is then titrated
with the solvent being tested to a turbidity end point that
occurs when the sharp outlines of 10-point print on a sheet
placed under the flask are obscured or blurred but are not
illegible. Turbidity at the end point is caused by precipitation
of the kauri resin at incipient incompatibility.
This test is not applicable to oxygenated solvents.
Aniline Point
Aniline point (or mixed aniline point) is another measure of
solvency of hydrocarbon solvents. In addition, it is often used
to provide an estimate of the aromatics content of hydrocarbon mixtures. Aromatic hydrocarbons (strong solvents) exhibit the lowest aniline points and aliphatics (weak solvents)
the highest. Naphthenes have values between those for aromatics and aliphatics. In homologous series, the aniline point
increases with increasing molecular weight, i.e., decreasing
solvency.
Aniline point is defined in ASTM Method D 611, Aniline
Point and Mixed Aniline Point of Petroleum Products and
Hydrocarbon Solvents, as the minimum equilibrium solution
temperature for equal volumes of aniline and solvent. The
reagent for this test is aniline, a clear liquid at room temperature. The procedure requires that equal volumes of aniline
and hydrocarbon solvent are placed in a jacketed tube and
mechanically mixed. The basic apparatus is shown in Fig. 2,
although ASTM D 611 also describes alternative variations in
the manual apparatus and an automatic apparatus as well.
Hydrocarbon solvents containing less than 50% aromatics
will generally form an incompatible, turbid mixture at room
temperature [8]. Therefore, the stirred mixture is heated at a
CHAPTER 1 8 - - S O L V E N T S
~ .~ANILINEPOINT
IL -11tl
FIG. 2-Aniline point apparatus.
controlled rate until the two phases become miscible and
dear. The stirred mixture is then allowed to cool at a controlled rate until it suddenly becomes cloudy throughout. The
temperature at this end point is recorded as the aniline point
of the solvent.
Hydrocarbon solvents containing more than 50% aromatics will generally form dear, miscible solutions with aniline
at room temperature [8]. When this occurs, the stirred mixture must be cooled below room temperature at a controlled
rate until the cloudy transition point suddenly appears. The
temperature at this cloud point is the aniline point.
With hydrocarbons having high aromatics content, the aniline point may be far below room temperature and below the
temperature at which aniline will crystallize from the anilinesample mixture. To treat this circumstance, it becomes necessary to perform a "mixed aniline point" test. Instead of
using equal volumes of aniline and sample, a mixture containing two volumes of aniline, one volume of sample, and
one volume of n-heptane of specified purity is made. The test
is then performed as described above, and the result is reported as the "mixed aniline point." Again, low values indicate strong solvency (the opposite of kauri-butanol values).
Unlike the continuous KBV scale, a disadvantage of the
aniline point and mixed aniline point is that the two scales
are not continuous. Therefore, it is difficult to directly compare high- and low-aromatic content solvents [8].
This test is not applicable to oxygenated solvents.
133
Dilution Limit
Some resins are soluble at high concentrations in a solvent
but become incompatible and precipitate when diluted below
a critical concentration, which is termed the dilution limit.
Sometimes, this concentration is within the range of practical formulations. Therefore, it is important to know whether
a dilution limit exists for a particular resin. To determine the
dilution limit, a known weight of resin is dissolved in the
solvent. Solvent is then added until precipitation, the first
persistent cloudiness, appears. Dilution limit is expressed as
the percent by weight of resin at the end point [8].
Viscosity Reduction
The relative solvency of different solvents for a given resin
may be compared with each other or with a reference solvent
by measuring the viscosities of different concentrations of the
given resin in each of the solvents. The viscosities are then
plotted as a function of resin concentration. An example is
shown in Fig. 3 [I].
Viscosities of resin solutions can be measured precisely by
ASTM Method D 445, Kinematic Viscosity of Transparent
and Opaque Liquids, or by ASTM Method D 1725, Viscosity
of Resin Solutions. A simpler, more wideJy used, but less
precise method for determining resin solution viscosities is
ASTM Method D 1545, Viscosity of Transparent Liquids by
Bubble Time Method (Gardner-Holdt Viscosity).
At high resin concentrations, solution viscosity will depend
on solvency of the solvent and solubility of the resin. However, at low resin concentrations, the solution viscosity becomes more influenced by viscosity of the pure (neat) solvent.
Viscosities of selected solvents are listed in Table 10 [17].
134
5OO
100
50
j,
0.5
0.2 1
0
10
20
30
40
50
60
Solubility Parameters
Great strides have been made in developing theoretical
models to describe solvency and to predict the capacity of a
pure solvent or solvent blend to dissolve a given resin. The
concept of solubility parameters was first proposed by
Hildebrand [9,10], and it was applied to practical applications in the coatings industry by Burrell [11]. Further refinements and enhancements to the solvency model made by
Burrell [12], Crowley [13], Hansen [14,15], and others have
resulted in the evolution of a model that is workable, reasonably accurate in its predictions, and useful as a formulating
tool.
The three-dimensional solubility parameter is the most
widely used method for predicting miscibility/solvency between solvents and polymers. In this method, each polymer
and each solvent is characterized by three solubility parameters: 8d representing dispersion forces, 8p representing polar
forces, and 8h representing hydrogen bonding forces. Therefore, polymers and solvents can be represented by points in a
three-dimensional plot using the three solubility parameters.
Each polymer point may constitute the center of a sphere,
the so-called "sphere of solubility," of radius R, known as the
radius of interaction. Solvents whose points lie at a distance
less than R from the center of the polymer's sphere, i.e.,
within the sphere, should dissolve the polymer. Conversely,
solvents whose point coordinates lie outside of the sphere are
not expected to dissolve the polymer [16]. A more thorough
Hydrocarbons
VM&P naphtha
Mineral spirits
Toluene
Xylene
High-flash aromatic naphtha
0.68
1.10
0.62
0.67
1.08
Ketones
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl isoamyl ketone
Methyl amyl ketone
Isophorone
0.31
0.41
0.56
0.73
0.77
2.3
Esters
Ethyl acetate
Isopropyl acetate
Isobutyl acetate
n-butyl acetate
n-amyl acetate
Propylene glycol monomethyl ether acetate
Ethylene glycol monoethyl ether acetate
Ethylene glycol monobutyl ether acetate
0.45
0.52
0.68
0.68
0.83
1.1
1.2
1.7
Alcohols
Ethanol
n-propanol
i-propanol
n-butanol
s-butanol
n-amyl alcohol
1.1
2.0
2.4
2.6
2.9
3.7
Glycol Ethers
Propylene glycol monomethyl ether
Ethylene glycol monoethyl ether
Ethylene glycol monobutyl ether
1.7
1.9
2.9
Vapor Pressure
All liquids have a tendency to vaporize and become gases,
depending upon their relative vapor pressures. A solvent's
CHAPTER 18--SOLVENTS
liquid vapor pressure is the pressure exerted by molecules at
the liquid surface in their attempt to escape the liquid phase
and penetrate their gaseous environment. In a physical sense,
vapor pressure is the force exerted on the walls of a dosed
container by the vaporized portion of the liquid. Conversely,
it is the force which must be exerted on the liquid to prevent it
from vaporizing further. For a given liquid solvent, vapor
pressure is a function purely of temperature. The more volatile a solvent, the higher the liquid vapor pressure at a specified temperature and the faster the vaporization, i.e., evaporation rate. A knowledge of the vapor pressure/temperature
relationship is important in the safe design of solvent storage
and distribution equipment to minimize solvent losses by
vaporization.
Relative vapor pressures of pure solvents and blends are
measured at 100~ (38~ by ASTM Method D 323, Reid Vapor Pressure (RVP). The RVP apparatus consists of a doublechamber bomb fitted with a pressure gage. The lower chamber, which has one quarter the capacity of the upper chamber, is filled with the liquid solvent sample. The sample and
its chamber are chilled to 0~ (32~ to reduce premature
evaporation, the bomb is sealed, and it is immersed in a 100~
(38~ water bath. To assure full opportunity for vaporization, the bomb is removed from the bath periodically for a
brief vigorous shaking. When an equilibrium temperature is
reached and when the bomb pressure gage (which initially
registered zero) has stabilized at maximum value, the pressure is recorded. After applying appropriate correction factors, the pressure is reported as Reid vapor pressure at 100~
(38~
Alternatively, vapor pressure of a solvent can be measured
over a wide range of temperatures by ASTM Method D 2879,
Vapor Pressure by Isoteniscope. This procedure utilizes a
differential manometer, one leg of which is exposed to saturated vapor while the other is evacuated. Measurements are
reported in absolute units. Absolute vapor pressures of selected solvents at 20~ are listed in Table 11 [6,17].
Evaporation Rate
Evaporation rate of a solvent is second only to solvency in
its importance to the coatings industry. Although solvents are
transient ingredients of a coating, they perform vital functions but must ultimately leave the coating film by evaporation. During application of a coating, solvents play a role in
controlling flow characteristics as the film forms. If solvent
evaporation is too fast, the coating film will not level and flow
out to form a smooth surface, the result being a rough, "orange peel" effect in spray-applied coatings, or brush marks if
brush applied. Conversely, if solvent evaporation is too slow,
the coating may run and sag on vertical surfaces, or solvents
may become trapped in the film as it cures, thus impairing
performance properties of the coating.
Proper solvent balance, the ratio of active solvent to diluent, is also important. If this balance becomes upset as a
result of composition changes during evaporation, resin precipitation can occur, thereby causing a loss of film integrity.
Therefore, solvent evaporation rate is a key factor in the
formulation of coatings. Relative evaporation rates of selected solvents of various types may be compared in Fig. 4
and in Tables 1 through 9.
135
Vapor Pressure
at 20~ mm Hg
Hydrocarbons
VM&P naphtha
Mineral spirits
Toluene
Xylene
High-flash aromatic naphtha
5.2
3.4
38
9.5
<1
Ketones
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl isoamyl ketone
Methyl amyl ketone
Isophorone
185
85
16
4.0
1.0
0.3
Esters
Ethyl acetate
Isopropyl acetate
Isobutyl acetate
n-butyl acetate
n-amyl acetate
Propylene glycol monomethyl ether acetate
Ethylene glycol monoethyl ether acetate
Ethylene glycol monobutyl ether acetate
76
48
12.5
7.8
4.0
3.7
1.7
0.29
Alcohols
Ethanol
i-propanol
n-propanol
s-butanol
n-butanol
n-amyl alcohol
44
31
15
12
4.4
2.0
Glycol Ethers
Propylene glycol monomethyl ether
Ethylene glycol monoethyl ether
Ethylene glycol monobutyl ether
11
4.1
0.9
136 P A I N T A N D C O A T I N G T E S T I N G M A N U A L
Aliphatic
Aromatic
HC
I~o_
Glycol
HC
Ketones
Ethers
Acetates
Alcohols
Others
~-H-exane~ACetone_R~l~
Methylene
Chloride
8O~ .
Cyclohexane~j
7 ~ ' i ~
~H e, .p't a n ]e i ' : ~i [ i
60~_!
II! ~;
:K'
50~
' ~
''"
1,1,1-Tri-
'
i~h~0roethane
Benzene
40~_
Lacquer~
~Diluent
i ITrichloro-
~ E t h y l i
[I I : '
....
] , ! 1 - ~ 1 :
I
Isopropyl=
~: ;
3D~
.I,,
:VM&P
Napht~
20~_
;Iii:i}I
;~iI]~Ii
~J:l,l;!:
Toluene
! I I ! I '
,
Lj
i
t
[9
-Isopropyl:
9i ; i i 1 .;:,
...
i,,
Isobutyl
Illli
'
~
,
'~
~
'~
~,
50_
'~-----:
'
7o_
0 ii
i,'~/;,,
ill. i i l l ~ l
'li~
~lil
~lil
2-Nitro--
n - P r o p y l _ ~
9C}
.80_
~o
li
I : :
n-Prop:
, ~
"
thyle?e
Il eetl
:ij,:ii'i,!ii:i
~ , ~
iiiii!:
:t
!i i; '
. .. ;~ ~_
Xylene=
..
.
~Methoxypropanol
s e c. - Bc u-t yBl ~ u t y l ~ ~
I E E E ~
Isobutyl-
~Metho
=ethanol
4o_ ~
_~
30_
20_
- ~
~
O~
::
n-Butyl
~
~
__
propyl
~= W a t e r
Turpentine
~ a
.
n o l ~~ A
iii
i_
~m
Ethoxyethyli
"Aromatic-
n.-
i'
. ~~
i
lOO
I
:: I 1:
. . .: . I
: :'
Mineral I
,,
Spirits
l
,
]o_.
9
7_.
6_
5_
'
'
; ; :; ; :
!II
ii',,
, I i
. ~, , I i [ , ,
=__
'
:i
I!
Aliphatic
HC
! I I!
',,,
I i I
I',,
'
! I'
,. . .. ., ,
~"
:,,,,
' ! I ~ . . . .
, i
, ~: :
; I,,,
....
- propanol~
pentene
:, ~ :
.......
ii;:,
===
~
~ethanol~--
....
1,
i !
.,. t I
,i,,,lili~,!!!
:,,,
Aromatic
HC
i ! i
,','~~
; i i L I ; ili ; i I i i i
=
, ~!;
li,i~!
IsophoroneJ,
i : i I, I
B
u
t
oxyethy
li' ~ ,u,,,
!
!
i I I i
'
,J!;,llltil
i I:l
i i
! ! ,, ',
,
i!!il:J
; : ~ i ~~i
I ~ , l l l i i I t
::
,,,,
.....
150
iil
I ! 1',
'~Aromatic
Deodorized
2-'t K e r o s,esneen e
L,
ill
Alcohol
~-.
Amyl~-
DiacetonelJiii
I ;
,
, ' '
....
, ,,
; ! i
l,aliiii
'
.
:
J ii i
- ,!~
--Methyl
". . . .
Ketones
Ill
i.!1
t!
~ ,i - I
! i i
I -~
! i
,,
i '. i
I : : i 11
DE(IMEi
:~lil!
jR
l
[
I] :
I
~ !
~ , ;
' ~
i!
,
'
',
-~
'.
ill
'~
'
,it
Acetates
,~
!1
DEGEE d
Glycol
Ethers
FIG. 4 - R e l a t i v e s o l v e n t e v a p o r a t i o n r a t e s .
Alcohols
Others
CHAPTER 18--SOLVENTS
solvent is spread on a known area of filter paper that is suspended from a sensitive balance in a controlled environment
cabinet. Weight loss of the filter paper/solvent liquid is measured as a function of time as the solvent evaporates.
Early models of the apparatus use a Jolly spring as the
gravimetric measuring device and require manual measurement of weight and time (Fig. 5). More recent models employ
an electrobalance and automatically record weight loss versus time (Fig. 6). The Shell Thin-Film Evaporometer and the
Chevron Research Evapograph operate under similar principles.
The basic procedure with both the manual and automatic
instruments is similar. The evaporation chamber and sample
are conditioned to 25~ (77~ Airflow rate (21 L/rain) and
relative humidity (less than 5%) in the chamber are set. A
filter paper, 90 m m in diameter, is horizontally suspended in
the evaporation chamber from the weight-sensing device.
The solvent sample (0.7 mL) is added from a hypodermic
syringe and distributed over the entire area of the filter paper
within a period of 10 s. Data are reported as time in seconds
for 10% solvent weight increments through the evaporation
cycle, and they are plotted as percent solvent evaporated
versus elapsed time (for example, see Fig. 7) [8,18]).
The procedure is repeated using n-butyl acetate as the reference standard. Elapsed time for 90% evaporation of specimen and standard are determined. Evaporation rate of the
solvent specimen is calculated as the ratio of 90% evaporation time for n-butyl acetate standard divided by the 90%
evaporation time for the solvent specimen and normalized so
that the evaporation rate of n-butyl acetate is 100 (or 1.0). The
90% evaporation time is generally used since some curvature
of the plot usually occurs above that data point. Evaporation
plots for pure solvents are nearly straight lines. Solvent mixtures or blends produce curved plots, the curvature becoming
more extreme as differences in the evaporation rates of individual blend components become greater. Several solvent
AIB
137
,=,, ~-~
ROT(
ORT
BRACKET
AIR
FIG. 5 - T h i n 4 i l m evaporometer,
138
100 - -
8O
40
20
0P"
0
10
2o
30
40
50
60
70
8o
Time. Minutes
FIG. 7-Evaporation rates of typical solvents (Chevron Research Evapograph at 80~
CHAPTER 18--SOLVENTS
139
I~F
at
--
I Xylene
"
Xylene from
9e . . .
,.c
60
.O
60
20
40
80
120
160
200
240
260
300
i ATM.
SOLVENT
VAPOR
PRESSURE
maHg
xlO0
TEMPERATURE
Boiling
Point
140
800
64)0
400
300
I00
80
60
C
40
30
20
lO
8
6
4
3
2
1
60
80
100
120
140
160
180
200
Flash Point
CHAPTER 18--SOLVENTS
141
Sample Type
ASTM D 86,
Wide-Boiling
Hydrocarbons
ASTM D 8 5 0 ,
Narrow-Boiling
Aromatics
ASTM D 1078,
Narrow-Boiling
Oxygenated
(and others)
Sample size, mL
Distillation flask size, mL
Number of specified thermometers
Insulating shield hole size, mm
Condenser temperature, ~
Rate of heat up to IBP, time, min
Rate of distillation, mL/min
95% point to EP, time, min
100
125
2
50
0-6~
5-15 a
4-5
5
100
200
8
25-50 a
10-20
5-10
5-7
.--
100
200
14
38
0-5~
5-154
4-5
5
.--Thermometer
Distillation.
Flask
Condenser~
'
Insulation ~
rd// IIII
~/Graduated
Cylinder
Shleld-.....~.
Burner ~
must be emphasized that these phenomena apply only to equilibrium, closed systems. F o r h y d r o c a r b o n solvents, the LEL is
usually a b o u t 1 vol% solvent v a p o r in air, a n d the UEL is
a b o u t 7 vol%, b u t for oxygenated solvents, these values can
vary over a wide range.
Flash p o i n t is one i n d i c a t o r of the relative f l a m m a b i l i t y
h a z a r d of solvents a n d solvent-containing products. The U.S.
D e p a r t m e n t of T r a n s p o r t a t i o n (DOT) a n d the U.S. Departm e n t of L a b o r (OSHA) designate "flammable liquids" as
those having flash points b e l o w 100~ (38~
These require
special p a c k a g i n g a n d handling. I n t e r n a t i o n a l cargo regulations specify a 140~ (60~ flash p o i n t as the u p p e r limit for
"flammable liquids." In a d d i t i o n to being used to classify
m a t e r i a l s in g o v e r n m e n t regulations, flash p o i n t limits are
142
often listed as one of the requirements in solvent specifications, for hydrocarbon solvents in particular. Flash point may
also be used to indicate the presence of impurities or contaminants in a given liquid, such as the presence of residual
solvents in solvent-refined drying oils.
Flash point is roughly inversely proportional to volatility.
The most volatile solvents tend to have the lowest flash
points, which are indicative of the greatest fire hazard. With
mixtures of miscible solvents, the component having the
CHAPTER 18--SOLVENTS
I/EL ~
6
SOLVENT
:~
~4 , ~ ,~- '
ii ~' :
+v~!+i- i . . . . .
I~
9
~I~
/,~
~0
F][.R~
---
--
I I I I I I 116
t
I
I
i
~
]
I
I
~
I
I
I
I
1
[
I
) ]
] J
[ i
I1
I
I
I
i
1l
I J
[ I
I I
1.5
'
~_
?-l!![!ii!!
ii j pili,~j
j~i~,~j],~jl]~kllj,ll]
I~kI I'~kl I'll] I [~11[11!1;I
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~
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Flash
Point
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I I I I i I i I 11111 ]li i II|
I ]llllllllll/[lllIll
6
7
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TEMPERATURE
144
03
j
r
FIG. 15-Tag open-cup flash point tester.
The s p e c i m e n is heated in a closed cup of s t a n d a r d design
in a suitable w a t e r b a t h at a rate of 1.O~ (0.5~ in not less
t h a n 1.5 rain so that the difference in t e m p e r a t u r e b e t w e e n
the s p e c i m e n in the cup a n d the b a t h never exceeds 3.5~
(2.0~
Flash d e t e r m i n a t i o n s are m a d e at intervals of n o t less
t h a n 1.5 rain. Since the s p e c i m e n is heated at a r e d u c e d rate,
a longer t i m e interval b e t w e e n each d e t e r m i n a t i o n is necessary to re-establish the s a t u r a t i o n c o n c e n t r a t i o n of v a p o r in
the air space above the s p e c i m e n after each flash test.
Equilibrium Flash~No Flash--ASTM M e t h o d D 3934, Flash/
No F l a s h T e s t - - E q u i l i b r i u m M e t h o d by Closed-Cup A p p a r a tus, does not d e t e r m i n e a finite flash point, b u t it verifies
w h e t h e r o r n o t flashing occurs at a single specified t e m p e r a ture, w h i c h m a y be a p r o d u c t specification or agency requirement. The d e t e r m i n a t i o n is m a d e m o r e a c c u r a t e b y ensuring
that the flash test is carried out only w h e n the m a t e r i a l u n d e r
test a n d the air/vapor mixture above it are in a p p r o x i m a t e
e q u i l i b r i u m at the specified t e m p e r a t u r e .
t,
PHYSICAL PROPERTIES
Density and Specific Gravity
Significance
Specific gravity is an i n h e r e n t p r o p e r t y w h i c h is listed as a
r e q u i r e m e n t in all solvent specifications a n d is often used to
set specifications. It is a good, simple, qualitative test w h e n
used with o t h e r tests to establish or confirm the identity of a
solvent. I n addition, it is useful for quality control, to provide
CHAPTER 18--SOLVENTS
PILOT~ ~ . ~
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Definitions
TYPE(FLAMETYPESHOWN) ~
145
l
IN CONTACTWITHTHE
INNER FACEOF COVER
THROUGHOUTITS
CIRCUMFERENCE
146
represented by:
141.5
131.5
sp gr 60/60~
No statement of reference temperature is required, since
60~ is included in the definition. API gravity applies
specifically to crude petroleum and to petroleum products such as hydrocarbon solvents. Gravities are determined at 60~ (15.56~ or are converted to values at 60~
by means of standard tables. These tables are not applicable to nonhydrocarbons nor to essentially pure hydrocarbons such as the aromatics.
A brief discussion of these definitions may be useful. In
scientific terminology, mass is a measure of the quantity of
material in a body, and it is constant regardless of geographical location, altitude, or atmospheric conditions as long as no
material is added or taken away. Weight is the force with
which a body is attracted to the earth, and it varies from place
tO place with the acceleration of gravity.
When an equal-arm balance is used to compare an object
with standards of mass ("weights"), the effects of variations in
the acceleration of gravity are self-eliminating and need not
be taken into account, but the apparent mass of the object is
slightly different from the true mass because of the buoyant
effects of the surrounding air. Mass can then be computed
from apparent mass by applying a correction for air
buoyancy. When a spring balance is used, an additional correction accounting for the local value of the acceleration of
gravity is required for the computation of mass.
For many commercial and industrial processes the scientific distinction between mass, apparent mass, and weight is
of no practical consequence and is therefore ignored. The
term "weight" in general practice has been accepted as being
the value secured when an object is weighed in air. This
"weight" or "weight in air" is often converted to "weight in
API gravity, degrees -
Hydrometer Methods
Hydrometer methods are the quickest, simplest means for
measuring density, specific gravity (relative density), and API
gravity, especially in the field. These methods are based on
the principle that the specific gravity of a liquid varies directly
with the depth of immersion of a body floating in it. The
floating body, called a hydrometer, is graduated in units of
density, specific gravity, or API gravity units. Hydrometers
are useful when accuracy to three decimal places is adequate.
The sample is brought to the prescribed temperature, and it
is transferred to a clear glass or plastic cylinder which is at
approximately the same temperature. The appropriate hydrometer, having the scale of interest, is lowered into the
sample and is allowed to float freely and settle. After temperature equilibrium has been reached, the hydrometer scale is
read. Note is made of the hydrometer scale graduation nearest to the apparent intersection of the horizontal plane surface of the liquid (Fig. 20). Temperature of the sample is read
from a separate thermometer or from a thermometer integrated into the design of the hydrometer.
Detailed descriptions of test methods for the proper use of
hydrometers can be found in ASTM Method D 891 (Method
j,,,
SEE DETAIL
LIQUID-
HORIZONTALPLANE
SURFACEOF LIQUID
- BOTTOMOF
MENISCUS
Tubing
Line Cut
Lmond Pencil
READSCALE
O.D.
~ ' i
DETAIL
FIG. 20-Hydrometer and Meniscus detail.
A), Specific Gravity, Apparent, of Liquid Industrial Chemicals; ASTM Method D 287, API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method); and ASTM
Method D 1298, Density, Relative Density (Specific Gravity),
or API Gravity of Crude Petroleum and Liquid Petroleum
Products by Hydrometer Method.
For hydrocarbon solvent naphthas, values can be measured
on a hydrometer at convenient temperatures, the readings of
density may then be reduced to 15~ and readings of relative
density (specific gravity) and API gravity at 60~ are obtained
by means of international standard tables. By means of these
tables, values determined in any one of the three systems of
measurement are convertible to equivalent values in either of
the other two systems so that measurements may be made in
the units of local convenience.
Pycnometer Methods
Pycnometer methods for measuring specific gravity are
more accurate and precise than hydrometer methods. They
are used when accuracy to four or more decimal places is
required. ASTM Method D 891 (Method B), Specific Gravity,
Apparent, of Liquid Industrial Chemicals, describes the general test method for using a pycnometer.
A pycnometer is a tared vessel which is filled with water
and weighed. It is then filled with the sample and weighed.
Water, sample, and pycnometer are at a specified temperature. The ratio of the weight of sample to weight of water in
air is the apparent specific gravity.
Bingham Pycnometer--A Bingham-type pycnometer may
be used when density or specific gravity needs to be determined to five decimal places (Fig. 2 I). Its use is described in
ASTM Method D 1217, Density and Relative Density (Specific
Gravity) of Liquids by Bingham Pycnometer.
The pycnometer is first carefully calibrated by determining
the weight of freshly boiled and cooled distilled water (distilled from alkaline permanganate through a tin condenser)
148
50 to 55 ~
.,-'8L
~6L4"
h,.
r--2
~illary
0.9 to 1.1, Uniform
: 01 Percent
oughout Scale Length
). - - 6.0 Max.
Juations
rt Lines at Each I mm
]er Lines at Each 5 mm
ibered as Shown
~"
~o
)
_+0.5 mL Capacity,
P. - - Approx. 20
Weight
30G Max.
Material-Pyrex Glass
ASTM Method D 2935, Apparent Density of Industrial Aromatic Hydrocarbons, describes the measurement of apparent
density in pounds (in air) per U.S. gallon at convenient temperature using a hydrometer and reporting values at any
specified temperature. This method contains tables of
"pounds in air per U.S. gallon" versus temperature. It applies
only to the following solvents: benzene, toluene, mixed xylenes, o-,m-,p-xylenes, ethylbenzene, and cyclohexane.
ASTM Method E 201, Calculation of Volume and Weight of
Industrial Chemical Liquids, presents tables for use in calculating the volume and weight of the following solvents: acetone, ethyl acetate (85 to 88 wt%), ethylene dichloride, ethylene glycol monomethyl ether, isobutyl alcohol, isopropyl
alcohol (anhydrous), isopropyl alcohol (91 vol%), methyl
ethyl ketone, methyl isobutyl ketone, and perchloroethylene.
A method is given for calculating the volume at 60~ from a
volume observed at another convenient temperature. (Tables
at 20~ can be calculated from the data and information
provided.)
Also, a method is given for determining the weight in
pounds per U.S. gallon (in air) at 60~ from an observed
specific gravity and to compute therefrom the weight in
pounds of a given volume of the liquid in U.S. gallons at 60~
Color
Platinum-Cobalt Color
ASTM Method D 1209, Color of Clear Liquids (PlatinumCobalt Scale), describes a procedure for the visual measurement of the color of nearly colorless liquids. It is used for all
oxygenated solvents, most other solvents, and is gradually
CHAPTER 1 8 - - S O L V E N T S
TABLE 13--Approximate comparison of platinum-cobalt and
Sayboh color scales.
Lightest
Dark amber
Platinum-Cobalt Color,
ASTMO 1209
Saybolt Color,
ASTMD 156
0
10
20
30
40
50
70
100
150
180
200
250
300
+ 30
+28
+26
+23
+21
+19
+ 15
+ 10
+3
0
- 3
-8
- 23
149
Odor
Odor is an inherent, characteristic property of most solvents. Evaluation of the characteristic odor by a trained person is a quick and simple means of identifying a solvent
(when combined with other tests) as well as for determining
its suitability for an application from an odor point of view.
Residual odor can be used to detect the presence of lowvolatility materials that may be associated with manufacture,
product degradation, or contamination during distribution.
ASTM Method D 1296, Odor of Volatile Solvents and Diluents, describes procedures for testing both the characteristic
and residual odors of solvents. It involves dipping strips of
filter paper into the sample and into a reference standard. To
judge characteristic odor, an immediate comparison is made
between the odor of the sample and reference standard on the
filter paper. Residual odor is judged by permitting the papers
to dry in air at room temperature and examining them at
suitable time intervals for differences in odor.
Electrical Resistivity
Control of electrical resistivity is critical to the application
of electrostatically sprayed coatings. It impacts the transfer
efficiency (efficiency of paint application), coating appearance, and economics. Electrical resistivity of the paint must
be properly adjusted to obtain optimum atomization characteristics and deposition. The adjustment is mainly accomplished through appropriate selection of solvents [36]. Nonpolar solvents, such as hydrocarbon solvents, have high electrical resistivity (low conductivity). Polar solvents such as
ketones, alcohols, glycol ethers, and esters generally have low
electrical resistivity (high conductivity), although some (e.g.,
higher molecular weight esters) have high resistivity. Typical
values for commercial solvents are shown in Table 14.
An ASTM method, Electrical Resistivity of Liquid Paint
and Related Materials is currently under development. It describes the use of two different test meters and probes,
Ransburg and BYK-Gardner. Electrical resistivity values are
often expressed in terms of "Ransburg megohms," which are
read from the meter scale. Multiplication of these values by
an appropriate cell constant, which is typically about 132,
converts Ransburg megohms to specific resistivity in megohm-era units.
Refractive Index
Saybolt Color
ASTM Method D 156, Saybolt Color of Petroleum Products, is used most often to measure the color of hydrocarbon
150
>20
<1
<1
<1
6
16
>20
3
3
TABLE 15--ASTM gas chromatography methods for analyzing purity and composition of
solvents.
Compound
Method
Benzene
D 4492
n-butyl acetate
/-butyl acetate
Cyclohexane
Dipropylene glycol
monomethyl ether
Ethanol (SD-3A)
2-ethoxyethyl acetate
D 3545
D 3545
D 3054
D 4773
Ethyl acetate
D 3545
Ethylene glycol
n-heptane
Methanol
Methyl amyl ketone
Methyl ethyl ketone
Methyl isoamyl ketone
Methyl isobutyl ketone
E 202
D 2268
E 346
D 3893
D 2804
D 3893
D 3329
E 1100
D 3545
Compound
Method
Mineral spirits
(aromatics content)
/-octane
n-propyl acetate
i-propyl acetate
i-propyl benzene
D 3257
Propylene glycol
Propylene glycol
monomethyl ether
Propylene glycol
monomethyl ether
acetate
1,1,1-trichloroethane
Trichlorotrifluoroethane
Turpentine
Xylenes (mixed)
o-xylene
p-xylene
E 202
D 4773
D
D
D
D
2268
3545
3545
3760
D 4773
D
D
D
D
D
D
3742
3447
3009
2306
3797
3798
CHAPTER 18--SOLVENTS
Any material other than the carrier gas going through the
detector will cause a peak to be plotted on a recorder chart.
The time required for a component to flow through the
column, under a given set of operating conditions, when
compared to the time for known compounds, helps to
identify the component. The amount of that component is
proportional to the area under the recorder chart peak. Modern gas chromatographs often have a digital integrator which
prints out the elution time and the area under the peak.
Temperature, column length and size, type and amount of
stationary liquid phase, carrier gas pressure and flow rate,
and sample size are some of the variables that can be changed
to effect desired separations.
Versatility of gas chromatography in solvent analysis is
very great. Good ASTM references on gas chromatography
include "ASTM Standards on Chromatography," second edition; ASTM Practice E 260, packed Column Gas Chromatography; and ASTM Practice E 355, Gas Chromatography
Terms and Relationships. Specific ASTM GC methods for
analyzing the purity and composition of solvents are listed in
Table 15.
nA
nA1
(9
.>_
ns
e-
n"
ne
t,,_
Liquid Chromatography
There are two ASTM methods which utilize a liquid chromatography procedure for measuring the volume percentages of aromatics, olefins, and saturated aliphatics (paraffins
and naphthenes) which comprise a hydrocarbon solvent
naphtha. Both methods involve the physical separation of
these hydrocarbon types by passing the hydrocarbon sample
through a tube packed with silica gel. The technique is based
on the principle that polar compounds are adsorbed more
strongly by silica gel than are nonpolar saturated compounds.
A hydrocarbon solvent sample is passed through a glass
column packed with silica gel. Then, alcohol, which is more
strongly adsorbed than any hydrocarbon, follows the sample
through the column, desorbing and forcing the hydrocarbons
out. Saturated compounds are eluted first, unsaturated compounds next, and then aromatics.
In ASTM Method D 936, Aromatic Hydrocarbons in OlefinFree Gasolines by Silica Gel Adsorption, small samples of the
emerging sample are periodically collected. The refractive
index of each fraction is measured. From this information,
the relative percentages of aliphatics and aromatics can be
determined, as illustrated in Fig. 23. Precision is good, but the
procedure is slow.
ASTM Method D 1319, Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption (FIA),
is a refinement of the silica gel adsorption procedure. A mixture of fluorescent dyes is added to the hydrocarbon solvent
sample before it is put into the silica gel column. When all of
the sample has been adsorbed on the silica gel, alcohol is
added under pressure to desorb and force the sample down
the column. The fluorescent dyes are also selectively separated with the sample fractions, and they make the boundaries of the aromatics, olefins, and saturates clearly visible
under ultraviolet light. The zone of aromatics fluoresces violet, and the zone of olefins fluoresces a chartreuse color. The
zone of paraffins plus naphthenes remains colorless. Volume
percentage of each hydrocarbon type is determined by mea-
151
VI
Saturates
Portion
VII
~mL~
VrV
VIII
End
Portion
~,~ Aromatic
Podion
|
(Aromatios
and
Ak~oho0
Volume of Percolate
I
FIG. 23-Typical adsorptogram by ASTM Method D 936.
suring the length of each zone in a long, narrow extension of
the silica gel column.
Purity o f Ketones
ASTM Method D 2192, Purity of Aldehydes and Ketones, is
an alternative to gas chromatography for measurement of the
purity of ketone solvents. This is a wet chemical procedure
and is applicable for testing ketones having greater than 98%
purity.
The test is based on the reaction of ketones with hydroxylamine to form an oxime. Hydroxylamine hydrochloride is
first converted in part to free hydroxylamine by reaction with
a known amount of aqueous triethanolamine.
H2NOH.HCI + (HOCH2CH2)3N
) H2NOH +
(HOCH2CH2)3N.HC1
152
Purity of Esters
ASTM Method D 1617, Ester Value of Solvents and Thinners, is an alternative to gas chromatography for the measurement of purity of ester solvents. It may also be used for
determining the ester content of lacquer thinners.
This is a wet chemical test and involves the reaction of the
solvent sample with a measured excess of aqueous potassium
hydroxide, using isopropanol as a mutual solvent if necessary
R~COOR 2 + KOH
IMPURITIES
Acidity
Solvents may have residual acidity from manufacturing
processes, or acidity may be present as a result of contamination or decomposition during storage or distribution. Acidity
is undesirable since it may cause corrosion of storage tanks
and lines. Also, it may cause reactions with basic pigments
resulting in color changes.
ASTM Method D 847, Acidity of Benzene, Toluene, Xylenes, Solvent Naphthas, and Similar Industrial Aromatic Hydrocarbons, expresses acidity in terms of milligrams of sodium hydroxide consumed when 100 mL of sample are
titrated using phenolphthalein indicator. If two drops or less
of standard 0.1 N sodium hydroxide solution produce a persistent pink end point, the sample is reported to contain no
free acid.
ASTM Method D 1613, Acidity in Volatile Solvents and
Chemical Intermediates Used in Paint, Varnish, Lacquer, and
Related Products, expresses total acidity in terms of weight
percent acetic acid or as milligrams of sodium hydroxide
required to neutralize one gram of sample. The test is performed by mixing 50 mL of sample with an equal volume of
water (or with an equal volume of alcohol if the sample is not
water soluble) and titrating with aqueous 0.05 N sodium hydroxide solution to the phenolphthalein end point.
Alkalinity
ASTM Method D 1614, Alkalinity in Acetone, specifically
covers the determination in acetone of alkalinity calculated
as ammonia (NH3). The sample is added to an equal volume
of water previously neutralized to the methyl red indicator
end point. If alkalinity is detected, it is titrated with 0.05 N
sulfuric acid and is reported as weight percent ammonia.
Benzene Content
Benzene is classed as a toxic and carcinogenic compound.
A knowledge of the concentration of benzene may be an aid in
evaluating the possible health hazards to persons handling
and using solvents, but the ASTM test methods are not intended to evaluate such hazards. In addition, benzene content is an important specification requirement for aromatic
hydrocarbons used as chemical intermediates.
ASTM Method D 4367, Benzene in Hydrocarbon Solvents
by Gas Chromatography, may be used to determine benzene
content of hydrocarbon solvents at levels from 0.01 to I vol%.
An internal standard, methyl ethyl ketone (MEK), is added to
the solvent sample, which is then introduced into a gas chromatograph equipped with two columns connected in series.
The specimen passes first through a column packed with a
nonpolar stationary liquid phase, methyl silicone, which separates components by boiling point. After octane has eluted,
the flow through the nonpolar column is reversed, flushing
out components higher boiling than octane. The octane and
lighter components then pass through a column with a highly
polar phase, 1,2,3-tris(2-cyanoethoxy)propane, which separates the aromatic and nonaromatic compounds. The eluted
components are detected by a conventional detector and are
recorded on a strip chart. Peak areas are measured, and the
concentration of benzene is calculated by reference to the
internal standard.
ASTM Method D 4534, Benzene Content of Cyclic Products
by Gas Chromatography, applies to cyclohexane, toluene,
individual C8 aromatics, cumene, and styrene. Benzene may
be determined over a range from 5 to 300 mg/kg (5 to
300 ppm). The test is performed with a gas chromatograph
equipped with a flame ionization or other detector and a
column containing a polar stationary liquid phase such as
tetracyanoethylated pentaerythritol. A reproducible volume
of sample is injected. Quantitative results are obtained from
the measured area of the recorded benzene peak by using a
factor obtained from the analysis of a blend of known benzene content.
CHAPTER 18--SOLVENTS
Nonaromatic Hydrocarbons in Aromatics
ASTM Method D 2360, Trace Impurities in Monocyclic Aromatic Hydrocarbons by Gas Chromatography, covers the
determination of total nonaromatic hydrocarbons and trace
monocyclic aromatic hydrocarbons at levels of 0.0005 to 1
percent by weight in high-purity benzene, toluene, and mixed
xylenes by gas chromatography. This inspection is of particular importance when these high-purity aromatics are used as
chemical intermediates.
This test method is performed using an internal standard,
n-butylbenzene, added to the specimen which is then introduced into a gas chromatographic column. The sample
passes through the column, which contains a polyethylene
glycol stationary liquid phase, and it is separated into nonaromatic and aromatic components. The components are detected by a flame ionization detector as they elute from the
column and appear as peaks on the chromatogram. Peak
areas are measured, and the concentration of the composite
nonaromatics and each trace aromatic component is calculated with reference to the internal standard.
Nonvolatile Residue
ASTM Method D 1353, Nonvolatile Matter in Volatile Solvents for Use in Paint, Varnish, Lacquer, and Related Products, describes the analytical measurement of residual matter
in solvents that are intended to be 100% volatile at 105 +_ 5~
Volatile solvents are used in the manufacture and application
of paint, varnish, lacquer, and other related products, and the
presence of any residue may affect the product quality or
efficiency of the process.
Nonvolatile residues may consist of oil contamination, dissolved solids, rust, sand, or dirt. Trace oil contamination,
which could cause cleaning solvents to leave an objectionable
deposit of oily residue, often will not be detected by any other
specification test.
This test is performed by evaporating to dryness 100 mL of
solvent in a carefully cleaned, dried, and tared evaporating
dish of platinum, aluminum, ceramic, or glass, first on a
steam bath and then in an oven at 105 _ 5~ Weight of any
residue remaining in the dish is determined, and the result is
reported as milligrams of nonvolatile residue per 100 mL.
153
Sulfur Content
Crude petroleum usually contains traces of sulfur compounds, the greater proportion of which are generally removed during refining since they might otherwise cause objectionable corrosive tendencies and foul odors in refined
products such as hydrocarbon solvents. There are several test
methods which directly measure sulfur content or which indicate their presence indirectly.
154
Doctor Test
The Doctor Test is a very sensitive qualitative test for detecting hydrogen sulfide and mercaptan sulfur in hydrocarbon solvent naphthas. It is described in section 6.1.10 of
ASTM Specification D 235 for Mineral Spirits.
The test is performed by vigorously shaking together in a
test tube the solvent being tested and an aqueous sodium
plumbite solution. A small amount of pure, dry flowers of
sulfur is added so that practically all of it floats on the interface between the solvent and the sodium plumbite solution
after shaking. If the solvent is discolored or if the yellow color
of the sulfur film is noticeably masked or discolored and
blackened, the test is considered positive and the solvent is
reported as "sour." If the solvent remains unchanged in color
and the sulfur film is bright yellow or only slightly discolored
with gray or flecked with black, the test is considered negative
and the solvent is reported as "sweet."
SO 3 -1- 31- + 2H +
~13 + 2e-
Water Content
Dissolved water can have adverse effects on solvent end-use
applications. For example, it can reduce solvency. Water can
cause reactions with isocyanates during polyurethane preparation and with moisture-cure polyurethane paints and varnishes causing polymerization and gelation during storage.
Metallic pigments can react with water to generate hydrogen
gas, which can expand and burst paint cans. Dissolved water
can act as a catalyst poison when a solvent is used as a
reaction diluent for polyolefin polymerization.
~ 2C5H5N.HI + C5H5N.SO 3
~ CsHsN-HSO4R
CHAPTER 18--SOLVENTS
in a 1 : 19 p r o p o r t i o n a n d agitating. A clear solution indicates
miscibility a n d low w a t e r c o n t e n t (less t h a n a b o u t 0.5 wt%) in
the solvent sample. A t u r b i d solution indicates i m m i s c i b i l i t y
a n d the presence of high w a t e r content in the solvent sample.
Water Solubility
Certain oxygenated solvents are completely miscible, e.g.,
m e t h a n o l , isopropanol, acetone. This p r o p e r t y can provide a
qualitative m e a n s for i n d i c a t i n g the presence or absence of
water-insoluble c o n t a m i n a n t s , such as oils, paraffins, olefins,
aromatics, high m o l e c u l a r weight alcohols, ketones, etc. Water-insoluble m a t e r i a l s in the solvents m a y interfere with
m a n y of their end-uses.
ASTM M e t h o d D 1722, W a t e r Miscibility of W a t e r - S o l u b l e
Solvents, covers the d e t e r m i n a t i o n of the miscibility of watersoluble solvents with water. The s a m p l e is diluted to 10 volu m e s of w a t e r in a glass g r a d u a t e d cylinder. The resulting
mixture is viewed t h r o u g h the length of the c o l u m n of liquid
t o w a r d a d a r k b a c k g r o u n d while being transversely illuminated. The s a m p l e is r e p o r t e d to pass the test if there is no
evidence of cloudiness o r t u r b i d i t y initially a n d after 30 rain.
REFERENCES
[1] Ellis, W. H., "Solvents," Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, October 1986.
[2] Thomas, A. M. Jr., "The Viscosity Reduction Power of the Xylenes," Official Digest, January 1962.
[3] Mellan, I., "Industrial Solvents," 2nd ed., Reinhold, New York,
1950.
[4] Fuller, W. R., "Solvents," Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, 1967, 1982.
[5] Flick, E. W., "Industrial Solvents Handbook," 3rd ed., Noyes
Data Corp., Park Ridge, NJ, 1985.
[6] "Physical Properties of Common Organic Solvents and Chemicals," brochure, CHEMCENTRAL Corp., Chicago, 1986.
[7] Busby, D. C., Glancy, C. W., Hoy, K. L., Kuo, A. C., Lee, C., and
Nielson, K. A., "Supercritical Fluid Spray Application Technology: A Pollution Prevention Technology for the Future," presented at the WaterBorne and Higher Solids Coatings Symposium, sponsored by the University of Southern Mississippi and
Southern Society for Coatings Technology, New Orleans, 21-23
Feb. 1990.
[8] Ellis, W. H., Paint Testing Manual, 13th ed., American Society
[or Testing and Materials, Philadelphia, 1972.
[9] Hildebrand, J. H., "Solubility," Journal of the American Chemical
Society, Vol. 38, p. 1453, 1916.
[10] Hildebrand, J. H. and Scott, R., "The Solubility of Non-electrolytes," 3rd ed., Reinhold, New York, 1949.
[11] Burrell, H., "Solubility Parameters for Film Formers," Official
Digest, Vol. 27, No. 369, October 1955, p. 726.
[12] Burrell, H., "The Challenge of the Solubility Parameter Concept," Journal of Paint Technology, Vol. 40, 1968, p. 197.
[13] Crowley, J. D., Teague, G. S., and Lowe, J. W., "A Three Dimensional Approach to Solubility: Part I," Journal of Paint Technology, Vol. 38, No. 496, 1966, p. 269, and "Part II," same journal,
Vol. 39, 1967, p. 504.
155
[14] Hansen, C. M., "The Three Dimensional Solubility Parameter-Key to Paint Component Affinities,"Journal of Paint Technology,
Vol. 39, No. 505, 1967.
[15] Hansen, C. M., "The Universality of the Solubility Parameter,"
Industrial Engineering Chemistry Product Research & Development, Vol. 8, 1969, p. 2.
[16] Huyskens, P. L. and Haulait-Pirson, M. C., "Dissolving Power of
Solvents and Solvent Blends for Polymers," Journal of Coatings
Technology, Vol. 57, No. 724, 1985.
[17] "Properties of Solvents," brochure, Shell Chemical Co., Houston, 1990.
[18] "Evaporation Rates of Solvents as Determined Using the Shell
Automatic Thin Film Evaporometer," Technical Bulletin
IC:69-39, Shell Chemical Co., Houston, 1969.
[19] Ellis, W. H., "Comparative Solvent Evaporative Mechanisms for
Conventional and High Solids Coatings," Journal of Coatings
Technology, Vol. 55, No. 696, January 1983, p. 63.
[20] Murdock, R. E. and Wirkus, W. J., "A Method for Measuring
Solvent Release Using Radiotracers," Official Digest, Federation
of Societies for Coatings Technology, Vol. 35, 1963.
[21] Hays, D. R., "Factors Affecting Solvent Retention: Carbon-14
Tagged Solvents in Poly(Methyl Methacrylate) Films," Official
Digest, Federation of Societies for Coatings Technology, Vol. 36,
1964.
[22] Sletmoe, G. M., "The Calculation of Mixed Hydrocarbon-Oxygenated Solvent Evaporation," Journal of Paint Technology, Vol.
42, 1970.
[23] Lesnini, D. G., "Concentrations of Evaporating Mixtures," presented at the Western Coatings Society, 10th Biennial Symposium, San Francisco, March 1970.
[24] Dante, M. F., Bittar, A. D., and Caillault, J. J., "Program Calculates Solvent Properties and Solubility Parameters," Modern
Paint and Coatings, September 1989, p. 46.
[25J "CO-ACT Solubility Parameter Calculator," brochure, Exxon
Chemical Co., Houston, 1989.
[26] Rocklin, A. L. and Bonnet, D. C., "A Computer Method for Predicting Evaporation of Multicomponent Aqueous Solvent
Blends at Any Humidity," Journal of Paint Technology, Vol. 52,
No. 670, November 1980, p. 27.
[27] Kalina, P., "CASS: Predicting Solvent Blends Using Computer
Programs," Modern Paint and Coatings, April 1987, p. 44.
[28] "Shell Solvents Computer Programs," brochure, Shell Chemical
Co., Houston, 1981.
[29] "ARCOCOMP Solvent Selector Computer Program," ARCO
Chemical Co., Newtown Square, PA, 1987.
[30] Yuhas, S. A., Jr., "Solvents Toxicology and Safety Manual," Exxon Chemical Co., Houston, 1977.
[31] McArdle, E. H. and Robertson, A. E., "Evaporation Indices o[
Hydrocarbon Thinners," Industrial and Engineering Chemistry,
Analytical Edition, IENAA, Vol. 16, 1944, p. 690.
[32] Wray, H. A., ASTM correspondence to J. J. Brezinski, 31 May
1991.
[33] Davidson, J. A., Harvey, T., Kurtz, S. S., Jr., and Lipkin, M. R.,
"Pycnometer for Volatile Liquids," Industrial and Engineering
Chemistry, Analytical Edition, IENAA, Vol. 16, No. 1, 1944, p. 55.
[34] "Standard Methods for the Examination of Water and Waste
Water," M. Franson, ed., American Public Health Association,
14th ed., 1975, p. 65.
[35] Hazen, A., "New Color Standard for Natural Waters," American
Chemical Journal, Vol. 14, 1892, p. 300.
[36] Olson, C., "Improving Resistivity Control in Coatings for Optimal Electrostatic Spraying Systems," American Paint and Coatings Journal, 4 Feb. 1991, p. 70.
[37] Keulemans, A. I. M., "Gas Chromatography," 2nd ed., Reinholdl
New York, 1959.
Part 6: Pigments
MNLI7-EB/Jun.
1995
White Pigments
by Juergen H. Braun 1
INTRODUCTION
ALMOSTEVERYTHINGMAN-MADEthat is white or light in color
contains white pigment in its surface: houses inside and outside, industrial articles, plastics, glazes, rubber, printed surfaces, many paper products, and even some foods. Only papers and textiles can be white without pigment.
Virtually all this whiteness and lightness is supplied by
titanium dioxide (TiO2) pigments. Void pigments make a minor contribution. The classic white pigments--lithopone,
zinc sulfide, and the white leads--have essentially disappeared from commerce because TiO 2 pigments perform
much better, are much cheaper, and are nontoxic. Zinc oxide
is still added to some paints as a mildewstat, but not as a
white pigment.
TiO2 pigments are manufactured by a major, globally distributed industry. Its products are sold for many applications;
however, more than half of all white pigment goes into paints.
In many coatings, white pigment is the single most expensive
ingredient. To select the right pigment grade and use it well is
an important challenge to the paint manufacturer.
This chapter will familiarize coating manufacturers with
white pigments and help them understand their options for
selection, utilization, and testing. Toward this objective, I will
first outline the commerce and manufacture of white pigments and then discuss their function, the substances that
serve this function, and the commodities available. I will
distinguish between product characteristics that describe the
pigment itself and product performance, which are properties of paint films, that is, systems composed of pigment and
binder.
Manufacture
TiO2 particles, the active ingredient of pigment, are made
by two processes:
1. The old sulfate route dissolves the ore in sulfuric acid,
purifies the aqueous solution of titanyl sulfate, precipitates
a hydrous titania gel, and calcines the gel to crystallize it
into aggregates of pigment particles, which, in turn, must
be ground.
2. The newer, "greener" chloride route chlorinates the ore
and purifies the TIC14 intermediate by distillation and
chemical treatments. TIC14 is then flame oxidized to pigmentary TiO2 particles and chlorine. The chlorine is recycled.
Commerce
159
www.astm.org
160
CHAPTER 1 9 - - W H I T E PIGMENTS
All
None
None
All
Some
Some
Some,in specificwavebands
None
All
Some
Black
White
Gray
Colored
T H E S U B S T A N C E OF W H I T E P I G M E N T
White pigments translate light scattering into hiding
power, brightness, and opacity of thin films. The films, in
turn, hide the color and contrasts of the substrate.
To serve as an effective white pigment, a substance must
meet requirements that limit the selection to less than one
dozen from among the thousands upon thousands of natural
and man-made chemicals. A potential white pigment must:
9 have an extremely high refractive index
In addition the substance must be:
9 stable
9 almost colorless
9 suitable for manufacture in optimized, colloidal particle
size
9 a solid
9 insoluble in water and organic solvents
9 safe in manufacture, end use, and as a waste
.2
161
.4
.6
.8
1.0
Diameter, pm
Calculations: W. D. Ross, Du Pont Company
FIG. 1-Scattering by spheres of rutile in resin. From Braun, J. H., Introduction to
Pigments, monograph in the Federation Series on Coatings Technology, Federation
of Societies for Coatings Technology (United States), 1993.
162
5
0
10
20
30
40
TiO 2 PIGMENTS
Titanium dioxide has obsoleted all other white pigments
because TiO 2 is cheaper to use and much safer than other
pigments. TiO2 pigments are the most effective scatterers of
visible light. They hide better and provide more lightness.
They are more stable and less toxic.
Figures 3 and 4 show what TiO 2 pigments "look" like. Figure 3 is a transmission electron micrograph of an uncoated
TiO 2pigment grade dispersed in a dispersant by conventional
techniques of grid preparation. Single crystals, twins, aggregates, and small agglomerates are visible. Weakly bonded
agglomerates, though, are not distinguishable from strongly
bonded aggregates because micrographs do not show
strength of bonding. Figure 4 shows a set of electron scanning
micrographs of dry pigment in bulk and as an individual floc.
Visible are masses and individual crystallites, single and
twinned. At highest magnification, scanning electron micros-
ment.
CHAPTER 1 9 - - W H I T E PIGMENTS
163
164
Pigment Characteristics
TiO2 pigment has to meet stringent specifications of crystal
phase, particle size, surface characteristics, and purity. As
with all chemicals, every product characteristic has some
effect on every performance quality. Some specific characterWParticle size measured as Stoke's settling diameters by sedimentation methods.
istics, however, dictate equally specific performance attributes. These crucial relationships are described.
Refractive index and density are paramount to optical
function, but they are not subject to manipulation. Crystal
phase impacts weathering and light-scattering performance.
Particle size controls light scattering and has effects on color.
Surface characteristics are designed into the product through
chemical treatments reflected by commodity composition.
The treatments improve dispersibility, durability, and gloss
performance. High purity of the pigment makes for brightness.
TiO 2 Crystallites
The active ingredients of a TiO2 pigment commodity are its
TiO2 crystallites. Other components of the commodity affect
the commodity density but do not affect the crystallite density nor the refractive index of the pigment. Neither the refractive index nor the density of any chemical can be manipulated independently by conventional technology. 11
Two crystal phases of titanium dioxide serve as pigments:
rutile and anatase. They differ in refractive indices, densities,
and weathering performance because rutile and anatase differ by the arrangement of the titanium and oxygen ions
within the crystals (Fig. 5). Rutile crystals are elongated, are
denser, and have higher refractive indices) 2 Because of their
higher refractive indices, rutile pigments scatter light more
effectively than anatase products. They are also much less
prone to chalk.
Rutile absorbs slightly more violet light than anatase and is
slightly more yellow in bulk. However, little, if any, of this
yellowness extends into pigment applications.
TiO 2 is a UV-energized oxidation catalyst of organic polymer. Anatase surface is about ten times more reactive than
rutile surface. It takes only 10% anatase in rutile to reduce to
one half the life expectancy of a paint film. Thus, for all
exterior applications, the phase purity of rutile pigments is
quite important.
During paint manufacture or usage, titanium dioxide cannot undergo transitions of crystal phase, that is, it cannot
change its lattice structure. This contrasts to most organic
pigments, many of which phase convert readily, usually with
dramatic loss of optical performance. For example, an
unstabilized a-copper phthalocyanine pigment, upon exposure to an aromatic solvent, grows into long needles of
/3-copper phthalocyanine, losing most of its color strength in
the process.
Typical Crystals
Crystal Structures
Rutile
~~
D ensity,
g/ml
Refractive
Index*
4.3
2.7
3.8
2.5
165
9Ttianuim
0 Oxygen
Anatase
grain boundaries and are thus strongly bonded. Agglomerates are associations of crystallites and aggregates bonded by
relatively weak forces. Flocs are weakly bonded associations
of crystallites, aggregates, and agglomerates formed spontaneously in a liquid or even in air.
The shear forces of paint application can disperse flocs.
However, they are likely to reassociate. Paint grinding breaks
most agglomerates if (1) the mill base is formulated to proper
viscosity and (2) the mill is operated well. Aggregates can be
broken only by high-intensity mills. Crystallites cannot ordinarily be broken. Aggregates and crystals, once broken, do
not reassemble because aggregate bonding and crystal
growth require thermal activation to m a n y hundred degrees
centigrade. TiO2 pigments do not degrade in conventional
paint and plastics processing.
The inclusion of casual contact in the definition of "particle" is important because it links size to concentration. At low
pigment concentration, the frequency of particle overlap in a
beam of light is low and the casual contact contribution to
effective size is small. At high concentration, casual contacts
are a b u n d a n t and contribute significantly to the particle size
as seen by a light beam penetrating a paint film.
Optimal scattering performance calls for optimal particle
size. Particles that are too small in the extreme, molecular
dispersions, scatter almost no light; particles too large, macroscopic crystals, are transparent. The particle size at which a
population of TiOz particles scatters a m a x i m u m a m o u n t of
light is about 0.2/zm for green ~5and white light. Blue light is
scattered more effectively by particles closer to about 0.16
15For whiteness and brightness, green light matters most because
166
36
,-~
32
28
24
20
r
12
8
9-~
9
4
0
.1
,5
.2
.3
.4
Particle D i a m e t e r , p m
FIG. 6-Particle size distribution of TiO2 pigment. From
Braun, J. H., Introduction to Pigments, monograph in the Federation Series on Coatings Technology, Federation of Societies
for Coatings Technology (United States), 1993.
Commodity Composition
The TiO~ in the pigment is its optically active ingredient.
Other components adapt it to its end use. The commercial
products have compositions that fall into one of three categories: (1) uncoated pigments, (2) coated pigments, and (3)
slurries.
Uncoated pigments contain 98% or more titanium dioxide;
some contain up to about 1% aluminum oxide (anhydrous),
and other products contain less than about 0.5% aluminum
oxide with some other inorganic, anhydrous oxides. Organic
additives and their decomposition products may be present
CHAPTER 1 9 - - W H I T E PIGMENTS
Particle
Frequency
by Weight
. ~ Optical Range
Tinting Strength
Hiding Power
Undertone
0.1
167
0:5
. . . .
loss
Dispersion
Film Fineness
1:0
510
. . . .
1(;.0
Diameter,
FIG. 7-TiO 2 aggregate size distribution. From Braun, J. H. and Fields, D. P., "Gloss of Paint Films, I1,"
Journal of Coatings Technology, Vol. 66, No. 828, 1994, p. 93.
in concentrations of fractional weight percents. Uncoated
pigments are used in plastics and paper. In coatings, wettreated pigments are preferred because they are easier to
disperse into liquids of low or moderate viscosity.
Minor constituents, either carded over from the ore or
added in the manufacturing process, can be important in
determining pigmentary properties because they can control
crystallite size. Sulfate pigments retain up to 0.3% niobium
pentoxide and 0.3% phosphorus pentoxide from the ore. They
also contain up to 0.2% alumina, added to compensate for the
presence of niobium. Compensation minimizes discoloration
by the semiconductor imbalance that pentavalent and trivalent cations can cause in the rutile lattice.
Chloride process pigments contain practically no unwanted impurities because the titanium tetrachloride intermediate can be purified effectively. They contain about 1%
pyrogenic alumina added for better process control and for
photochemical stability improvement.
Trace constituents are generally unimportant except for
transition metals such as iron, chromium, vanadium, etc.,
which degrade color by semiconductor mechanisms.
Besides inorganic constituents, most uncoated and many
coated pigments contain up to 0.5% of an organic grinding
aid to improve flow in the fluid energy mill to achieve a more
uniform grind. The grinding aids are usually polyhydroxyl
compounds (for example, trimethylol propane, triethanolamine, etc.) that can undergo some pyrolytic degradation in
the mill.
For use in coatings, i.e., to be dispersible by the conventional paint-making equipment, TiO2 pigments are "coated."
In aqueous suspension, hydrous aluminum oxides are precipitated onto the surfaces of pigment particles. Interior grades
contain a coating of up to 5% hydrous alumina for ease of
dispersion. Durable grades have another coating that usually
consists of about 2% silica and sometimes also oxides of
zirconium, boron, zinc, cerium, and tin, usually in concentrations of less than 1%.
Rutile pigments are made suitable for extreme exposure by
encapsulating individual particles in glassy silica sheaths. Silica surface treatments on TiO2 pigments were once considered detrimental to gloss performance. Silica on pigment,
however, comes in two distinct modifications, either "fluffy"
or "dense." Fluffy silica does indeed reduce gloss and is precipitated onto pigments intended for dry hiding paints to
increase oil absorption. Dense silica is used to encapsulate
the TiO2 particle in a distinct shell to make the pigment
durable in severe exposure.
Special high oil absorption products are made for paints
formulated for dry flat hiding, that is, above the critical pigment volume concentration. They contain fluffy coatings, 5 to
15% hydrous silica and 2 to 6% hydrous alumina, for better
spacing and improved optical efficiency in vehicle-starved
formulations. The fluffy silica increases oil absorption and
water demand by the pigment. Gloss is reduced.
Slurry products for coatings applications are usually based
on coated pigments. In addition to the coated product, they
contain organic dispersants and stabilizers. Predispersed pigments, sold as aqueous slurries, contain from 60 to almost
80% titanium dioxide by weight. They are stabilized with low
concentrations of organic chemicals.
Odorless amines are added for pH control. Together with
preservatives, about 1% of organic material is present. Pigment loading in slurry is limited by the concentration at
which the slurry becomes too thick to be pumped. Slurries of
lightly treated grades are available at higher solids contents
than slurries of heavily treated, dry flat grades. The slurries
can be shear thickening. Effects can be severe.
The pigment industry describes its products and the hydrous oxides they contain in terms of their analytical equivalents, alumina (A1203), silica (SiO2), and water (H20) or tools-
168
Elemental Analysis--Chemical analysis of pigments presents no particular problems. The quality of the data meets
the requirements of pigment and coatings technologies. For
routine analyses, conventional, wet analytical methods, for
example, ASTM Test Methods for Chemical Analysis of White
Titanium Pigments (D 1394-76), have been replaced by instrumental techniques for cost savings, not data quality. Alum i n u m and silicon contents are usually determined by X-ray
fluorescence techniques. Water content is analyzed as weight
loss of volatiles by thermogravimetric analysis (TGA).
Pigment Surface
Because pigment particles are so very small, their surfaces
are enormously large. One pound of untreated TiOz has a
surface of about one acre. Thus, surface characteristics have
a profound impact on a pigment's interactions with all the
other components of paints. Furthermore, pigment surfaces
are complex composites reflecting the nature of the commodity.
The rutile component of most TiO2 pigments contributes 0
to 10 m2/g of surface area. Inorganic treatments with hydrous
aluminas and silicas can more than double the total surface
area of a pigment. Most pigment surfaces are composites of
Ti--O, Ti--OH, A1--O, and A1--OH groups. Many pigment
surfaces include Si--O and Si--OH units. Silica-encapsulated grades have few if any Ti--O and T i - - O H surfaces.
The surface areas themselves are not homogeneous. Usually they are composites to which TiO2 contributes 0 to 10
m2/g TiO2 and 5 to 10 m2/g pigment, hydrous aluminas with
about 200 m2/g A12Oa.xH20 and 2 to 8 m2/g pigment, silicic
acid with about 150 m2/g SiO2.xH20 and 0 to 10 m2/g pigment,
silica glass 5 to 10 m2/g SiO2 and 5 to 10 m2/g pigment, etc.
The chemical and physical characteristics of the surface are
specific to the component. Granted, the components share
important similarities. They are all hydrophilic oxides with
high-energy surfaces.
Even the surfaces of titanium dioxide crystallites themselves are not just composed of titanium and oxygen ions. In
the sulfate process, while the ruffle crystallites grow, insoluble components accumulate on their surfaces. Those compo-
nents are either impurities present in the ore and not removed in the purification process or additives designed to
control crystal structure and growth and to regulate agglomeration. This fortuitous surface is not necessarily suitable for
a given end-use application; thus, crystallite surfaces are
modified by treatments.
The surfaces of TiO 2 pigments are wetted readily. They are
usually hydrophilic and disperse spontaneously into water.
The energy of wetting is high, aiding dispersion into organic
liquids. The ease of wetting of TiO 2 pigments contrasts with
wetting problems of organic color pigments, most of which
are hydrophobic and have a low negative free energy of
wetting. Water does not wet them without the help of surfactants. Suitable organic solvents may wet organic pigments
but often only sluggishly.
Since unmodified pigments tend to cake and flow poorly,
they are treated with up to 0.5% of a grinding aid, usually
organic polyhydroxyl compounds, to improve dry flow. These
organic materials remain on the pigment surface. Silicone
treatment can be used to make dry pigment flow like sand,
but the pigment becomes hydrophobic and unsuitable for
most coatings applications.
169
Contaminants
Extraneous metal ions within rutile crystallites can degrade the brightness of pigment. Nickel and chromium can
be detrimental in concentrations as low as a few parts per
million. Involved are semiconductor mechanisms. Substitution of extraneous ions for Ti4 in the TiO2 lattices discolors
the crystals usually towards gray or yellow,
Impurities and co-products introduced by the treatment
chemicals are far less detrimental to brightness. Co-products
can, however, affect specialized performance requirements.
Certain ions can, for example, inhibit cure of acid or basecatalyzed coatings or cause film defects in electrocoatings.
Purity and brightness of TiO2 crystallites are process related. TiO2 crystallites made by the chloride process are purer
and brighter than sulfate products.
The co-product content of a pigment commodity is usually
not a matter of poor operating practice but set by complex
compromises between conflicting performance requirements.
90-
70
60
50
40
30
Dark Gray
20
100.4
Black
I
.5
.6
.7
Wavelength, gm
FIG. 8-Reflectances of white, gray,and black
paints. From Braun, J. H., Introduction to Pigments, monograph in the Federation Series on
Coatings Technology, Federation of Societies
for Coatings Technology (United States), 1993.
170
100
Relative
Hiding
Power,%
I ....
.0~ ~
8r
60
Non Porous
Films
Porous
Films
4C
2C
10
20
30
40
Pigment
Volume
Concentration, %
,
I
>
50
CPVC
FIG. 9-Hiding power of paint films. From Braun, J. H., Introduction to Pigments, monograph in the
Federation Series on Coatings Technology, Federation of Societies for Coatings Technology (United States),
1993.
white, gray, and black paints pigmented with only TiOz, with
TiO z and carbon black, and with only carbon black, respectively. Absorption of far violet light imparts a slight yellow
hue to large crystals. The anatase absorption edge is at a
shorter wavelength than rutile, shifted almost completely
into UV wave lengths. Thus, anatase crystals are slightly less
yellow. All this does not matter m u c h in coatings. For highpurity pigment, dry powder color does not correlate with end
use color because most polymers contribute far more yellowness than the pigment.
Pigment brightness matters less in most coatings applications than one might presume. Most coatings, even white
ones, are toned, that is, their brightness is reduced intentionally by addition of carbon black or color pigments. Purity,
thus brightness, is important only for white coatings that are
usually not toned: coatings for light fixtures, m a n y coil coatings, most inks, and ink-similar paints.
Chloride process pigments are intrinsically brighter and
whiter than their sulfate counterparts. Typically, chloride
process pigments average 99.5% L .18 lightness, 19 and 98.5%
sulfate pigments, z~ The difference between chloride and sulfate pigments, an L* lightness difference of 1%, is about ten
times larger than the least visible difference.
TiOz particle size has a significant effect on the color of
tinted coatings and thin white films. Smaller particles scatter
taCIELAB (Commision International de l'Eclairage, 1978) metric
of lightness.
~gBrightness/lightness of a dry pressed pigment pellet.
2~ very first approximation, a TiO2 pigment with an L* lightness
of 98.5% contains a three times higher concentration of colorant
impurities than a pigment of 99.5% brightness: 1.5%/0.5% = 3.
2.25
~
2.00
~-~ ,-,
1.75
171
[a
\
1.(X)
O.75
0
10
15
20
25
30
35
Pigment Performance
The TiO2 industry sells light scattering for the price of TiO 2
because there is no better and cheaper way to achieve effective hiding by thin films that are white or light in color. Thus,
optical effectiveness is the primary performance characteristic of the pigment. However, TiO 2 pigment is well optimized
and functions near its theoretical potential. Between products developed for similar end use, light scattering differences are too small to matter or be measured. Thus, secondary performance characteristics can be commercially
decisive.
172
Dispersibility
To make a paint, dry powder has to be distributed in liquid
composed of binder and solvent. The process is called dispersion or paint grinding.
The ease with which a powder can be dispersed in a liquid
depends primarily on its particle size. As pigments go, TiO2 at
0.2 /~m size is large and easy to disperse, almost as easy as
extenders, much easier than most color pigments. For all but
glossy coatings, TiO 2 can be stirred into liquids with highspeed agitators. High-gloss finishes require more powerful
equipment: media, roll, or ball mills.
Dispersing involves four distinct stages during which most
of the energy of grinding converts to heat:
1. Liquid replaces air-solid interfaces with liquid-solid interfaces.
The ease of wetting depends on (a) energy characteristics of the surface of the solid and (b) the chemical
affinity between solid and liquid. TiO2's high-energy surface wets well. By contrast, the low-energy surfaces of
organic color pigments wet only with difficulty.
2. Bonds between particles are broken.
TiO2 crystals are not broken in ordinary mills. Bonds
between crystals range in strength from strong within
aggregates to weak within agglomerates. Weak aggregates can be broken in the high-energy mills of pigment
and plastics technologies, not, though, by equipment
common in coating technology. Agglomerates break in
high-speed dispersers.
3. Particles are distributed throughout the liquid.
The more viscous the liquid, the more power is required
to mix and distribute and the more effective the grind.
2SThick enough so that a further increase in thickness does not
affect reflectance.
CHAPTER 1 9 - - W H I T E PIGMENTS
Degradation of coatings occurs because paint films are
slowly oxidized by air. Sunlight triggers the degradation reactions. In the dark, paint films can last for centuries, even
millennia. In light, durability depends on binders, pigments,
and the conditions of exposure. High humidity, particularly
condensation, aggravates degradation.
Only the ultraviolet (UV) portion of sunlight causes degradation directly because it has an energy content sufficient to
break chemical bonds. The degradation of UV-A and UV-B
light 24 is irreversible for polymers and for all organic and
some inorganic pigments. A few inorganic pigments are thermodynamically stable. Titanium dioxide is stable, but its
catalytic characteristics are activated by UV above 3.08 eV. In
effect, the band gap of TiO225 is within the energy levels
present in sunlight. All white pigments share some of this
attribute. Extenders are stable and inert. Their band gaps are
too large to be activated by the UV components of sunlight.
Titanium dioxide affects the durability of paint films in two
distinct and opposing ways: (1) As a strong UV absorber, TiO 2
protects the paint film, and (2) as an UV-activated oxidation
catalyst, TiO2 degrades binders [7].
Three characteristics of TiO 2 are functionally disparate but
are manifestations of a single fundamental characteristic of
dielectric matter: (1) its unique refractive index, which makes
TiO2 the best white pigment; (2) its extreme UV absorptivity;
and (3) UV catalytic activity of the TiO2 surface.
Light of more than 3.08 eV, water, and oxygen are all
essential for the TiO2-catalyzed degradation of binder. Their
reactions combine into a cycle that generates two free radicals from each active UV photon [8].
H20 + 02 + hv(uv)
TiO 2
) .OH + .HO2
~ CO2 + 4 H20
173
174
Compatibility
CHAPTER 19--WHITE
Product Types
ASTM D 476-84 distinguishes four types of TiO2 pigments
(Table 2): one anatase type and three ruffles: interior, exterior, and pigment for paints formulated above the critical
pigment volume concentration. The standard was formulated
in 1939 with two classes of pigments. In the years since, the
design of pigments has progressed to where the coatings
industry can now select the most suitable pigment grade for a
specific application from far more than two or four TiO2
types, Granted, a single TiO 2 grade could serve diverse needs
but would do so only moderately well. Optimal performance
in any application demands specialized pigment grades that
satisfy specific requirements of optics, surface chemistry, and
dispersion technology. Some of these requirements can be
met only through compromise.
The diversity of products can be described in terms of four
specific performance dimensions: durability, gloss, dispersibility, and undertone. Then there are products aimed at
specific applications: enamel paints, dry hiding paints, pigment slurries, acid-catalyzed coatings, electrocoated primers,
etc. Finally, pigment grades are designed for the specific
requirements of whole industries: coatings, plastics, paper,
and ink.
These are the products designed to specific performance
dimensions in coatings:
9 Durability: Interior--Exterior--Severe Exposure
Interior grades are unfit for exterior applications except
when used underneath top coatings that absorb all light
of wavelengths below 400 nm. All-purpose pigments are
exterior durable in appropriately durable vehicles at
moderate severity of exposure and for moderate appearance requirements. Severe exposure grades are intended
29Slurry grades do contain some organic surfactant,
PIGMENTS
175
for satisfactory performance including high gloss at exceptionally severe conditions, for example, at the horizontal position in the humid subtropics.
Durability must be manufactured into the pigment surface.
9 Gloss: Conventional--Flashy
Conventional pigments satisfy the gloss requirements of
most architectural and trade-sales applications and of
many industrial coatings. High-gloss pigments are aimed
at automotive and some flashy industrial finishes.
High-gloss application call for pigments of small agglomerate size and low oil absorption.
9 Dispersibility: Conventional--Low Shear
Conventional pigments are designed to be dispersed by
equipment developing moderate to high shear3~ media
mills, ball mills, roller mills, and high-speed dissolvers at
low rates of throughput. Special pigments are available
for low-shear, high-rate dispersion by high-speed dissolvers and for stir-in with screening.
Dispersibility is promoted by surface treatments at some
detriment to gloss.
Unlike many color pigments, TiO 2 pigments are dispersible enough not to require predispersion.
9 Undertone: Neutral--Blue
In coatings applications, the undertone of the pigment,
blue, neutral, or red, is rarely an issue. Thus, most coating grades have a neutral undertone. Blue undertone pigments are preferred in applications at very low pigment
volume concentration. Red undertone pigments do not
appear to be in demand.
Undertone is affected by pigment volume concentration
and controlled by the size of the primary TiO 2 particle,
small for blue, intermediate for neutral, and large for red.
There are also specific coatings applications addressed by
special product designs.
9 Grades intended for coatings below the critical pigment volume concentration.
Most TiO2 pigments, conventional interior and exterior
grades, conventional and high-gloss products, conventional and low-shear dispersible pigments, the neutral
and blue undertone pigments, are all suitable for applications below the critical pigment volume concentration.
9 Grades intended for applications above the critical pigment
volume concentration.
Heavily treated, low-gloss products perform better in
dry-hiding paints than grades made for high and moderate gloss. In effect, the pigment contains its own, exceptionally effective extender.
9 Slurries intended for waterborne paints.
Aqueous slurries are suited only for waterborne applications. The costs of dispersion operations are borne by
pigment manufacturers. For medium- and large-scale operations, savings from the elimination of a process step
outweigh the costs of slurry-handling facilities.
9 Other specialized grades are made as opportunities are recognized and solutions developed.
3~
shear within coatings technology. The plastics industry
uses several more powerful mills.
176
TABLE 2--Excerpt from ASTM Standard D 476-84: Specification for titanium dioxide pigments.
Type I
Typical
Application
Anatase
Free chalking
White exterior house
paints; interior use
TiO2, min, %
94
Type II
Ruffle
Medium chalk resistant
Low-medium PVC
Medium-high PVC
enamels and
enamels; alkyd
lacquers
and emulsion
flat wall paints
92
80
Type III
Ink
Inks require pigments that are high in gloss. Compatibility with a wide range of solvents and vehicles is often
important.
9 Miscellaneous end uses
Type IV
Ruffle
Highly chalk resistant
Exterior coatings requiring
excellentdurability and
gloss retention
80
CHAPTER
19--WHITE
PIGMENTS
177
Intended
PVCa
Lowb
Lowb
Lowb
Lowb
Love~
Love~
Lowb
Lowb
Lowb
Lowb
Lowb
Lowb
Highk
Highk
Intended
Gloss
Intended
Exposure
Flashy:
Flashy:
Flashy:
Flashy:
Flashy:
Flashy:
Discreet a
Discreetg
Discreete
Discreete
Discreeff
Discreet g
Discreet g
Discreetg
Indoors
Indoors
Outdoors
Outdoors
Extremef
Extremef
Extremer
Extremef
Extremer
Extremef
Extremef
Extremef
Indoorsl
Indoorst
Pigment
Delivery
Dry
Slurry:
Dry
Slurry~
Dry
Slurry~
Dry
Slurry:
Dry
Slurry:
Dry
Slurry*
Dry
Slurry~
Intended
Dispersion
High Sheard
Dispersed
High Sheard
Dispersed
High Sheara
Dispersed
Low S. h'i'i
Dispersed
Low S. h'i'i
Dispersed
Low S. h'i'/
Dispersed
Low S. h ' '
Dispersed
Another, less successful product, P i t t m e n t | generated pigment-sized air voids in p a i n t films by evaporation of droplets
of a n organic solvent emulsified in the paint.
If the voids are of sub-pigmentary size, small enough to
lose their individual optical identity, they do not scatter m u c h
light b u t collectively decrease the refractive index of the matrix. A composite refractive index of polymer a n d air takes the
place of the index of polymer alone. This decrease of matrix
FIG. 13-Rhopaque| From Braun, J. H., Introduction to Pigments, monograph in the Federation Series on Coatings Technology, Federation of Societies for Coatings Technology
(United States), 1993.
!78
FIG. 14-Vesiculated beads. From Braun, J.H., Introduction to Pigments, monograph in the Federation Series on
Coatings Technology, Federation of Societies for Coatings
Technology (United States), 1993.
refractive index has a p o t e n t effect on the scattering of a n y
true p i g m e n t p r e s e n t in the p a i n t film.
A p r o d u c t c o m p o s e d of vesiculated a n d p i g m e n t e d p o l y m e r
b e a d s m a k e s use of this effect. The product, Spindrift | (Fig.
14), is suitable only for low-sheen paints b e c a u s e the b e a d s
act as a flatting agent. They have to be larger t h a n TiO2
particles b e c a u s e each b e a d has to a c c o m m o d a t e several pigm e n t particles plus voids a n d s o m e binder.
A third a p p r o a c h to void hiding, the use of stretched foam,
is very efficient. Hiding can be achieved w i t h o u t any p i g m e n t
with less p o l y m e r on the s u b s t r a t e t h a n by any conventional
paint. But f o a m coatings are p r e s s u r e sensitive. They are too
sensitive for p a i n t a p p l i c a t i o n s b u t are suitable for opacification of textiles, c u r t a i n fabrics in particular.
Acknowledgments
I a m i n d e b t e d to m y f o r m e r colleagues for advice, counsel,
a n d the insights I developed d u r i n g m y c a r e e r in DuPont's
white a n d color p i g m e n t s businesses. Special thanks go to A.
Baidins a n d R. E. Marganski, m y co-authors in a literature
review of Ti02 technology, a n d to D. A. H o h z e n and R. C.
Crafl-Tulloch, w h o helped review a n d revise the manuscript.
REFERENCES
[1] Braun, J. H. and Fields, D. P., "Gloss of Paint Films, I and II,"
JournalofCoatings Technology, Vol. 63, No. 799, 1991, p. 43, and
Vol. 66, No. 828, 1994, p. 93.
[2] Braun, J. H., "TiO2's Contribution to the Durability and Degradation of Paint Films: II. Prediction of Catalytic Activity," Journal of Coatings Technology, Vol. 62, No. 785, 1990, p. 37.
[3] Asbeck, W. K. and Van Loo, M., "Critical Pigment Volume Relationship," Industrial and Engineering Chemistry, Vol. 41, 1949, p.
1470.
[4] Bruehlman, R. J., Thomas, L. W., and Gonick, E., "Effect of
Particle Size and Pigment Volume Concentration on Hiding
Power of Titanium Dioxide," Official Digest, Vol. 33, No. 433,
1961, p. 252.
[5] Fitzwater, S. and Hook, J. W., "Dependent Scattering Theory: A
New Approach to Predicting Scattering in Paints," Journal of
Coatings Technology, Vol. 57, 1985, p. 39.
[6] Braun, J. H., "Crowding and Spacing of Titanium Dioxide Pigments," Journal of Coatings Technology, Vol. 60, No. 758, 1988,
p. 67.
[7] K~impf, G., Papenroth, W., and Holm, R., "Degradation Processes in TiO2-Pigmented Paint Films on Exposure to Weathering," Journal of Paint Technology, Vol. 46, 1974, p. 56.
[8] V61tz, H., K~mpf, G., Fitzky, H. G., and Kl~iren, A., "Experimentelle Techniken zur Erfassung des inneren Abbaus und der
Schutzwirking durch TiO2-Pigmente in Anstrichen bei Bewitterung," Farbe+Lack, Vol. 82, 1976, p. 805.
[9] Werner, A. J., "Titanium Dioxide Pigment Coated with Silica
and Alumina," U.S. Patent 3,437,502 (1969).
[lo] Braun, J. H., "Titanium Dioxide's Contribution to the Durability
of Paint Films," Progress in Organic Coatings, Vol. 15, 1987, p.
249.
[11] Simms, J. A., "The Acceleration Shift Factor and its Use in Evaluating Weathering Data," Journal of Coatings Technology, Vol.
59, 1987, p. 45.
BIBLIOGRAPHY
Published scientific a n d technical i n f o r m a t i o n on p r o d u c t s
of this highly competitive i n d u s t r y is sparse. The i n f o r m a t i o n
p r e s e n t e d here is b a s e d largely on insights developed d u r i n g a
c a r e e r in p i g m e n t technology, s u p p l e m e n t e d b y these texts:
Braun, J. H., White Pigments, monograph in the Federation Series on
Coatings Technology, Federation of Societies for Coatings Technology (United States), in preparation.
Braun, J. H., Introduction to Pigments, monograph in the Federation
Series on Coatings Technology, Federation of Societies for Coatings Technology (United States), 1993.
Braun, J. H., Baidins, A., and Marganski, R. E., "TiO 2 Pigment Technology--A Review," Progress in Organic Coatings, Vol. 20, No. 2,
1992, pp. 105-138.
Hunter, R. S. and Harold, R. W., The Measurement of Appearance,
2nd ed., John Wiley & Sons, New York, 1987.
Judd, D. B. and Wyszecki, G., Color in Business, Science and Industry,
3rd ed., John Wiley & Sons, New York, 1975.
Patton, T. C., Pigment Handbook, Vols. I, II, III, John Wiley & Sons,
New York, 1973.
Patton, T. C., Paint Flow and Pigment Dispersion, 2nd ed., John Wiley
and Sons, New York, 1979.
Steig, F. B., Jr., "Opaque White Pigments in Coatings," ACS Symposium Series 285, Applied Polymer Science, 2nd ed., R. W. Tess and
G. W. Poehlein, Eds., American Chemical Society, Washington,
DC, 1985.
Thiers, E., Will, R., Leder, A., and Shimosato, J., "Titanium Dioxide
Pigments," CEH Marketing Research Report, SRI International,
Menlo Park, CA, 1991.
MNL17-EB/Jun. 1995
i
Black Pigments
by Frank R. Spinelli 1
Mineral Blacks
Mineral blacks are finely ground derivatives of coal and
shale and are mixtures of carbon, aluminum silicates, silica,
and iron oxides. They can be characterized as having poor
jetness, very low tinting strength, low oil absorption, very
brown undertone, and poor dispersibility. Consequently, they
are rarely used in the paint industry.
Bone Blacks
Bone blacks are made by destructive distillation of solventextracted cattle and sheep bones and contain only from 8 to
17% carbon with the remainder mostly calcium phosphate.
During the "calcination" (8 h at 800~ the organic matter is
decomposed and the resulting carbon forms a thin, porous
film on the surface of the mineral network, creating a large
carbon surface area per unit of weight. Consequently, they
have high color and great adsorptive ability, but very weak
tinting strength. Oil absorption is quite low, and aqueous
dispersibility is excellent. Bone blacks are used only in specialty finishes where high color with low oil absorption is
essential.
179
Copyright9 1995 by ASTM International
www.astm.org
180
Source
Specification
Oil
Gas
Oil
Oil and gas
Gas
...
D 561
D 209
...
...
Coal
Bones
D 210
Copper
Ore
D 769
...
NOTE: From ASTM Paint Testing Manual, Black Pigments 2.8.4; 13th ed., 1972.
(AROMATIC
RADICAL)
c ~ C H 3
CH4 +
(DICARBON
RADICAL)
*~,'~*
"4" C2
"~" H 2
T ~
INTERACTIO~NOF
REACTIVE SPECIES
(HEXAGONALLATTICE
LAYERPLANE)
(NUCLEATIONOR
CRYSTALLITEFORMATION)
FIG. 1-Formation of carbon black. Asterisks indicate active sites.
crystallites are going t h r o u g h the described processes, b u t
not in phase. Those particles a n d aggregates which b e g a n
f o r m a t i o n sooner w o u l d have longer growth times a n d w o u l d
be larger. By choice of h y d r o c a r b o n feedstock a n d careful
control of r e a c t i o n conditions, the key p r o p e r t i e s of p r i m e
particle size, p r i m a r y aggregate size, porosity, structure, a n d
surface c h e m i s t r y are varied to create the s p e c t r u m of commercial c a r b o n blacks.
CRYSTALLITE
~ , , g P - -
PRIME PARTICLE
PRIMARYAGGREGATE
FIG. 2-Growth to particles and aggregates.
This process can produce carbon blacks of particle sizes ranging from about 30 to less than 10 nrn. The resultant blacks
have typically higher volatile contents (chemisorbed oxygen
complexes on the surface) because of the presence of oxygen
during formation. Though channel blacks have virtually disappeared from industry, a variant called roller process
blacks, made from feedstocks other than natural gas, are still
produced in limited quantities in Germany.
Furnace Process Blacks. These are made by partial combustion of a hydrocarbon in a closed reactor (or furnace)
under well-defined conditions. The precursors of m o d e r n oil
furnace blacks were the gas furnace blacks, which are no
longer produced.
Oil Furnace Process. A hot flame is first created by burning
gas with air inside a closed furnace, and then a liquid hydrocarbon is atomized into the hot flame zone. Furnace designs
and reactor configurations vary considerably, but the principle is the same (Figs. 5a and 5b). The feedstock is usually a
medium-molecular-weight aromatic oil that must be heated
to 200 to 250~ to have sufficient fluidity. Yields are high (30
to 60%), air pollution is virtually nil, and it offers superior
process control capability. Blacks ranging in prime particle
size from 100 down to about 10 nm, with variations in structure level (degree of aggregation of prime particles), can be
produced by varying furnace conditions, feedstock properties, residence times (time in hot zone), and quench distances
(how far downstream the cooling sprays are introduced into
the furnace).
Oil Furnace Carbon Blacks. These essentially satisfy all requirements of industrial blacks and account for 95% of all the
carbon black produced today.
Thermal Cracking or Thermal Decomposition--A final category of carbon black processes uses thermal cracking or thermal decomposition of a gaseous hydrocarbon in the absence
of flame. This includes thermal blacks and acetylene blacks,
which are not used in the coatings industry.
TABLE 2--Typical analyses of carbon black grades from five different processes.
Property
Average particle
diameter, nm
Surface area (BET), m2/g
DBPA, mL/100 g
Tinting strength, % SRF
Benzene extract, %
pH
Volatile material, %
Ash, %
Composition, %
C
H
S
O
Type: Furnace
Symbol: HAF
ASTMNo.: N-330
28
181
Thermal
Channel
MT
FT
EPC
N-990 N-880 Acetylene $300
500
180
75
103
210
0.06
7.5
1.0
0.4
47
36
35
0.3
8.5
0.5
0.3
13
33
65
0.8
9.0
0.5
0.1
97.9
0.4
0.6
0.7
99.3
0.3
0.01
0.1
99.2
0.5
0.01
0.3
40
65
250
108
0.1
4.8
0.3
0.0
99.7
0.1
0.02
0.2
28
Lampblack
Lb
65
115
100
180
0.00
3.8
5
0.02
22
130
90
0.2
3.0
1.5
0.02
95.6
0.6
0.20
3.5
98
0.2
0.8
0.8
182
8"
='
! Steel channel I
Enlarged view
pipe //
of burner and Returnj/
burnerchannel.,Hot__ air //,,
Blower
.,,/l"t'~houses~,/l"~"~.
Bolter
t""
~
,/ Burner I~ "~
I
I I f~channels II ~
-'-- , Air .......
II i
,I
I.!.,1
Screw conveyor
Cyclone
~collector
Black /
:lent j. /
tir y(,
i Er~
J
,~Bulkstora""
:' %e
. >~ )elletizedI
.~ ~
I Agitator |
Pelletizing ~ 1-1
Lv.
tank...-J ~/"
.,equipmentBelt ',~
".~.~,::-'.'~-.:,'7-1
] ' S,tandardi
--=I'I'' k~
L conveyor,
hopperl
L o"0.
discharge black
Jetness
The industry term for degree of "blackness" is "jetness,"
which increases with decreasing aggregate size for two reasons: (1) increasing light absorption efficiency and (2) decreasing light-scattering efficiency. As primary aggregates become smaller, incident light must penetrate more carbon,
resulting in more light absorption per unit weight of black.
Also, despite the individual variations of absorption and scattering efficiencies per unit weight shown in Fig. 7, the ratio
[4] of absorption efficiency to scattering efficiency, A/S, essentially increases continuously with decreasing aggregate
size. Thus, both mechanisms, absorption and scattering, are
synergistic with respect to jetness, and the degree ofjetness is
controlled by the A/S ratio. The smaller the aggregate, the
higher the A/S ratio and the jetter the black.
Structure can also be a measure of aggregate size for a
given prime particle since it reflects the number of prime
particles composing a primary aggregate. In this sense it is
also an indicator of scattering efficiency. Low-structure
blacks have smaller primary aggregates, exhibit less scattering, and have higher A/S ratios. High-structure blacks have
larger primary aggregates, exhibit more scattering, and have
lower A/S ratios. Given two carbon blacks of comparable
prime particle size, the black of lower structure (smaller,
more compact primary aggregates) will show the higher
jetness because of a higher A/S ratio.
Tinting Strength
Carbon black's primary tinting application is to make gray
colors by blending with a white pigment. Addition of a fixed
amount of a number of different carbon blacks to a titanium
dioxide, TiOz, dispersion, for example, will result in various
depths of gray color. The darkest gray will represent the carbon black highest in tinting strength. Since even a dark gray
surface reflects a great amount of light relative to a black
surface, the increment of light scattered by the carbon black
is insignificant. For this reason, the controlling mechanism in
tinting strength is light absorption [7]. Finer primary aggregate size, which favors increased absorption, will enhance
tinting strength (Fig. 9). As the primary aggregate size is determined both by prime particle size and structure, higher
tinting strength is favored by fine-particle-size, lower structure blacks. However, as shown in Fig. 7, at an aggregate size
equal to one third the wavelength of incident light, the absorption efficiency, and consequently tinting strength, levels
off and becomes independent of further decreases in size.
This phenomenon can be seen in Fig. 9 as well.
Opacity
The extent to which a coating will cover or "hide" a substrate is a function of the nature of the pigment and its
loading level. As mentioned earlier, the opacity loading level
of carbon black in a coating system is usually 3% by weight or
less for normal paint film thicknesses (around 1.0 mil). With
much thinner films, higher loadings would be required to
achieve opacity. In other words, there must be a sufficient
number of primary aggregates dispersed throughout the film
to prevent any significant amount of incident light from passing through.
Carbon black creates opacity through the two mechanisms
cited earlier, absorption and scattering of visible light. In fact,
opacity of carbon black can be considered as being directly
proportional to the sum of_the absorption coefficient and the
scattering coefficient, (A + S). This means simply that light
that is either absorbed or scattered is not transmitted through
the film. From this relationship, it is also possible to predict
that optimum opacity, as a fixed loading, would be rendered
by blacks having an aggregate size close to one third the
wavelength of incident light (in short, blacks in the regular to
medium color categories for white light of 180 nm, as per Fig.
7).
One convenient way to express the opacity of films is to use
the parameter called optical density. This is a function of the
percent of incident light transmitted as follows:
Optical Density
- LOG10T~
where
Tx = Transmitted light/incident light, and
h = Wavelength of incident light.
An optical density of 1.0 would indicate a transmission of
1% (0.01), 2.0 would indicate a transmission of 0.1% (0.001),
etc. Since T will vary somewhat with wavelength, it is necessary to use the subnotation to denote the wavelength of the
incident light. Further, there is a logarithmic relationship
with film thickness (expressed as weight of coating per unit
area) for a fixed carbon black loading, i.e.
Optical Density -- - In (grams/m 2)
Water Quench
"'X AA, A/
gasair,,~.,..
feedstock ~/~___.w~,"
......
PRODUCTS
CARBON BLACK
2100 - 3 0 0 0 ~ F
Yield: 30 - 6 0 %
-,,
400 ~ F /
CO 2
CO
H~
N2
H20
" 3 ? "
Refectory
Burner ~, r ~ " ~ m -~i~l'~-"-~--- ~
~
~
2%.
.~' ~
"-d
SliderBelt ~ P e l ~ : i u Z ~ g } ~
II
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Bag Filter
CoveredHopperCar
Feeder
Compartments
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~ 1 1 ~ X ~ I,~X~ MagneticSeparator
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.
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~
J
l
/ I~lC ~__VibratingScreens
PrimaryCyclone / \ ~ ~i,----. Bag Filter'~ ,t:'
~~__~.~l~lv,e'r~~o, ,~~1. _ _ ~ l[tJ"l~ ~Air Fan.~'.Belt Conveyor
/ -~ ~ l J
,Exhauster, II
~: ~
.LI II ~ ~ ~ _
w~-~=,,~;IrF~terBags- "~r]L
/11 ~:
Bag Berquist
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"Packing Tank/
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L~.~IIltt~I~!~'~-~~]~.
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Absorption ////
o
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I
''.o
,l/~
o l9
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"
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* "0
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i .5 ,
41.
Low
Lig
~ Scattering
~ "
9 9
" ~"
ll~t:;
t'~& 9
-~-
"l
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-UlBi
9 #, : . , : 1
....
. .
185
,is
ir
~-,.~
Qo9
MEDIUM
"1
HIGH
Undertone
FIG. 8-Structure comparison.
In the carbon black industry, blacks are visually characterized as having a blue or brown undertone or some gradation
in between when dispersed in a coating system. In a black
coating it is called mass tone and in a gray it is called tint
tone. The phenomenon of undertone results from the fact
that both scattering and absorption efficiencies of carbon
black vary with wavelength [8]. Preferential absorption of
blue light tends to make the unabsorbed light reaching the
observer favor the red end of the spectrum (browner tone).
The degree of preferential absorption/scattering of the blue
end of the spectrum increases with decreasing aggregate size.
Thus, in a gray finish, where the absorption mechanism is in
'
'1''1
,J,
"
'
'
20O
~-3
Absorption
300
I S-
~%
100
so
b.
* D
Scattering
V
High Color
Blacks
Medium Color
Blacks
AGGREGATE SIZE
zo
50
75
, I
100
200
Da(nm)
I'~
500
Particle Size
FIG. 9-Tinting strength of a range of carbon blacks.
750
186
control, the finer the aggregates the browner the tint tone. In
mass tone we have the more complex situation where both
preferential scattering and preferential absorption, each with
a separate wavelength dependency, contribute to undertone.
Gloss
The term gloss is generally taken to mean the specular
reflectance of a surface measured at some specific angle (for
example, 60~ As with any pigment added to a transparent
vehicle, the gloss of the dried film will be influenced by the
loading and the properties of the carbon black. Starting with
an unpigmented coating having optimal gloss in the dried
film and adding a given carbon black incrementally (assuming excellent dispersions), a point will be reached where gloss
begins to deteriorate until eventually the finish becomes flat.
Since it is the resins in the dry film which create the smooth
surface for reflection, the addition of particulate substances
such as pigments or fillers in significant concentrations can
only interfere with the "smoothness" of the surface.
The properties of carbon black that affect the gloss of a
coating are: aggregate size, structure, and surface chemistry.
Other factors being constant, the finer the aggregate size the
less the effect on surface texture. The finer aggregate blacks
tend to give coatings with higher gloss when properly dispersed.
Higher structure, which means more void space and therefore higher oil absorption, tends to work against gloss. This is
because more vehicle is "tied up" for a given loading of black
in comparing a higher structure with a low structure black.
Once again we must emphasize the importance of quality of
dispersion. Since higher structure blacks are somewhat easier to disperse, the effect of structure can only be properly
observed in cases where optimal dispersion has been
achieved.
Surface chemistry generally refers to the amount of volatile
content or chemisorbed oxygen complexes on the surface
(that is, hydroxy|ic, carboxylic, quinonic, or lactonic groups).
Carbon blacks often are chemically oxidized after formation
(aftertreatment) to increase volatile content. While this is
usually done to improve rheological properties (for example,
flow, viscosity), it normally creates improved gloss as well.
The volatile content acts as a built-in dispersing agent, serving to reduce the amount of vehicle needed to completely
wet the surface of the black.
1. Incorporation (Wetting)--This step involves the displacement of occluded air and covering the surface of agglomerates with vehicle, yielding a workable dispersion mix.
Sometimes this is referred to in the coatings industry as premixing.
2. Pellet Breakdown--When pelleted black is used, Step 1,
Incorporation, is easier since initial mixing causes little, if
any, pellet fracture. Thus, at the worst, larger pellet fragments
need to be "wetted" by vehicle. Pellet breakdown must then be
accomplished by the application of additional energy (for example, longer mixing) after Step 1.
3. De-Agglomeration--This is the principal step in achieving optimal dispersion and the one that consumes most of the
applied energy. Interaggregate attractive forces must be overcome to break down agglomerates into their constituent primary aggregates.
TABLE 3--Preferred form of carbon black.
Preferred Form
Equipment
Two-roll mill
Three-roll mill
Steel ball mill
Attritor
Disk disperser
Sand/shot mill
Fluffy
Pellets
X
X
X
X
X
X
230-560
200-220
45-140
25-40
3.5/1 to 4.5/1
2.5/1 to 3.0/1
1.5/1 to 2.0/1
1.0/1
187
that is, using color and/or gloss development, which are extremely sensitive to small variations in degree of microdispersion.
Black Coatings
For coloring purposes, a grade of carbon black should be
selected that is as low as possible in surface area, but consistent with end use color specifications. This enables the formulator to take advantage of the greater ease of dispersion
and lower cost associated with the lower surface area. The
desired structure level would be high enough to give acceptable dispersibility, but not so high as to adversely affect gloss
or rheology. In some cases the use of aftertreated grades will
give an edge in dispersion and gloss as well as protect the
rheology at higher loadings. Normally, at opacity level loadings, rheology is only a problem when more concentrated
mill bases are used.
Implicit in the selection of a grade of carbon black is the
choice of the fluffy or pelleted form. The choice is usually
made on the basis of dispersion equipment available or on
ease of incorporation or both. Listings of preferred forms for
best results with each of the major pieces of equipment are
helpful (Table 3). Regarding ease of incorporation, if, for
example, a steel ball mill which is a very effective disperser is
to be used, the edge in dispersion provided by the fluffy form
is not really needed, so it is wise to consider the pelleted form
which will "wet in" quickly and which creates less dust on
handling.
Candidate grades must be dispersed in the specific formulation in which they are intended to be used. Keeping in mind
the sensitivity of color and gloss development to dispersion
quality, it is useful to evaluate jetness and gloss both at the
end of the prescribed grind cycle and again after an extended
cycle. This technique not only identifies which of the candidates will provide the color and gloss levels needed, but also
indicates whether or not full color value from a given grade
will be achieved under the prescribed dispersion conditions.
The factors of carbon black cost and dispersibility must be
weighed against desired color and gloss levels in making a
final decision. Some commonly used oil furnace grades for
the coatings industry are listed in Table 5.
188
Grade
ASTM Test
m2/g
Particle
Size,
nm
N/A
D 3037
N/A
Jetness
Index~
Surface
Area (BET),
DBP
Absorption,
cc/100 g
Fluffy
Pellets
D 2414
Tinting
Strength,
%
Volatile
Content,
%
D 3265
D 1620
Density,
lb/ft3
Fluffy
Pellets
D 1513
High
color
HCF 3
HCF 2
HCF i
60
64
69
560
560
340
13
13
16
90
100
105
80
90
100
100
100
116
9.0
9.5
9.5
17
16
11
27
25
24
Medium
color
MCF 4
MCF 3
MCF 2
MCF 1
70
74
73
78
230
220
210
200
15
16
17
18
70
112
74
122
64
105
68
117
120
122
120
118
2.0
1.5
1.5
1.5
14
8
15
9
29
21
28
19
Flow
grades
83
84
138
96
24
25
60
72
55
69
112
112
5.0
3.5
15
14
32
30
Regular
color
RCF
RCF
RCF
RCF
4
3
2
1
83
84
87
90
112
94
80
85
24
25
27
27
65
70
85
100
60
65
72
.-.
116
110
104
92
1.0
1.0
1.0
1.0
15
19
13
12
31
28
29
...
Low color
grades
LCF 4
LCF 3
LCF 2
LCF 1
93
95
96
99
43
42
35
25
37
41
50
75
95
...
...
72
...
121
90
64
80
62
60
58
1.0
1.0
1.0
0.5
11
..-..
18
...
22
27
33
[11].
10,000 I 6,000
Jetness
Jetness or blackness is a function of B E T surface area, i.e.,
inversely p r o p o r t i o n a l to aggregate size (Fig. 10). Traditionally, the industry assigned n i g r o m e t e r "scale" values, w h i ch
are a direct function of the a m o u n t of light reflected by
dispersed samples (coatings, plastics, etc.). S m a ll e r "scale"
values indicated jetter carbon blacks. However, the m o d e r n
a p p r o a c h is to m e a s u r e the spectral reflectance of a black
dispersion, w h i c h is m a d e possible by the e n h a n c e d sensitivity of cu r r en t instrumentation. The spectral reflectance
curves can then be converted to H u n t e r L, a, b; or CIE coordi-
--
4,000 I -
/s
/
2,000[
0,< 3,000 r
o ~r~
300
+4-
100|
50
60
I
70
80
90
Nigromater value
I
100
I
110
120
Undertone
The mass tone is m e a s u r e d as described above in the section on jetness. This is an i m p o r t a n t tool b ec a us e visual
ratings of jetness are usually influenced by u n d e r t o n e variations a m o n g blacks being rated.
189
Tinting Strength
As illustrated in Fig. 9, tinting strength increases with decreasing particle size. The differential m e a s u r e m e n t technique, d e s c r i b e d above, is u s e d to assign tinting strength
values. The procedure, ASTM Test D 387-86, Test M e t h o d for
Color a n d Strength of Color Pigments with a Mechanical
Muller, involves dispersing c a r b o n b l a c k together with a
white p i g m e n t in a wetting oil or other suitable vehicle. The
refectance of this d i s p e r s i o n versus a s t a n d a r d gray tile or
gray vitreous e n a m e l is t h e n a m e a s u r e of its tinting strength.
While it was c u s t o m a r y in the c a r b o n b l a c k i n d u s t r y for m a n y
years to r e p o r t tinting strength as a p e r c e n t of a reference
black (for example, IRB No. 4), some suppliers are n o w using
an i n d e p e n d e n t tinting strength index, allowing strength
c o m p a r i s o n s only within their own p r o d u c t lines.
Gloss
Clearly, this p r o p e r t y a n d the m a n n e r in w h i c h it is measured is not u n i q u e for c a r b o n black coatings. W h e t h e r the
p i g m e n t a t i o n is black o r any o t h e r color, the test (for example, for 60 ~ gloss) is the same.
SUMMARY
Individual key c a r b o n black p a r a m e t e r s have b e e n viewed
from the s t a n d p o i n t of their influence on the optical function.
It is i m p o r t a n t to emphasize, however, that these p a r a m e t e r s
do not o p e r a t e separately. The effect on optical functioning,
a n d therefore on p i g m e n t a r y properties, is a c o m b i n e d one.
E a c h p a r a m e t e r w h e n varied influences the o t h e r p a r a m e ters, w h i c h are also varying. Thus the situation is d y n a m i c
a n d complex.
REFERENCES
[1] Spengeman, W.F., ASTM Paint Testing Manual, Black Pigments, 2.8.4, 13th ed., 1972.
[2] Boonstra, B. B., "A, B . . . . Z of Carbon Black," an internal publication of Cabot Corporation.
[3] Dannenberg, E. M., "Carbon Black," Encyclopedia of Chemical
Technology, Vol. 4, 3rd ed., Wiley-Interscience, New York, 1978,
pp. 631-666.
[4] Donoian, H. C. and Medalia, A. I., Journal of Paint Technology,
Vol. 39, 1967, p. 716.
[5] Mie, G., Annalen der Physik, Vol. 25, No. 4, 1908, p. 377.
[6] Kubelka, P. and Munk, F., Zeitschrift f~r Technische Physik, Vol.
12, 1931, p. 593.
[7] Medalia, A. I. and Richards, L. W., "Tinting Strength of Carbon
Black," Journal of Colloid and Interface Science, Vol. 40, 1972, p.
233.
[8] Donnet, J. B. and Voet, A., Carbon Black, Marcel Dekker, New
York, 1976.
[9] Cabot Corporation, Special Blacks Division, Technical Report
S131, 1989.
U0] Judd, D. B. and Wyszecki, G., Color in Business, Science, and
Industry, 3rd ed., Wiley, New York, 1975.
{11] Cabot Corporation, Special Blacks Division, Technical Report
S136, 1988.
NOTE:
References 2, 9, a n d 11 are Cabot C o r p o r a t i o n internal publications copies of which are available from:
Cabot C o r p o r a t i o n
Special Blacks Division
157 Concord R o a d
Billerica, MA 01821
Phone: 800-462-2313, Fax: (508) 670-7035
TLX: 947119
MNL17-EB/Jun. 1995
iiii
21
D E F I N I T I O N OF A P I G M E N T
INTERNATIONAL NOMENCLATURE--THE
C.I. S Y S T E M
"Pigments are colored, black, white or fluorescent particulate organic and inorganic solids which usually are
insoluble in, and essentially physically and chemically
unaffected by, the vehicle or substrate in which they are
incorporated. They alter appearance by selective absorption and/or by scattering of light.
Pigments are usually dispersed in vehicles or substrates
for application, as for instance in inks, paints, plastics or
other polymeric materials. Pigments retain a crystal or
particulate structure throughout the coloration process.
As a result of the physical and chemical characteristics of
pigments, pigments and dyes differ in their application;
when a dye is applied, it penetrates the substrate in a
soluble form after which it may or may not become
insoluble. When a pigment is used to color or opacify a
substrate, the finely divided insoluble solid remains
throughout the coloration process."
In any m o d e m publication discussing pigments of any description, it is likely that the author will make use of the
coding system as published as a joint undertaking by the
Society of Dyers and Colourists (SDC) in the United Kingdom
and the Association of Textile Chemists and Colorists
(AATCC) in the United States.
This system is known as the "Colour Index," [1 ] and as such
is a recognized trademark, hence the retention of the "u" in
"colour" whenever reference is made to a "Colour Index"
name or number.
The Colour Index (C.I.) identifies each pigment by giving
the compound a unique "Colour Index Name" and a "Colour
Index Number." This description is proving to be most valuable to persons within the coatings industry responsible for
assembling data on the composition of a coatings formulation for documents such as Material Safety Data Sheets or
hazard data sheets. As such the identification of a pigment by
mention of its C.I. name and number unequivocally identifies
the chemical composition of the pigment in a manner acceptable to most government bodies. For example, DNA Orange
has the Colour Index name of Pigment Orange 5 (PO 5) and
the Colour Index number of 12075.
The Colour Index Name for a pigment is abbreviated as:
PB-PBr-PM-PV-PW--
190
Copyright9 1995 by ASTMInternational
www.astm.org
Pigment Blue
Pigment Brown
Pigment Metal
Pigment Violet
Pigment White
PBk-PG-PO-PR-PY--
Pigment Black
Pigment Green
Pigment Orange
Pigment Red
Pigment Yellow
191
CLASSIFICATION OF P I G M E N T S BY
CHEMISTRY
Pigments used in paints and coatings may be broadly divided into opaque or hiding whites and colored toners. All the
opaque whites are inorganic compounds and as such fall
outside the contents of this chapter. For the sake of clarity it
should be noted that such compounds include the following:
Lithopone (co-precipitate of barium sulfate and zinc
sulfide)
Zinc oxide
White lead (basic lead carbonate)
Antimony oxide
Titanium white (mixture of titanium dioxide and blanc
fixe)
Titanium dioxide (rutile form)
The colored pigments as covered in this section are all
organic in nature and as such contain a characteristic grouping or arrangement of atoms known as a "chromophore,"
which imparts color to the molecule. In addition, the molecule is likely to feature a number of modifying groups called
"auxochromes" that alter the primary hue of the pigment in a
more subtle way such as shifting a red to a more yellow shade
or a blue to a more red shade while still maintaining the
primary hue of red or blue rather than pushing the hue over
to an orange or a violet.
Perhaps the most important of the chromophores is the azo
chromophore ( - - N = N - - ) . The naphthol reds, monoarylide
and diarylide yellows, benzimidazolones, pyrazolones, and
azo condensation pigments are all examples of organic pigments that feature the azo chromophore. Of equal importance is the phthalocyanine structure based upon the compound tetrabenzotetra-azaporphin; halogenation of this
compound results in a major shift in hue from a blue to a
green. Pigments are also derived from heterocyclic structures
such as translinear quinacridone and carbazole dioxazine
violet. Finally there are pigments that result from the vat
dyestuffs and miscellaneous metal complexes.
HO COOPR 57
H3~SO N=N~
C
3
140 COOC~.~__ N=N~
RED2B
CH3~CI Exchange
Positions
PR 48
CH3
SO3- ~
HO CO0PR 52
C ~ N=N~ CHa--,C2H
BON
RsEMethyl
D ene(--CH~--)
Ct
CLASSIFICATION OF P I G M E N T S BY COLOR
Addition
SO3-
Reds
HO
C2HS
LITHOL
CI RUBINE
Add
PR 200
COO-
~'~
I ~ S O N=N- - ( ~
C
a-
-Co0- Subtract-COOH
HO
C2Hs
NN
CLARIONRED
C~Hs--~CH3 SubtractCH2
PO46
HO
CH~
PR 53
NN
CI~SO_=
REDLAKEC
192
so;-
H~___/COON=N
2-naphthylamine-l-sulfonic acid
Ca 2"
HO
NO2
N=N
CH MNPT
Beta Naphthol
FIG. 3-Structure of Toluidine Red, PR 3.
193
HO
NO~
N =N ~
ParaRed(PR 1)
kL.__/
p-nitroaniline
)beta naphthol
HO
NO2- ~ N c I
----N
ParachlorRed(PR4)
o-chloro-p-nitroanUine
,beta naphthol
HO
CI
~N----N~
NO2
ChlorinatedParaRed(PR6)
p-chloro-o-nitroaniline
> beta naphthol
FIG. 4-Structure of the para reds.
overstriping fastness have limited its more widespread use.
Lightfastness at both tint and full shade is rated good.
Pigment Orange 38, C.I. No. 12367. A very yellow shade,
bright red with good solvent fastness. Can be used in baking
enamels at high concentrations without showing any tendency to bloom.
Pigment Red 5, C.I. No. 12490. Showing only marginal
fastness to heat and solvents this pigment, nevertheless, finds
application in implement coatings. The opaque grade of this
pigment can be combined with iron oxide to give an economical red with high hiding.
Pigment Red 146, C.I. No. 12485. A very blue shade red that
finds its major use in interior architectural applications. Its
poor exterior durability makes the pigment unsuitable for
outdoor finishes.
Pigment Red 170, C.I. No. 12475. Increasingly important as
a medium performance, moderately priced red, this pigment
is available as both a transparent and an opacified grade.
Manufacturing techniques are used to produce the pigment
in two crystal phases, each exhibiting a unique hue. The
opaque grade finds use in farm tractor and implement finishes. Its use with iron oxides allows a practical approach to
formulating reds with acceptable lightfastness, hiding, and
economics.
Pigment Red 187, C.I. No. 12486. A transparent pigment
with excellent heat fastness, moderate durability, and good
bleed resistance. Its uses extend to bicycle coatings, coil, and,
powder coatings.
Pigment Red 188, C.I. No. 12467. A yellow, clean shade red
with acceptable durability at all depths of shade. It is fast to
194
P A I N T AND COATING T E S T I N G M A N U A L
6
5
N~
Colour Index
Number
2 ......................
7
9 ......................
10 . . . . . . . . . . . . . . . . . . . . .
14 . . . . . . . . . . . . . . . . . . . . .
17 . . . . . . . . . . . . . . . . . . . . .
22 . . . . . . . . . . . . . . . . . . . . .
23 . . . . . . . . . . . . . . . . . . . . .
112 . . . . . . . . . . . . . . . . . . . .
.
N[
12310
12420
12460
12440
12380
12390
12315
12355
12370
H
I
2'
Cj
II
4'
5'
Substituents
5
2'
4'
5'
CI
CH3
CI
CI
H
CI
H
H
CI
H
CI
CI
H
CH3
H
H
CI
H
CH3
H
H
H
H
NOr
CH3
CHa
OCH3
CI
CI
H
H
H
CI
H
NO2
NOa
NO2
CI
CH 3
CH3
H
H
CHa
H
H
H
H
H
H
H
H
NO2
H
OCH 3
II
II
High-Performance Reds
H
:
O
O
: <
t:'1
These types of pigments may be broadly defined as products that will meet the exacting demands of the automotive
industry with respect particularly to the outdoor exposure
requirements demanded by exposure in Florida and Arizona
for as little as two and as long as five years.
The high-performance reds considered fall into four basic
classes: quinacridone reds and violets, vat dyestuff based reds
such as perylenes, benzimidazolone reds, and disazo condensation reds.
Quinacridone Reds--These are heterocyclic in nature since
their structure comprises a fused ring in which the ring atoms
are dissimilar, being a combination of carbon and nitrogen
rather than only carbon as we have seen in the previous
pigments discussed, as shown in Fig. 6. Addition of differing
auxochromic groups such as methyl (--CH3) and chlorine
(--C1) gives Pigment Red 122 and Pigment Red 202, respectively, both described as magentas.
The theory behind the superior durability of pigments with
the quinacridone structure is that considerable hydrogen
bonding occurs between molecules through the carbonyl
(wC~-~O) and imino (~--~N--H) ring atoms.
As a group of pigments the quinacridones find their primary uses in automotive, industrial, and exterior finishes. A
minor use is in the preparation of quality furniture stains and
finishes. The pigments combine excellent tinctorial properties with outstanding durability, solvent fastness, lightfastness, heat fastness, and chemical resistance. Table 1 lists
those shades currently commercially available.
Vat Reds--Vat Red pigments based upon anthraquinone
include such structures as Anthraquinone Red (PR 177),
Perinone Red (PR 194), Brominated Pyranthrone Red (PR
216), and Pyranthrone Red (PR 226) as shown in Fig. 7.
The term "vat pigments" originates from the fact that this
class of pigments is related to the vat dyestuffs used originally
hydrogen
bond
formation
[I
II
in the dyeing of cotton. Only their high cost limits the more
widespread use of these pigments throughout the coatings
industry.
Anthraquinone Red, PR 177, C.I. No. 65300. A medium
shade red with excellent all round fastness properties. Again
finds major use in the automotive industry for the production
of clean, bright red coatings.
Hue
Comments
Gold
Magenta
Red-yellow
Magenta
Maroon
Scarlet
Red-yellow
Violet-blue
Red-yellow
Maroon
Quinacridone quinone
2,9-dimethyl
Mono methyl
2,9-dichloro
Solid solution
4,11-dichloro
3,10-dichloro
Beta crystal
Gamma crystal
Solid solution
195
NH2
R
IJ
C"" N__ R
IL
0
II
NH2 O
Anthraquinone Red (PR 177)
R = -06H3002H5
R = -CBH3(CH3)2
R = -CH3
R = -CsHsOCH3
R=-H
R = -C6HsCI
PR 123
PR 149
PR 179
PR 190
PBr 26
PR 189
Vermillion
Scarlet
Maroon
Red
Bordeaux
YellowShade Red
PR 178 Red
N~C~___~C%N
Perinone Red (PR 194)
Br3
CI
II
O
O
LI
Br2
IL
O
Pyranthrone Red (PR 226)
FIG. 7-Structure of typical vat reds.
OH
Co|our
Index
Name
PR 171
OCH3
PR 175 COOCH3
PR 176 O C H ~
PR 185 OCH3
PR 208 C00C4H9
FIG. lO-Structure
~ . / . . , . ~ N/
|
H
NO2
H
CONHCsHs
S02NHCH3
H
of the benzimidazolone reds.
196
AN
co-NHR NHC
c cF3
N
//
\\
NH ' - - ( ~ _ ~ N H ~
CI
FIG. 12-Structure of Pigment Red 242.
NNA
CI~.
CI
C I ~
N
//
N
A
CI
CI
N
\\
N
R
Pigment
Red 144
M.Wt. 828.5
CI
FIG. 13-Structure of Pigment Red 214.
CI
A
CI
Red
M.Wt. 863
CI
CI
c,.@
CHa
Red
M.Wt. 803
FIG. 11-Structure of the disazo condensation reds.
--CHa
-H
-Br
-H
PR 86
-H
-H
-H
-H
-H
-CI
-CI
PR 87
PR 88
-H
-H
-CI
-CI
-CI
-H
-H
-H
-H
-CH3
-CH3
-CH3
PR 181
PR 198
PV 36
PV 38
-CI
-CH3
-CI
-H
-CHa
197
CI
CI~
CI
Ni
I/I--O
/~
."
N'--H
N~..]//
N=
CI
CI
FiG. 15-Structure of Pigment Red 257.
"~/~
O
[I
~I=C~C--,N,
N
II
I; ,[ )N--e,,--N( IL "I
N
LI
N
I
D
FIG. 16-Generic structure of
pyrazoloquinazolone (basis of
Pigment Red 251 and 252),
Pigment Reds 251 and 252 are both based on the
pyrazoloquinazolone structure as shown in Fig. 16. These
pigments are monoazo compounds derived from pyrazolo(5,1-b)quinazolones as the coupling component and substituted anilines or polycyclic amines as diazo component.
Each pigment exhibits excellent brightness of hue at full
shades, good gloss retention, and high scattering power combined with good light and weather fastness. As such, they are
finding increased use in industrial and automotive coatings.
Recently a series of novel reds based upon the pyrrolopyrrole structure, Fig. 17, have been marketed into the automotive coatings industry. The first pigment marketed is a
bright red with excellent color intensity that will find use
alongside quinacridones and perylenes in automotive formulations.
Blues
c ~-....y
but its inferior heat stability and its poorer chemical fastness,
coupled with a price almost three times that of the copper
containing salt, has resulted in a rapid decline in its consumption for all but very special applications.
Copper phthalocyanine is commercially available in two
crystal forms, the alpha and the beta form. The alpha crystal
is described as Pigment Blue 15, 15 : 1 and 15 : 2 and is a clean,
bright red shade blue. The beta crystal is described as Pigment Blue 15:3 and 15:4 and is a clean green or peacock
shade.
The beta form is the most stable crystal form and readily
resists recrystallization. The alpha form, conversely, is the
least stable or meta form, which readily converts to the more
stable, green shade, beta crystal. As such the crystal requires
special proprietary treatments to produce a red shade product that is stable to both crystallization and flocculation.
Copper phthalocyanine gives excellent performance in
most coatings applications but there is considerable variation
between both the chemical and crystal types available. The
coatings formulator should bear this in mind when choosing
a grade for a specific application. Use of any of the
unstabilized grades in strong solvents or in systems that
experience heat during dispersion or application will result in
a shift in shade to the greener side and a loss of strength as
recrystallization takes place within the unstabilized crystal.
Pigment Blue 15 (C.L No. 74160) is a red shade, alpha
crystal. It is the least stable of the family and as such is
referred to as crystallizing red shade (CRS) blue.
Pigment Blue 15 : 1 is a modified alpha crystal also having a
red shade but with modifications to stabilize the structure
against phase transformation to the beta crystal. Most commonly the molecule is chlorinated to the extent of one molecule of chlorine per molecule of copper phthalocyanine to
give "monochlor" blue (C.I. No. 74250).
198
Pigment Blue 15:2, described as "non-crystallizing nonflocculating" (NCNF), red shade blue, is an alpha crystal that
is stabilized against both flocculation and recrystallization
using additive technology. Such additives are introduced during the manufacturing or blending operation and are essentially derivatives of copper phthalocyanine that confer stability by a steric hindrance mechanism.
Pigment Blue 15 : 3 represents the most stable crystal, green
shade, beta copper phthalocyanine. Pigment Blue 15:4 is
descriptive of a beta blue that has been modified with phthalocyanine-based derivatives to confer flocculation resistance to the crystal such that it can safely be used in strong
solvent systems.
Other specialized, more expensive crystal modifications
also exist such as P.B. 15 : 5, a red shade, g a m m a crystal and
P.B. 15:6, a very red shade, epsilon crystal.
Copper phthalocyanine is a pigment that offers brightness,
cleanliness, strength, and economy with all round excellent
fastness properties. The only drawback to this pigment is its
tendency to change to a coarse, crystalline nonpigmentary
form when used in strong solvent systems if the crystal has
not been adequately stabilized and has a tendency to flocculate from white pigments such as titanium dioxide when used
to tint such paint and lacquer systems. Another negative is
the fact that copper phthalocyanine blues exhibit the phenomenon of bronzing when applied at masstone levels, deep
tints, and in metallic systems.
Miscellaneous Blues
Indanthrone Blue--Pigment Blue 60, C.I. Number 69800.
Belonging to the class of pigments described as "vat pigments," indanthrone blue is a very red shade, nonbronzing,
NO2
PY 1
Hansa G
H~C
Yellows
Monoarylide Yellows
Azo pigments whose manufacture is based upon the diazotization and coupling sequence as mentioned when dealing
with azo reds. The structures of the major rnonoarylide yellows are represented in Fig. 19.
Itansa Yellow G - - P i g m e n t Yellow 1, C.I. Number 11680.
A bright yellow pigment, made by coupling diazotized 2nitro-4-methyl aniline onto acetoacetanilide, that has a major
use in trade sales, emulsion, and masonry paints. Its major
disadvantages are its poor bleed resistance in most popular
solvents, poor lightfastness in tint shades, and very inferior
bake resistance due to its tendency to sublime.
Hansa Yellow 10G--Pigment Yellow 3, C.I. Number 11710.
A very green shade yellow made by coupling the diazo of 4chloro-3-nitro aniline onto 2-chloro acetanilide. Greener in
shade than Pigment Yellow 1, this pigment is used in the
same types of applications and suffers from the same deftCH
COCH3
__~
I
N=N--CH--C--NH
PY 75
Jl
C1
N = N--C,CO-HN
OC2H 5
O
NOt
CI
OCH3
PY 97
Hansa 10G
o r - -
H3CO--~
OCH3
NO~
PY 65
H3CO
HaCO
NO2
N= N--CHOC#i--NH -- ~
PY 98
ooo.3
PY 73
Cl
PY 74
o
CI
H3CO
COCH
9
CH3
i
,--/
PY 116
N=N--CH--C--NH
II
O
OCH3
H~NOC
C-OH
N=N--C--COHN
HaCO
o2N
CH3
c, -LV# -
O
NO2
OCH3
#
o
FIG. 1 9 - S t r u c t u r e s of the major m o n o a r y l i d e yellows.
NHCOCH 3
199
light chrome yellow (PY 34) and shows improved light, heat,
and solvent fastness as compared to the other monoarylide
yellows. As may be expected from its shade, this pigments
major use is in lead-free coatings.
Diarylide Yellows
The structures of this commercially important range of
organic yellows are shown in Fig. 20. This figure clearly
shows the similarity between each of these pigments, which
are principally a backbone structure centered on 3,3'-dichlorobenzidine with modifications to the shade and properties by variation of the coupling component used in the diazotization reaction. Table 2 gives a summary of the properties
of the major diarylide yellow pigments of commercial significance.
Each of the diarylide yellows offers low-cost, reasonable
heat stability, and moderate chemical resistance. The major
worldwide market for this class of yellows is the printing ink
industry. These yellows are approximately twice as strong as
the monoarylide yellows dealt with previously; furthermore,
they offer improved bleed resistance and heat fastness. Nevertheless, none of the diarylide yellows have durability properties that would allow for their use in exterior situations and
as such should never be considered for an outdoor paint
application.
Minor applications in the area of toy enamels and pencil
coatings are found for the diarylide yellows, especially if a
lead-free formulation is specified.
A range of opacified diarylide yellows is available, having
undergone an after treatment that has reduced their surface
area and consequently given increased opacity that has resulted in these specific types exhibiting improved fastness
properties when compared against their nonopacified counter parts.
Benzimidazolone Yellows
Illustrated in Fig. 21, these yellows take their name from
the fact that each features the 5-acetoacetyl-aminobenzimidazolone molecule within its structure. Additionally
each is an azo pigment with an acetoacetylarylamide nucleus.
The exceptional fastness to heat, light, and overstriping is
attributed directly to the presence of the benzimidazolone
group within the pigments structure, first described in 1964
and offered to the marketplace in 1969.
Used initially for the coloring of plastics, these pigments
are now finding increased use in the coatings industry where
their excellent fastness properties are demanded. Table 3
gives a summary of the properties of this class of pigments.
Heterocyclic Yellows
All these yellow pigments contain a heterocyclic molecule
within their structure as shown by the examples presented in
Fig. 22. In spite of their apparent complexity, these new highperformance yellows continue to be introduced to satisfy the
exacting demands of the coatings industry. Pigments such as
Isoindoline Yellow (PY 139) and Quinophthalone Yellow (PY
138) are typical examples of such complex, novel chromophores introduced as recently as 1979 and 1974, respectively.
All of these pigments find application in high-quality coatings where the end use can justify the price of these highperformance products. Table 4 summarizes the properties of
PY 12
PY 13
PY 14
c, 1
0o0.3 ~
<~..-c-c.-N=N~
PY 81
O
I
NH--C--
PY 83
NH--C-- CH-- N = N ~ J
NH--C--CH-- N=N
PY 106
F
.~
PY 113
C I ~
c,
0o0.3 ?_~
NH--C--CH--N=N~
c, 1
N,-O-c,-H~|
O
NH--C--CH-- N=N
II
O
CI
-}
COOH,
COCH3
o0~3
PY 55
CI
OCH3
PY 17
C I ~
CI
OCH3
COCH3
PY 16
OH. COCH.~. 1
000.3
co. c#l
NH--C--CH-N=NII
O
PY 114
PY 126
PY 127
CI
coc.,
PY 152
----J2
Oranges
Table 5 lists those orange pigments that have significance
in todays marketplace.
Azo-Based Oranges
These oranges show considerable variation in structure as
can be seen from Fig. 23; all, however, have the azo chromo~
phore ( - - N = N - - ) featured within the molecule. The benzimidazolone oranges all feature the azo chromophore in addition to all being produced using 5-acetoacetylaminobenzimidazolone as the coupling agent.
Orthonitroniline Orange--Pigment Orange 2, C.I. Number
12060.
Prepared by the classical diazotization and coupling technique used for all azo pigments, this pigment is the product of
coupling diazo orthonitro aniline onto beta naphthol. Its
major outlet is in printing inks, and its use is not recom-
Common Name
PY 12
AAA Yellow
PY 13
PY 14
MX Yellow
OT Yellow
PY 17
OA Yellow
PY 55
PT Yellow
PY 83
Yellow HR
PY 106
Yelow GGR
PY 113
Yellow H10GL
PY 114
Yellow G3R
PY 126
Yellow DGR
PY 127
PY 152
Yellow GRL
Yellow YR
N=N--CH--~-- NH
PY 120
NH
H3COC\\
O
Yellow NCG
Yellow H10G
NH_C ~ O
Properties
Poor lightfastness. Poor bleed
resistance. Major use in printing
inks
PY 16
PY 81
201
~O
COOH
NH-- I
? OCH3
PY 151
O
PY 154
~O
N"-i
=.
O
CI
NH--C/'~O
coc.
N.
PY 156
O
~O
CI
N.-- C
N=N--CH--C-- NH
PY 175
II
O
NH
Colour Index
Name
Common Name
PY 120
Yellow H2G
PY 151
Yellow H4G
PY 154
Yellow H3G
PY 156
Yellow HLR
PY 175
Yellow H6G
Properties
202
c,
o . C -- N-- C2Hs
I
N=N--CH
NI
\#
PY 60
~ 2
"]
O
/N~
/ N\
/~-NxH
O=C
C=C
C=C
C=
XN----/~ ~
//~--N/H
PY139
'
CH3
H' o ~ _ ?
Arylide Yellow
Isoindoline Yellow
OH
OH
py,
O
~ N ~~x
CH=N--N=CH
O
kk NH
~ -//- I ~ H
O
PY 101
Pyrimidine Yellow
Methlne Yellow
NH~C -- O
CH,,
CH3
Cl
PY 109
N~
CI. ~
Cl
ICl NH[~NH/~.~
cl . - ' - . ~ / ~ c ~
/
/ N ~ fN~
Q Ni.. Q-H
II
C
11 -- NH
C H 3 - - C - - --~
PY 153
\C-'~.y__.~ Cl
II
CI
H--O..# ~ N ~ O
(31
I I /
Cl
O%/OCH3
C
[~
./C ~
C,
PY 155
PY 110
C," t
"1~
CI O
~" ~ "
O CI
C,
OcOH,.,
\\ /
O
/C\\ N
H3CO O \C / \ N ~
I
/n.,.%
Tetrachloroisoindollnone Yellow
H3C
O%/OCH3
H
" ~
Io1
/C%
H3CO 0
-o" c u ~ + \ ~
PYl17
a 2
CH=N
~ N - ~
PY 173
N%
= R2 = CI
r~C'NH~H ~0~ 30%R~
70%R~ = H, R2 = CI
"%0
Azomethine Yellow
O//,..
Isoindolone Yellow
PY 138
,,N,
O=C C=O
_~
c,
o,
CI
.~
%cOCH,
? c,
/C~CI
C%
I< )1
c-'--..7~ c,
O CI
PY ,8~
~
~
H~OO
H"~
N//N" C'/C~O OCH3
~2"m.
o o~LJ"o
I
CI
Quinophthalone Yellow
FIG.
22-Structures of the
Triazinyl Yellow
heterocyclic and azo c o n d e n s a t i o n yellows.
Properties
PY 60
PY 101
PY 109
PY 117
PY 129
PY 138
PY 139
PY 150
PY 153
PY 155
PY 173
PY 182
203
Miscellaneous Oranges
F i g u r e 24 illustrates the structures of those oranges that fall
into a "miscellaneous" category as far as such structures have
b e e n declared. Table 6 s u m m a r i z e s the p r o p e r t i e s of this
series of pigments, each of which is finding increased use
within the coatings industry.
Greens
industry.
Colour Index
Name
Colour Index
Number
PO 2
PO 5
PO 13
PO 16
PO 31
PO 34
PO 36
PO 38
PO 43
PO 46
PO 48
PO 49
PO 51
PO 52
PO 60
PO 61
PO 62
PO 64
PO 67
12060
12075
21110
21160
20050
21115
11780
12367
71105
15602
n/aa
n/a
rda
n/a
11782
11265
11775
12760
12915
Chemical Type
Azo
Azo
Bisazo
Bisazo
Bisazo condensation
Bisazo
Benzimidazolone (Azo)
Azo
Perinone
Azo
Quinacridone
Quinacridone
Pyranthrone
Pyranthrone
Benzimidazotone (Azo)
Tetrachloroisoindolinone
Benzimidazolone (Azo)
Heterocyclic Hydroxy
Pyrazoloquinazolone
204
NO~
HO
ure 25 illustrates the proposed structures of the phthalocyanine greens. The most highly brominated product, Pigment Green 36, sometimes referred to as "green 6Y" or "green
8G," has an extreme yellow shade and contains 12-13 chlorine atoms.
Both greens exhibit outstanding fastness properties to solvents, heat, light, and outdoor exposure. They can be used
equally effectively in both masstone and tints down to the
very palest depth of shades. Metallic automotive paints may
feature phthalocyanine green at all shade depths. Approximately 50% of the worldwide production of copper phthalocyanine green is consumed by the coatings industry.
PO 2
OrthonitroanilineOrange
_._/
PO 5
NO~
HO
k._.._
O2N--/{'I~"k7-- N= N --~/("~~
Miscellaneous Greens
DinitroanilineOrange
PO 13
N CH--N=N
',\C/
I
CHa
PyrazoloneOrange
CH3 -~
coo.,
PO 16
DianisidineOrange
-H3C~F-
N C #O
Cl
-]
PO 34
Toly!Orange
Health and Environmental Concerns
CI
HO
C--NH
NHCOCH3
PO 38
NaphtholOrange
PO 46
C l ~
N=N
SO a -
Ba2"
~
ClarionRed
FIG. 2 3 - S t r u c t u r e s
of the a z o - b a s e d oranges.
205
O
II
~---------~
N%C~--
PO 43
CI
~O
C\
N
PO 51
o~ ~
Perinone
0
Pyranthrone Orange
O
II
O
II
CI
O
II
CI
CI~--CI
II
0
PO 48
and
PO 49
II
0
II
0
CHa
H
PO 61
CI--~CI
CI
CI
Tetrachloroisoindolinone
FIG. 24-structures of the miscellaneous oranges.
cI
PigmentGreen7 C I ~
CI
N=C //C--N
PO 48
c,
Properties
Perinone. Red shade. Strong clean vat
pigment with excellent fastness properties.
Used in metallized finishes and high grade
paints. Shows slight solvent bleed
Quinacridone gold. Yellow shade. Excellent
lightfastness. Lacks brightness in
masstone. Used in metallic finishes
CI / ' ~
c
Br
Pigment
Green36~6Y
Br
PO 51
PO 52
PO 61
PO 64
PO 67
Br
Br ~
II
II
/
(3
I .-N..
N= C
--.
"C
N=C
.~C--N
\N ~
II
c,
If
C--N
CI ~
C I ~
N=C
PO 49
cI
Cl
CI
CI
Br
Br
..c ~ . . . r ~ Br
LI
C-- N
N~C
C--N
c, I
N~C
Pigment
Green36-3Y
II
C--N
CI
Br
Br
FIG. 25-Proposed structures for phthalocyanine greens (PG
7 and PG 36),
206
Chemical Name
Properties
PG 1
Brilliant Green
(Triphenylmethane PTMA)
PG 2
Permanent Green
(Triphenylmethane PTMA)
PG 4
Malachite Green
(Triphenylmethane PTMA)
PG 8
Pigment Green B
(Nitroso)
PG 10
Green Gold
(Nickel azo
complex)
207
Exposure Testing
It is n o w generally a c c e p t e d within the coatings i n d u s t r y on
a w o r l d w i d e basis that the true test of a h i g h - p e r f o r m a n c e
p i g m e n t is t h r o u g h p r o l o n g e d o u t d o o r exposure at specifically chosen sites in the state of Florida. To this end, m a n y
c o m m e r c i a l e s t a b l i s h m e n t s exist in the state t h a t will provide
a controlled service to expose s p r a y e d panels of p i g m e m e d
coatings angled in a p r e d e t e r m i n e d w a y t o w a r d s the sun for
p e r i o d s up to five years with assessments at intervals d u r i n g
this five-year period. Typically m a n y duplicate panels will be
exposed p e r test with a panel being r e t u r n e d to the formulator every six m o n t h s such t h a t a m e a s u r e of the system's
w e a t h e r a b i l i t y as a function of t i m e is m a i m a i n e d on r e c o r d
for each p i g m e n t a n d each system used in o u t d o o r situations.
Fastness Tests
The t e r m "fastness" is used in this context to relate to h o w
susceptible o r d u r a b l e a p i g m e n t is to the p a r a m e t e r u n d e r
test. As such, the p i g m e n t s fastness to light, heat, solvents,
etc. can all be m e a s u r e d a n d quantified using a "Fastness
Scale" w h i c h rates a p i g m e n t from 1 (poor) to 5 (excellent) in
all cases except lightfastness w h i c h is subdivided i m o 1
t h r o u g h 8, 1 being total failure to 8 being outstanding.
Among those p r o p e r t i e s i m p o r t a n t to the f o r m u l a t o r are
fastness to solvents, where bleeding is observed by allowing a
q u a n t i t y of the d r y p i g m e n t to stand for 24 h in contact with a
solvent a n d observing any d i s c o l o r a t i o n of the solvent that
occurs, fastness to heat, w h e r e the effect of stoving t e m p e r a tures on the p i g m e n t f o r m u l a t e d into a finished coating are
observed, fastness to acidic or alkaline e n v i r o n m e n t s a n d
fastness to light, where several tint levels of a f o r m u l a t i o n are
exposed in such artificial sources as the X e n o n o r c a r b o n arc
f a d e - o m e t e r (ASTM D 822: Practice for Conducting Tests on
REFERENCES
[1] NPIRI, Raw Materials Data Handbook, Vol. 4: Pigments, 1983, p.
6.
[2] ColourIndex, American Association of Textile Chemists and Colorists, Research Triangle Park, NC, 27709, 1980. Pigments supplementary volume.
BIBLIOGRAPHY
American Association of Textile Chemists and Colorists, Research
Triangle Park, NC, 27709.
Dry Color Manufacturers Association, North 19th St, Arlington, VA,
22209.
Ehrich, F. F., "Pigments," in Encyclopedia of Chemical Technology,
Vol. 15, John Wiley & Sons, New York, 1968.
Fytelman, M., "Pigments," in Encyclopedia of Chemical Technology,
3rd ed., Vol. 15, John Wiley & Sons, New York, 1978.
Geissler, G., Polymers Paint and Colour Journal, 30 Sept. 1981, pp.
614-623.
Hopmeir, A. P., "Pigments," Encyclopedia of Polymer Science Technology, Vol. 10, Interscience, New York, 1969, pp. 157-193.
Lewis, P. A., "Pigment Handbook," Vol. 1, 2nd ed., John Wiley &
Sons, New York, 1987.
Lewis, P. A., "Organic Pigments," FSCTMonograph Series, Philadelphia, PA, 1988.
Lewis, P. A., "Organic Pigments," Coatings Technology Handbook,
Marcel Dekker, Inc., New York, 1991.
Lubs, H. A., "The Chemistry of Synthetic Dyes and Pigments," ACS
Monograph, No. 127, American Chemical Society, Reinhold, New
York, 1955.
208
Muzall, J. M. and Cook, W. L., Mutagenicity Research, Vol. 67, Elsevier Press, Amsterdam, 1979, pp. 1-8.
Moser, F. H. and Thomas, A. L., "Phthalocyanine Compounds," ACS
Monograph No. 157, American Chemical Society, Reinhold, New
York, 1963.
Mills, W. G. B., Paint Chemists Handbook, Scott Greenwood, London, 1962.
NPIRI Raw Material Data Handbook, Vol. 4, "Pigments," Lehigh
University, Bethlehem, PA, 1983.
NPCA Raw Materials Index, Pigments Section, Washington, DC
20005.
MNL17-EB/Jun. 1995
C L A S S I F I C A T I O N OF I N O R G A N I C
P I G M E N T S BY C H E M I S T R Y
12FeSO4.H20 + 302
C L A S S I F I C A T I O N OF P I G M E N T S BY COLOR
Most likely, when searching for a color to fulfill a particular
specification, the coatings formulator is likely to begin the
search on the basis of color rather than chemistry. Accordingly, the remainder of this section will concentrate on the
classification of inorganic pigments based upon their color
rather than their chemistry.
Reds
4FeO.Fe203 + 02
) 6Fe203
3. Precipitated red oxide can be prepared in an aqueous medium by growing seed nuclei in the presence of a ferrous
salt and scrap steel, the lightness/darkness of the resulting
pigment being determined by the crystal size distribution
of the precipitate.
4. By calcining synthetic yellow iron oxide to give the dehydrated product, Fe203.
The wide range of red iron oxide shades available, in addition to their acid and alkali resistance and their economy,
accounts for the large volume of these pigments used in
today's coatings marketplace.
Molybdate Orange
This pigment is, in fact, Pigment Red 104, a very yellow
shade of red that has the common name of molybdate orange,
a pigment based upon oxides of lead, chromium, and
molybdenum with the empirical formula of PbCrO4.
xPbMoO4.yPbSO4, a solid solution of lead chromate, lead molybdate, and lead sulfate.
Molybdate orange is produced by the addition of a solution
of sodium chromate, sodium molybdate, and sodium sulfate
under carefully controlled conditions into a solution of lead
nitrate at a temperature between zero and 40~ to precipitate
the mixed crystal. Control of particle size, particle-size distribution, and crystalline shape combine to determine the actual hue of the pigment, from a red shade of yellow to a red
shade of orange with specialty hues such as "chili red."
An opaque pigment with high solvent fastness, moderate
heat fastness, and good economy, molybdate orange finds its
major outlet in the coatings industry, particularly industrial
finishes. On the negative side, the pigment has poor alkali and
acid resistance; nontreated grades also tend to darken markedly on prolonged exposure to the environment. Additionally,
the pigment is based upon lead, which has been under an
"environmental cloud" for some years, a fact which has resulted in molybdate orange being replaced by more expensive, but less toxic, organic reds in decorative paints and
almost all original equipment manufacturer (OEM) automotive paints made in the United States.
209
Copyright9 1995 by ASTM International
www.astm.org
210
CdS.xCdSe.yBaSO4
LEAD CHROMATES
Pigment Yellow 34
PbCrO4.xPbSO4
Molybdate orange
Pigment Orange 21
PbO-xPbCrO4
Pigment Green 15
Pigment Yellow 42
Pigment Yellow 43
Fe203.xH20
Pigment Brown 6
Pigment Brown 7
Fe203
Pigment Green 17
Cr203
Pigment Green 18
Cr203.2H20
Violets
SULFIDESAND SULFOSELENIDES
Pigment Yellow 35
CdS.xZnS.yBaSO4
Pigment Yellow 37
CdS
Cadmium yellow
Pigment Orange 20
CdS.xCdSe.yBaSO4
Cadmium red
MISCELLANEOUSTYPES
Technically blue shade reds, the two most important inorganic violet pigments are Pigment Violet 15, ultramarine
violet, prepared by the oxidation of ultramarine blue, Pigment Blue 29, and Pigment Violet 16, manganese violet, prepared when manganese dioxide and diammonium phosphate
are slurried at high temperatures in phosphoric acid.
Ultramarine violet has good heat and light fastness and a
brilliant red shade. The pigment will react with metals to
form sulfides and finds use in cosmetic applications and specialty acrylic poster paint and artists colors.
Manganese violet does not possess the same brightness of
hue as Pigment Violet 15 and has only moderate opacity and
poor alkali resistance. On the plus side, the pigment has high
lightfastness and superior fastness to solvents and overstripe
bleed. Major uses are in the plastics and cosmetics industry.
Blues
Iron Blue
Pigment Blue 27
Fe(NH)4Fe(CN)6.xH20
Pigment Blue 28
COA1204
Cobalt blue
Pigment Blue 29
Na6_sa16si602452_4
Ultramarine blue
Pigment Violet 16
MnNH4P207
Manganese violet
Bismuth vanadate/molybdate
yellow
Cadmium Red
Cadmium sulfoselenide red, Pigment Red 108, is a solid
solution of cadmium sulfide and cadmium sulfoselenide produced by calcining co-precipitated cadmium sulfide and sulfoselenide, the pigment's hue is determined by the amount of
cadmium sulfoselenide incorporated into the solid solution
and, to a lesser extent, the temperature of processing. Pigment Red 108:1 is a co-precipitate with barium sulfate having the empirical formula
Ultramarine Blue
Going by such varied common names as Laundry Blue,
Dolly Blue, and lapis lazuli, this pigment, made by the controlled grinding of a mixture of calcined kaolin, soda ash,
sulfur, coal, and sodium sulfate, is Pigment Blue 29. Empirically the product is Na6A16Si6024S4, and its major use is as a
component of laundry powders and detergent soaps. Less
than 5% of the production is used in the coatings industry for
interior emulsion paints that require high alkali resistance
and lightfastness.
Yellows
Strontium Yellow
Strontium chromate, SrCrO4, prepared by precipitating a
suitably soluble chromate with an appropriate strontium salt,
is Pigment Yellow 32. Finding a primary use in corrosioninhibiting coatings, this pigment has poor tint strength, low
opacity, and unsatisfactory alkali and acid resistance, which
limits its more widespread use in the coatings industry.
Chrome Yellow
Zinc Chromate
Also called zinc yellow, this pigment is identified as Pigment Yellow 36, as opposed to the lithopone version incorporating barium sulfate which is Pigment Yellow 36: 1. It is a
bright, green shade of yellow made by the precipitation of
hydrated zinc potassium chromate from the reaction of sodium bichromate with zinc oxide and potassium chloride.
The lithopone version is merely a co-precipitate of zinc chro-
212
Oranges
Chrome Orange
A basic lead chromate, Pigment Orange 21, is formed under
alkaline conditions to give a product of empirical formula
PbCrOg.xPbO, shades varying from a yellow shade to red
shade dependant upon the alkalinity maintained during the
reaction sequence.
As with all lead-containing pigments, the product will
darken on exposure to the atmosphere, the rate dependant
upon the sulfur content. The pigment offers low cost and
moderate lightfastness and finds use in the protective coatings marketplace with some use as a shading pigment for
road traffic paints.
) CO + N a 2 C O 3 -k Cr203
Browns
Cadmium Orange
Pigment Orange 20, cadmium sulfoselenide orange, is a
solid solution produced by calcining cadmium selenide with
cadmium sulfide at approximately 1000~ (1800~ A change
in the ratio of the solid solution components gives pigments
that are bright yellow (PY 35) to bright red (PR 108). Barium
sulfate added or produced during the processing will form
the lithopone grade, Pigment Orange 20: 1.
This pigment is used in industrial coatings, for color coding
applications, where chemical and heat resistance are principal requirements.
Greens
Chrome Green
These pigments are merely mixtures of a green shade
chrome yellow (PY 34) and iron blue (PB 27). As such, Pigment Green 15 offers a range of hues with a light yellow shade
to a deep dark shade, providing good hiding, high tint
strength, and a moderate chemical resistance at an economical price. It can be used for bake enamels where the bake
temperature does not exceed 148~ (300~ but is restricted
to exterior and industrial coatings applications as opposed to
decorative finishes because of its lead content.
213
REFERENCE
BIBLIOGRAPHY
[1] Gosselin, R. E. and Smith, R. P. et al., Clinical Toxicology of Commercial Products, 5th ed., Williams and Wilkins, Baltimore, 1984,
p. VI 172.
MNL17-EB/Jun. 1995
Ceramic Pigments
by Richard A. Eppler 1
CERAMIC P I G M E N T S U S E D IN ORGANIC
PAINTS
The major criterion used in selecting ceramic pigments for
organic paints is hardness. The pigments listed in Table 1 and
discussed below are those that can be used in paint processing equipment without causing excessive wear. Property attributes of the pigments are given in Table 2. All are compatible with most polymer systems, with manganese-doped
ruffle especially useful when it is necessary to avoid iron.
Nickel-doped ruffle, which is often called Sun Yellow, is
produced from a mixture of various amounts of titanium (IV)
oxide, nickel (II) oxide, and antimony (V) oxide by high1Eppler Associates, 400 Cedar Lane, Cheshire, CT 06410.
temperature calcination [1 ]. The result is formation of a crystalline matrix of rutile that has the basic chemical formula
(Ti,Ni,Sb)O2. The pigment is used for coloring high-performance industrial coatings, wire coatings, vinyl sidings, automotive and other exterior paints, as well as for roofing, granules, porcelain enamels, and ceramic bodies.
Chrome-doped rutile is prepared from a mixture of varying
amounts of titanium (IV) oxide, chrome (III) oxide, and antimony (V) oxide by high-temperature calcination [1]. The
resultant crystalline ruffle matrix has the basic chemical formula (Ti,Cr,Sb)O2. The orange-yellow pigment is used for
coloring the same systems as nickel-doped ruffle.
Manganese-doped rutile is prepared from a mixture of various amounts of titanium (IV) oxide, manganese (II) oxide,
and antimony (V) oxide by high-temperature calcination [1].
The resulting crystalline ruffle matrix has the basic chemical
formula (Ti,Mn,Sb)O2. The brown pigment is used for coloring the same systems as nickel-doped futile.
Spinel brown pigments are an example of the 2-4 inverse
spinels [4]. The basic pigment is prepared by a high-temperature calcination of titanium (IV) oxide and iron (II) oxide [1].
The resulting crystalline matrix of spinel is brown in color
and has the basic chemical formula Fe2TiO4. The spinel phase
permits extensive substitution, within defined limits, with
other compounds to provide a variety of shades of brown.
Modifiers used for substitution include Al203, CoO, Cr203,
Fe203, MnO, and ZnO. The pigments are used for coloring
high-performance industrial coatings, wire coatings, vinyl
sidings, and automotive and other high-quality exterior
paints.
Titanate green and blue-green pigments are also produced
by high-temperature calcination of mixtures of titanium (IV)
oxide, cobalt (II) oxide, nickel (II) oxide, and zinc (II) oxide to
form a crystalline matrix of inverse spinel [1 ]. The pigments
have the basic chemical formula (Co,Ni,Zn)/TiO 4. The pigments are used for coloring the same systems as the spinel
brown pigments.
Cobalt blue pigments are crystalline spinels formed by
high-temperature calcination of cobalt (II) oxide and aluminum (III) oxide in varying amounts [1 ]. The basic cobalt blue
pigment (CAS 68186-86-7) has the chemical structure
CoAl204. The lighter-colored cobalt blue is prepared by addition of zinc (II) oxide to the ingredients used for the basic
pigment. The chemical structure of the resultant material
(CAS 68186-87-8) is (Co,Zn)Al204. Blue-green shades are produced by introduction of chromium (III) oxide, partially replacing aluminum (III) oxide in the basic cobalt blue system.
It has the chemical formula Co(Al,Cr)204. In addition to being
214
Copyright9 1995 by ASTM International
www.astm.org
CHAPTER 2 3 - - C E R A M I C PIGMENTS
215
Pigment
Powder Color
Ceramic Pigment
Nickel-doped rutile
Chrome-doped rutile
Color Index/Name
Yellow
Orange-yellow
or maple
Brown
Brown
Green
Manganese-doped futile
Spinel brown
Titanate greens and
bluegreens
Cobalt blue
Cobalt-zinc blue
Blue (basic)
Blue (lighter
than basic)
Blue-green
Purple
Purple
Jet black
Jet black
CAS Number
77788/Pigment Yellow 53
77310/Pigment Brown 24
71077-18-4
68186-90-3
68412-38-4
68187-02-0
68186-85-6
77346/Pigment Blue 28
77347/Pigment Blue 72
68186-86-7
68186-87-8
77343/Pigment
77360/Pigment
-..
77428/Pigment
66502/Pigment
68187-11-1
13455-36-2
10101-66-3
68186-91-4
68186-97-0
Blue 36
Violet 14
Black 28
Black 27
TABLE 2--Properties of recommended ceramic pigments (see Table 1 for color and pigment reference numbers).
Ceramic
Pigment
Heat
Stability
Weathering
Properties
Light
Fastness
Acid/
Alkali
Resistance
Hydrolytically
Stable
Nonmigrating/
Bleed
Nickel-doped
rutile
Chrome-doped
rutile
Manganese-doped
rutile
Spinel brown
Titanate greens
and bluegreens
Cobalt blue-basic
Cobalt zinc blue
Cobalt chromite
blue
Cobalt phosphate
violet
Manganophosphate
violet
Ceramic Jet black
Ceramic Jet
black--stronger
High
Excellent
Excellent
Excellent
Yes
Yes
High
Excellent
Excellent
Excellent
Yes
Yes
High
Excellent
Excellent
Excellent
Yes
Yes
High
High
Excellent
Excellent
Excellent
Excellent
Good
Excellent
Yes
Yes
Yes
Yes
High
Excellent
Excellent
Excellent
Yes
Yes
High
High
Excellent
Excellent
Excellent
Excellent
Excellent
Excellent
Yes
Yes
Yes
Yes
High
Excellent
Excellent
Excellent
No
Yes
High
Excellent
Excellent
...a
No
Yes
High
High
Excellent
Excellent
Excellent
Excellent
Excellent
Excellent
Yes
Yes
Yes
Yes
~Manganophosphate violet has good acid resistance, but poor alkali resistance.
used to color the s a m e systems as the rutiles, the c o b a l t blues
are used in c e r a m i c glazes.
Cobalt p h o s p h a t e violet is p r e p a r e d b y h i g h - t e m p e r a t u r e
calcination of cobalt (II) oxide a n d p h o s p h o r u s (V) oxide to
form a crystalline p h o s p h a t e [1]. It has the f o r m u l a Co3(PO4) 2.
It is used for coloring the s a m e systems as the spinels a n d in
p r i n t i n g inks. M a n g a n o p h o s p h a t e violet is p r o d u c e d by a
p r e c i p i t a t i o n process from a m m o n i u m salts of m a n g a n e s e
(IID a n d p h o s p h o r u s (V) [3]. This p i g m e n t has the c h e m i c a l
f o r m u l a NH4MnP207. It is used for inks a n d other applications w h e r e h e a t stability is of less i m p o r t a n c e .
One c e r a m i c b l a c k is a jet black p o w d e r p r o d u c e d b y calcin a t i o n of mixtures of c o p p e r (II) oxide a n d c h r o m i u m (III)
oxide to form a crystalline spinel [1]. The basic jet b l a c k has
the f o r m u l a CuCr204. A m a r g i n a l l y stronger black is prod u c e d b y a h i g h - t e m p e r a t u r e calcination of cobalt (II) oxide,
i r o n (III) oxide, a n d c h r o m i u m (III) oxide in varying
a m o u n t s , also to form a spinel. The p r o d u c t has the c h e m i c a l
216
T E S T I N G OF CERAMIC P I G M E N T S
Ceramic pigments are usually tested for two important
properties--particle size and tinting strength. Hardness is
essentially a property of the pigment crystal produced and is
insensitive to production details. Hence, handbook values for
the crystal are usually adequate for most purposes.
There are three aspects of particle size to be considered: (1)
the particle-size distribution; (2) the concentration of coarse
particles; and (3) the particle shape as it affects the formulation of the paint. The measurement and reporting of particlesize distribution of pigments in paints is contained in ASTM
Practice for Reporting Particle Size Characteristics of Pigments (D 1366) [6]. The practice covers measurements by
microscopic techniques, sedimentation methods, turbidimetric methods, absorption, and permeability methods. The recent laser dispersion and electric sensing zone techniques are
not yet dealt with in this standard. The procedures described
in ASTM Test Method for Particle Size Distribution of Alumina or Quartz by Electric Sensing Zone Techniques (C 690)
and ASTM Test Method for Determining Particle Size Distribution of Alumina or Quartz by Laser Light Scattering
(C 1070) should be applicable to ceramic pigments [7].
Determination of the concentration of coarse particles that
may cause defects in a coating is covered by ASTM Test
Methods for Coarse Particles in Pigments, Pastes, and Paints
(D 185) [6].
The amount of pigment which may be added to a paint
formulation is a strong function of the shape of the pigment
particles. Higher loadings are possible for pseudo-spherical
particles than is possible with plate-like particles. This prop-
erty of a pigment is measured by determining the oil absorption characteristics of the pigment as described in ASTM Test
Method for Oil Absorption of Pigments by Spatula Rub-out
(D 281) [6].
Tinting strength is the other important characteristic that
needs to be evaluated. The determination of the color of a
pigment requires that it be dispersed into a medium similar
to that in which it is to be used. It is never acceptable to imply
application color from the color of a dry pigment. The techniques for dispersing a pigment in a suitable vehicle and then
measuring the color in both masstone and letdown are detailed in ASTM Test Method for Color and Strength of Color
Pigments with a Mechanical Muller (D 387) [6].
REFERENCES
[1] DCMA Classification and Chemical Description of the Mixed Metal
Oxide Inorganic Colored Pigments, 2nd ed., Dry Color Manufacturers' Association, Arlington, VA, 1982.
[2] Eppler, R. A., "Ceramic Colorants," in Ullmann's Encyclopedia of
Industrial Chemistry, Vol. A5, VCH Verlagsgesellschaft mbH,
Weinheim, Germany, 1986.
[3] Product literature from Shepherd Color Company, Cincinnati,
OH.
[4] Muller, O. and Roy, R., "The Major Ternary Structural Families,"
Springer Verlag, Berlin, 1974.
[5] Calbo, L. J., Ed., Handbook of Coatings Additives, Marcel Dekker,
Inc., New York, 1987, especially pp. 511-539.
[6] ASTM Annual Book of Standards, Part 6.02: Paint--Pigments, Resins, and Polymers.
MNL17-EB/Jun. 1995
Extender Pigments
by Henry P. Ralston 1
CALCIUM CARBONATE
Description
Calcium carbonate, also known as calcite, whiting, or limestone, has the chemical formula CaCO3. It is produced by dry
or wet grinding of limestone or by precipitation via carbonization of slaked lime. Product from ground limestone is dependent upon both the initial crude mineral and the subsequent degree of processing or beneficiation. Limestone ore is
crushed and milled; the dry ground product is air classified to
different particle-size fractions. Wet ground product is milled
as a slurry, undergoes flotation to remove impurities, and is
then filtered and dried. The coarser dry-ground grades of
calcium carbonate are used as inexpensive fillers.
Precipitated calcium carbonate is produced by heating natural limestone to form calcium oxide, which is then slaked in
water and reacted with carbon dioxide to form a low-solids
slurry. The precipitate is vacuum filtered, dried, and ground.
Both particle shape and size of precipitated grades can be
~Technical Service Engineer, Engelhard Corporation, 101 Wood
Avenue South, Iselin, NJ 08830.
Physical Properties
Calcium carbonate products are differentiated further by
physical properties such as particle size, brightness, residue,
and, for precipitated grades, oil absorption. Fine-particle-size
products have an average particle size of from less than 1 to
about 4 ~m with coarse-particle-size grades ranging up to
about 15 ~m. Most are high in brightness, ranging from 90 to
98, with a pH of 9 to 10. Ground carbonates have low oil
absorption which correlates with low resin demand in coatings.
Coatings Performance
Calcium carbonate is widely used in water-based trade
sales architectural coatings since it is less expensive than
titanium dioxide, a primary pigment in paints and coatings,
and significantly lowers raw material cost. Fine-particle-size
calcium carbonate functions as an extender by spacing titanium dioxide and maintaining or improving optical properties of the dry coating film at lower titanium dioxide levels.
Higher-oil-absorption (binder demand) precipitated grades
may contribute to opacity. Finer-particle-size grades tend to
develop high gloss; high brightness can have a positive effect
on the color of the coating.
Coarser grades of calcium carbonate are primarily used as
fillers to reduce cost but also contribute to flatting and enhance low sheen control. Some grades may cause frosting
and chalking in exterior applications.
KAOLIN
Description
Kaolin, also known as china clay, is an aluminum silicate
with the chemical formula A12Oa.2SiO2.2H20, which is commercially available in both hydrous and calcined (anhydrous)
forms. Domestic deposits occur primarily in South Carolina
and Georgia. It has a platy particle shape with finer particles
present as individual platelets and coarse particles present as
stacks of platelets or booklets.
217
Copyright9 1995 by ASTM International
www.astm.org
Physical Properties
Kaolins are also differentiated by properties such as particle size, brightness, residue, and oil absorption. Hydrous
kaolins have an average particle size ranging from an extremely fine 0.2 up to 5 ~m depending on the product. Dry
brightness ranges from 85 to 90%, and most water-washed
grades are very low in residue. Acid grades have a pH of 4 to 5,
while predispersed grades are 6 to 7. Kaolins are chemically
inert. Water-washed grades are lower in impurities such as
soluble salts than are air-float grades.
Calcined grades range from below 1 to 2.5 p.m in average
particle size and are usually higher in brightness than all
except premium hydrous grades. These grades have a more
irregular particle shape and higher oil absorption than the
hydrous grades.
Coatings Performance
Fine particle-size hydrous kaolins are commonly used in
latex and alkyd trade sales paint. Finer particle size improves
opacity and allows for cost reduction by extending/reducing
the amount of titanium dioxide. Finer particle-size products
also develop higher gloss and are particularly useful in
enamels and semigloss formulations. Chemically modified
hydrous kaolins are effective in high-solids and water-reducible industrial coatings.
Delaminated grades also develop good opacity, and the
platy particle shape improves barrier resistance and film integrity. Delaminated grades or coarser hydrous grades are
more suitable for exterior trade sales formulations and exhibit more controlled chalking and better overall durability.
Air-floated grades are not used significantly in coatings because the higher water-soluble salt content can cause viscosity instability.
Calcined kaolins are widely used in interior latex and alkyd
trade sales fiats to develop dry hiding and reduce cost at lower
titanium dioxide levels. Dry hiding is due to the higher oil
absorption (binder demand) of the calcined grades, resulting
TALC
Description
Talc is a hydrated magnesium aluminum silicate with the
chemical formula 3MgO.4SiO2.H20. Deposits are found domestically in New York, Vermont, Montana, Texas, and California. Talc varies widely in purity depending on its source
and may also contain dolomite, limestone, and silica, among
others. Western talcs are highly platy, while eastern talcs
have an acicular particle shape. Both dry and wet grinding
techniques are used in its beneficiation. Ore flotation processes are used to produce high-quality products. Dry processing includes use of jaw crushers, Raymond mills, and
cyclones. Advanced milling technologies eliminate oversized
particles.
Physical Properties
Key properties for talc include composition, color, particle
size, water solubility, and oil absorption. Some grades are
available with an average particle size of 1 to 3/~m, but most
are around 5 to 15/~m. Brightness ranges from 70 to 85 for
inexpensive grades and 87 to 92 for premium grades. Oil
absorption depends on particle shape and size but in general
fits in between calcium carbonate and kaolin. Slurry pH is
basic at 9 to 10. Talcs are hydrophobic and organophilic [7].
Coatings Performance
Talcs are used in many different types of coatings including
interior and exterior trade sales paints, primers, traffic paints,
and industrial coatings. Western platy talcs develop good
flatting and provide good chemical and water resistance due
to high-purity and low-soluble calcium. These are best for
sanding primers because of softness and good sealing properties, while coarse grades help develop surface roughness
("tooth"). Platy talcs have good flow properties and improve
barrier resistance and durability in exterior trade sales paints
and enamel hold-out in interior applications. Talcs also enhance durability of traffic paints. Eastern acicular talcs have
better color and develop lower viscosity at high loadings due
to lower oil absorption.
SILICA
Description
Silica is a general term describing products with the chemical formula SiO2 of which both natural and synthetic types
are available. Those most widely used in paint and coatings
are crystalline, microcrystalline, diatomaceous, precipitated,
and fumed. They differ in method of production, physical
properties, and function.
CHAPTER 2 4 - - E X T E N D E R PIGMENTS
Crystalline silica is produced by crushing, grinding, and
classifying quartz. Microcrystalline differs from crystalline in
that its deposits, found principally in Arkansas, have a higher
concentration of fine particles. It is produced in a similar
manner as crystalline, but the ore is finer in particle size. Both
are decreasing in usage because of reported health and safety
issues related to crystalline silica.
Diatomaceous silica, also known as diatomaceous earth or
simply diatomite, consists of the skeletal remains of singlecelled aquatic plants called diatoms. Domestic deposits are
located in California, Nevada, and Washington. The ore is
crushed, milled, dried, and air-classified. Calcined grades are
processed in high-temperature rotary kilns and separated
into selected particle size ranges by air classification. These
products have superior color and are preferred for coatings
applications.
Synthetic silicas are produced by a number of differing
chemical and thermal processes. Precipitated silica is produced by acidification of sodium silicate to form aggregates
of ultra-fine particles. Aggregate size and degree of structuring are controlled by reaction conditions. Fumed silica,
produced via high temperature hydrolysis of silicon tetrachloride with hydrogen, also exists in aggregates of ultra-fine
particles, and particle size and surface area are also dependent on reaction conditions.
Physical Properties
Since processing of crystalline silica is essentially a size
reduction operation, particle size and particle-size distribution are the primary means of differentiating products. Crystalline silicas range from 2 to 10-/~m average particle size.
Microcrystalline grades are easier to disperse and are less
abrasive than crystalline grades. Brightness is from 85 to 90%
and pH from 6 to 7. Oil absorption is intermediate between
calcium carbonate and hydrous kaolins. These extenders ae
translucent and don't contribute to hiding as do some calcium carbonates and kaolin. Diatomaceous silica is a very
high oil absorption material found in aggregates ranging in
mean particle size of 2 to 20/zm. Calcined grades have a
brightness of 87 to 90%.
The synthetic silicas are differentiated by surface area and
particle size. Surface area of precipitated types is about 60 to
300 m2/g, while fumed silica ranges from 50 to 400 m2/g. Ultimate particle size of the individual particles are less than
0.1 /~m for both; however, precipitated may develop larger
aggregates. Fumed silica has a pH of 3 to 4, and precipitated
is 6 to 8. These grades are often made hydrophobic by reaction with organofunctional silanes to improve performance
in coatings.
Coatings Performance
Crystalline silica is used in trade sales, industrial coatings,
and primers. It is an inexpensive extender which contributes
to low sheen control, burnish resistance, and durability with
minimal impact on theology in latex trade sales paints. It is
also used in powder coatings where its low binder demand
does not affect flow properties.
Diatomaceous silica is primarily used as an inexpensive
flatting agent in latex trade sales paints because of its high
219
MICA
Description
Mica is a family of hydrous aluminum potassium silicates
of which one, muscovite, has the chemical formula
K20.3A12Oa.6SiO2.2H20. Micas are best known for a very
platy particle shape and high aspect ratio. These are coarser
in particle size than most extenders. Higher-aspect-ratio
micas are produced by frictional wet grinding. Dry processing in high-pressure air jets to both delaminate and reduce
the particles results in lower-aspect-ratio mica.
Physical Properties
Most coating grades of mica have an average particle size
of 5 to 50/zm. Residue of 325 mesh varies from less than 1 to
as high as 50%, depending on the particle size of the product.
Brightness ranges from 65 to 80%, low compared to other
extenders, while pH is 7 to 8. Oil absorption is higher than
other hydrous minerals and is closer to coarse calcined kaolins.
Coatings Performance
Mica is best known for its very platy particle shape, which
forms layers parallel to the paint film. Mica reinforcement
increases durability and resistance to moisture penetration,
corrosion, checking, heat, and chemicals. It helps prevent
cracking in exterior architectural coatings and traffic paint. It
prevents cracking and sagging in textured coatings. Mica
provides good barrier resistance in primers and roof coatings
[9]. Its platy particle shape, however, limits loading levels due
to rheology constraints.
BARIUM SULFATE
Description
Barium sulfate (BaSO4) is available as barytes, its naturally
occurring form, or as blanc fixe, a synthetic precipitate.
Barytes has a nodular particle shape with deposits found predominantly in Nevada, Georgia, Missouri, Montana, Tennessee, Illinois, and Washington. The ore is beneficiated by flotation techniques and then wet ground to obtain the required
particle size and bleached to improve color. Some higher
quality ores are dry ground and air classified. Blanc fixe is a
very white, fine-particle-size extender not as widely used in
paints and coatings as barytes. It is precipitated to a specific
particle size from solutions of barium salts and sodium sulfate. Blanc fixe is also used to make lithopone (extended)
grades of pigments. Multistage washing and filtration removes soluble impurities, and the products are then dried
and ground.
220
Physical Properties
3Na20.4.5A1203-20SiO2 and is mined and beneficiated in Canada. It has high brightness (95 to 98%) and is relatively coarse
in particle size (2 to 16 p.m). Its low binder demand makes it
particularly effective in exterior trade sales architectural
coatings. Nepheline syenite provides good tint retention and
prevents checking and cracking in exterior paints and also
develops good scrub resistance in interior latex paints.
Barytes is best known for its high density and very low oil
absorption relative to other extenders. Particle size ranges
from about 1 to more than 10/~m depending on the grade.
Brightness also varies from below 70 to greater than 90%
depending on the source and degree of beneficiation. Slurry
pH runs from 4 to 10. Blanc fixe is a more uniform product
with a 1 to 2-~m average particle size and high brightness (95
to 98%).
Sodium Aluminosilicates
Synthetic sodium aluminosilicates are produced by reacting aluminum sulfate with sodium silicate to produce a structured extender. These have high brightness (92 to 98%) and
relatively coarse particle size of 5 to 6/~m. Sodium aluminosilicates are used as partial replacements for titanium dioxide
in latex trade sales paints similar to calcined kaolin but at
higher cost; some of the highly structured grades are used as
flatting agents in latex paint.
Coatings Performance
Barytes is used in industrial and automotive primers and
undercoats. Its low oil absorption allows for high loadings
with less impact on rheology compared to higher binder
demand extenders. It helps develop a smooth surface with
minimal impact on the gloss of subsequent coats. Because
extenders are sold by weight, its high density can be a disadvantage in trade sales coatings where more weight is needed
to fill a given volume. Higher density relative to other pigments can increase settling and cause stability problems.
Blanc fixe has been used to develop dry hiding as a partial
replacement for titanium dioxide in trade sales and industrial
coatings [10].
Alumina Trihydrate
Alumina trihydrate (ATH) has the chemical structure
AI(OH)3 and is produced from bauxite ore as an intermediate
in aluminum production. It is most commonly used as a
flame retardant and smoke suppressant in thermoplastic and
thermoset polymer applications. ATH has a brightness ranging from 85 to 98% depending on the grade. Some very fine
particle size grades, less than 1 /~m, may be effective in spacing titanium dioxide in trade sales paints.
OTHER
Wollastonite
Wollastonite is a calcium metasilicate with the chemical
formula CaO-SiO2 of which the primary domestic sources are
New York and California. It has an acicular particle shape
and is brown to white in color. It is principally produced by
dry processing. Typical coating grades range from 2 to 10/zm
in mean particle size. Brightness ranges from 80 to 95%, and
pH is 9 to 10. Its acicular particle shape provides some reinforcement in coatings, and high pH is effective in buffering
latex systems. Surface-modified grades improve performance
in industrial coatings by both reducing resin demand and
improving bonding between the mineral and resin [11].
COMPARISON OF DIFFERENT E X T E N D E R
PIGMENTS
Physical Properties
Physical properties of the pigment extenders described
above are compared in Tables 1 and 2. Calcium carbonates
are available in different particle size grades and are very
white in color and high in brightness. Low oil absorption
enables high loading levels with minimal influence on rheology. High pH makes these products appropriate for latex
paints. Surface-treated grades are available for solvent-based
systems. Precipitated forms are higher in brightness, finer in
particle size, and have higher oil absorption approaching that
of calcined kaolins.
Nepheline Syenite
Nepheline Syenite is an anhydrous sodium potassium
aluminum silicate with the chemical formula K/O.
Precipitated
Calcium
Carbonate
Hydrous
Kaolin
Calcined
Kaolin
Talc
Crystalline
Silica
Mica
0.5
2.71
0.5
2.71
1.0
2.58
0.5
2.63
0.2-.5
2.8
0.3
2.65
0.5
2.82
90-95
85-90
97-98
...
88-90
85-88
90-95
...
75-92
70-92
85-90
85-90
...
65-80
1-3
5-12
9.5
0.01-I
10-20
0.5-1.5
. .
9-10
<0.05
30-60
0.8-2.5
1-3
5-15
9-10
0.01-1
25-55
2-3
5-10
6-7
<1-4
20-30
...
5-50
7-8
1-50
60-65
0.2-5
. .
4-7
0.01-.1
30-50
.
4-5
0.01
50-100
CHAPTER 2 4 - - E X T E N D E R PIGMENTS
221
Precipitated
Silica
<1
2.30
87-90
<1.5
2.20
96
3-4
5-10
9-10
< 1-3
90-130
0.01-0.05
. . .
6-8
0.01
100-300
Sodium
AluminoSilicate
Fumed
silica
Barytes
5
2.20
white
<1
4.40
80-95
<1
2.90
80-95
<1
2.1-2.3
92-98
<1
2.60
95-98
0.01-0.05
.
3-4
0.01
100-400
1-4
8-12
4-10
<1
10-15
2-4
7-10
9-10
<0.1
20-40
...
5-6
7-10
<0.5
75-115
2-4
7-16
10
<0.5-6
20-30
Wollastonite
Nepheline
Syenite
Hiding contribution
Gloss
Enamel holdout
Stain removal
Abrasion resistance
Adhesion
Water spot resistance
Chemical resistance
Viscosity
Stability
Suspension
Ease of brushing
Leveling
Calcium
Carbonate,
5/zm
Hydrous
Kaolin,
0.5/xm
Hydrous
Kaolin,
4.8 ~m
Calcined
Kaolin,
1.8 ~tm
Talc,
8/xm
Silica,
5 & 10 ~m
Very low
Low
Poor
Poor
Fair
Poor
Poor
Very poor
Very low
Poor-very good
Poor
Fair
Excellent
Very high
Moderate
Excellent
Excellent
Poor
Very good
Excellent
Very good
High
Excellent
Excellent
Excellent
Very good
Moderate
Low
Very good
Very good
Poor
Very good
Excellent
Very good
Low
Excellent
Very good
Excellent~
Very good
Very high
Low
Poor
Poor
Excellent
Fair
Excellent
Good
High
Very good
Very good
Good
Good
Moderate
Low
Fair
Fair
Good
Good
Good
Good
High-rood.
Poor-very good
Very good
Fair-poor
Fair
Moderate
Low
Poor
Fair
Good
Very good
Excellent
Excellent
Low
Excellent
Poor
Good
Very good
Title
Specifications
D
D
D
D
D
D
D
602-81
603-66
604-81
605-82
607-82
1199-86
3619-77
Standard
Standard
Standard
Standard
Standard
Standard
Standard
Specification for
Specification for
Specification for
Specification for
Specification for
Specification for
Specification for
Barium Sulfate
Aluminum Silicate Pigment (Hydrous)
Diatomaceous Silica
Magnesium Silicate (Talc)
Wet Ground Mica
Calcium Carbonate
Aluminum Silicate Pigment (Anhydrous)
Analytical
D
D
D
D
D
715-86
716-86
717-86
718-86
719-86
Physical Properties
E 70-90
D 153-84
D 281-84
D 1210-79
D 1366-86
D 1483-84
D 2448-85
D 3360-80
D 4139-82
222
Hydrous kaolins are the finest particle size naturally occurring extenders. Neutral predispersed grades are available for
latex systems, and acid grades are available for solvent-based
systems. These products have very low residue, which improves gloss development. The calcined grades have slightly
better color, and higher oil absorption contributes to opacity.
Talcs are available in a wide variety of grades depending on
the source. These are more similar to calcium carbonate in
particle size, although brightness is somewhat deficient. Platy
particle shape is a key parameter. Crystalline silica has lower
binder demand than kaolin or talc. Coarser grades are effective flatting agents. Mica is much coarser in particle size than
most extenders. It also has lower brightness and high residue,
which limit the levels at which it may be used.
The high oil absorption of diatomaceous earth makes it an
effective flatting agent. Precipitated and fumed silica, as more
carefully controlled reaction products, are more appropriate
for industrial coatings applications. Barytes, wollastonite,
and nepheline syenite are coarser particle-size products
which are less broadly used than finer particle-size extenders.
REFERENCES
[1] Lewis, P. A., Ed., Pigment Handbook, Vol. 1, 2nd ed., John Wiley
& Sons, New York, 1988.
[2] Kroschwitz, J. I., Encyclopedia of Polymer Science and Engineering, Vol. 7, Wiley, 1987, pp. 53-73.
[3] Katz, H. S. and Milewski, J. V., Handbook of Fillers and Reinforcements for Plastics, Van Nostrand Reinhold, New York,
1978.
[4] Madson, W. H., White Hiding and Extender Pigments, Federation
Series on Coatings Technology, 1967.
[5] Engelhard Technical Literature TI 226, "ASP & Satintone Extender Pigments--Performance Products for the Paint & Coatings Industry," Engelhard Corporation, Iselin, NJ, June 1984.
[6] Engelhard Technical Literature TI 218, "Satintone Specialty
Pigments in Coating Applications," Engelhard Corporation,
Iselin, NJ, October, 1986.
[7] Grexa, R. W., "North American Talc-Competition in Every Direction," Industrial Minerals, June 1987, pp. 52-54.
[8] Johns-Manville Technical Literature, "Functional Fillers for Industrial Applications," Johns-Manville, Denver, CO, January
1985.
[9] KMG Minerals Technical Literature, "White Wet Ground
Muscovite Mica," KMG Minerals Inc, Kings Mountain, NC.
[10] Sachtleben Technical Service Note, "Blanc Fixe Micro, a New,
Multi-Purpose Barium Sulphate Extender," Sachtleben Chemie
GmbH, Duisburg-Homherg, Germany, 1982.
[11] Hare, C. H. and Fernald, M. G., "Wollastonite Extenders in Anticorrosive Alkyd Metal Primers," I&EC Product Research &
Development, 1985, pp. 24, 84.
MNL17-EB/Jun. 1995
25
Metallic Pigments
by Russell L. Ferguson 1
Properties
Metallic pigments share similar properties; however, each
is distinct enough to be considered separately.
Aluminum
Aluminum pigments are manufactured from aluminum
metal with a purity ranging from 99.3 to 99.97%, depending
on the grade being manufactured. Although amphoteric in
nature, the pigment exhibits a high degree of chemical resistance. Aluminum pigments owe their aesthetic and functional
properties to the geometry of the particle, particle-size, and
particle distribution. The pigment is a flake-like particle (lamellar) and has either a round or irregular perimeter. Once
formulated into a coating, they orient parallel to the substrate
and film surface. This orientation provides for exceptional
barrier properties in the appropriate coating system. Metallic
or polychromatic coatings containing aluminum flake pigments, either by themselves or in combination with transparent colors, offer a two-tone quality often sought after. The
two-tone, or flop, feature is an important characteristic in
many automotive top coats.
There are two general types of aluminum pigment: leafing
and nonleafing. Leafing grades are manufactured using a saturated fatty acid as the lubricant (typically stearic acid),
which allows the flakes to float at, or near, the surface of a
paint film. This continuous layer of flakes provides a solid
silver color, unable to be tinted with other pigments. The
nonleafing grades utilize an unsaturated fatty acid as the
lubricant (typically oleic acid) which allows the flakes to
orient throughout the paint film. Nonleafing pigmented coatings can be tinted with organic pigments to offer a polychromatic appearance.
Aluminum flakes range in size from 0.1 to 2.0/~m in thickness, and 0.5 to 200/~m in diameter. Generally, aluminum
flakes are supplied in a paste form with a typical composition
223
Copyright9 1995 by ASTM International
www.astm.org
224
Gold Bronze
Gold bronze pigments are neither gold nor bronze, but are
typically manufactured from a composition of copper and
zinc alloy. By altering the copper-zinc ratios, four standard
gold bronze colors can be produced. The standard alloy subdivisions are: (1) copper--100% copper, 0% zinc; (2) pale
gold--90% copper, 10% zinc; (3) rich pale gold--85% copper, 15% zinc; and (4) rich gold--70% copper, 30% zinc.
Further oxidative treatments can be utilized to produce special colored bronzes, varying from brown-golds to oranges
and reds. Additionally, blending of any of the above-mentioned bronze powders will result in an almost unlimited
pallet of gold-bronze colors.
Gold-bronze pigments are flake-like particles (lamellar)
with an irregular perimeter. In a coating or ink application,
they orient parallel to the substrate and film surface [4].
Leafing Grades
The standard grade category is composed of a series of
grades from very coarse flakes (having water coverage from
6000 to 9000 cm2/g) to very fine flakes (having water coverage
in the area of 35 000 cm2/g). These grades are used, primarily,
in trade sales and maintenance coatings. Their leafing values
are traditionally 50% minimum.
The ultra-leafing grades are characterized by very high leafing values (in the area of 90 + %) and exceptional brightness.
Their uses include aerosol coatings and ink applications.
Zinc Pigment
Zinc dust is the only metallic pigment that is not found in a
lamellar form. Produced through the condensation of zinc
vapor in an inert atmosphere, the zinc dust is a spherical
particle averaging about 8/zm in diameter. Zinc dust is predominantly zinc metal (96 to 97%), with some zinc oxide (3 to
4%), and traces of lead, cadmium, iron, and other elements.
Stainless Steel Flake
Stainless steel is a composition of iron, chromium, nickel,
manganese, and molybdenum. There are three groups of
stainless steel alloys available: (1) martensitic, (2) ferritic,
and (3) austenitic, differentiated according to alloy composition. Of the three groups, austenitic is the most corrosion
resistant and typically used to manufacture stainless steel
flake. Austenitic alloys owe their corrosion resistance to
higher levels of nickel and molybdenum. Stainless steel pigment has a lamellar geometry and will orient itself parallel in
a coating system. Stainless steel flake has a high degree of
durability and will resist tarnishing, abrasion, and chemical
attack. Additionally, stainless steel flake is able to maintain
stability in water-based systems.
Nickel
Nickel pigments can be found in either powder or flake-like
form. They are typically composed of nickel metal, with
traces of carbon, oxygen, sulfur, and iron. Nickel flake powders are available dry, as a paste in mineral spirits, or as a
paste in mineral oil. Nickel powders have good electrical
conductivity [5].
Nonleafing Grades
The standard grades are represented by a full range of
products from very coarse, low-opacity to very fine, highopacity grades. They are used in diverse applications from
maintenance coatings to general industrial applications and
automotive refinish.
The automotive grades are distinguished from standard
grades by possessing improved aesthetics, including brighter,
more sparkling appearances, with tighter control on particlesize distribution. Many subcategories exist under this heading, including specialized grades for base coat/clear coat systems, circulation resistance, etc.
Plasticized and polymer-modified grades are represented
by a full range of products designed for end-use systems that
cannot tolerate solvents (mineral spirits). The primary end
use is plastic and ink applications.
The dedusted grade category comprises dry aluminum
flakes held loosely together by Teflon bonds, resulting in a
nondusting product. These grades are used in some general
industrial coatings; however, the primary application is to act
as a sensitizer for slurry explosives.
The surface-treated grades include aluminum flakes whose
surface chemistry has been altered to allow for improved
aluminum flake performance. These grades are used in powder coatings and some solvent-borne coatings where improvements in flake orientation and performance are desired.
The aqueous grade category consists of aluminum pigments treated with various chemical components to stabilize
the flake for use in waterborne systems. Various levels of
inhibition and performance are available.
Zinc Pigment
Aluminum Pigments
Aluminum pigments are more widely used than any other
metallic pigment and can be divided into a number of different categories. The grade classification is, in general, determined by the intended use. Most of the following categories
The zinc pigment, dust and flake, is used in coatings, primarily for corrosion-resistant properties. The categories
available are:
1. Regular Zinc Dust--7 to 8-/zm particle-size diameter.
2. Fine Zinc Dust--5 to 6-p~m particle-size diameter.
225
The powder and flake are used in coating and plastic systems to provide electrical conductivity and corrosion-resistance characteristics.
F O R M U L A T I O N A N D APPLICATION
GUIDELINES
Market Applications
Formulation Considerations
Metallic flake pigments, by the nature of their geometry
and composition, are malleable and therefore somewhat
fragile. The dispersion of these flakes into a coating system is
critical in maintaining optimum aesthetic and functional performance. The preferred dispersion process involves the addition of vehicle or solvent to the metallic pigments, with
slow-speed mixing, to gently separate the flakes. Once a thick,
uniform slurry of metallic flakes, solvent, and vehicle is
achieved, the formulator can continue to let down to final
product composition. Severe dispersion techniques such as
Cowles high-speed mixers, sand mills, etc. will destroy the
flake integrity, resulting in loss of aesthetic and perhaps functional properties. Zinc pigment, which is not a flake, can be
dispersed using conventional paint dispersion techniques.
Appropriate selection of vehicle, solvents, and additives
must also be considered when formulating with metallic pigments. The leafing properties of aluminum and bronze flakes
can be detrimentally affected by such properties as acid value
of the resin; polar solvents, or solvents with low-surface tension; moisture in the system; and additives, including driers
that are good wetting agents. Since most metallic pigments
contain mineral spirits, coating system compatibility must be
considered.
The current trend toward waterborne coatings also poses
problems in formulation. Dispersion of metallic pigments
can be accomplished through the correct selection of an appropriate coalescing solvent. However, even good dispersion
will not guarantee good coating performance. Metallic waterborne coatings have the potential for hydrogen gas generation. This potential has been addressed by many manufacturers through various inhibiting processes. While many
inhibited grades are available on the market today, performance may vary in different aqueous systems. In addition to
the potential for hydrogen gas generation, tarnishing and
printability have been addressed by manufacturers of gold
bronze flakes. Stainless steel flakes, because of the very nature of their composition, can be used in waterborne coating
formulations without the possibility of gas generation.
Another solution to the VOC (volatile organic compound)
problem is the use of powder coating systems. Specialized
grades of aluminum pigments have been developed to meet
Metallic pigments are widely used in the coating, ink, plastic, and explosive markets. In the coating industry, metallic
pigments offer both functional and aesthetic properties.
Those pigments that are lamellar (aluminum, gold bronze,
stainless steel, and nickel) are opaque and orient parallel to
substrate and coating film surface. Thus, they provide a barrier to ultraviolet (UV) and infrared (IR) light, along with
moisture and oxygen penetration. Zinc pigment, while not a
flake, possesses superior corrosion protective properties for
steel or iron substrates. Because zinc is higher in the electromotive series, it acts as the anode of a corrosion cell. The
iron or steel substrate is protected by the zinc because of the
formation of insoluble compounds with lower oxidation
states.
The aesthetic benefits of metallic pigments are widely
known in the coatings industry. In the area of trade sales and
maintenance coatings, aluminum pigments provide very
bright, silvery finishes typically found in many roof coatings,
aerosol applications, and bridges. In general industrial
and automotive coatings, various polychromatic and
metallescent appearances are produced utilizing nonleafing
grades.
In the ink and plastic industries, the primary benefits derived are from aesthetic properties. Gold bronze flakes, along
with aluminum flakes, provide attractive polychromatic finishes.
The explosives industry utilizes aluminum flake pigment as
a sensitizer in slurry explosives.
Economics o f Use
The extensive markets for metallic pigments has mandated
their use in a wide range of systems for many years. Their
properties, both functional and aesthetic, along with the traditional economic values associated with their properties,
have established them as an important raw material in the
coating, ink, and plastic markets. The economics of these
pigments are dependent on a number of factors, including
cost of the raw material, degree of sophistication of the pigment, and the end product for which it is intended.
226
TESTING
Particle-Size Analysis
One of the key elements in any metallic pigment is the
particle-size distribution. Instruments are available on the
market today to characterize, or fingerprint, metallic pigments. Unfortunately, most of these instruments are incapable of characterizing lamellar-shaped pigments; however,
their increased sophistication has allowed for a very close
approximation. In addition to providing a distribution of the
particles in a pigment, also provided are surface area, average
particle size, and percentages at various levels.
Water Coverage
This test can be used to determine the particle-size thickness and surface area of leafing and nonleafing metallic flake
pigments. This test has been fully described by Edwards and
Ray [6]. A dry, metallic pigment is dusted onto a surface of
clean, distilled water, which is contained in a shallow, rectangular pan. The accurately weighed flake metallic pigment is
dusted onto the surface of the water and separated until it is
one flake thick. The coverage of metallic flake on the water
to determine the gas generation potential and stability characteristics of metallic flake pigmented aqueous coating systems. Approximately 200 mL/s of a metallic pigmented coating is charged into an Erlenmeyer flask. Attached to the flask
is a glass condenser with Tygon tubing coming out of the top
and extending into an inverted buret filled with water. The
Erlenmeyer flask is suspended in a hot oil bath, which accelerates the potential for hydrogen gas evolution. This test is
operated for seven days (168 h) at a temperature of 52~ The
acceleration of the environmental conditions will allow for
hydrogen gas generation, which will pass out of the Edenmeyer flask, through the Tygon tubing, and into the inverted
buret. The water in the inverted buret is displaced by the
hydrogen gas and generation can be easily read through this
displacement (Fig. 2). The specifications for gas generation
should be designed around the metallic flake pigment and
coating system tested. The specification for gas generation
should not exceed the volume of the buret (typically,
100 mL/s).
Degradation Test
This test is designed to determine the level of flake deterioration in a coating system when subjected to severe stress.
Automotive coating systems are often circulated through
pumps, regulators, and long piping and tank systems to keep
all the components of the coating in suspension. Circulation
may have detrimental effects on the metallic flake integrity,
causing bending, curling, and even breakage of the metallic
flake. The loss in aesthetic properties due to flake deformation results in a darkening of the coating, along with a change
in the flop characteristic. This test is designed to evaluate the
capability of the metallic flake to resist deformation under
these stress conditions.
A metallic pigmented coating is placed into a waterjacketed Waring blender. Using a standard cutting blade, the
blender is operated at high speeds for 5 to 15 min. The metallic coating is a sprayed pre- and post-blender operation, and
visual and instrumental comparisons are made. The degree of
flake deformation can be translated into numerical data
based on the brightness of the metallic coating (face and
flop).
Electrical Resistivity~Conductivity
In waterborne coating systems it is often useful to know the
conductivity or resistivity of the components of the system. In
order to measure metallic pigments, it is necessary to disperse the metallic pigment in an isopropyl alcohol/deionized
water mixture. This mixture should be agitated using an air
mixer for at least 5 min, after which the metallic pigment
should be filtered out. The resultant filtrate can be tested for
resistivity/conductivity using a conductivity meter (i.e.,
Jenway Conductivity Meter, Model 4010).
Gassing Test
Aluminum and other metallic pigments, by their very nature, will react with water to generate hydrogen gas. Today,
due to VOC regulations, more and more coating and ink systems are moving toward waterborne technologies. Metallic
pigment manufacturers have developed technologies to inhibit the aluminum flake pigments, and this test is designed
pH Measurement
In waterborne coatings and ink systems, it is often necessary to know the pH of the components of the system. The pH
Exit W a t e r
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t't"
25
I.IJ
I'-
20
15
Inlet W a t e r
I
II
..I
m
10
..J
.j
"-
5
0
Aluminum
Sample
iioii!iiiii!ii ii!iiiii
!iBa !!!ii!!iiii! _
ii::iiiiiiiii!iiiii!iiiiiiiilEiiiiiiiiiii
Heater
Water
FIG. 2 - G a s evolution test for metallic coatings.
228
Aesthetic Properties
Metallic p i g m e n t s are used for the aesthetic p r o p e r t i e s they
lend to coating systems. E a c h metallic p i g m e n t grade offers a
slightly different a p p e a r a n c e p r o p e r t y to these coatings, a n d
it is necessary to be able to assess these differences. Visual
a n d quantitative d a t a can be generated b a s e d on a n u m b e r of
these properties. F o u r of the m o s t i m p o r t a n t p r o p e r t i e s are:
9 The face-color, or head-on-brightness, attribute generally refers to the a m o u n t of reflected light f r o m a metallic pigm e n t e d coating w h e n viewed at a p p r o x i m a t e l y 20 to 25 ~ off
of specular.
9 The flop, flip/flop, or metallic travel angle refers to the
a m o u n t of reflected light w h e n viewing a metallic pigm e n t e d coating at an angle that is 70 to 110 ~ off of specular.
Metallic travel is often referred to as the degree in change of
brightness going from the face angle to the flop angle.
9 Seed level refers to the degree of p r o t r u s i o n of the metallic
flake t h r o u g h a coating film surface.
9 DOI (distinctness of image), closely related to gloss, refers to
the reflection of an image f r o m a metallic p i g m e n t e d coating b a c k to the observer. The clearer, o r m o r e distinct, the
reflected image, the higher the DOI value. Typically, the
finer the pigment, the higher the level of DOI.
9 Patina is the packing a p p e a r a n c e of the metallic flakes in
coating systems. A good p a t i n a is often d e s c r i b e d as having
a smooth, velvety a p p e a r a n c e , lacking individual flake identity in the coating. If an observer sees only a c o n t i n u o u s
metallic film w i t h o u t breaks, protrusion, or individual flake
identity, the metallic coating is c o n s i d e r e d to have a good
patina. Many coating systems a n d p i g m e n t p a r a m e t e r s affect the p a t i n a of a coating system. Typically, higher solids
coatings, p o o r a p p l i c a t i o n methods, coarse pigments, a n d
p o o r flake o r i e n t a t i o n c o n t r i b u t e to p o o r e r p a t i n a p r o p e r ties.
REFERENCES
[1] Hall, E. J., U.S. Patents 1,501,499 (1924); 1,545,253 (1925);
1,569,484 (1926); and 2,002,891 (1935).
[2] Ruddick, D. H., "Zinc Pigment," Pigments Handbook, Vol. I,
Properties and Economics, John Wiley and Sons, New York, 1988,
pp. 811-817.
[3] Ferguson, R. L., "Aluminum Flake," Pigments Handbook, Vol. I,
Properties and Economics, John Wiley and Sons, New York, 1988,
pp. 785-801.
[4] Humphrey, S. A. and Laden, P. J., "Gold Bronze Pigment,"
Pigments Handbook, Vol. I, Properties and Economics, John Wiley
and Sons, New York, 1988, pp. 803-810.
[5] Antonsen, D. H., "Nickel Powders and Nickel Flake Powders,"
Pigments Handbook, Vol. I, Propertiesand Economics, John Wiley
and Sons, New York, 1988, pp. 823-827.
[6] Edwards, J. D. and Wray, R. I., "Aluminum Paint and Powder,"
Reinhold Publishing, New York, 1955, pp. 18-22.
BIBLIOGRAPHY
Other literature, with m o r e extensive i n f o r m a t i o n on functional p r o p e r t i e s a n d applications, is listed below:
Hare, C. H. and Fernald, M. G., "Anti-Corrosive Barrier Finishes,"
Modern Paint and Coatings, Vol. 74, No. 10, 1978, pp. 138-151.
Humphrey, S. A. and Laden, P. J., "Stainless Steel Flake," Pigment
Handbook, Vol. I, Properties and Economics, 2nd ed., John Wiley
and Sons, New York, 1988.
Smith, A., Inorganic Primer Pigments, Federation Series on Coatings
Technology, Philadelphia, PA, 1988.
MNL17-EB/Jun. 1995
Pearlescent Pigments
by Carl J. Rieger 1
HISTORY
The earliest use of pearlescent pigments is credited to
French rosary makers in the 17th and 18th centuries. They
used the scales of fish to impart pearl effects to the glass
beads used in making rosaries. The modern era of pearlescent
pigments began in the late 1920s when scales of fish, namely
herring, were used to make simulated pearls for costume
jewelry. Because "natural pearl essence," as the material extracted from the fish scales came to be called, was so expensive, synthetic pearl pigments were developed in the 1930s.
These early synthetic pearl pigments were mainly lead salts.
They possessed both the high refractive index and thin platelet shapes required for pearlescent pigments.
The moderu commercial forms of pearlescent pigments
consist of:
1. Titanium dioxide and ferric oxide coatings on mica.
2. Bismuth oxychloride crystals grown from a solution of
bismuth salts.
1Vicepresident, The Mearl Corporation, Applications and Development Laboratory, 3 Greentown Rd., Buchanan, NY 10511.
229
Copyright9 1995 by ASTMInternational
www.astm.org
230
OPTICAL PROPERTIES
Pearlescent luster is developed by the specular reflection of
light as it strikes the broad surfaces of the platelets. These
platelets are dispersed throughout the depth of the paint or
ink film or plastic article. This reflection of light from
pearlescent pigment particles dispersed throughout the
thickness of the coating reinforces the luster and differentiates it from a strictly surface reflection as featured by leafing
aluminum flake.
The requirements for a good pearlescent pigment are:
1. A high refractive index preferably greater than 2.
2. An optical thickness, i.e., the geometrical thickness of the
layer multiplied by the refractive index, of approximately
100 to 140 nm for pearl (white) pigments. As interference
pigments are produced by increasing the geometrical
thickness, this optical thickness increases to 200 nm for
gold, 250 nm for reds, 300 nm for blues, and 370 nm for
green interference colors.
3. A high aspect ratio primarily derived from the mica. the
larger the diarueter-to-thickness ratio (the aspect ratio),
the better the pearl effect. Another way of describing this
would be to term it a "platey" structure. The mica itself
plays no role in the optics and functions merely as a substrate upon which the high-refractive-index material is deposited.
4. Proper particle-size distributions are needed. Optimum
luster occurs when the size distribution, measured by laser
diffraction methods, falls between about 10 to 40/zm.
Smaller particles, 5 to 10/zm, act as light scatterers and
detract from luster. Particles larger than 40/~m give a
grainy effect and reduce opacity. Pearlescent pigments are
essentially transparent pigments and, as such, do not have
good opacity or hiding.
APPLICATIONS
Industrial Coatings
Pearlescent pigments have been used in many industrial
coating applications. One such use is coil coatings. Polymers
often used in these applications, such as fluoropolymers, require high baking temperatures. Since they have been calcined at over 800~ during their manufacturing process,
pearlescent pigments can tolerate high bake temperatures of
500 to 600~ (260 to 315~ without any damage to pigment
mechanical integrity or optical properties. Not all organic
pigments can be used in such coil coating applications because of temperature limitations.
Pearlescent pigments find application in ink formulations
such as gravure, silk screen, flexographic, and, to a lesser
extent, offset printing inks. The particle size of some
pearlescent pigments is too large for most offset applications.
Bismuth oxychloride pigments have been used for many
years as coatings on wood furniture to sharply bring out the
"grain" of the wood. Also, bismuth pigments have been utilized in the costume jewelry industry for coating and dipping
beads and pearls.
Other applications for these pigments include roller and
knife coating of leather and paper as well as coating of various types of toys and balls. The pigments are also used in the
popular craft industry.
Automotive Coatings
Pearlescent pigments were first used in original-equipment-manufacture (OEM) automotive paint in the early
1980s, and they became a major styling tool about 1985
[9,10]. Since pearlescent pigments, chiefly the coated mica
types, are transparent in nature, they do not "gray out" or
"muddy up" the expensive transparent organic coating colorants used in automotive coatings. These pigments add to the
chromatic effect of organic pigments and contribute to the
"flop" or polychromatic effect desired in these coatings. Flop
is defined as a change of color as viewing angle changes.
For the 1991 model year, it is estimated that nearly 40% of
all U.S. automotive OEM coatings contained pearlescent pigments. European and Japanese paint companies are also using pearlescent pigments in their OEM paint formulations.
Pearlescent pigments have been stabilized by various methods to give the durability required for automotive end uses.
Panels have been weathered outdoors in Florida and Arizona
for five or six years with little or no change in color or gloss.
The use of the color base coat and clear top coat now favored
in the automotive industry has also added to the gloss and
weathering stability of coatings formulated with pearlescent
2Brunauer, S., Emmett, P. H., and Teller, E., Journal of the American Chemical Society, Vol. 60, 1938, p. 309.
Powder Coatings
Pearlescent pigments have been successfully used in powder coatings for a number of years [15]. Since they are nonmetallic in nature, these pigments are free of some of the
arcing and flashing problems that occur in electrostatic spray
application of powder coatings.
One limiting factor found with the use of pearlescent pigments in powder coatings is their inability to be used in the
"melt mix" method of incorporation. This calls for the extrusion of pigments and the powdered polymer to encapsulate
the pigment. The use of an extruder is not the problem since
pearlescent pigments are extruded in the plastics industry.
The problem arises through the use of hammer-mill type mill
used to reduce the size of the polymer mass into a powder
that will spray through an electrostatic spray gun. Pearlescent pigments must retain their platey or flake-like shape to
properly reflect light and produce luster. If these pigments
are broken or smashed by milling, the pearlescent effect is
greatly reduced. This leaves only dry mixing of the
pearlescent pigment and the powdered polymer as an alternative method of incorporation. Such a technique has certain
drawbacks such as separation due to different specific gravities, different particle sizes, and so on that can take place due
to vibration during shipping, handling, and application.
A new method called the "bonding" method has recently
been used with pearlescent pigments and metallic flakes in
powder coatings. This technique involves "bonding" of the
pigments to the powder by various proprietary methods.
Pearlescent pigments have been used to powder coat automotive wheel covers, bicycles, and outdoor furniture.
Water-Based Coatings
Since pearlescent pigments are chemically very inert and
not sensitive to pH, they make ideal pigments for use in
water-based coatings. Because of their inert nature, they do
not evolve hydrogen gas or react with water-borne systems.
Pearlescent pigments are hydrophilic in nature and as such
disperse very well in most water-based systems.
Pearlescent pigments have been successfully used in Canada in water-based truck-paint finishes for several years. Currently they are being used as the automotive industry
switches from high-solids to water-based coatings with lower
volatile organic compound content.
Ink formulations based on water-borne systems have also
been developed for both the coated mica and bismuth oxychloride pigments. These are being used in Europe to replace
the metallic ink formulation that may be an environmental
problem.
231
Water-based coatings containing exterior grade pearlescent pigments have been tested in outdoor exposure in
Florida for three years. These show good weatherability with
optimum gloss and color retention.
COLOR MEASUREMENT
Visual
Instrumental color analysis of coatings pigmented with
pearlescent pigments is rather difficult. As mentioned earlier,
the phenomenon known as goniochromaticity complicates
instrumental measurements. As a result, much color observation has been done visually using both draw down cards with
nitrocellulose lacquers and coated panels. Comparing a sample and a standard on a black-and-white draw-down card is
an effective way of making color comparisons since both the
interference color and the absorption color can be seen. Due
to the transparency of pearlescent pigments, the color appears different over the black and the white portions of the
card.
The interference color can be best seen and visually compared to the standard by looking at the black portion of the
draw-down card. The absorption color can be best evaluated
and compared by viewing the white portion of the card. Color
appears more intense over the black portion because the
incident light is reflected and the complementary color is
absorbed. On the white portion of the card, the reflected light
and the complementary color are both reflected back to the
viewer with only a slight diminishing of the specular effect.
Side-by-side draw downs of samples against a standard
batch are so effective that they can be used in process control
with samples taken at various intermediate stages of the manufacturing process. Also, final quality control judgments can
be made using visual assessment of side-by-side draw downs.
232
Goniospectrophotometers
When the color of coatings with pearlescent pigments or
metallic flake is measured, it is necessary to measure at more
than one angle. The reason for this is that the color of these
types of coatings changes with viewing angle. An instrument
capable of making multi-angle color measurements is called
a goniospectrophotometer. These instruments are usually capable of changing the angle of incident light (illumination),
changing the angle of viewing (reception), or tilting the specimen under investigation. For most of the commercial quality
control instruments, only the angle of viewing is changed and
the other variables are held constant with the incident-light
angle usually fixed at 45 ~.
Figure 1 shows the viewing angles used in some of these
commercial instruments. The optics used are called normalized reflective angles, which means all viewing angles are
referred to the specular angle that is sometimes called the
gloss angle. Incident light strikes the ample at 45 ~, and thus
the specular angle is also 45 ~. The near specular angles are
usually 15 to 20~ off the specular angle to exclude any gloss
from affecting the color readings. To completely characterize
pearlescent pigmented finishes, it is necessary to measure at
least three angles. This is usually near specular, i.e., about 15
to 20 ~ off specular, at 45 ~ off specular, and at several far
diffuse angles, usually 70 to 115 ~ off specular. All commercially available goniospectrophotometers will measure reflected light at a minimum of three angles, and several instruments measure at more angles, with one measuring at twelve
angles. Research goniospectrophotometers that allow angle
variation of about 5~ off specular to 110~ in five-degree intervals are also commercially available.
The importance of measuring at more than one angle is
apparent from Figs. 2 and 3. In Fig. 2 the reflection curves
taken at near specular angle are nearly identical, whereas in
Fig. 3, when this same set of panels was measured at a diffuse
angle, markedly different reflection curves are obtained.
These data were obtained using one gold interference
pearlescent pigment to which a small amount of phthalocyanine blue had been added and another gold interference pearlescent pigment to which a small amount of phthalocyanine green had been added. At the near specular
angle, the gold interference color is apparent, and, since both
coatings used the same gold pigment, the two curves are
nearly identical. However, at the diffuse angle, the colors of
the organic pigment added to the pearl finish are now apparent, with one curve typical of a blue and one curve typical of a
green colorant. If this same pair of panels were presented to a
70~
45~ INCIDENT
BEAM
110 ~
45~
20~
/~
'
SPECULAR REFLECTION
45 ~ /0 o
TESTING
Weatherability Testing
Weatherability tests with pearlescent pigments take the
form of both accelerated and outdoor testing. Accelerated
testing includes use of such devices as QUV exposure chambers, condensation testers, and water-bath soaking. Outdoor
testing may include exposure in Florida and/or Arizona at 5~
South or Black Box. Specimens consist of painted metal test
panels, pieces of pearlized plastic film, or injection-molded,
pigmented parts.
Color and gloss readings are made on the original test
panels before exposure, and panels are exposed in replicates.
Panels are removed from the test fences at various times and
tested for changes in color and gloss. Testing with the stabilized exterior grades of pearlescent pigments usually goes on
for at least five years, and the panels are viewed and examined
every six to twelve months. Such testing has shown that exterior-grade pearlescent pigments have the capability of standing up to the weathering stresses found in modern automotive coatings along with other exterior uses. Accelerated
40
36
30
- - - I - - - Blue
26
Reflectance, %
20
16
10
:
400
440
I'
480
',
',
620
660
600
640
680
700
Nanometers
FIG. 2-Reflection as a function of wavelength at near the specular angle for a gold
pearlescent pigment containing a blue or a green colorant.
80
70
6O
60
Reflectance, % 40
30
Blue
2o
10
0
I
400
440
I
480
I'
620
I
660
I
SO0
!
640
'I
680
Wavelength, nanometers
FIG. 3-Reflection as a function of wavelength at a diffuse angle for a gold pearlescent
pigment containing a blue or a green colorant.
233
234
40,
L*
~,
A
=
=v
~ , ."-.
..,=
. , r
..
~-
20
10
i
10
20
30
40
60
60
70
80
90
100
110
50
v
4O
30
a=
2O
10
0
10
20
30
40
'
50
60
70
80
90
100
110
50 84
40
C v A. . #Av v r
~
30
A
v
84
b*
20 84
10
0
10
20
30
40
50
60
70
80
90
100
110
weathering has proven to be reliable and capable of differentiating between the stabilized exterior grades and the untreated types generally used in plastics or inks.
Particle S i z e
Early methods for determining the particle-size distribution of pearlescent pigments involved manually counting
particles viewed under a microscope. The microscopist usually counted about 1000 particles, grouped them in 5-/zm
intervals, and then created a distribution curve. The technique was tedious and time consuming, plus it did not give
enough statistical data about the large particles.
More modern methods that have been tried include the
Coulter Counter, automated sedimenters, and sieving. Most
had difficulties because of the shape of pearlescent pigments,
i.e., they are flakes with very thin thickness and very broad
surfaces. These pigments are roughly the same size as metallic flake pigments, but they are much larger in size than
organic colorants and most inorganic pigments. The most
successful instruments found thus far for measuring particle
size of these pigments are the laser diffraction types. These
give good relative measurements. The numbers obtained,
however, are not absolute values since the theory for these
devices is based on spherical particles and not platelets. Calibration of these laser diffraction instruments with standardized glass spheres have shown them to be reliable and reproducible with pearlescent pigments.
As mentioned above, pearlescent pigments are classified
into particle-size distributions for various end uses. Automotive coating sizes are carefully controlled by sieving to remove
any particles over 50/zm. Such large particles can lead to
CHAPTER 2 6 - - P E A R L E S C E N T PIGMENTS
235
140,
120,
100,
L~ 80,
60
40
20
0
10
20
30
40
50
60
70
80
90
100
110
5
4
3
2
I
a*
-1
-2
-3
-4
-5
10
20
30
40
50
60
70
80
90
100
110
10
20
30
40
50
60
70
80
90
100
110
5,
4,
3
2
1
b* 0
-1
-2
-3
.4
-5
Viewing Angles Away from Specular
FIG. 5 - V a r i a t i o n of color in a metallic flake-coated panel as a function of viewing
angle.
Chemical Testing
Chemical testing of pearlescent pigments consists of analyses of the chemical composition, i.e., percentage of TiO2 or
ferric oxide (Fe203), of mica, and of other ingredients. Also,
trace analyses for heavy metals such as lead, arsenic, Cr +6,
are clone by atomic absorption, ICP instrumentation, and Xray fluorescence. Both extractions in 0.5 N HC1 and total
dissolution methods are used in these analyses. Extraction
methods usually give less than 20 ppm lead and 3 ppm arsenic in pearlescent pigments. Other tests performed include
conductivity, pH in aqueous solution, specific gravity, bulk
density, and, when a solvent is present, flash point.
236
40
2O
0
10
20
30
40
50
60
70
80
90
100
110
75
55
a*
35
-5
60
A
~
-20
b*
-40
-60
-80
f
0
A
v
20
30
40
50
60
70
80
90
100
1 10
Viewing
Angles
Away
from
Specular
FIG. 6-VariaUon of color in a pearlescent pigment-coated panel as a function of
viewing angle.
Health--O
Flammability--O
Reactivity--O
Personal P r o t e c t i o n - - E
If dusting occurs when h a n d l i n g the dry products, a d u s t
m a s k should be worn. Several grades are also available in a
"wetted out" form to p r o d u c e n o n d u s t i n g products. M a n y
pearlescent p i g m e n t s have been used for years in cosmetic
applications. These cosmetic grade p e a r l e s c e n t p i g m e n t s
have FDA approval for use as cosmetic ingredients a n d color
additives.
REFERENCES
A general reference for pearlescent pigments is Greenstein, Leon
M., Pigment Handbook, Vol. 1, 2d ed., Peter A. Lewis, Ed., Wiley and
Sons, New York, 1988.
[1] Simon, H., The Splendor of Iridescence, Dodd, Mead and Co.,
New York, 1971.
[2] Bolomey, R. A. and Greenstein, L. M., Journal of Paint Technology, Vol. 44, No. 566, March 1972.
[3] Linton, H. R., U.S. Patent 3,087,828 (1963).
[4] Armanini, L. and Bagala, F., U.S. Patent 4,146,403 (1979).
[5] Quinn, C.A., Rieger, C.J., and Bolomey, R.A., U.S. Patent
3,437,515 (1969).
237
1990,
[12] Teaney, S., Welker, J., and Rieger, C. J., Detroit Color Council,
15 Nov. 1989.
MNL17-EB/Jun. 1995
Inorganic Anti-Corrosive
Pigments
by M. Jay Austin 1
W H A T IS C O R R O S I O N ?
and mechanisms. For our purposes, we will limit our discussion to examination of the following five mechanisms of protecting metals by using coatings:
9 Barrier effect of film or vehicle.
9 Barrier pigment effect.
9 Sacrificial pigments.
9 Vehicle enhancement (film formulation and development).
9 Active inorganic inhibitive pigmentation.
Barrier Effect
Among the oldest inhibitive methods known, barrier coatings provide a protective, physical shield between a metal and
air, moisture, or chemicals. While the composition and thickness of barrier coatings vary widely, they generally have a low
permeability or moisture vapor transmission rate. As a rule,
the lower the transmission rate, the less likelihood that oxygen and moisture will reach the substrate. Some common
barrier coatings include organic paints and lacquers, metallic
coatings (hot dip), and heavy mastics.
Sacrificial Pigments
Zinc is a "natural" for use in protective coatings since zincrich coatings offer cathodic protection when applied to
ferrous substrates, that is, the zinc acts as a cathode during
the corrosion process, receiving the attack normally suffered
by the ferrous metal [5]. To some degree, the duration of the
pigment's efficacy is dependent on the thickness of the sacrificial coating.
T H E U S E OF COATINGS TO P R O T E C T
METALS AGAINST C O R R O S I O N
Before the beginning of recorded time and ever afterward,
mankind has battled corrosion with a multitude of methods
Vehicle Enhancement
1Vice President and technical director, HALOX Pigments, a division of H a m m o n d Lead Products, 1326 S u m m e r Street, H a m m o n d ,
IN 46320-2240.
The formulation of a coating itself can add greatly to corrosion protection. The addition of pigments, for example, can
238
www.astm.org
Unreinforced Coating
Wa~r
Water
I I
[~11
..'--E
lit
?,
J l ~
239
Ill
I I
OOQ
=,Ooo~176
/11/11111111/111111
Substrate
Substrate
FIG. 1 -Barrier pigment effect. Water takes a straight path through an unreinforced film,
but is forced to take an extended path through lamellar particles of a metallic flake or
mica-reinforced film (after Alan Smith, Inorganic Primer Pigments [2]).
help reinforce film structure and reduce permeability (as
mentioned earlier). Some pigments, such as red lead, react
with components in linseed oil/alkyd primers to produce lead
soaps which increase the corrosion resistance of the paint
film [6]. Other additives are used to enhance other coating or
film characteristics, such as drying time, flow, adhesion, and
mildew resistance. Binder selection and manufacturing
methods may also be adjusted to offer maximum corrosion
prevention.
enhancing polarization by raising the concentration of positively charged hydrogen ions at the cathode.
Inhibitive pigments such as zinc chromate, phosphate, silicate, and borate suppress corrosion by enhancing anodic
passivation in acid solutions. In neutral solution, the pigments are adsorbed onto the metal surface, reducing anodic
activity.
Oxidativepassivation--Though oxidation is usually thought
to contribute to the deterioration of a metal, oxidation sometimes creates a protective layer on a metallic surface. Passivation can occur if a metal is oxidized to a stable compound that
is part of the electrolyte [9]. Consider, for example, the protective layer of aluminum oxide on aluminum metal. The
oxide minimizes atmospheric corrosion despite the reactive
nature of the metal.
Strong oxidizing conditions are normally required for passivation to occur. Take the case of iron and nitric acid.
Exposed to concentrated nitric acid, iron will develop a very
thin inhibitive passive film; dilute nitric acid, however, will
attack the metal [10].
Neutralization--Another mechanism of inhibitive pigments is neutralization of corrosive substances as sulfates,
acids, and chlorides. This can often be achieved through the
use inhibitors in a basic environment, which decrease the
corrosive effect of acids and enhance the precipitation of
corrosive elements.
S O M E W E L L - K N O W N I N O R G A N I C ANTICORROSIVE PIGMENTS
Coatings industry suppliers are developing high-performance inorganic pigments to meet the growing demand for
nontoxic inhibitive coatings that are both economical and
highly effective. The section that follows discusses the chemistries, physical properties, functions, advantages, and disadvantages of some of the most common inorganic inhibitive
pigments.
Wherever available, the specific gravity, color, pH, oil absorption, and water solubility of each pigment is recorded,
supplied in most cases from pigment manufacturers' published data. Large discrepancies can exist between such data
240
Metallic conductor
,n
Anode
(Metal 1)
Oxidation
reaction
occurring . . . .
at anode
/ M1
~,.
Cathode
(Metal 2)
~
~
Oxygeninelectrolyte
Electrolyte
Reductionreaction
occurring at cathode
Borates
A. Barium Metaborate (BaO-B203.H20) [11-14]
The grades shown in Table 1 indicate three grades of commercially available modified barium metaborate, the most
commonly used borate inhibitor. Grade I is the primarily
barium metaborate, and Grades II and III are modifications
of Grade I which are said to decrease the reactivity of the
pigment, thus increasing its formulation versatility. Grade II
includes approximately 27% zinc oxide, and Grade III includes approximately 18% zinc oxide and 29% calcium sulfate.
Modified barium metaborates may be used in many kinds
of applications in a broad range of solvent and water-based
resin systems. The pigment's alkalinity contributes to inhibi-
Specific gravity
Color
pH
Oil absorption
Water solubility
Typical loading levels:
G r a d e II
G r a d e III
3.30
3.70
3.30
White
White
White
10.0
9.1
10.0
30
20
23
0.3%
0.2%
0.4%
3 to 15%, based on total weight.
Some heavy duty maintenance
coatings may require up to 40%
B. Zinc Borate
Zinc borate, usually used to provide flame retardancy in
plastics and cellulosic fibers, is not normally thought of as an
inhibitive pigment. However, recent research indicates that
zinc borate, used in combination with modified barium metaborate or zinc phosphate, exhibits synergistic performance
properties resulting in enhanced corrosion prevention. This
241
Chromates
Chromates have long been used as inhibitors since the
soluble chromate ion is itself inhibitive and the chromate
passivating ion is among the most efficient passivators
known. Unfortunately, chromates are less widely used than in
the past since hexavalent chromium pigments are either confirmed or suspected human carcinogens [15]. Evidence indicates that strontium, calcium, and zinc chromates are among
the most carcinogenic forms of hexavalent chromium. Also,
lead chromate is considered a suspected carcinogen by the
American Conference of Governmental Industrial Hygienists
(ACGIH), while zinc chromate is considered a confirmed
carcinogen [16].
3.45
Yellow
7.5
25
0.1% [17]
3.65
Yellow
7.5
53
<0.01%
Often referred to as basic zinc chromate, zinc tetraoxychromate is commonly used in the manufacture of twopackage poly(vinyl butyryl) (PVB) wash primers, which consist of phosphoric acid and zinc tetraoxychromate dispersed
in an alcoholic poly(vinyl butyryl) solution. These primers,
also called etch primers or tie coats, are used to passivate
steel, galvanized, and aluminum surfaces, improving the adhesion of topcoats. Because they are usually low in solids and
Specific gravity
Color
pH
Oil absorption
Water solubility
3.70
Yellow
8.5
~35
0.05%
Leads
Lead, though not a direct inhibitor, reacts with certain
resin systems to form lead soaps which are active inhibitors.
Lead pigments have proven themselves over the years to be
outstanding anti-corrosives which perform particularly well
over insufficiently prepared surfaces.
However, since it accumulates in body tissue, lead is generally considered an acute and chronic toxicant and has become the subject of strict environmental regulations, especially regarding waste disposal and worker protection.
Although they are still used to produce heavy duty maintenance coatings and lead chromate colors, regulations have
caused the use of lead pigments to decline.
8.85
Orange
6.5
6
<0.001%
One of the first recorded inhibitors and still one of the most
effective, red lead has been widely used in primers for structural steel. The pigment is available in four grades containing
from 85 to 98% Pb304.
While red lead is an oxidizing agent, its inhibitive mechanism is much more complicated than mere oxidation. When
formulated with linseed oil, red lead forms soaps which, in
the presence of water, release soluble lead compounds and
organic acids. These soaps also improve the mechanical
properties of the paint film and promote passivation through
three mechanisms:
9 Anodic adsorption of soluble lead compounds.
9 Anodic adsorption of acid molecules.
9 Anodic precipitation by oxidation [19].
242
4.1
Orange
14
<0.01%
Molybdates
Molybdate-based pigments are anodic passivators, preventing corrosion by forming a protective layer of ferric molybdate on the surface. This layer is insoluble in neutral and
basic solutions. However, since most commercial molybdate
pigments contain zinc, the formation of inhibitive zinc soaps
in oleoresinous systems may add to the anti-corrosive properties of molybdate products.
Although molybdate inhibitors are free of lead and chromate, they are limited in market value due to their expense.
To make these more accessible, molybdate/phosphate compositions have been introduced, though these are difficult to
disperse. Micronized versions of molybdate/phosphate are
available to counteract the dispersion problem.
Following are the four most popular molybdate inhibitors
available on the market today.
5.06
White
6.5
14
<0.01%
5 to 15%
3.0
White
8.5
18
2.5 to 10%
4.0
White
5.5
14
<0.01%
Recommendations are the same as for basic zinc molybdate. This product, however, is reported to provide enhanced
performance over rusted steel substrates.
3.0
White
7.5
l8
5 to 15%
Phosphates
A. Zinc Phosphate [Zn3(PO4)2-2HzO]
Specific gravity
Color
pH
Oil absorption
Water solubility
Typical loading levels
3.2
White
7.5
25
<0.01%
5 to 10% in waterbased systems;
5 to 15% in solventbased industrial systems;
10 to 30% in
maintenance coatings
Grade I
Grade II
Grade III
3.0
White
6.5
37
1%
3.1
White
6.5
32
1%
3.0
White
6.5
30
1%
Phosphites
C. A l u m i n u m Triphosphate [26]
Available commercially in three grades (Table 2), aluminum triphosphate is a relatively recent chromate-free inhibitor. A condensation product, it is often modified with zinc ion
or silicate to minimize its solubility and reactivity. Inhibition
is thought to result from the tripolyphosphate ion's ability to
chelate iron ions, as well as higher phosphate levels resulting
from the depolymerization of the tripolyphosphate ion into
orthophosphate ions. These pigments exhibit typical phosphate performance relative to loading levels.
Each grade is recommended for specific applications:
Grade / - - F o r use in solvent-based primers (alkyds and
epoxides). Grade I is modified with zinc and silicate.
Grade H - - F o r use in solvent and water-based systems. The
pigment's lower water solubility apparently makes it more
243
Specific gravity
Color
pH
Oil absorption
Water solubility (Max.)
Typical loading levels
3.9
White
7.0
18
0.04%
10-25% in
maintenance applications;
5-15% in general
industrial and waterbased applications
Silicates
Silicate pigments contribute to corrosion inhibition in several ways, chiefly through anodic and cathodic passivation.
In addition, in oleoresinous systems, these pigments form
inhibitive soaps of barium, calcium, strontium, and zinc. The
inhibitive value of silicate pigments is further enhanced by
their alkalinity and solubility.
244
Specific gravity
2.65
Color
White
pH
10.1
Oil absorption
36
Water solubility
0.35%
(max)
Typical loading levels 10-20%
Grade II
Grade III
2.71
White
10.1
27
0.34%
2.65
White
10.1
41
0.37%
10-20% in primers,
2.5-10% in
topcoats and DTM
finishes
10-20%
B. Phosphosilicates [31-34]
Four modifications (see Table 4), each representing a different commercial grade, are available for a variety of uses.
Calcium Barium Phosphosilicate (Grade/)--This pigment
is for use in conventional and high solids solvent-based
epoxy systems. The pigment is also used in organic zincrich primers as an anti-settling agent.
Calcium Barium Phosphosilicate (Grade II)--A low-oil-absorption version of this pigment, Grade II is for use in most
water-borne systems, including latexes and water-reducible systems. When formulated in alkyds, this product, like
many other phosphate pigments, will demonstrate excellent real-world performance, but poor performance in accelerated testing.
Calcium Strontium Phosphosilicate (Grade III)--This pigment is for use in most water-based acrylic lacquers, as well
as water-reducible caulks and sealants. When the product
used with zinc phosphate in water-based lacquer systems
in a 1:1 ratio, a synergistic effect is produced which improves performance.
M i s c e l l a n e o u s Inhibitive Pigments
1.8
White
9.2
50 [35]
B. Zinc Oxide
Research has suggested that zinc oxide possesses both passivating and cathodic inhibitive capabilities [36,37]. Also,
when used in latex metal primers and certain oleoresinous
systems (such as SSPC Paint No. 25) [38], zinc oxide exhibits
obvious anti-corrosive action.
~
Often used with more conventional active inhibitors such
as zinc chromate and calcium borosilicates, zinc oxide appears to raise the cross-link density of many paint films,
making them harder. Zinc oxide may also absorb ultraviolet
light, thus protecting the resin. Since the pigment tends to
have seeding problems and can cause film brittleness, care
must be taken when using zinc oxide in inhibitive coating
applications.
GradeII
GradeIII
GradeIV
2.97
2.90
3.01
White
W h i t e White
8.3
7.8
7.0
31.5
53.5
26.0
0 . 0 2 % 0 . 0 3 % 0.02%
5-10%
5-10%
2.5-15%
Barrier Pigments
A. A l u m i n u m Flake
Aluminum flake, typically supplied as a slurry, is produced
by atomizing molten aluminum and ball-milling the powder
into a solvent. The resultant flake is frequently used to improve the appearance and anti-corrosion performance of
B. Steel Flake
Stainless steel and a number of steel alloys are sometimes
used to make steel flake, which is used in coatings for applications requiring m a x i m u m resistance to abrasion.
4.9
Dark Gray
11
30-50%
A naturally occurring form of hematite with an Fe2Oa content of about 92 to 95%, MIO has been used in protective
coating formulations for over 100 years. Because of its lamellar structure, it is typically used in primers to improve their
barrier resistance. Used in topcoats, MIO enhances resistance to ultraviolet light.
245
ENVIRONMENTAL CONSIDERATIONS
Health and safety factors have always been seriously considered during the development and evaluation of new
protective coatings. Use of lead, hexavalent chromium compounds, and other toxic pigments is constantly monitored to
ensure that current, acceptable limits are met. Environmental regulations have driven the inhibitive coatings industry to
increase efforts to develop and evaluate new, nontoxic products to replace lead, chromates, and traditional inhibitors
with long-standing performance records.
Two primary environmental concerns within the industry
are worker protection and waste disposal. Several steps have
been taken to ensure worker safety. For example, all workers
have the right to know the dangers involved with handling the
materials they are exposed to every day and the right to be
offered the capability to handle these materials safely. Because absorption of toxic pigments through inhalation is a
major concern, workers are protected by engineering controls (ventilation), respiratory controls (masks, filters, and
other equipment), and extensive safety training. The preferred option is to completely eliminate the hazardous material and substitute a less toxic pigment, if possible.
Waste disposal pertains to plant waste produced by paint
manufacturing and waste from painting operations. The latter includes overspray and spent blast abrasives contami-
Pigment volume concentration (PVC) is the ratio of pigment volume to the total nonvolatile volume in a coating.
Probably the most important formulation factor to consider
when evaluating anti-corrosive pigments, PVC is especially
crucial when two or more inhibitors are being considered for
a given application.
Essential to the understanding of the importance of PVC is
the concept of a "formulation window." This term represents
the PVC range at which an inhibitive pigment will give its best
performance and is clearly depicted in Fig. 3. Here, the performance in a salt fog cabinet of three popular chromate-free
inhibitors is compared to that of zinc chromate in a medium
oil alkyd primer. Loadings are equal--about 10% of total
formula weight--across a PVC ladder at constant volume
solids.
In the figure, the three nontoxic inhibitors each yielded
performance equivalent to zinc chromate, but only within a
specific PVC range, a rather narrow formulation window.
Conversely, zinc chromate offered far greater formulation
versatility, performing over a much broader PVC range.
The figure illustrates both the importance of addressing the
variable of PVC and poses a problem facing the formulator:
None of the environmentally acceptable inhibitors--including the three in the figure--come close to matching the
traditional lead and chromate-based pigments for overall efficiency and formulation flexibility. While each of the three
chromate-free inhibitors was formulated to equal the per-
246
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....
.~%
v<>~
"..\
-. ~.
.-"
a.
"...
,.
\
30
35
40
<>0 ".
%'.1
oo-j
~-.~
I
45
50
~d
J
55
PVC
INHIBITIVE PIGMENT
m
9999 9
Zinc Phospho-oxide
Borosilicate
Chromate
formance of zinc chromate, each performed at a much narrower formulation window, thereby severely restricting its
use.
Many factors influence the formulation window of an inhibitive pigment in a given formulation. All these factors must
be satisfied to maximize the performance of an inhibitor.
Crucial factors to consider in association with PVC are: (1)
specific gravity, oil absorption, and other physical properties
of an inhibitor; and (2) the effect of these properties on CPVC
(critical pigment volume concentration).
The concept of CPVC, introduced in the late forties, postulates the existence of a level of pigmentation in a dry paint
film at which there is just enough binder to coat the pigment
particles and fill the spaces between them [39,40]. Since
many nontoxic inhibitors are lower in specific gravity and
higher in oil absorption than more traditional inhibitors, it is
easy to formulate anti-corrosive coatings which exceed CPVC
and therefore deliver unacceptable levels of inhibition. To
avoid this situation, it is necessary to evaluate inhibitive pigments across a PVC range to achieve optimum performance.
To do this, coatings should be made at each extreme of the
PVC range; then weight blends of these paints may be used to
generate the intermediate levels.
Extender Pigments
Although a wide choice of extenders is available for inhibitive coatings formulation, extender selection traditionally
has not received much attention. This may be the result of the
former widespread use of lead and chromate-based inhibitors, whose excellent performance masked any flaw contributed by an extender. With emphasis on environmentally acceptable (and less effective) inhibitors, however, selection of
suitable extenders is an important factor in the formulation
of inhibitive coatings.
Figure 4 contains the results of work in latex maintenance
coatings. The data here clearly show that the performance of
extender pigments depends to a great extent on the type of
vehicle and inhibitor used in the formulation, that is, the
performance of extenders will vary from system to system.
Selecting the appropriate extender, therefore, may be as crucial to coating performance as selecting the vehicle system or
inhibitive pigment [41].
A P P L I C A T I O N A N D P R O T E C T I V E COATING
PERFORMANCE
Coating application (how, where, why, and for how long a
coating will be used) must be carefully considered when formulating environmentally acceptable alternatives to traditional toxic inhibitors. The length of time a protective coating
can effectively protect a ferrous surface has been said to
10
Clay
w
O
z
<
=E
nO
iJ.
n-
247
Calcium
Carbonate
Calcium
Carbonate
Ill
a.
Clay
0
ACRYLIC LATEX
STYRENE-ACRYLIC LATEX
FIG. 4-Extender performance properties: accelerated performance measurements.
248
depend on the following application factors: the environment, how the coating is applied, the substrate, and the
surface preparation of the substrate [44].
Consider the environment where the inhibitive coating will
be used: Will the coating be exposed to harsh chemicals,
abrasion, industrial atmospheres, heavy traffic, high heat, or
other extreme conditions? Or will it be used in a rural setting,
exposed to the elements? Answering these questions will help
determine the proper vehicle system and application techniques to be used with the coating.
Other factors to consider when deciding how to apply a
protecting coating include the type of applicator (brush,
roller, spray, or dip), adequate and uniform film thickness
[45], drying time, and temperature. Though application techniques are often given little attention, they can profoundly
affect the performance of a protective coating.
Substrates are also important factors in testing protective
coatings and inhibitive pigments. For example, untreated
cold rolled steel generally shows more undercutting at scribes
than sandblasted hot-rolled steel or treated steel. Because it is
easier to differentiate between pigments on untreated steel,
that substrate is frequently used to compare the performance
of different inhibitive pigments. On the other hand, use of a
phosphatized substrate seems to improve the performance of
protective coatings, apparently enhancing adhesion, passivating the surface, and improving the coating's inhibitive
properties.
A word of caution: When selecting substrates for testing
inhibitive coatings systems, care must be taken to conduct
final evaluations of a system on the substrate that the coating
will be applied to in actual use. For screening purposes,
however, evaluations m a y be conducted on any appropriate
substrate.
Protective coatings are frequently applied to the following
ferrous substrates [46]: cold-rolled steel; polished cold-rolled
steel; zinc phosphate-treated cold-rolled steel; iron phosphate-treated cold-rolled steel; hot-rolled steel; abrasive
blasted hot-rolled steel; pre-rusted hot rolled steel, and galvanized steel.
No matter what the substrate, the surface preparation of
the substrate, or its condition, is vital to the evaluation of
protective coatings and an important factor in determining
the life expectancy of a coating system. In addition to cleaning a surface, improving adhesion, and maximizing the performance of the inhibitive pigment, surface preparation
helps remove contaminants--such as chlorides and sulf a t e s - f r o m the substrate's surface [47].
Though many methods of surface preparation exist, their
effectiveness varies widely. For example, studies suggest that
a protective coating will last four times longer on a blasted
surface than on a hand-cleaned or weathered substrate [48].
This improved longevity is attributed to better adhesion and a
more intimate contact between substrate and coating, which
allows the inhibitor to maximize its performance.
Some of the commonly used surface cleaning techniques
are [49]: centrifugal blasting; metallic and nonmetallic abrasives; abrasive air blasting and water blasting; by hand and
power tools; chemicals; pickling. Less common methods include hot gas, flame, bacterial, zinc shot, ice particles, and
ultrasonic.
249
Statistical Analysis
Another method of correlating performance data and predicting coating performance is the use of statistical analysis,
which is growing in popularity. Various techniques used to
design more meaningful, accurate evaluations include correlation methods, survival analysis, curve fitting, time series
analysis, and reliability and life analysis.
Several techniques have been developed for assessing macroscopic damage to protective coatings. Though coatings
have traditionally been assessed by visual inspection, these
procedures can apparently detect early stages of corrosion,
giving more relevant, accurate information in a shorter exposure period.
250
O t h e r Testing Procedures
Driven by changing r e g u l a t o r y s t a n d a r d s a n d the industry's
need for p r o m p t p r o d u c t development, a variety of alternative accelerated testing p r o c e d u r e s are being r e s e a r c h e d a n d
developed. The challenge is to m a k e accelerated testing accurately reflect real-world conditions a n d yield meaningful, realistic results. The Corrosion C o m m i t t e e of the F e d e r a t i o n of
Societies for Coating Technology (FSCT) c o m m i s s i o n e d a
survey [52] on this subject directed to m a n u f a c t u r e r s a n d
users of protective coatings. The results of the survey s h o w e d
that the p a r t i c i p a n t s were exploring the use of the following
kinds of modified accelerated testing techniques: (1) cyclic
tests; (2) cyclic n a t u r a l exposures; (3) electrochemical testing;
a n d (4) physico-chemical, physical, a n d m e c h a n i c a l testing
procedures.
The Steel Structures Painting Council (SSPC) is evaluating
the m o s t p r o m i s i n g of these accelerated cyclic c o r r o s i o n
tests. The survey itself is too extensive to be included here b u t
is readily available from the FSCT.
CONCLUSION
Before the b e g i n n i n g of r e c o r d e d history a n d ever since,
p r o t e c t i n g ferrous surfaces from the disintegrating effects of
c o r r o s i o n has been one of m a n k i n d ' s m o s t c o m m o n a n d perplexing battles. F r o m the lead c o m p o u n d H o m e r ' s blacksmiths s m e a r e d on their w a g o n wheels to the sophisticated
protective coatings used today, the science of preventing corr o s i o n is as complex as the corrosion process itself. Over the
years, m a n y factors have arisen w h i c h d e m a n d consideration: s u b s t r a t e selection, surface p r e p a r a t i o n , vehicle a n d
p i g m e n t selection, a n d PVC, to n a m e just a few.
N o w the coatings i n d u s t r y is engaged in a new a p p r o a c h to
the age-old c o r r o s i o n - p r o t e c t i o n problem: developing effective n e w nontoxic inhibitors to take the place of t r a d i t i o n a l
lead a n d c h r o m a t e - b a s e d pigments. The r e s e a r c h is well underway, a n d the next ten years m a y well see the w i d e s p r e a d
a c c e p t a n c e of these safe, h i g h - p e r f o r m a n c e alternatives. This
progress will b e a c c o m p l i s h e d not by scientific curiosity o r
c o m m e r c i a l d e m a n d alone, b u t also b y c o n c e r n for the protection of o u r fragile h u m a n habitat.
REFERENCES
[1] Chilton, J. P., Principles of Metallic Corrosion, The Royal
Institute of Chemistry, W. Heifer and Son LTD, Cambridge,
England, 1964.
[2] Smith, A., Inorganic Primer Pigments, Federation Series on
Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1988.
[3] Chilton, J. P., Principles of Metallic Corrosion, The Royal Institute of Chemistry, W. Heifer and Son LTD, Cambridge, England,
1964.
[4] Schweitzer, P. A., What Every Engineer Should Know About
Corrosion, Marcel Dekker, Inc., New York and Basel, 1987.
[5] Gleekman, L. W., "Selecting Materials of Construction,"
Corrosion and Corrosion Protection Handbook, P. A. Schweitzer,
Ed., Marcel Dekker, Inc., New York and Basel, 1983.
[6] Eickhoff, A. J,, "Corrosion Inhibitive Pigments and How They
Function," Steel Structures Painting Manual, Vol. 1, Good Paint-
BIBLIOGRAPHY
American Conference of Governmental Industrial Hygienists,
"Threshold Limit Values for Chemical Substances and Physical
Agents and Biological Exposure Indices," pamphlet, 1990- 1991.
251
MNL17-EB/Jun. 1995
28
by Joseph V. K o l e s k e I
MIXING A PIGMENT WITH LINSEED OIL and m a k i n g a paste is a
p r e l i m i n a r y test a p p l i e d to p i g m e n t s that has been in use in a
systematic m a n n e r for a l m o s t a century a n d p e r h a p s even
longer in a less defined m a n n e r . Results from the test are
usually qualitative in c h a r a c t e r a n d give an a p p r o x i m a t i o n of
color a n d texture. If the test is c o n d u c t e d in a quantitative
m a n n e r , the a m o u n t of oil n e e d e d to m a k e a stiff paste is
obtained. It has been felt that the oil a b s o r p t i o n test is a
m e a s u r e of an oil-based paint's resistance to flow or consistency. F o r example, Mills [2] i n d i c a t e d that if equal volumes
of "oil a b s o r p t i o n paste" are m i x e d o r t h i n n e d with equal
volumes of thinners, the paints p r e p a r e d have equal resistance to flow, viscosity, or consistency. Also, Stieg [3] f o u n d
that if the oil a b s o r p t i o n value is d e t e r m i n e d by the ASTM
r u b - o u t m e t h o d (described below) a n d expressed on a volume
basis, it is p r o p o r t i o n a l to the critical p i g m e n t volume concentration. This test is also related to the p i g m e n t packing
factor (PPF) a n d critical p i g m e n t volume c o n c e n t r a t i o n
(CPVC).
M E T H O D S F O R D E T E R M I N I N G OIL
ABSORPTION
There are two ASTM m e t h o d s for d e t e r m i n i n g oil absorption that will be d e s c r i b e d briefly as well as related m e t h o d s
that, for the m o s t part, are t a b u l a t e d and referenced (Table 1).
Gardner-Coleman M e t h o d
This classical m e t h o d or some variation of it [11] has been
in use for a b o u t three quarters of a century. The c u r r e n t
m e t h o d , ASTM D 1483: Test M e t h o d for Oil A b s o r p t i o n of
Pigments by G a r d n e r - C o l e m a n M e t h o d [12], has been in use
for over 32 years. In this test, a soft paste is f o r m e d from the
p i g m e n t by drop-wise a d d i t i o n of r a w linseed oil with an acid
n u m b e r of 3 _+ 1 from a b u r e t t e to the gently stirred pigment.
As the oil is slowly added, the mixture is c o n t i n u o u s l y stirred
a n d folded so the oil strikes d r y p i g m e n t as long as any
remains. The mixture is not vigorously r u b b e d as in the rubout method. Eventually the mixture collects in small l u m p s
that gradually coalesce. The rate of oil a d d i t i o n is r e d u c e d as
the end p o i n t is reached. The a m o u n t of oil r e q u i r e d to form a
paste is used to calculate the oil a b s o r p t i o n value. The end
p o i n t for paste f o r m a t i o n is t a k e n to be the p o i n t w h e n the
l u m p s of wet p i g m e n t form a single ball or w h e n an excess of
oil s m e a r s the wall of a c o n t a i n e r (Fig. 1). This will take place
within one or two d r o p s of oil. It is i m p o r t a n t that there is no
r u b b i n g o r grinding w h e n this test is carried out. 'Mthough
the c u r r e n t test calls for use of a steel spatula with p a r t i c u l a r
d i m e n s i o n s a n d a glass flask for the test, variations of these
tools have been used [13,14].
Oil Absorption, A, is expressed as g r a m s of oil p e r 100 g of
p i g m e n t a n d is calculated as follows
MECHANISM
W h e n the oil a b s o r p t i o n test is performed, the surface of
each p i g m e n t particle is wet a n d s a t u r a t e d to a certain extent
with oil a n d thus is encased in a n oil shell that has been
e s t i m a t e d to be as thick as eight molecules [3, 4]. The a m o u n t
of oil n e e d e d d e p e n d s on the specific p i g m e n t area, w h i c h is a
function of particle size, roughness, and porosity. W i t h temp e r a t u r e a n d h u m i d i t y constant, the oil a d s o r p t i o n value
d e p e n d s on the d u r a t i o n a n d vigor of the r u b b i n g o p e r a t i o n
a n d on the affinity of the oil for the pigment. As oil is a d d e d
b e y o n d the particle e n c a s e m e n t stage, the interstices b e t w e e n
the oil-encased particles b e c o m e filled with oil. The a m o u n t
of oil r e q u i r e d for this stage of the test is a function of the type
packing taken on b y the particles. Packing can range f r o m
r h o m b e h e d r a l to cubic. In addition, the presence of aggregates, which are clusters of p i g m e n t not b r o k e n up b y the
r u b b i n g process, a n d agglomerates, which are clusters of pigm e n t f o r m e d after the p i g m e n t has been wet, have a n effect
on the a m o u n t of oil needed. A g g l o m e r a t i o n is affected by the
n a t u r e of the oil, a n d linseed oil that meets ASTM D 234:
Specification for R a w Linseed Oil [5], except that it should
www.astm.org
Comment
Reference
Azam
15
Bessey-Lammiman
British Standards
Institution
16
17
National Lead
Company
18
Smith-Stead
19
253
sorption values obtained by this test and the above GardnerColeman test are given in Table 2.
Azam M e t h o d
The Azam Method [15] is essentially the same test as ASTM
D 281 with the main difference being a more rigorously defined end point. The end point is defined as the point where
the paste just adheres to the spatula and the paste was termed
a "complete" paste. Azam found that a complete paste absorbed no more oil when immerse in oil, but an "incomplete"
paste would absorb oil in an amount sufficient to make it a
"complete" paste. The end point check was made by immersing the rub-out mass in a known amount of oil and then
determining the change after two or three days.
254
FIG. 1 [/]-Critical states in the Gardner-Coleman test. Left photograph is the oil/
pigment mass just before the end point where the mass retains its rigidity. The right
photograph is the mixture at the end point where the mass undergoes slight flow and
smears the glass.
13.5
18
30
30
51
33.5
33
23
32
60
26
32
52
SpatulaRub-Out
Test
...
13.0
12.8
15.0
30.0
...
21.5
...
29.0
..18.5
17.5
19.5
16.661b 2 . 0 k g
gallon - litre
255
FIG. 2 [ I ] - A , B, and C in the top photograph represent 1 g of zinc oxide that has
been mixed with increasing amounts of linseed oil. Rub-Out A (top) is crumbly and
breaks up when an attempt is made to lift it with a spatula. Rub-Out B (lower left) is
coherent and tends to form a roll when deformed with the spatula. Rub-Out C (lower
right) contains too much oil and does not roll. It can be lifted as a sheet and the
mixture is beyond the end point. The bottom two photographs are additional examples of the mixture condition just before the end point is reached. A single drop of oil
will convert the crumblings into coherent masses,
Twenty millilitres of the dispersion are then used to determine the PPF using the same procedure as that used for
CPVC. If the PPF is to be compared with oil absorption
values, it must be converted to a weight basis, PPFweight, by
means of
F(100 - PPF)(specific gravity of oil)]
PPVweight = "[_( - - P P F - ) ( ~ y
~
_]" (100)
C o l e M e t h o d f o r CPVC
The CPVC depends on pigment particle packing or orientation [9,26], and Cole [27] noted that spherical particles may
pack similarly in both liquid and dry films. To demonstrate
this, a dry-film method was developed. The method is based
on the fact that below the CPVC dry film volume, V, is a sum
of the pigment, Vv, and binder solids, Vb volumes
v=vp+vb
and that above the CPVC the volume of the voids must also be
considered with
V = PVp
M e t h o d f o r CPVC
This method [28] also used paint films, but it treated the
data in a different manner by introducing specific volume
256
Pigment
Barium titanox
Carbon black, super
Calcium titanox
CP cadmium red
CP cadmium yellow
CP Chinese blue
CP chromium oxide
CP chrome orange, medium
CP glen green DD
Chromium hydroxide, green
Lampblack
Lithol toner
Lithopone, high strength
Madder Lake
Titanium dioxide
Toluidine red
Ultramarine blue
Zinc Oxide
Zinc Sulfide
27.6
179.0
37.2
26.0
48.4
145.0
29.5
19.5
78.0
80.0
118.0
65.0
35.4
106.0
54.3
31.9
65.0
28.3
37.2
24.2
147.0
39.4
26.2
50.5
136.5
24.7
21.0
72.5
76.6
126.0
50.5
32.5
81.0
47.2
20.0
55.0
25.2
34.1
17.0
106.0
22.0
14.0
37.2
41.1
17.0
7.5
28.9
53.0
145.0
50.0
24.0
51.4
22.5
35.0
31.6
14.5
15.7
[29-31] a n d actually are two ways of stating the same concept: i.e., CPVC is the c o n c e n t r a t i o n of p i g m e n t in a pigmentb i n d e r system that contains just sufficient b i n d e r (oil) to fill
the space between the p i g m e n t particles [1 ]. If the parameters
are to be equated, it is necessary to determine the oil absorption value (OA) by the spatula m e t h o d a n d to express the
results in volume terms. If OA is expressed as X v o l u m e s of oil
per Y volumes of pigment, then
V
w
- - - - v J ~
wp+wb
CPVC -
X+Y
+ vdb
OA-
CPVC
1 - CPVC
and
1
I +OA
CPVC - - v = % , - v~)f,, + vb
I f v is plotted as a f u n c t i o n offp, a straight line of slope (vp Vb) a n d intercept of Vb should result.
Above the CPVC, the volume of the film is given by
V = PvpWp
where P is a packing factor. If both sides of this expression are
divided by W, the expression
V = Pvpfp
is obtained. If dry film specific volume, v, is plotted against
the weight fraction of pigment, fv, a straight line of slope Pvp
passing through the origin results. The intersection of this
TABLE 4--[1] Comparison of the critical pigment volume concentration calculated by the
Pierce-Holsworth method [28] and comparison with results from physical property
measurements.
Paint System
47
47
42
46
41
42
4l
42
44
44
44
45
48
47
44
48
Pigment
PPF
Calculated
from PPF
10
34
27
37
29
39
33
456
41
46
32
128
50
104
20
225
24
25
27
131
199
45
GardnerSpatula
Coleman Rub-Out
M e t h o d Method
212
33
33
24
70
27
87
55
105
62
19
124
20
24
19
51
25
51
34
65
48
12
CHARACTERIZATION OF D I S P E R S I O N S AT
T H E OIL A B S O R P T I O N P O I N T
E x a m i n a t i o n of the d i s p e r s i o n s (pastes) f o r m e d b e t w e e n
oil a n d p i g m e n t at the oil a b s o r p t i o n p o i n t is a source of
considerable information. Large differences exist in such
TABLE 6--Physical conditions that exist at the end points of pigment packing factor and oil absorption test
Parameter
PPF
Dispersion
257
Gardner-Coleman
Only a few of the largest
aggregates are broken down
and the interstices are filled
with oil.
[1,9].
Spatula Rub-Out
More aggregates are broken
down than in the GardnerColeman methods and the
interstices are filled with oil.
Electrokinetic equilibrium
Agglomeration is incomplete
Agglomeration is incomplete
because of low system fluidity.
because of low system fluidity.
Satisfied
Work of dispersion
Work of packing
Substantially satisfied
Observation Point
At wet point
Good Dispersion
Shines without tapping or with light
tapping; dry and difficult to knead
At intermediate stage
.-.
At flow point
Very small
Fair Dispersion
Poor Dispersion
-..
Very large
258
REFERENCES
[1] "Oil Absorption of Pigments," Chapter 3.5, Paint Test Manual,
13th ed., G. G. Sward, Ed., The American Society for Testing
and Materials, Philadelphia, PA, 1972.
[2] Mills, G., "Pigment Surfaces," Journal of the Oil and Colour
Chemists' Association, Vol. 34, 1951, p. 497.
[3] Stieg, F. B., Jr., "Color and CPVC," Official Digest, Federation of
Paint and Varnish Production Clubs, Vol. 38, 1956, p. 695.
[4] Long, J. S., "Creative Imagination as it Applies to the Decorative
and Protective Industry," Official Digest, Federation of Paint and
Varnish Production Clubs, Vol. 32, 1954, p. 989.
[5] Annual Book of ASTM Standards, Vol. 06.03.
[6] Marsden, E., "Oil Absorption: A New Assessment, Part I," Journal of the Oil and Colour Chemists'Association, Vol. 42, 1959, p.
119.
[7] Mill, C. C. and Bank, H. W., "An Interpretation of the Oil Absorption of Pigments," Journal of the Oil and Colour Chemists'
Association, Vol. 32, 1949, p. 599,
[8] Bessey, G. E. and Lammiman, K. A., "The Measurement and
Interpretation of Oil Absorption," Journal of the Oil and Colour
Chemists' Association, Vol. 34, 1951, p. 519.
[9] Asbeck, W. K., Laiderman, D. D., and Van Loo, M., "Oil Absorption and Critical Pigment Volume Concentration," Official Digest, Federation of Paint and Varnish Production Clubs, Vol. 30,
1952, p. 156.
[10] Davidson, R. R., "Whiting Dispersions, Particle Packing, and
Surface Adsorption," Journal of the Oil and Colour Chemists
Association, Vol. 43, 1960, p. 307.
[ll] Gardner, H.A. and Coleman, R. E., "Oil Absorption of Pigments," Scientific Section Circular, No. 85, National Paint, Varnish, and Lacquer Association, Washington, DC, 1920.
[12] Annual Book of ASTM Standards, Vol. 06.02.
[13] Haugen, O.A. and Hentzen, H. D., "Oil Absorption of Paint
Pigments," Chemical and Metallurgical Engineering, Vol. 29,
1923, p. 840.
[14] van Wullen-Scholton, W., "Oil Absorption of Pigments," Farben
Zeitung, Vol. 344, 1929, p. 2940.
[15] Azam, M., "Oil Absorption of Pigments, Industrial and Engineering Chemistry," Analytical Edition, Vol. 14, 1942, p. 545.
[16] British Standards Institution, Standard 3483, 1962, p. 11.
[17] Bessey, G. E. and Lammiman, K. A., "Oil Absorption of Pigments and Extends," Journal of the Oil and Colour Chemists'
Association, Vol. 33, 1950, p. 411.
[18] "Oil Absorption," Brochure No. TP-P-OA, National Lead Company, Titanium Division, New York, 10 April 1953.
[19] Smith, F. M. and Stead, D. M., "Determination of Oil Absorption: A New Method," Journal of the Oil and Colour Chemists'
Association, Vol. 37, 1954, p. 194.
[21] Wolff, H., "Oil Absorption of Pigments," Farben Zeitung, Vol. 34,
1929, p. 2940.
[22] Wolff, H., "The Critical Oil Content of Paints," Farben Zeitung,
Vol. 37, 1931, p. 374.
[26] Asbeck, W. K. and Van Loo, M., "Critical Pigment Volume Relationships," Industrial and Engineering Chemistry, Vol. 41, 1949,
p. 1470.
[27] Cole, R. J., "Determination of Critical Pigment Volume Concentration in Dry Surface Coating Films," Journal of the Oil and
Colour Chemists' Association, Vol. 45, 1962, p. 776.
[28] Pierce, P. E. and Holsworth, R. M., "Determination of Critical
Pigment Volume Concentration By Measurement of Density of
Dry Paint Films," Official Digest, Federation of Paint and Varnish
Production Clubs, Vol. 37, 1965, p. 272.
[29] Smith, A., "Inorganic Primer Pigments," Federation Series on
Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, 1988.
[30] Philadelphia Paint and Varnish Production Club, "Determination of CPVC by Calculation," Official Digest, Federation of Paint
and Varnish Production Clubs, Vol. 33, 1961, p. 1437.
[31] Philadelphia Paint and Varnish Production Club, "Determination of the Oil Absorption and Critical Pigment Volume Concentration of Multicomponent Pigment Systems," Official Digest,
Federation of Paint and Varnish Production Clubs, Vol. 31, 1959,
p. 1491.
[32] Stieg, F. B., Jr., "The Determination of CPVC by the OA Test,"
American Paint Journal, Vol. 45, No. 4, 1958, p. 41.
[33] Stieg, F. B., Jr., "A Complex Problem and a Simple Answer,"
Part 7: Additives
MNL17-EB/Jun. 1995
29
microorganisms enable
9
9
DESCRIPTION
In-can Preservation
Problems frequently associated with unpreserved, waterbased paints have increased in recent years, mainly because
water-based paints have become much more common. These
formulations are susceptible to attack by bacteria and unicellular fungi (yeasts) and occasionally filamentous fungi. There
are several food sources available for growth of microorganisms in common coatings formulations; cellulosic thickeners,
surfactants, and defoamers are all molecules used as a carbon
source by microorganisms. Good discussions can be found in
Refs 3-5. The problems most commonly encountered in water-based paints include those shown in Table 1.
To prevent these problems from occurring, an effective
biocide should be incorporated into the coating. It must be
cost effective, be compatible with coating ingredients, impart
no color to the formulation, have no objectionable odor, be
nonyellowing in the dried film, and be environmentally acceptable in manufacture, handling, and release into the environment.
The best understood problem in coating film preservation
is the disfiguring growth of organisms on the exterior surface
of the film itself [6, 7], such as on ships, bridges, and interior
and exterior walls of buildings. Less understood are problems
associated with loss of adhesion from fungi growing underneath the coating film and the corrosion problems on equip-
Definition o f Terms
Following are definitions of the terms used:
9 A biocide is a substance that kills organisms. The use in this
OF MICROBIAL PROBLEMS
www.astm.org
262
paints.
Type of Problem
Type of Problem
Common Cause
Common Cause
Discoloration/dirt
entrapment
Loss of adhesion
Corrosion
Fungi.
Moisture produced by fungi.
Production of growth
promoting substances
Destruction of cultural
objects
Gassing--swelling
or exploding
cans
Viscosity loss
Odors
pH change/physical
instability
Gelation
Discoloration
Slime formation
Bacteria
G R O U P S OF M I C R O O R G A N I S M S R E L A T E D
TO BIOCIDAL EFFICACY
implicated.
work,
Microbicide toxicity a n d efficacy are often concerns w h e n
preserving coating films. Fungicides a n d algicides are frequently m o r e toxic t h a n m o s t c o m m o n bactericides since
fungal a n d algal cells share m a n y similarities with cells from
higher organisms, while b a c t e r i a l cells a r e distinctly different. Most m i c r o b i c i d e s are limited to efficacy against one
group, a n d s o m e of the m o r e effective a n t i m i c r o b i a l s target
specific m e t a b o l i c p a t h w a y s u n i q u e to one group of organisms.
Several recent studied [8, 9] have s h o w n a relationship between bacterial growth, their polysaccharides, a n d subsequent colonization of surfaces by fungi o r other organisms. It
a p p e a r s that colonization succession occurring on dry films is
s i m i l a r to that occurring on ship bottoms. This implies that
there should be a bactericide and a fungicide i n c o r p o r a t e d for
coating film protection. S o m e biocides can provide b o t h
functions. In tropical climates, disfiguring g r o w t h of algae on
the exterior of the films is also a p r o b l e m [10,11]. Table 2
indicates p r o b l e m s in p a i n t a n d coating film preservation.
Aerobic b a c t e r i a
G r a m positive b a c t e r i a
endosporeforming bacteria
G r a m negative b a c t e r i a
Anaerobic b a c t e r i a
G r a m positive b a c t e r i a
endosporeforming bacteria
G r a m negative b a c t e r i a
Fungi
Multicellular (molds)
Unicellular (yeasts)
Algae
Green algae
Blue-green algae (cyanobacteria)
NOTE: All of these o r g a n i s m s are described in m o r e detail
elsewhere.
M O D E OF ACTION OF M I C R O B I C I D E S /
S P E C T R U M OF ACTIVITY
It is very i m p o r t a n t to note the difference in the activity of a
p a r t i c u l a r biocide a g a i n s t the different o r g a n i s m s w i t h i n a
group, a n d differences are to be expected. The m o s t i m p o r tant c o n s i d e r a t i o n is to k n o w w h i c h o r g a n i s m s one is trying
to protect against a n d to use an effective agent. W h e n the
m o d e of action of a biocide has b e e n elucidated, it frequently
explains the differences in activity. The lists below are not
m e a n t to b e comprehensive. They describe s o m e m a t e r i a l s
well k n o w n to the industry a n d r e p o r t on the o r g a n i s m s
against which the c o m p o u n d s are m o s t effective [12-14].
M O D E OF ACTION OF S O M E
ANTIMICROBIAL AGENTS
The following is not intended to explain all possible modes
of action, but to give a general overview of the terms used in
the biocide listings. More detailed explanations can be found
in the references listed at the end of this chapter.
Effective Against
Broad spectrum
Fungi
Broad spectrum
Broad spectrum, except
gram negative
bacteria
Fungi, algae
Fungi
Fungi
263
264
TABLE 4--Some nitrogen and/or sulfur-containing microbicides used in paints and coatings.
Composition
Effective Against
4,4-dimethyl-oxazolidine +
3,4,4-trimethyloxazolidine
Bacteria
Bacteria
2(hydroxymethyl)aminoethanol
Bacteria
2 [(hydroxymethyl)-amino]-2methyl- 1-propanol
Bacteria
Methylenebis(thiocyanate)
Bacteria/fungi/algae
1,2-dibromo-2,4dicyanobutane
Bacteria/fungi/algae
2-(4-thiazolyl)benzimidazole
Fungi
2-mercaptobenzo-thiazole
Fungi/bacteria (?)
1,2 -benzisothiazoline-3-one
Bacteria/fungi/yeast
5-chloro-2-methyl-3(2H)isothiazoline + 2-methyl3(2H)-isothiazolone
4-(2-nitrobutyl)-morpholine +
4,4'-(2-ethylnitrotrimethylene
dimorpholine
Fungi/bacteria
Bacteria
Fungi/bacteria
Zinc 2-pyridinethiol-N-oxide*
Fungi
Tetra-hydro-3,5-di-rnethyl2H-1,3,5-thiadiazine-2-thione
Bacteria/fungi
N-trichloromethyl-thio-4cyclohexene-l,2dicarboximide
Fungi
Bacteria
2 -n-octyl-4-isothiazoline-3-
Fungi
1-(3-chloroallyl)-3,5,7-triaza1-azonia-adamantane chloride
Bacteria
1-methyl-3,5,7-triaza-1azonia-adamantane chloride
Bacteria
2,4,5,6-tetrachloroisophthalonitrile
Fungi
3-iodo-2-propynyl butyl
carbamate
Fungi
Chelation?
N-(trichloromethylthio)phthalimide
Fungi
2-(thiocyanomethylthio)benzothiazole
Fungi/anaerobic; bacteria/
algae
Fungi
Potassium N-hydroxy-methylN-methyl-dithiocarbamate
Fungi
2 -(thiocyanomethylthio)benzothiazole +
methylenebis (thiocyanate)
Bacteria/fungi/algae/anaerobic
bacteria/mollusks
Sodium 2-pyridinethiol-ioxide
Fungi
one
Diiodomethyl-p-tolyl sulfone
Parabens (ethyl, or
propyl, methyl, or
butyl
parahydroxybenzoate)
Quarternary
ammonium
compounds
Chlorine biocides
Reported Effective
Against
PutativeMode of
Action
Bacterial
spores,
bacteria,
fungi, algae
Fungi
Reaction with
proteins
Bacteria, a l g a e
Generalized
membrane
damage
Deactivation of
proteins
Broad spectrum
Membrane activity
and integrity
265
Other Mechanisms
Coagulation is a term denoting a general deactivation of
proteins or cells without specifying the molecular action.
Interference with active transport (of food molecules into
cells) may be from deactivation of transport proteins or by
adsorption of molecules onto the cell surface, blocking the
transport proteins. Ergosterol is an important lipid component of the fungal membrane, and interference with its synthesis would be fungistatic in low concentrations and fungicidal in high. Inhibition of respiration (oxidative phosphorylation) results in the cell being unable to generate
energy (ATP or adenine triphosphate) through metabolism,
eventually killing it. Interference with DNA (deoxyribose nucleic acid; chromosome material), RNA (ribose nucleic acid),
or protein synthesis would hinder reproduction and metabolism, eventually killing the cell.
Cationic Agents
266
Addition
temperature
Nonionic
surfactants
Low solubility
Leachability
Can components
Formulation
components
Stabilizing
agents
UV light
frequency
M E T H O D S F O R D E T E R M I N A T I O N OF
B I O C I D E EFFICACY
There are n u m e r o u s m e t h o d s d e s c r i b e d in the literature for
d e t e r m i n i n g the efficacy of a p r o p o s e d biocide, b o t h for incan preservation a n d for p a i n t film use. The a p p r o p r i a t e
ASTM m e t h o d s are: D 2574-86, Test M e t h o d for Resistance
of E m u l s i o n Paints in the Container to Attack b y Microorganisms; D 3273-86, Test M e t h o d for Resistance to G r o w t h of
Mold on the Surface of I n t e r i o r Coatings in an E n v i r o n m e n tal Chamber; a n d D 3456-86, Practice for D e t e r m i n i n g by
Exterior E x p o s u r e Tests the Susceptibility of Paint F i l m s to
Microbiological Attack. These m e t h o d s are c o n t a i n e d in
Section III, "Microbiological C o n t a m i n a t i o n a n d Biodet e r i o r a t i o n Assessment," of ASTM Standards on Materials and
Environmental Microbiology, first edition, 1987 [19]. Several
o t h e r m e t h o d s in this section are also of interest. A c o m p l e t e
fungicide testing p r o g r a m is d e s c r i b e d in Ref 20, a n d an
electronic r a p i d m e t h o d for d e t e r m i n i n g c o n t a m i n a t i o n in
coating r a w m a t e r i a l s (and b y extension, preservation efficiacy) has recently b e e n p u b l i s h e d [21]. Other m e t h o d s are
d e s c r i b e d in Ref 22. Testing of algicides for tropical locations
is d e s c r i b e d in Ref 23.
REFERENCES
[1] Gabriele, P. D. and Iannucci, R. M., "Protection of Mildecides
and Fungicides from Ultraviolet Light-Induced Photo-Oxidation," Journal of Coatings Technology, Vol. 56, 1984, pp. 33-48.
[2] McLaurin, M. C., Modified Barium Metaborate in Properties and
Economics, Vol. 1, 2nd ed., John Wiley & Sons, Inc., New York,
1988.
MNL17-EB/Jun. 1995
30
LIST OF A B B R E V I A T I O N S
AQ Aqueous
ASE Alkali-swellable and/or soluble emulsion
ATRM Associative thickener and/or rheology modifier
BCARB Butyl Carbitol |
BP Biopolymer
CMC Carboxymethyl cellulose
CTRM Conventional thickener and/or theology modifier
DS Degree of substitution
DUEV Dynamic uniaxial extensional viscosity
EHEC Ethyl hydroxyethyl cellulose
HASE Hydrophobe modified alkali-swellable/soluble emulsion
HBMC Hydroxybutylmethyl cellulose
HEC Hydroxyethyl cellulose
HEEASE Hydrophobe modified ethoxylate ester alkaliswellable/soluble emulsion
HEMC Hydroxyethylmethyl cellulose
HENN Hydrophobe modified ethoxylate nonionic
non-urethane
HEUR Hydrophobe modified ethoxylate urethane
HEURASE Hydrophobe modified ethoxylate urethane
alkali-swellable/soluble emulsion
HMC Hydrophobe modified cellulosic
HNS Hydrophobe modified nonionic synthetic
HMEHEC Hydrophobe modified ethyl hydroxyethyl cellulose
HMHEC Hydrophobe modified hydroxyethyl cellulose
HPG Hydroxypropyl guar
HPMC Hydroxypropylmethyl cellulose
HSV High-shear viscosity
ITRM Inorganic thickener and/or rheology modifier
LIQ Liquid
LSV Low-shear viscosity
MC Methyl cellulose
MS Molar substitution
MSV Medium-shear viscosity
NA Data not available
ORG Organo or organic
PAA Polyacrylic acid
ITechnology manager, Thickeners and Rheology Modifiers, Union
Carbide Corp., UCAR Emulsion Systems, 410 Gregson Drive, Cary,
NC 27511.
pEO
PG
PVC
RM
SOLV
T
TRM
VOC
XCPS
Polyethylene oxide
Propylene glycol
Pigment volume concentration
Rheology modifier
Solvent
Thickener
Thickener and/or rheology modifier
Volatile organic components
Xanthamonas campestris polysaccharide
(Xanthan gum)
INTRODUCTION
DEMANDS ON THE APPLICATIONand flow properties of coatings
have increased substantially, and because thickeners and rheology modifiers (TRMs collectively) play a key role in performance, they are among the most important components in
a coatings system. Although TRMs are used in minor
amounts in most formulations and are generally considered
additives, aqueous coatings usually contain at least one, often
two, and sometimes several to obtain the desired balance of
properties. Due to present-day environmental concerns and
the use of TRMs predominantly in aqueous coatings, the
focus of this chapter is on water-borne, and especially latexbased systems. TRMs also find utility in solvent-borne coatings where they function primarily as flow modifiers and
thixotropes. These products are discussed in later sections of
this chapter.
Thickeners
Thickeners, as traditionally defined, are components that
substantially increase viscosity (resistance to flow) at relatively low concentrations. For coatings, thickeners are normally used to increase viscosity at moderate shear rates
approximating those encountered during pouring, stirring,
or mixing. The viscosity in this shear rate range is often
referred to as the coating "consistency" or medium-shear viscosity (MSV). To be effective, a thickener should produce the
desired consistency at a low-use level that is often expressed
in units of lb thickener solids per 100 gal of liquid coating (g/L
where metric units are used). For architectural coatings, the
total amount of thickener typically used is less than about 15
lb/100 gal ( - 1 8 g/L) and can be as low as 3 lb/100 gal ( - 4 g/L)
or less, depending on coating solids, pigment volume concentration (PVC), vehicle type, and other components present in
the formulation. As discussed later, selection of components
268
www.astm.org
(Medium-Shear Viscosity).
Rheology Modifiers
Presently, there is no universally accepted definition of the
term "rheology modifier." In fact, the terms "thickener" and
"rheology modifier" are often used interchangeably in commerce, especially for associative TRMs. All thickeners modify
rheology to varying degrees when incorporated; consequently, all thickeners, technically, are also rheology modifiers. Some modify rheology in a positive way, and others
modify rheology adversely depending on the desired effect.
Although all thickeners can be considered theology modifiers, not all rheology modifiers are considered thickeners,
and herein lies a distinction. For purposes of classification,
rheology modifiers are defined here as additives which influence viscosity at high and/or low shear rate (generally above
1000 s -1 or below 10 s -1) but contribute little to consistency
(that is, they change rheology but are inefficient thickeners).
If a rheology modifier as defined was used as the sole thickener for consistency, typically more than about 15 lb/100 gal
( - 1 8 g/L) would be required, and 30 to 60 lb/100 gal ( - 3 5 to
75 g/L) would not be unusual. When used as primarily intended (as a rheology modifier with one or more other thickeners present), amounts much less than this normally suffice.
Like thickeners, rheology modifiers may also influence the
elastic or elongational (extensional) properties of coatings,
which can be measured on some relatively sophisticated
rheometers. Frequently, a single thickener or combination of
thickeners is effective in meeting all of the rheological requirements (low, medium, and high-shear) of a given coating
formulation, and a rheology modifier is not needed in this
situation. If the rheological requirements cannot be met with
thickeners alone, a rheology modifier is often included to
augment flow properties. A common example of this is the
incorporation of a rheology modifier to raise the high-shear
viscosity (HSV) of a coating. This increases viscosity on application which, in turn, provides increased film build (film
thickness) for improved substrate protection or one-coat hiding.
In some situations, a rheology modifier is efficient enough
to function as an effective thickener such as in the presence of
a small-particle-size latex, water-insoluble coalescing aids, at
high binder concentrations, or at high-volume solids. This
effect, which will be discussed in detail later, especially ap-
269
plies to associative rheology modifiers where strong interactions occur between the TRM and other coating components.
INCORPORATION OF TRMs
Coating manufacturing operations generally consist of
several stages of processing, and TRMs are important in each.
Some common stages are the "premix" (ingredients added
prior to pigments), "grind" (pigment added and reduced in
size for optimum dispersion), and "letdown" (where polymer
or latex is normally added). Some but usually not all of the
thickener is added to the premix to increase viscosity in the
grind for improved pigment dispersion (deagglomeration).
Under laminar flow conditions, rate of shear during grinding
is set by the tip speed of the impeller and the depth of the
shear gradient. One theory suggests that increased viscosity
allows better energy transfer by decreasing turbulence at the
impeller, which, in turn, increases the shearing collisions that
attrite the pigment agglomerates. However, too much thickener at this stage impedes mixing and actually slows down
the grinding process. The remaining thickener is usually
added to the letdown to provide proper suspension and product consistency. Finally, post-adjustments with additional
thickener or rheology modifier may be required to bring the
product "into specification" for application and appearance
properties.
RHEOLOGY
AND VISCOSITY
Shear Flow
Most low, medium, and high shear rate coating phenomena involve shear flow that is normally characterized in the
laminar regime (where the shear field produces Reynold's
Numbers below the critical characteristic for the fluid). Shear
flow in the Turbulent regime (high Reynold's Numbers) is not
normally characterized, since most parameterizing equations
fail here. The vast majority of viscometers produce shear flow
and measure the ratio of shear stress to shear rate (viscosity).
With coatings, it is useful to determine viscosity at several
shear rates to obtain a complete rheology profile which is
normally represented in log-log form. These profiles are also
conveniently divided into three shear rate regions--"at rest,"
"processing," and "application," which correspond to the lowshear, medium-shear, and high-shear regions, respectively,
as depicted in Fig. 1. Optionally, the viscosity profile can be
approximated by single-point measurements of low-shear
viscosity (LSV), medium-shear viscosity (MSV), and highshear viscosity (HSV). Some of the coating processes and
270
VISCOSITY (Pa.s)
10,000
1,000
AT REST
PROCESSINO
LOW S H E A R
MID S H E A R
APPLICATION
HIGH S H E A R
100
BRUSHING
ROLLING
10
0.1
LEVELING
SPRAYING
SAGGING
TROWELING
SETTLING
MIXING
SYNERESIS
CONSISTENCY
APPEARANCE
0.01
PUMPING
0.001
I
0.1
I I IIIlll
I
1
I I IIIII
I I III111
10
100
I ~ IIIIli
1,000
I I Illlll
I I IIII
10,000
100,000
Time-dependent shear thinning (thixotr0py) and zeroshear yield value are two other rheological coating properties
that may be very important. For example, a thixotropic fluid
with high yield value may exhibit good leveling if the time
required to rebuild viscosity is long compared to the time
needed for flowout. The viscoelastic properties of a coating
may also be important. The elastic component of shear can be
determined on some advanced cone-plate or parallel plate
rheometers either by measuring the shear storage modulus
(G') in oscillatory simple shear or by measuring normal
forces (for example, first normal stress difference, N]), which
are perpendicular to the plane of shear.
Elongational Flow
In addition to the simple shear flow fields generated during
the mixing and application of coatings, elongational (extensional) flows may also be induced during the application
processes of spray, roll, or blade coating. The study of extensional flows and their importance in coatings has been examined [6-11]. During these application processes, the fluid is
accelerated as it approaches the applicator orifice or nip, and
the TRM polymer molecules become stretched and aligned.
The viscosity related to the induced elongational flow is
termed by Glass [7] as the "dynamic uniaxial extensional
viscosity" (DUEV). One coating property that has shown
some correlation with DUEV is roller spatter that can be
rated using ASTM Test Method for Measurement of Paint
Spatter Resistance to Roller Application (D 4707-87). Other
properties that have shown some correlation with DUEV are
ribbing, web formation, and misting in roll coatings, and the
atomization process in spray coatings. Until recently, the
TRM CLASSIFICATION
Polymeric organic thickeners for aqueous media are often
classified into two basic types: "conventional," which thicken
predominately by hydrodynamic and flocculative mechanisms, and "associative," which thicken predominantly by associative mechanisms. Unfortunately, these are mechanistic
THICKENING MECHANISMS
The three primary thickening mechanisms for polymeric
water-borne thickeners are "hydrodynamic," "flocculative,"
and "associative." Each of these mechanisms may be further
divided into subclasses, if desired, which have their own individual rheological and coating characteristics. Consequently,
it is important to consider these mechanisms when making
TRM selection for increasing coating consistency, for rheology modification, or for other coating properties.
Thickening is often a complex process. For example, the
flocculation mechanism is frequently a byproduct of hydrodynamic thickening but may also occur in associative systems that are improperly formulated or in those where a
controlled degree of flocculation is desired. Some associative
thickeners (for example, alkali-swellable types) are sufficiently high in molecular weight that an appreciable
hydrodynamic component of thickening is also present.
Depending on their chemical architecture, strength of the
hydrophobic associations, and other formulation components present, some ATRMs actually function to varying
degrees with several associative and nonassociative mechanisms at the same time. Outlined in Table I are some possible
thickening mechanisms for conventional and associative
thickeners.
271
Flocculative Mechanisms
Because CTRMs take up so much volume in solution, they
induce flocculation in coatings, forming latex-rich and thickener-rich domains by a mechanism commonly referred to as
'volume restriction," "volume exclusion," or "depletion" flocculation. This process is now recognized as the primary mode
of thickening for conventional thickeners in disperse phase
systems (such as, in coatings with pigment or latex particles
272
ASSOCIATIVE MECHANISMS
The primary thickening mechanism for ATRMs is via
intermolecular hydrophobic association and association
of the thickener hydrophobes with disperse phase (colloidal
phase) hydrophobic components in the coating formulation
[21-24]. When a water-soluble polymer contains both hydrophilic and hydrophobic moieties, the potential for associative
interaction exists. Among the simplest associative structures
are nonionic surfactants. These molecules have a hydrophilic
polymer segment on one end (usually polyethylene oxide)
and a hydrophobic group on the other (typically a long chain
alkyl or alkyl aryl group). At a sufficiently high concentration
known as the critical micelle concentration (CMC), these surfactants spontaneously form micelles in aqueous solution. At
or above this concentration, the hydrophobes aggregate at
the interior of the micelle, and the hydrophilic tails orient
outward into the water phase. The key driving force for micellization is not the London Van der Waals attractive forces
between hydrophobes, but rather the change in free energy
on transfer of a hydrophobe in the aqueous phase to a more
oil-like environment at the interior of the micelle.
If a hydrophobe is chemically attached to the other end of a
nonionic surfactant, a simple associative thickener is formed.
However, because the thickener has a hydrophobe at each
end, micelle formation is not a favorable process and is not
observed except for certain chemical architectures at extremely low concentrations. Instead, the associative molecules aggregate into a three-dimensional network structure
that inhibits flow and raises the viscosity of the aqueous
solution or coating. The driving force is similar to that for
micelle formation. Although each associative polymer type
has an optimum molecular weight, high molecular weight is
not a requirement of associative thickeners, and most are
significantly lower in molecular weight (typically <50 000)
TRM FUNCTIONS
The primary function of TRMs are the control of viscosity
and rheology throughout the applicable shear rate spectrum:
consistency is measured and adjusted in the medium-shearrate range, application properties in the high-shear-rate
range, and film formation and container storage properties in
the low-shear-rate range. The viscosities associated with
these ranges may be referred to as the medium-shear viscos-
in the medium-shear range by varying the amount of thickener added. The target viscosity is normally based on prior
experience or on a previously established specification range
for a particular type of coating. One popular rheometer used
for measuring and facilitating consistency adjustment in architectural coatings is the Stormer ~ viscometer. Viscosity determination with this instrument is conducted in accordance
with ASTM Test Method for Consistency of Paints using the
Stormer Viscometer (D 562). This rheometer provides a paddle-type mixing action during measurement that is similar to
stirring, and viscosity is expressed in Krebs Units (KU). Many
coatings fall within the range of 60 to 120 KU, and a typical
specification range for a semigloss architectural coating, for
example, might be 90 to 95 KU.
The Brookfield | viscometer is another popular instrument
for determination of consistency when operated at higher
speeds (for example, 20 to 100 rpm). It is also useful at lower
speeds (for example, 0.3 to 5 rpm) for determination of lowshear processes such as leveling [see later in this section
under Leveling, Sag, Syneresis, Settling (Low-Shear Viscosity)]. Both of these measurements can be conducted in
accordance with ASTM Test Method for Rheological Properties of Non-Newtonian Materials by Rotational (Brook:field)
Viscometer (D 2196). Both the analog and digital Brookfield
models provide viscosity in centipoise (mPa-s), and cylindrical spindles are commonly used for the measurement. Another Brookfield viscometer recently introduced has a paddle
configuration similar to the Stormer viscometer. Readout on
this model is in Krebs Units.
The Rotothinner ~ is another viscometer which can be used
to determine consistency. It provides an even greater mixing
action that is capable of stirring the entire container contents
while the viscosity measurement is being made. While this
instrument can be used for more conventional coatings, it is
ity (MSV), high-shear viscosity (HSV), and the low-shear viscosity (LSV), respectively. Several film properties are also
affected and may be manipulated by the appropriate choice
and amount of TRM in the coating [27]. Two examples of
coatings improperly formulated with TRMs are represented
in Fig. 5. A clear understanding of the rheology profiles depicted and their impact on application and film properties
will become apparent in the following subsections.
VISCOSITY (Pa.s)
10,000
AT REST
PROCESSING
APPLICATION
__=
1,000
POOR LEVELING
100
10
0.1
0.01
FORMULATED TO
SAME CONSISTENCY
-_=
0.001
0.1
t i liIlll
I
1
I IIIIII
i
10
273
t I lltlll
i
100
I ililSl
i
1,000
I i iilfli
10,000
i I llili
100,000
274
275
Cellulosic polysaccharides
Carboxymethyl cellulose (CMC)
Carboxymethyl hydroxyethyl cellulose
Ethyl hydroxyethyl cellulose (EHEC)a
Hydroxyethyl cellulose (HEC)b
Hydroxypropyl methyl cellulose (HPMC)b
Methyl cellulose
Cellulosics
Prior to the introduction of ATRMs, conventional cellulosics were by far the most commonly used TRMs in aqueous
coatings. They still dominate, but their use is in decline today.
The reduction has been somewhat offset with the introduction of associative cellulosics, which are discussed later in
this chapter under Hydrophobe Modified Cellulosics
(HMCs). Cellulose (C6H1005)n is a naturally occurring polysaccharide composed of repeating anhydroglucose units. Because of its relatively straight and stiff polymer chain and
strong intermolecular and intramolecular hydrogen bonding,
the polymer itself is highly crystalline and consequently insoluble in water. Nonetheless, with chemical modification, cellulose can be readily converted to amorphous water-soluble
polymers. Hydroxyethyl cellulose (HEC), hydroxypropyl
methyl cellulose (HPMC), carboxymethyl cellulose (CMC),
and ethylhydroxyethyl cellulose (EHEC) are among those
that have been used in aqueous coatings.
The reactions used to produce water-soluble cellulose polymers are relatively uncomplicated. They typically involve
treatment of cellulose with alkali to swell the polymer, followed by the chemical addition of the appropriate substituent. Each of the commercial polymer types is available in a
variety of grades that are differentiated by molecular weight,
levels of substitution, uniformity of substitution, and treatment for ease of dispersion. As molecular weight increases
Biopolymer polysaccharides
Gellan gum
Rhamsan gum~
Whelan gum
Xanthan gum (XCPS)~
Other potysaccharides
Guar gum
Hydroxypropyl guar (HPG)a
Sodium alginate
Synthetic hydrocarbonpolymers
Poly acrylamide and copolymers
Poly ethylene oxide (PEO)
Poly hydroxyethyl (meth)acrylate
Poly (meth)acrylic acid copolymers (ASE)b
Poly olefinic sulfonate copolymers
Poly vinyl alcohol (PVOH)
Poly vinyl pyrolidonea
Poly styrene/maleic anhydride (SMA)
Poly methylvinyl ether/maleic anhydride
NOTE:"These have some use in architectural coatings. ~Thesehave significant use in architectural coatings. All others have little or no current use in
architectural coatings.
for a given polymer type, the amount of thickener required
for constant MSV decreases (thickening efficiency improves).
At the same time, LSV increases and HSV decreases. The
effect on film build is predictable (lower); however, some
investigators have actually reported improved leveling with
higher MW cellulosics. The modifications are defined in two
ways: the degree of substitution (SD), which is the average
number of hydroxyl groups which have been substituted per
anhydroglucose unit, and the moles of substitution (MS),
which is the average number of moles of substituents per
anhydroglucose unit for those substituents which generate
repeating units (such as ethylene oxide in HEC).
HEC
Of the cellulosics, hydroxyethyl cellulose unquestionably
has been the most popular TRM used in coatings. HEC is a
nonionic polysaccharide manufactured by reacting ethylene
oxide with the reactive hydroxyls on the anhydroglucose
units of cellulose. The ethylene oxide also reacts with previously substituted hydroxyls, resulting in short pEO side
chains (usually two or three units in length). The ratio of
molar substitution (MS) to degree of substitution defines the
number of EO groups per side chain. The most popular products have MS values in the range of 1.5 to 3.0 and DS values of
about 0.85 to 1.35. Optimizing reaction conditions results in
a more uniform distribution of substitution to produce bioresistant polymer grades.
Presently there are two major international producers of
HEC, and the products are available in several regular and
enzyme-resistant grades. Of these, the medium- and highmolecular-weight bio-resistant grades have been of greatest
utility in coatings as thickeners. Low-molecular-weight
grades are used as secondary TRMs to modify rheology (improve flow or film build). Some grades also have surface treat-
276
TABLE 3 - - C o n v e n t i o n a l TRMs (CTRMs)--U.S. suppliers a n d trade names for aqueous architectural and industrial coatings.
Solids, %
Typical
Viscosity,
mPa-s
Co-solvent
Water in
Volatiles, %
ASE
ASE
ASE
ASE
ASE
ASE
ASE
ASE
28.0
29.0
30.0
20.0
40.0
20.0
40.0
30.0
14
50
50
50
20
50
20
50
None
None
None
None
None
None
None
None
100
100
100
100
100
100
100
100
7 Series
9 Series
250R Series
250B Series
FPS | HB
FPS | MB
FPS | G
CMC
CMC
HEC
HEC
HEC
HEC
HEC
100.0
100.0
95.0
95.0
20.0
20.0
25.0
Solid
Solid
Solid
Solid
7000
7000
7000
None
None
None
None
None
None
None
...
...
.-.
..100
100
100
Methocel |
Methocel |
J Series
K Series
HPMC
HPMC
100.0
100.0
Solid
Solid
None
None
10
10
Carbopol |
Carbopol |
600 Series
900 Series
PAA
PAA
100.0
100.0
Solid
Solid
None
None
13
Aqua Thix |
...
HPG
100.0
Solid
None
14
14
14
14
14
Rhamsan
Welan
Kelzan |
Kelzan | S
Kelgin |
K7C233
K 1A96
Xanthan
Xanthan
F, MV, HV
BP
BP
XCPS
XCPS
Algin
100.0
100.0
100.0
100.0
100.0
Solid
Solid
Solid
Solid
Solid
None
None
None
None
None
15
15
Flocon |
Flocon |
4800
4800C
XCPS
XCPS
4.0
13.5
4000
13000
None
None
100
100
18
Colloid |
1560
ASE
28.0
None
100
19
19
19
19
19
19
19
Acrysol ~
Acrysol ~
Acrysol |
Acrysol ~
Acrysol ~
Acrysol |
Acrysol |
ASE-60
ASE-75
ASE-95
ASE- 108
G-1 l0
GS
HV- 1
ASE
ASE
ASE
ASE
ASE-NH4
ASE-Na
ASE-Na
28.0
40.0
18.0
20.0
22.0
12.5
10.0
4
20
50
200
130
15000
17500
None
None
None
None
None
None
None
100
100
100
100
100
100
100
23
23
Cellosoze |
Cellosoze |
QP Series
ER Series
HEC
HEC
100.0
100.0
Solid
Solid
None
None
25
25
Rhodopol |
Rhodopol |
23
50MD
XCPS
XCPS
87.0
87.0
Solid
Solid
None
None
Company
Code
TRM
Trade Name
TRM Code
TRM Class
1
1
1
1
1
1
1
1
Alcogum |
Alcogum |
Alcogum |
Alcogum |
Alcogum |
Alcogum |
Alcogum |
Alcogum |
L- 11
L- 12
L- 15
L-27
L-31
L-36
L-45
L-52
2
2
2
2
2
2
2
Aqualon |
Aqualon |
Natrosol |
Natrosol |
Natrosol |
Natrosol |
Natrosol |
6
6
HPMC
H y d r o x y p r o p y l m e t h y l cellulose, a d e r i v a t i v e o f w a t e r - s o l u b l e m e t h y l c e l l u l o s e (MC), is a n o t h e r n o n i o n i c p o l y s a c c h a ride which has wide acceptance in coatings. Two other lesser
known water-soluble analog derivatives of MC are hydroxye t h y l m e t h y l c e l l u l o s e ( H E M C ) a n d h y d r o x y b u t y l m e t h y l cel-
EHEC
Ethyl hydroxyethyl cellulose is another water-soluble polymer with utility in water-borne paints with many properties
similar to HPMC. The principal commercial product line
consists of two series where the degree of molar substitution
for the hydroxyethyl group is 0.8 and 2.1, respectively, and
the ethyl group is the same for all grades with DS of approximately 0.8. All grades are also available with surface treatment for fast dispersion and adjustable dissolution rate. Like
HPMC, EHEC is soluble in cold water and insoluble in hot
water. Increasing hydroxyethyl substitution increases water
solubility, improves salt tolerance, and decreases the tendency for gellation on heating.
CIVIC
Sodium carboxymethyl cellulose (CMC) is an anionic water-soluble polymer which has been of limited use in coatings
because the modification constituent (sodium carboxylate)
leaves the dried films more water-sensitive than most nonionic polysaccharides. CMC is prepared by reaction of cellulose with monochloroacetic acid after treatment with alkali.
Commercial grades have DS for carboxylate substitution
ranging from 0.4 to 1.4, and the most popular products are
MS 0.7 to 0.8. As with most other conventional polysaccharides, the viscosity is primarily controlled by varying the molecular weight of the cellulosic chain. Some technical grades
of CMC contain by-product salts (primarily sodium chloride
and sodium glycolate) that further limits their use in coatings
applications (for example, to dry-mix paints where the CMC
functions to control viscosity and wet edge). A purified grade
referred to as cellulose gum is preferred for use in latex
paints. Various procedures for characterization of CMC may
be found in ASTM Test Methods for Sodium Carboxymethylcellulose (D 1439).
Biopolymers
The use of biopolymers in paints and coatings has also
been limited; nonetheless, at least two products are being
277
Xanthan Gum
Perhaps the most well known and commercially important
biopolymer is Xanthomonas campestris polysaccharide
(XCPS), better known as Xanthan gum. This polymer was
initially "cultured" in USDA laboratories using fermentation
technology with the bacterium Xanthomonas campestris [30].
Xanthan gum is a high-molecular-weight (approximately 2
106), branched polysaccharide which is characterized as having high yield values and a high degree of pseudoplasticity
(high LSV and low HSV). Total and immediate recovery of
viscosity after sheafing is also characteristic. Other features
are its relative insensitivity to pH, temperature, and the presence of most salts. Applications for Xanthan are similar to
those for HPG with somewhat better efficiency and even
more shear thinning rheology (higher LSV). Xanthan gum is
normally sold as a solid; however, liquid versions of this
polymer (Xanthan broths) are now available that are easier to
handle--supplied at relatively low concentrations (3 and
15%) with viscosities of about 4000 and 14 000 mPa.s, respectively. The side-chain functionality of the fluid polymer is
significantly different (much higher in pyruvate content)
from conventional solid Xanthan, but the rheology is still
very shear thinning. The active biopolymer in these products
is also claimed to be a more effective viscosifier than solid
Xanthan.
Rhamsan Gum
Rhamsan gum is another biopolymer that has some application in coatings. One of the more outstanding characteristics of this polymer is its exceptional suspending power
(produces very high LSV in coatings). In approximate order
of decreasing suspending ability are Rhamsan gum >
Xanthan gum > HP guar > CMC > HEC < CMC. Rhamsan
gum also reportedly has good salt tolerance and improved
stability to high-shear mixing.
278
H E N N (Subclass o f HNS)
Synthetic nonionic associative thickeners lacking urethane
functionality are the latest entry into the ATRM arena. At this
writing, there is one commercial offering and two developmental products. Being synthetic, nonionic, and containing
terminal hydrophobes, the chemical makeup of HENN polymers is generally similar to HEUR with the exceptions that
the polyether segments may not be limited to ethylene oxide
alone (that is, EO-PO blocks may be present), the molecular
weights may be lower than some HEURs, and the products
lack urethane linking groups (may contain ether, amide, or
279
TRM
Trade Name
TRM
Code
TRM
Class
TRM
Subclass
TRM
Type
Total
Solids,
%
Typical
Viscosity,
mPa.s
1
1
1
1
Alcogum|
Alcogum|
Alcogum|
Alcogum|
PT-33
SL-70
SL-76
SL-98
HASE
HASE
HASE
HASE
HEEASE
HEEASE
HEEASE
HEEASE
T
T
T
T
30.0
30,0
30,0
30.0
20
20
20
20
None
None
None
None
100
100
100
100
2
2
2
2
Natrosol |
Natrosol |
Natrosol |
Natrosol |
Plus 330
Plus 430
FPS | Plus 330
FPS | Plus 330
HMC
HMC
HMC
HMC
HMHEC
HMHEC
HMHEC
HMHEC
T
T
T
T
95.0
95.0
25.0
25,0
Solid
Solid
7000
7000
None
None
None
None
100
100
100
100
11
11
DSX
DSX
1514
1550
HNS
HNS
HEUR
HEUR
T
T
40.0
40.0
3000
1500
NA
NA
NA
NA
17
17
17
Rheolate |
Rheolate |
Rheolate |
1
101
300
HASE
HASE
HNS
HEEASE
HEEASE
HENN
T
T
T
30.0
100.0
32.0
30
Solid
2400
None
None
BCARB
100
100
82
19
19
19
19
19
19
19
19
19
19
19
19
19
19
Acrysol|
Acrysol|
Acrysol|
Acrysol|
Acrysol|
Acrysol |
Acrysol|
Acrysol|
Acrysol|
Acryso] |
Acrysol |
Acrysol|
Acrysol|
Acrysol |
RM-3
RM-4
RM-5
RM-825
RM-1020
RM-2020
QR-708
TT-615
TT-935
TT-950
SCT-200
SCT-215
SCT-270
SCT-275
HASE
HASE
HASE
HNS
HNS
HNS
HNS
HASE
HASE
HASE
HNS
HNS
HNS
HNS
HEEASE
HEEASE
HEEASE
HEUR
HEUR
HEUR
HEUR
HEEASE
HEEASE
HEEASE
HEUR
HEUR
HEUR
HEUR
RM
RM
RM
T
RM
RM
T
T
T
T
T
T
T
T
30.0
30.0
30.0
25.0
20.0
20.0
35.0
30.0
32.0
30.0
20.0
15.0
20.0
17.5
50
50
100
2500
2500
3000
3500
110
30
40
4800
10000
10000
3000
None
None
None
BCARB
BCARB
None
PG
None
None
None
BCARB
BCARB
BCARB
BCARB
100
100
100
75
88
100
40
100
100
100
80
80
80
75
101
102
103
104
107
106HE
111
9820
9823
HASE
HASE
HASE
HASE
HASE
HASE
HASE
HASE
HASE
HEURASE
HEURASE
HEURASE
HEURASE
HEURASE
HEURASE
HEURASE
HEURASE
HEURASE
T
T
T
T
T
T
T
T
RM
25.0
25.0
25,0
25.0
25.0
25.0
25.0
25.0
25.0
50
50
50
50
50
50
50
50
50
None
None
None
None
None
None
None
None
None
100
100
100
100
100
100
100
100
100
100
HMC
HMHEC
95.0
Solid
None
100
Company
Code
22
22
22
22
22
22
22
23
23
23
Ucar |
Ucar |
Ucar |
Ucar*
Ucar |
Ucar |
Ucar*
Ucar |
Ucar*
Polyphobe |
Polyphobe |
Polyphobe |
Polyphobe |
Polyphobe|
Polyphobe |
Polyphobe |
Polyphobe|
Polyphobe |
Cellosize|
Spatter Guard |
s o m e other linkage). Like the H E U R polymers, H E N N thickeners co n t ai n cosolvent and are supplied as m o d e r a t e l y viscous aq u eo u s solutions. Little i n f o r m a t i o n is currently
available; however, based on advertising claims for c h e m i c a l
c o m p o s i t i o n an d p e r f o r m a n c e , the rheological characteristics of these products are expected to be similar to H E U R
ATRMs. The c h e m i c a l c o m p o s i t i o n a n d physical f o r m w o u l d
also suggest that the handling a n d p e r f o r m a n c e limitations
are similar to those of HEURs. I m p r o v e d color acceptance,
color stability, and block resistance are c l a i m e d for the comme r ci al product, an d i m p r o v e d shear stability d u e to l o w er
m o l e c u l a r weight is c la im e d for the d e v e l o p m e n t a l p r o d u c t s
but at the expense of thickening efficiency [46].
Co-solvent
Water,
%
280
the past, they are not commercial today (for example, products with ether linkages were marketed in the 1960s but were
later discontinued). Like ASEs, the HASE polymers may also
be cross-linked to varying degrees with small amounts (typically less than 1%) of a polyfunctional m o n o m e r to increase
swellability. Although HASE polymers are anionic and, therefore, predicted to be more water sensitive than nonionic
ATRMs, many HASE products are more efficient (less thickener is required for consistency), which minimizes the effect
of the anionic character. Additionally, performance of
HASEs in exterior coatings can be improved with ZnO or zinc
complexes which cross-link the carboxyl functionality present [50,51], which is lacking in the HNS polymers. Being
polyanionic, the HASE polymers also have dispersant character that contributes to hiding and gloss. The carboxyl groups
in HASE polymers can also covalently cross-link with melamine, urea, and epoxy resins in thermoset coatings, and being
acidic, they catalyze the cross-linking process.
281
particle surface, w h i c h is often modified with organic treatm en t s to r e n d e r it hydrophilic (usually for w a t e r - b o r n e coatings) or h y d r o p h o b i c (usually for solvent-borne coatings).
ITRMs are also s o m e t i m e s ad d ed to aq u eo u s f o r m u l a t i o n s as
seco n d ar y thickeners to i m p a r t s o m e degree of antisag, antisettling, or antisyneresis to coatings containing p r i m a r y
conventional or associative thickeners. The m o s t c o m m o n
types of modified and u n m o d i f i e d ITRMs are attapulgite
clays, b en t o n i t e clays, organoclays, and treated and u n t r e a t e d
synthetic silicas [61]. Table 6 details s o m e i m p o r t a n t domestic (U.S.) suppliers of modified and unmodified ITRMs for
aq u eo u s and solvent-borne coatings systems.
Attapulgite Clays
The attapulgite clays are the m o s t c o m m o n l y used ITRMs
in latex paints because they are e c o n o m i c a l an d also function
as extender pigments. The principal m i n er al in attapulgite
TABLE 6--Inorganic TRMs (ITRMs)--U.S. suppliers and trade names for aqueous and solvent-borne architectural & industrial coatings.
Company
TRM
Trade Name
TRM
Code
TRM
Class
System
Use
Form,
mPa.s
Total
Solids, %
3
3
3
Cab-o-sil |
Cab-o-sil|
Cab-o-sperse |
L, M, H Series
TS Series
A Series
Fumed Silica
Treated Fumed Silica
Fumed Silica
AQ/SOLV
AQ/SOLV
AQ
Solid
Solid
LIQ
100
100
12
4
4
Neosyl|
Gasil
TS
DP
Precipitated Silica
Precipitated Silica
AQ/SOLV
AQ/SOLV
Solid
Solid
100
100
Aerosil|
Fumed Silica
AQ
Solid
100
Aerosil|
130-380
Series
R972, R974
Fumed Silica
SOLV
Solid
100
Korthix|
Korthix|
Regular
Refined Bentonite
Refined Modified Bentonite
AQ
AQ
Solid
Solid
100
100
Attagel|
40 & 50
Attapulgite Clay
AQ/SOLV
Solid
100
9
9
9
Minugel |
Minugel|
Minugel|
AR
LF
200, 400
Attapulgite Clay
Attapulgite Clay
Attapulgite Clay
SOLV
AQ/SOLV
AQ/SOLV
Solid
Solid
Solid
100
100
100
12
Zeothix|
Precipitated Silica
AQ/SOLV
Solid
100
16
16
16
Hi-sil|
Hi-sil|
Hi-sil|
Precipitated Silica
Fumed Silica
Fumed Silica
AQ/SOLV
.-.
.-.
Solid
Solid
Solid
100
100
100
17
17
17
17
17
Benaqua |
Bentone |
Bentone |
Bentone |
Bentone |
4000, 8000
27, 34 & 38
SD-1, 2 & 3
EW
LT
Hectorite Clay
Organoclay
Organoclay
Smectite Clay
Bentonite Clay
AQ
SOLV
SOLV
AQ
AQ
Solid
Solid
Solid
Solid
Solid
100
100
100
100
100
20
20
20
20
20
Aquamont |
Bentolite|
Claytone|
Laponite |
Lapomer e
600
...
Series
Series
40
Modified Bentonite
Purified Bentonite
Organo-mod. Montmorillonite
Synthetic Hectorite Clay
Laponite Clay + Org Polymer
AQ
AQ
SOLV
AQ
AQ
Solid
Solid
Solid
Solid
Solid
100
100
100
100
100
21
21
Troythix|
Troythix|
A-SS
A-S
Organoclay
Silicate
Solid
Solid
100
100
24
24
Tixogel|
Tixogel|
VP & VZ
LX
Organoclay
Organoclay
SOLV
AQ
Solid
Solid
100
100
25
Van gel|
AQ
Solid
100
282
clays is attapulgite, which is chemically described as hydrated magnesium aluminum silicate. The lath-shaped particles of this mineral as supplied are colloidal (less than 0.5
t~m), and the crystal structure is chain-like. In an aqueous
environment, attapulgite is nonswelling and essentially inert.
Thus, coatings containing attapulgite clay thickened not by
swelling, but instead by the structured reflocculation of the
pigment particles into a colloidal interaction network after
shearing. In coating preparation, attapulgite clays can be
added as powders or as pregelled dispersions throughout the
formulation process. However, they are normally added in
the grind using high-speed mixers for dispersion and hydration. The thickening power of these clays is high, and salts
have little or no effect on viscosity. However, like many other
ITRMs, the amount of attapulgite clay required for thickening is generally higher than for organic TRMs, and the water
demand is high (water is pulled from the aqueous phase to
wet the particle surface, thereby increasing effective coating
solids).
Bentonite Clays
Bentonite clay is obtained from the mineral montmorillonite (a Fuller's earth mineral), which is described as
an aluminum silicate with varying degrees of aluminum replacement with magnesium, calcium, and sodium. The crystal structure is a three-layer sheet which forms flake-like
colloidal particles of less than 0.5 p,m. In aqueous media,
bentonite is naturally hydrophilic and readily dispersible.
The water is taken up between the mineral laminae, causing
the lattice structure to stretch and swell. Thickening is due to
a combination of swelling and particle network interaction,
and purified forms of unmodified bentonite are highly effective as thickeners in aqueous coatings. Although the thickening mechanism is rather different than that of attapulgite
clays, most bentonite clays also require wetting, high-shear
for dispersion, and time for complete hydration. Some modified grades are, however, readily dispersible with conventional agitators. For effective incorporation, pH must be
carefully regulated. If it is too high, excessively rapid hydration occurs, and if it is too low, hydration times are long with
loss in thickening efficiency. The presence of salts (electrolytes) may cause flocculation, rendering bentonite ineffective
in highly ionic environments.
Organoclays
Many different grades of organoclays are available for both
solvent-borne and aqueous coatings. Although these products
differ in modification, the mechanism for thickening and
rheology control is substantially the same. Bentonite clay is
one of the principal minerals used to prepare organoclays,
and, being both hydrophilic and oleophobic in its natural
form, it must be modified for dispersion in organic solvents.
Only after a sophisticated purification process followed by
cation exchange with organic a m m o n i u m bases is the surface
rendered sufficiently organophflic for use in nonaqueous media. As supplied, organoclay thickeners are in the form of
agglomerated platelet stacks. Conventional organoclays require wetting and shear for deagglomeration and the addition
of a chemical polar activator for full theological develop-
ment. The chemical activator serves to disperse the organoclay and also carries water into the hydrophobic organic
solvent to insure full hydrogen bonding. Some newer products still require wetting and shear but are functional without
the chemical polar activator. Although not essential, elevated
temperatures are preferred for efficient processing. High-performance organoclays have recently been developed with
greater thixotropy and improved sag resistance [62].
Special grades of organoclays (organophilic clays) have
also been designed for aqueous coatings. Some of these depend on shear, wetting, and hydration for full rheological
performance, while others are available in readily activated
slurry form. The efficiency of these products is generally
independent of pH [63].
Synthetic Silicas
Another class of inorganic thickeners are certain types of
synthetic amorphous hydrophilic and hydrophobic silicas.
Both are widely used in solvent-borne coatings; however,
excessive hydration generally limits the utility of the hydrophilic silicas in aqueous media. Two forms of amorphous
hydrophilic silica are commercially available and get their
names, "precipitated silica" and "fumed silica," from the
manufacturing processes. A proposed thickening mechanism
for these silicas is based on hydrogen bonding between the
silica particles and with other coating components to form a
three-dimensional structure. High water demand may also
contribute to thickening with these products.
Precipitated Silica
Precipitated silica is obtained in a wet process by the neutralization of sodium silicate solution. This results in a polar,
fully hydroxylated surface. Consequently, hydrogen bonding
is strong, and excellent thickening comparable to that of
fumed silica is obtained especially in nonpolar media. However, because of the competition between hydroxyls on the
silica and those in the continuous phase, precipitated silica
tends to be less efficient than fumed silica in polar (for example, aqueous) media.
Fumed Silica
Fumed silica is fumed silicone dioxide which is prepared
by hydrolysis of silicon tetrachloride vapor in a hydrogenoxygen flame. The product gets its name from the smoke-like
appearance as it forms in the flame. In the fuming process, a
partially hydroxylated surface containing silanol, siloxane,
and hydroxyl groups is generated, which is somewhat less
polar than that of precipitated silica, pH does have a significant effect on the thickening efficiency of fumed silica in
aqueous systems. To be effective, pH must be below about pH
7.5. Above this pH, electrostatic repulsion keeps the particles
far enough apart to inhibit hydrogen bonding.
Organosilica
Hydrophobic silica is produced when freshly manufactured hydrophilic fumed silica is treated with organosilane or
organosiloxane compounds [64]. This is a chemical modification in which many of the surface hydroxyl groups are replaced with organic functionality. After treatment, these
products have minimal surface silanol groups left for hydro-
ORGANIC T R M s F O R S O L V E N T B O R N E
COATINGS
Besides the inorganic p r o d u c t s described above, a variety
of organic additives also function as thickeners, rheology
modifiers, a n d thixotropes in solvent-borne systems. These
p r o d u c t s are mostly available in liquid p a s t e a n d p o w d e r
form. M a n y require s o m e d i s p e r s i o n a n d activation for thickening, a n d the r e c o m m e n d e d process t e m p e r a t u r e s often dep e n d on the strength of the solvent p r e s e n t in the coating
formulation. Careful f o r m u l a t i o n p r o c e d u r e s are r e q u i r e d to
avoid seeding, "false body," or loss in thickening efficiency.
A m o n g the m a n y types of organic p r o d u c t s available for use
as thickeners a n d flow control agents for solvent-borne syst e m s a r e c a s t o r oil derivatives [62], modified acrylic copolymers, polyethylene glycol, p o l y a m i d e s [65], p o l y m e r i z e d oil
derivatives, organic esters, c o m p l e x polyolefins, a n d a r a m i d
p u l p fibers [66]. Because of the n u m b e r of products, their
diverse nature, a n d the fact t h a t little i n f o r m a t i o n is available
on m a n y due to their p r o p r i e t a r y status, no a t t e m p t will be
m a d e here to classify o r categorize these p r o d u c t s a n d their
suppliers. Resources for this i n f o r m a t i o n are available elsew h e r e (for example, see McCutcheon's F u n c t i o n a l Materials
in the Bibliography).
REFERENCES
[1] Patton, T.C., "Fundamentals of Paint Rheology," Journal of
Paint Technology, Vol. 10, No. 522, July 1968, pp. 301-307.
[2] Rohn, C. L., "The Rheology of Coatings and Dispersions," Journal of Water-Borne Coatings, August 1987, pp. 9-17.
[3] Fearnley-Whittingstall, P., "Paint Rheology," Journal of the Oil
and Colour Chemists' Association, Vol. 10, 1991, pp. 360-368.
[4] Dutt, N.V.K. and Prasad, D. H. L., "Relationship Between
Rheological Properties and Paint Performance," Pigment and
Resin Technology, January 1985, pp. 10-18.
[5] Sarkar, N. and Lalk, R. H., "Rheological Correlation with the
Application Properties of Latex Paints," Journal of Paint Technology, Vol. 46, No. 590, March 1974, pp. 29-34.
[6] Odell, J. A., Keller, A., and Muller, A. J., "Extensional Flow Behavior of Macromolecules in Solution," Chapt. 11 in Polymers in
Aqueous Media: Performance Through Association, Advances in
Chemical Series No. 223, J. E. Glass, Ed., 1989, pp. 191-244.
[7] Fernando, R. H., Lundberg, D. J., and Glass, J. E., "Importance
of Elongational Flows in the Performance of Water-Borne Formulations," Chapt. 12 in Polymers in Aqueous Media: Performance Through Association, Advances in Chemistry Series No.
223, J. E. Glass, Ed., 1989, pp. 245-259.
[8] Fuller, G. G. and Cathey, C. A., "Extensional Viscometry of Polymer Solutions," Chapt. 3 in Polymers as Rheology Modifiers, ACS
Symposium Series No. 462, J. E. Glass and D. N. Schulz, Eds.,
1991, pp. 48-60.
[9] Soules, D. A., Gustav, P. D., and Glass, J. E., "Dynamic Uniaxial
Extensional Viscosity," Chapt. 20 in Polymers as Rheotogy Modifiers, ACS Symposium Series No. 462, J. E. Glass and D. N.
Schulz, Eds., No. 462, 1991, pp. 322-332.
283
[10] Barnes, H. A., "The Role of Molecular Morphology in Establishing the Extensional (Elongational) Viscosity of Polymer Solutions and Melts--A Review," Proceedings of the ACS Division of
Polymeric Materials: Science and Engineering, Inc., Vol. 61, 1989,
pp. 30-37.
[11] Soules, D. A., Dinga, G. P., and Glass, J. E., "Elongational Viscosity of Filled Systems by the Vacuum Draw Technique," Proceedings of the ACS Division of Polymeric Materials: Science and
Engineering, Inc., Vol. 61, 1989, pp. 43-46.
[12] Schwab, F. G., "Advantages and Disadvantages of Associative
Thickeners in Coatings Performance," Chapt. 19 in Water-Soluble Polymers, ACS Advances in Chemistry Series No. 213, J. E.
Glass, Ed., 1986, pp. 369-373.
[13] Hall, J. E. et al., "Influence of Rheology Modifiers on the Performance Characteristics of Latex Paints," Journal of Coatings
Technology, Vol. 58, No. 738, July 1986, pp. 65-73.
[14] Sperry, P. R., "Morphology and Mechanism in Latex Flocculated by Volume Restriction," Journal of Colloid and Interface
Science, Vol. 99, May 1984, pp. 97-108.
[15] Sperry, P. R., Thibeault, J. C., and Kostansek, E. C., "Flocculation and Rheological Characteristics of Mixtures of Latices
and Water-Soluble Polymeric Thickeners," Proceedings: Eleventh International Conference Organic Coatings Science Technology, 1985, pp. 371-388.
[16] Belbin, D., Buscall, R., Mumme-Young, C. A., and Shankey,
J. M., Polymer Latex II, Proceedings, Plastics and Rubber Institute, London, 1985.
[17] Gast, A. P., Hall, C. K., and Russel, W. B., Faraday Discussions,
Chemical Society, Vol. 76, 1983, p. 338.
[18] Dickinson, E., "A Model of a Concentrated Dispersion
Exhibiting Bridging Flocculation and Depletion Flocculation,"
Journal of CoUoidand Interface Science, Vol. 132, 1 Oct. 1989, pp.
274-278.
[19] Heyes, D. M., McKenzie, D. J., and Buscall, R., "Rheology of
Weakly Flocculated Suspensions: Experiment and Brownian
Dynamics Simulation," Journal of Colloid and Interface Science,
Vol. 142, No. 2, 15 March 1991, pp. 303-316.
[20] Massouda, D.F., "Analysis and Prediction of Roller Spatter
from Latex Paints," Journal of Coatings Technology, VoL 57, No.
722, 1985, pp. 27-36.
[21] Schaller, J. E., "Rheology Modifiers for Water-Borne Paints,"
Surface Coatings Australia, October 1985, pp. 6-13.
[22] Jenkins, R. D., The Fundamental Thickening Mechanism of Associative Polymers in Latex Systems: A Rheological Study, dissertation thesis, Lehigh University, Bethlehem, PA, 1990.
[23] Bieleman, J. H., Riesthuis, F. J. J., and Van Der Velden, P. M.,
"The Application of Urethane Based Polymeric Thickeners in
Aqueous Coating Systems," Polymers Paint Colour Journal, Vol.
176, No. 4169, 11 June 1986, pp. 450-460.
[24] Char, K., Frank, C. W., and Gast, A. P., "Conformations of Hydrophobe Modified Chains on Polymeric Latices," Proceedings of
the ACS Division of Polymeric Materials: Science and Engineering, Inc., Vol. 61, 1989, pp. 528-532.
[25] Karunasena, A. and Glass, J. E., "Effect of Surface Acids on the
Rheological Response of Hydrophobically-ModifiedWater-Soluble Polymer Thickened Coating Formulations," Proceedings of
the ACS Division of Polymeric Materials: Science and Engineering, Inc., Vol. 56, 1987, pp. 624-628.
[26] Santore, M. M., Russel, W. B., and Prud'homme, R. K., "The
Influence of Associating Polymers on the Physical Properties of
Dispersions," International Polymer Colloids Group Newsletter,
Vol. 20, No. 1, June 1989, pp. 60-64.
[27] Whiton, A., "Formulating with Rheological Additives for Latex
Paints," Paint and Ink International, August 1991, pp. 10-14.
[28] Beeferman, H. L. and Bergren, D. A., "Practical Application of
Rheology in the Paint Industry," Official Digest, VoL 38, No. 492,
1966, p. 9.
284
[47] Fernando, R. H., Murakami, T., and Glass, J. E., "HydrophobeModified Alkali-Swellable Emulsion (HASE) Thickeners," Proceedings of the ACS Division of Polymeric Materials: Science and
Engineering, Inc., Vol. 61, 1989, pp. 409-41 l.
[48] LeSota, S., Lewandowski, E. W., and Schaller, E. J., "Hydrophobically-Modified Alkali Soluble Emulsions as Thickeners for
Exterior Latex Paints," Chapt. 28 in Polymers in Aqueous Media:
Performance Through Association, ACS Advances in Chemistry
Series No. 223, J. E. Glass, Ed., 1989, pp. 543-549. Also in
Journal of Coatings Technology, Vol. 61, No. 777, 1989, pp.
135-138.
[49] Rogers-Moses, P. J. and Schaller, E. J., "A Better Thickener for
Latex Paints," American Paint and Coatings Journal, 6 Aug. 1984,
pp. 54-58. Also in Resin Review, Vol. XXXIII, No. 4, 1984, pp.
20-31.
[50] Evani, S. and Rose, G. D., "Water Soluble Hydrophobe Association Polymers," Proceedings of the ACS Division of Polymeric
Materials: Science and Engineering, Inc., Vol. 57, 1987, pp.
477-481.
[51] Gambino, J. J. and Schaller, E. J., "Rheology Modified for Latex
Paints," Modern Paint and Coatings, July 1982, pp. 35-40.
[52] Schaller, E. J. and Rogers-Moses, P. J., "A Nonionic Associative
Thickener," Resin Review, Vol. XXXVI, No. 2, 1984, pp. 19-26.
[53] Shay, G. D. and Rich, A. F., "Urethane-Functional Alkali-Soluble Associative Latex Thickeners," Journal of Coatings Technology, Vol. 58, No. 732, 1986, pp. 43-44.
[54] Shay, G. D., "A New Class of Associative Thickener for the 90's,"
presented at the Spring Meeting of FSCT, Philadelphia, 1991.
[55] Shay, G. D., Kravitz, F. K., and Brizgys, P. V., "Effects of Process Variables on the Emulsion and Solution Properties of Hydrophobically Modified Alkali-Swellable Emulsion Thickeners,"
Chapt. 7 in Polymers as Rheology Modifiers, ACS Symposium
Series No. 462, J. E. Glass and D. N. Schulz, Eds., 1991, pp.
121-141.
[56] Goodwin, J. W. et al., "The Rheological Properties of a Hydrophobically Modified Cellulose," Chapt. 19 in Polymers in Aqueous Media: Performance Through Association, ACS Advances in
Chemistry Series No. 223, J. E. Glass, Ed., 1989, pp. 365-378.
[57] Fu, E. and Young, T.-S., "Associative Behavior of Hydrophobically Modified Hydroxyethyl Cellulose in Latex Coatings,"
the ACS Division of Polymeric Materials: Science and Engineering, Inc., Vol. 57, 1987, pp. 497-501.
[61] Griffith, K.A., Leipold, D. P., and Burrneister, L.A., "Rheological Modifiers in Aqueous Systems," Journal of Water-Borne
Coatings, Nov. 1987, pp. 2-16.
[62] "Rheological Control Using Organoclay Technology," European
Polymers, Paint and Colour Journal, Vol. 183, No. 4321, 13/27
Jan. 1993, pp. 19-20.
[63] Tso, S. C., Beall, G. W., and Gordon, J., "New Generation of
Water-Based Thickener," Journal of Water-Borne Coatings, August 1987, pp. 3-8.
BIBLIOGRAPHY
Handbook of Coatings Additives, L. J. Calbo, Ed., Marcel Dekker Inc.,
New York, Vol. I, Chapts. 1-5, 1987, pp. 1-147.
Handbook of Coatings Additives, L. J. Calbo, Ed., Marcel Dekker Inc.,
New York, Vol. II, Chapt. 4, 1992, pp. 105-164.
Handbook of Water-Soluble Gums and Resins, R. L. Davidson, Ed.,
The Kingsport Press, Chapts. 4, 6, 12, 13, 17, and 24, 1980.
McCutcheon's Functional Materials, Vol. 2: North American Edition,
McCutcheon Division, MC Publishing Co., 1993.
Polymers as Rheology Modifiers, ACS Symposium Series No. 462, J. E.
Glass and D. N. Schulz, Eds., No. 462, Chapts. 1-4, 1991, pp. 2-87.
Polymers in Aqueous Media: Performance Through Association, ACS
Advances in Chemistry Series No, 223, J. E. Glass, Ed., 1989.
LIST OF P R O D U C E R S A N D S U P P L I E R S
*Company Reference Numbers for Tables 3, 5, and 6
1. Alco Chemical Corp,, Div. of National Starch & Chemical, 909 Mueller Dr., P.O. Box 5401, Chattanooga, TN 374060401.
2. Aqualon, 1313 N. Market St., P.O. Box 8740, Wilmington, DE 19899-8740.
3. Cabot Corp., Cab-O Sil Division, P.O. Box 188, Tuscola,
IL 61953-0188.
4. Crosfield Co., 101 Ingals Ave., Joliet IL 60435.
5, Degussa Corp., Pigments Div., 425 Metro Place North,
Dublin, OH 43017.
6. Dow Chemical USA, Larkin Lab, 1691 N. Sweede Rd.,
Midland, MI 48674.
285
MNL17-EB/Jun. 1995
31
by Raymond D. Brockhaus 1
INTRODUCTION
Measure of Quality
In the open marketplace, the business person and the customer have this rule of thumb--let the buyer beware. Testing
for quality of the shipment is best done on-the-spot, quickly,
and in a way that is highly reliable. If you are in charge of the
wine and ale stocks of a restaurant, one method of determining the quality of the goods obtained would be verification of
the density with flotation probes called hydrometers. Similarly, the purchasers of metals such as gold, lead, silver, and
copper could use various methods of determining density to
keep from being cheated and assuring quality.
In our more modern world, with instruments capable of
assaying individual chemical compounds in complex mixtures, verification of density has become a manufacturing
tool for in-process control. Density measurement becomes an
indirect assurance that the ingredient(s) of interest exists in
the material of exchange at the proper concentration. For
paint, ingredients such as solvents, polymers for binders, and
pigments have a different range of density typical of that
material. Partial omission of a major component, for example, a solvent, can make the paint density change from the
1Research Associate, E. I. Du Pont, Automotive Products, 400
Groesbeck Highway, Mt. Clemens, MI 48043.
Regulatory Concerns
In addition to customers and producers, government can
express concerns in the exchange of materials. Government's
concern is for regulation. Paints or other similar heterogenous materials are mixtures in which only the nonvolatile
portion of the bulk material being exchanged is of true value
to the customer. The "carrier" portion of the bulk material
must be accounted for because it is a discarded material and
thus a "pollutant." The carrier portion, solvents, and viscosity
reducers are used to aid in transporting the solids to the work
surface to form a thin film. These pose disposal problems and
impact landfills, air and water quality, which are under goverument regulations. Paint volume solids and critical pigment volumes are two significant concepts which must be
understood and accounted for when dealing with modern
government regulations [1].
289
Copyright9 1995 by ASTM International
www.astm.org
290
(2)
Dynamic Model
Density is a m a t h e m a t i c a l value describing a b a l a n c e of
physical forces acting on a m a t e r i a l called m a s s occupying a
k n o w n v o l u m e of space u n d e r k n o w n t e m p e r a t u r e conditions. This e q u a t i o n is identical to that given in the static
model. Density is expressed as a single value, b u t is really an
average value of forces d y n a m i c a l l y fluctuating, b o t h internal
to the m a t e r i a l a n d external as the s u r r o u n d i n g environment.
Two definitions are included here. The first (static) is the
t r a d i t i o n a l model. It has c h a n g e d only slightly over the ages,
being u p g r a d e d with the t e r m s "mass" in place of weight a n d
"in vacuo" after v a c u u m bell j a r s were developed. The s e c o n d
(dynamic) is a m o r e f u n d a m e n t a l model, dealing with m a t e r i als on a m o l e c u l a r level, w h e r e the concepts of c h e m i c a l
functionality, kinetic a n d potential energy, a n d interfacial
b o u n d a r i e s c o m e into play. W i t h the second model, we can
u n d e r s t a n d a n d deal with mixtures of c h e m i c a l s a n d m a t h e m a t i c a l l y deal with h o w a single c o m p o n e n t ' s densities interact w h e n mixed.
The attractive forces exerted on a p r i m a r y m a s s o r collection of particles by a second m a s s m u c h larger t h a n the first
m a s s is called weight. This is a n attractive action, resulting in
c o m p r e s s i o n a n d increasing the density of the p r i m a r y mass.
The dispersing forces are caused b y t h e r m a l energy a b s o r p tion, resulting in particles of increasing m o t i o n or kinetic
energy. This manifests as t e m p e r a t u r e of the material.
The volume of space o c c u p i e d by a m a s s of particles that
exists at an average kinetic energy level expressed as the
t e m p e r a t u r e of the physical m a t e r i a l is the volume. This includes the voids of space b e t w e e n the particles on a m o l e c u l a r
level.
The average kinetic energy level of the m a t e r i a l is expressed
in the m o t i o n of the particles of the material. Material is
m a d e u p of m a n y small particles that are i n d e p e n d e n t in t h e i r
motion. These m o t i o n s are r a n d o m , such that the overall
m o t i o n in the X, Y, a n d Z directions cancel each o t h e r a n d the
net m o t i o n of the total m a s s is zero. As the kinetic energy
level, expressed as t e m p e r a t u r e , increases, the distances between particles increase a n d the m a t e r i a l is identified as expanding.
Special cases used as s t a n d a r d m e a s u r e m e n t reference
points:
9 One cubic c e n t i m e t r e (cm 3) of p u r e w a t e r (H20) at 4.0~ is
defined to weigh 1.0000 g.
Densitywater = 1.000 g/1.000 c m 3
9 1.000 mole of a gaseous c o m p o u n d occupies 22.4 L of volu m e at 0~ (273~ at 1.000 a t m o s p h e r e p r e s s u r e (a m o l a r
volume).
F o r air, whose c o m p o s i t i o n is 22% by weight oxygen a n d 78%
by weight nitrogen (ignoring o t h e r gases), 1 m o l e weight =
(32 g 0.22) + (28 g 0.78) = 28.88 g. Density = 28.88
g/22 400 c m 3 = 0.001 29 g/cm 3 or 1.29 g/L [3].
D e t e r m i n e d Density A at T 1
D e t e r m i n e d Density W a t e r at 0~
(3)
Density, g/cm3
0.999
0.998
0.998
0.998
0.998
0.998
0.997
0.997
0.997
0.997
0.997
0.996
0.996
0.996
0.995
0.996
099
943
744
595
405
203
992
770
538
296
044
783
512
232
944
565 6
G mine
T
= mg
(4)
where
G = a gravitational c o n s t a n t for E a r t h -- 6.670
10 -11 N.m2/kg m 2,
mE -- m a s s of the E a r t h = 5.98 1027 g, a n d R is the
r a d i u s of the E a r t h = 6370 km,
m -- m a s s of a second b o d y (Newton's law) [5],
gE = 9.80 m/s 2 o r 32.0 ft/s 2, a n d
gMoon
5.333 f t / s 2 o r 1/6 that for Earth.
=
gDist. . . .
/;
m
292
Plumbline
SmallObject-agallonof liquid
rge~
ry massive object
\
l eters
a orn 3822
c mieels
\
Center of gravity
9b)of Earth
SmalObject-l
agallonofliquid
Value~
Place
Valuea
Cambridge, Massachusetts
Eagle City, Alaska
Greenwich, England
Madras, India
Panta Delgada, Azores
980.398
982.183
981.188
978.281
980.143
Denver, Colorado
Galveston, Texas
Honolulu, Hawaii
New Orleans, Louisiana
Reykjavik, Iceland
979.609
979.272
978.946
979.324
982.273
aCentimetres per second per second. Use of centimetres emphasizes the differences which are occurring in the second through sixth numerical place.
m 3 =
900 g/m 3
FIG. 7-Simple model of particles of matter
in solid state.
Escaping Vapor
8O
OO
b8
294
0
0
O0
0
0
O0
0 0
0
0 0
0 0
0
O0
0
00
0 0
0
O0
0 0
0
0
0
O0
[6,7].
Figure 10 contains drawings of several pycnometers as
seen in a commercial scientific supplies catalog. The catalog
text descriptions for two pycnometers have been included to
inform you as to sizes, capacities, materials of construction,
etc. The features discussed identify attributes of importance
to the end user.
Liquids have other properties that can be used to test for
density. One of these is sound transmission. Replacement of
air with a liquid in a container will cause that container to
shift a tone impulse to higher frequencies. The extent of the
shift is related to the liquid's density and can provide a direct
measurement with different degrees of accuracy depending
on the sophistication of the instrument.
For solids, the task is more complex. Two paths are available. Either shape the solid into a known geometric figure
and calculate the volume or use the solid to displace a material such as a liquid or a gas which has a known density. The
solid can be shaped by mechanical, thermal, or chemical
means. Mechanical means can be employed to cut, carve, and
shape, then weigh. Thermal shaping is changing the solid into
a liquid using heat to melt the solid, pouring the liquid into a
mold, cooling to form a solid, and then weighing. Chemical
shaping is dissolving the solid in a "carrier" liquid (solvent),
pouring the solution into an open mold, and evaporating the
solvent, leaving behind a solid property shaped to accommodate testing. The drawbacks of this technique are:
I. Complete solvent removal is often difficult.
2. Chemical reshaping of solids can cause problems if the
original solid had small air pockets or if the solvent used is
trapped in these voids, thus actually changing the solid and
affecting its apparent density. Solids which demonstrate
the latter behavior have a bulk density different than their
skeletal density.
The principle of buoyancy, discovered in the third century
by Archimedes, provides a means to determine volume [5].
Determination of volume by displacement requires acquiring
a weight in air and a weight in a liquid of known density at the
testing temperature. Complete submersion of the solid object
or a representative portion of the material in a liquid of
known density is required while determining the material's
apparent weight. See Fig. 11. The weight difference is equal
to the weight of the volume of liquid displaced. Knowing the
liquid's density and the weight difference, the volume for the
tested portion can be calculated by the following formula:
gDist
....
fromEarth
1.0 x 106 km = gE
(6370 km) 2
(1.0064 x 106)2
= O.O04g E
(5)
$2305-05
S2335
S2365
S2367
9 1[ Stopper I ASTM
For use in place of $2335 in accordance with ASTM D70;
especially for viscous fluids and semisolid samples.
Conical shape with wide bottom for increased stability and
ground solid stopper, concave on bottom. Capacity, 25
mL; bottom diameter, 40 ram; diameter of mouth, 25
ram; height without stopper, 45 ram; weight empty, less
than 40 grams. With 24112 short length g grinding and
1.6 mm hole in stopper to allow air to escape.
S2365 . . . . . .
geneous, the density is also a fixed value for a fixed t e m p e r a ture. W h e n two different materials, h o m o g e n o u s o r heterogeneous, are m i x e d together, they b e c o m e a new, heterogeneous material, a n d the resultant density is a n e w fixed
value for a fixed t e m p e r a t u r e . Depending on w h e t h e r the interactions are ideal or nonideal, the density c a n be p r e d i c t e d
b y calculation or a deviation in the density will result. Paints
are f o r m u l a t e d as ideal mixtures, b u t they d o n ' t always follow
this a s s u m p t i o n . The relationships b e t w e e n these values are
given b e l o w [8].
wAp~
WA + WA
(6)
(7)
A + A has A s density w h i c h is
w~pA +
WB+WB
where
W = weight of c o m p o n e n t ,
p = density of the c o m p o n e n t .
M a n y i m p o r t a n t m a t e r i a l s are available as c o m p l e x mixtures in today's world. These mixtures can be h e t e r o g e n e o u s
in t e r m s of phase. Gasoline for the car a n d lawn m o w e r can
c o n t a i n b u t a n e dissolved into the heavier h y d r o c a r b o n s .
Paints, inks, a n d c e m e n t s c o n t a i n liquids a n d solids, with t h e
liquid p h a s e either n e u t r a l or reactive. If the liquid's role is
296
M E A S U R E M E N T S Y S T E M UNITS,
C O N V E R S I O N S , D E N S I T Y , A N D RELATIVE
DENSITY
Today's world uses three systems of measurement [4].
1. International System of Units (SI), previously referred to
as the metric system, based upon powers of ten. This was
called the MKS system, standing for meters (distance),
kilograms (force), and seconds (time). A common form of
this system uses millimetres, grams, and seconds as the
units. By universally accepted definition, 1.0000 g of distilled water occupies 1.0000 cm 3 (or 1.0000 mL) at 4.00~
2. The British system uses the British yard (distance), pound
(force), and second (time).
3. The United States (U.S.) system uses the U.S. yard (distance), pound (force), and second (time).
The British and U.S. systems use the same basic linear
distance and force units, but, when measuring volumes, the
systems do not have equivalency. A British gallon of water
(volume) weighs 9.993 lb at 77~ (25~ while a U.S. gallon of
water weighs 8.321 lb at 77~ (25~ [7].
Conversion between the three systems can be accomplished using the following relationships:
2.54 cm
231 in. 3
453.6 g
=
=
=
or
277.4 in. 3 =
1.00 in.
1.00 U.S./gal
1.00 lb
1.00 British (Imperial) gallon
From SI to U.S.:
(9)
(10)
(11)
(12)
lb
at 4~
U.S. gallon
LIQUIDS
Densities of Liquids--Methods of Determination
Buoyancy-Hydrometers
Hydrometers are flotation devices that are calibrated using
water at various temperatures. When placed in clear liquids,
the relative density is read directly from the scale on the
hydrometer. The hydrometers range from low-cost, low-precision, to expensive, high-precision devices. Better-grade hydrometers also have incorporated thermometers for temperature corrections and greater independence of reading
liquids in an as-is condition. A balance or a known volume
device is not needed with this technique. Simplicity is the
advantage of this technique. Shown in Figs. 12 and 13 are two
types of hydrometers. The catalog text has been included to
explain ranges and features unique to these devices.
ASTM methods using hydrometers are [9,10]
Test Method for Apparent Density of Industrial Aromatic Hydrocarbons (D 2935)
Test Method for Calculation of Volume and Weight of Industrial Aromatic Hydrocarbons (D 1555)
Displacement--Submersion--Specific Gravity
Balances
A specific gravity balance is similar to the hydrometer. It is
actually a balance which measures the counter weight applied to balance a plummet submerged in the liquid sample.
The weight and volume of a mercury-filled elongated glass
bulb (plummet) is determined by comparison with standards
established by regulatory agencies and traceable back to wellcharacterized standards, referred to as primary standards,
established by national scientific bureaus. The plummet is
..~i..
=~=
. s-w see ~
. . . . .
oo
(~at. NO.
S41885-F
$41885-G
A series of short range hydrometers with an accuracy of 0.001,
S41885-H
calibrated 60 ~176
Design corresponds with ASTM
S41885-1
specification E l 0 0 for plain hydrometers. With smooth, easily
S41885-K
S41885-L
cleaned shapes, solid metal ballist, and cemented paper scales.
S41885-M
Subdivisions, 0.001.
FIG. 12-Hydrometers--specific gravity scale--plain design [6].
Ronqo
1.000
1.060
1.120
1.180
1.240
1.300
1.360
to
to
to
to
to
to
to
1.070
1.130
1.190
1.250
1.310
1.370
1.430
298
P A I N T A N D COATING T E S T I N G M A N U A L
Chain Balance
For liquid densities from O.0001 to 2.110
Chain gravitometer balance determines specific gravity of liquid with
high degree of accuracy. Uses both plummet displacement principle
and chain weight system for weighings. No calculations or riders are
needed.
Instrument is prebalanced at zero reading by adjusting counterbalance weights, Plummet is immersed in liquid sample, Balance is
zeroed again. Single roller-type weight is moved to notch on beam
where equilibrium is approached; final adjustment is accomplished by
raising or lowering one end of rhodium-plated bronze chain. Specific
gravity is determined by adding rider and chain-support readings.
FIG. 14-Specific gravity balances--chain balance and Mohr
Westphal balance with catalog text instruction and comments
[11]. (Courtesy of Fisher Scientific)
299
FIG. 15-Monk cup (weight per gallon cup) (courtesy of C. J. Monk and Journal of
Oil and Color Chemists' Association) [2]. See Ref 2for a discussion of Parts A to M.
volatile solvents, use of larger size vessels offsets the weight
drift seen d u r i n g weighing.
The p r o b l e m of e n t r a p p e d air can be c o u n t e r e d in two
ways:
1. The M o n k cup is designed to pressurize the s a m p l e to 150
lb/in. 2 in a k n o w n volume of space. This p r e s s u r e compresses the e n t r a p p e d air in the s a m p l e to such an extent
t h a t o c c l u d e d a i r b u b b l e s a r e r e d u c e d to a negligible volume. E n t r a p p e d air of up to 10 vol% can be dealt with by
this technique. The v o l u m e p r o d u c e d is still larger t h a n the
true volume, a n d a density e r r o r is still present. E n t r a p p e d
air should n o t be a c c o u n t e d for if the air escapes before use
or the air is a n artifact of s a m p l e mixing before testing. The
M o n k cup is large a n d heavy a n d requires use of n o n a n a lytical b a l a n c e s [2]. Figure 15 is a s c h e m a t i c d i a g r a m a n d
picture of a M o n k p r e s s u r e weight-per-gallon cup.
2. An alternative technique is to mix a m e a s u r e d weight of the
u n k n o w n density m a t e r i a l with the weight of a k n o w n
diluent from a full weight p e r gallon cup. The blend is t h e n
p l a c e d b a c k into the cup and then weighed. The following,
enclosed in quotes, is copied directly from the GARDCO
m i n i c a t a l o g N u m b e r 9, including the diagrams, with perm i s s i o n from GARDCO [7].
X
WunknownBlend
wt per gallon
10B)
WB
(13)
300
TESTING
MANUAL
STAINLESS STEEL
MINI
WEIGHT
PER GALLON
CUPS
METHOD OF USE
1. Determine the weight.of a clean cup in grams. As an alternative, the cup
may be supplied with an accurate tare weight for use with two-pan
laboratory balances. Note: Do not interchange tare weights between
cups as each cup and tare weight is matched.
2. Remove cover and fill to within 1.7mm of rim with material to be tested.
3. Carefully replace cover so that the air and excess material is expelled
through vent.
4. Wipe over cover to remove surplus and reweigh. By subtracting the
original weight of the cup, the weight of the contents will be found. If
a tare weight was used at the start, the balance will show the weight of
the contents. Clean thoroughly immediately after use.
TEMPERATURE
C.
21
22
23
24
25
26
27
WEIGHT
F.
69.8
71.6
73.4
75.2
77.0
78.8
80.6
Grams
8.329
8.327
8.325
8.323
8.321
8.319
8.316
APPAREN
TRUE
VOLUME
WITHOUq
AIR
:RAMs
I
W
A
B
FIG. 18-Diagram for mixing known and unknown density materials [7]. Figure provided by Paul N. Gardner Co., Inc.
VOLUME
UNDER
cPRESSUR]
)
I =:s L
(14)
B = T 2 - (A .da)
(15)
CHAPTER 31--DENSITY
301
SOLIDS
where
Tw = observed period of oscillation for cell containing water,
Ta = observed period of oscillation for cell containing air,
dw = density of water at test temperature,
da = density of air at test temperature,
t = test temperature expressed in degrees Kelvin,
p = test barometric pressure expressed in t o m
da (g/mL) = 0.001 293 (273 + t) x (p + 760)
dw (g/mL) = 0.997 04 at 25~ (273 + 25 = 298~
Constant A is used by the instrument's c o m p u t e r to calculate constants Kc and Kcr. Constant B is used by the instrument's computer to return the reading for air density.
Modern digital density instruments are equipped with
heating and cooling devices internal to the instrument, such
that the sample can be equilibrated within the instrument in
a matter of seconds. This leaves the pressure term, P, as a
visible variable. Pressure changes can occur over a period of
time due to weather changes.
The sample tube must be cleaned after each use. The tube's
condition needs monitoring to verify that it is at original
condition. Frequent calculation of the instrument cell constant Kc overcomes both of these problems.
For density values
K~ -
d~-d~
- - -
r~w- T~
(16)
(17)
1 . 0 0 0 0 - d~
r~w- T~
(18)
(19)
where
Ts
Kc
K~r
d~ (g/mL)
t
Displacement of Liquids
This was discussed in the section on Solids, Liquids, and
Gases as concepts and under ideal conditions.
Density gradient column systems (Fig. 19) are another
form of submersion test methodology, inverted from the
plummets of the density balances. Here the fluid is the calibrated, k n o w n test media, and the solid is the unknown. A
vertical column tank with black background is carefully filled
with a mixture of liquids in a very strict order to establish a
heavy-to-light liquid density gradient. Measurements are
made by adding in both u n k n o w n solid materials such as
fibers, film pieces, powders, and glass particles and reference
materials of known density. The particles will sink to the level
of their own density. Using the proper reference materials,
exact matches can be established within 0.0001 g/mL. There
is a problem when the sample interacts with the fluids and
302
FIG. 1 9 - D e n s i t y gradient column systems with text from supplier catalog [6]. (Courtesy of Fisher Scientific)
absorbs them or interacts in other chemical ways which perturb the normal test action as with inert materials such as
glass or plastics. Powders with irregular surfaces can also
experience surface wetting problems and air pocket entrapment. Densities can be determined from 0.79 to 2.89
g/mL with this technique [24].
The test is of long duration, requiring a settling time of
usually several hours. Several caution notes are included
concerning thin film samples and their handling which could
change the density. Potential users should review ASTM
D 1505 to assess the applicability of this technique to their
own personal needs and use.
ASTM methods using displacement of liquid and gases are
[17-19]:
Standard Test Method for Volume Nonvolatile Matter in
Clear or Pigmented Coatings (D 2697)
Test for Specific Gravity (Relative Density) and Density of
Plastics by Displacement (D 792)
Standard Test Method for Density of Plastics by the DensityGradient Technique (D 1505)
Displacement--Gases
Helium pycnometers have been available for a number of
years with many people expressing interest in using these
devices to determine the volume of solids of known weight.
These instruments are usually relatively expensive and only
recently have become sufficiently automated to reduce the
intense manual labor required to do a good job. Test method
activities are being pursued with ASTM paint committee
D 01.21 for thin film (ASTM D 2697) volume solids [1,12].
Apparent Density
Many pigments or powders are tested without regard to the
air entrapment on the particle surfaces or in the voids between where the particles touch. These materials are placed
in a graduated transparent container, and a vibrator is
touched to the container wall. The particles pack down, and a
weight is taken. This is referred to as apparent density.
ASTM methods based on apparent density include [22-24]:
Test Methods for Methylcellulose (D 1347)
Test Methods for Sodium Carboxy Methylcellulose (D 1439)
Test Methods for Hydroxypropyl Methylcellulose (D 2363)
///////
FIG. 20-Pigment volume relationships.
Analytical Determination
CRITICAL P I G M E N T V O L U M E S
Definition
A c o n d i t i o n w h e n a p a i n t has too m u c h p i g m e n t a n d too
little p o l y m e r such that internal voids are c r e a t e d w h i c h t r a p
air o r solvent in the v a p o r state [1].
Effect
A solid is c r e a t e d w h i c h has a h i g h e r a p p a r e n t v o l u m e t h a n
really exists. See Fig. 20.
REFERENCES
[1] Manual on Determination of Volatile Organic Compounds,
MNL4, J. J. Brezinski, Ed., ASTM, Philadelphia, 1989, pp. 1-13.
[2] Paint Testing Manual, ASTM STP 500, G. G. Sward, Ed., ASTM,
Philadelphia, 1972, pp. 165-172.
[3] Lee, G. L., Principles of Chemistry--A Structural Approach, International Textbook Co., Scranton, PA, 1970, p. 40, "Gases," pp.
64-88, "Solids and Liquids."
[4] Sears, F. W. and Zemansky, M. W., University Physics, 3rd ed.,
Part 1, Addison-Wesley Publishing Co., Palo Alto, CA, 1963, pp.
102-107.
[5] The Book of Popular Science, Vol. 2, Grolier Society Inc., New
York, 1966, pp. 30-32, 317-318.
[6] Sargent-WelchCatalog, 1992, pp. 39, 104, 149, 752,756 (Pycnometers and Hydrometers).
304
[17] Test Method for Volume Nonvolatile Matter in Clear or Pigmented Coatings (D 2697-86), Vol. 06.01, ASTM, Philadelphia,
1993, pp. 168-169.
[18] Test Method for Specific Gravity (Relative Density) of Plastics by
Displacement (D 792-91), Vol. 08.01, ASTM, Philadelphia, 1992,
pp. 288-291.
[19] Test Method for Density of Plastics by the Density Gradient
Technique (D 1505-90), Vol. 08.03, ASTM, Philadelphia, 1992,
pp. 455-460.
[20] Test Method for Density of Solid Pitch by Helium Pycnometer
Method (D 4892-89), Vol. 04.04, ASTM, Philadelphia, 1992, pp.
354-355.
[21] Test Method for Density of Polyethylene by the Ultrasound
Technique (D 4883-89), Vol. 06.02, ASTM, Philadelphia, 1992,
pp. 669-670.
[22] Test Method for Methylcellulose (D 1347-89), Vol. 06.02, ASTM,
Philadelphia, 1992, pp. 226-231.
[23] Test Methods for Sodium Carboxymethylcellulose (D 1439-89),
Vol. 06.02, ASTM, Philadelphia, 1992, pp. 253-260.
[24] Test Methods for Hydroxypropyt Methylcellulose (D 2363-89),
Vol. 06.02, ASTM, Philadelphia, 1992, pp. 355-363.
MNLI7-EB/Jun.
Particle-Size Measurements
1995
32
by George D. Mills I
305
Copyright9 1995 by ASTMInternational
www.astm.org
306
P A I N T A N D COATING T E S T I N G M A N U A L
-- -- 807.Pel Hum
Des~ca/ed
3
.51
Sc~n~,stre~/e~~ follows
13
II
/2
, ,
/
jJ
5
/'5
I/
/ 9
/ I
l / ,iJ
;
/ I
/: :/I:
/1"
0
i ~
5
/0
20
~5
50
L o # d - ~ / o g m m s p e r S y Cm
FIG. 1-Stress-strain curves of some paint films. These illustrate the effect of the
particle size of zinc oxide on the strength of paint films.
307
Icm
DETECTION
TYPE OF
DISPERSION
.I cm
mm
~ IOMIL
,01 cm
GRIND
=o
O0~u
:- 4
I MIL
.O01cm
HEGMAN
O~
6
7
71/2
.I MIL
.0001 c m
~u
IO-Scm
I,u
7 3/4
ULTIMATE SIZE OF
TYPICAL PIGMENT
PARTICLES
COATING
APPEARANCE
VISIBLY COARSE
f
INCREASING
TEXTURE
1
DECREASING
GLOSS
t
PERFECT
GLOSS
8
10"Tcm
)m,u
~/u (10/~)
z
o
LtJ
13.
0
MAGNESIUM SILICATE ( T A L C )
CALCIUM CARBONATE
CALCIUM SULFATE
BARIUM SULFATE
IRON OXIDE , ZINC OXIDE
LEAD S U L F A T E , LITHOPONE
TITANIUM DIOXIDE
z
bJ
O.
tO
~_j~r
o
3E
t~J
z~
PHTHALOCYANINES
IO'Scm
uJ
o
w
-->.
<,,,
z
DYES
CARBON BLACKS
oo
p-u~
Do
ujn~
it.)
QcJ~
5Q:
z
o r
foQ
3_
iO-acm
~,
FIG. 2-Dimensions of granular pigments and their relation to surface properties (from Ref 12). (Courtesy of the Journal of Paint
Technology.)
stability during pigment dispersion are a function of properties that are related, in part, to polymer particle size. Surfactant demand and effectiveness are a function of polymer particle size (as well as other binder variables). Because of the
importance (dependence) of many coating properties on the
small finite size of the pigment, fillers, catalysts, and polymers formulated into the coating, the demand for rapid,
accurate analysis of particle characteristics has lead to the
refinement of many techniques.
CONSIDERATIONS IN SAMPLING
TECHNIQUES
Normally, when a particle-size determination is made, one
will not work with the total collection of particles comprising
the bulk sample. A "representative" collection of particles is
usually chosen. This sample is then reduced in size a few
more times until only a few milligrams remain for the actual
instrumental testing. The assumption is usually made that
the fraction actually evaluated is, in fact, "identical" in particle size, size distribution, shape, and nature to the total of the
bulk material. This sample test fraction, which usually does
not exactly represent the bulk, can be a major source of error,
introducing considerable bias and distortion to the results.
The reliability of any measurement depends on the degree of
representitiveness of the test sample. Thus, the sampling
technique is as important (if not more so) than the actual
particle-size measurement, though in reality there is little
308
Var(pi)-P(1--P)
(1)
Theoretically, the expected deviation (i.e., standard deviation), ~, is the square root of the variation. Since the use of
the weight fraction is often more convenient, the equation for
variance is given by
Var(Pi)-P(1-P)[PWn+w (I--P)WA]( 1 - W )
(2)
where the weight fraction in the sample and bulk are Pi and P,
respectively, W and w are the bulk weight and sample weight,
respectively, and wa and w8 are the weights of individual
grains of A and B, respectively.
Even with the "perfect" sample, there is a finite probability
that the measured sample will deviate from the actual bulk by
some predictable value. To minimize this "guaranteed" deviation, a minimum sample size is required. One may calculate
the minimum sample size required to yield values within
preset statistical limits [13]. The equation relating the minimum sample weight of a gross sample is given by
Ms = 89
where
Ms
p
02
wx
2]d 3 x 103
(3)
=
=
=
=
PARTICLE CHARACTERIZATION
METHODOLOGY
Particles that are perfect spheres can be described by a
single value representing the sphere's diameter. Calibrated
microscopes are useful in reading such values directly from
the reticule. They have some utility with spherical resin parti-
5.762
6.312
2.11%
1.10%
0.27%
0.09%
6.812
5.142
2.09%
1.01%
0.132
0.08%
309
cles and with visual measurement of standardized test materials. Classification of most powders, on the other hand, must
address particles of various shapes and sizes.
A particle-size determination utilizes some size-dependent
property that can be measured and then relates this property
to a linear dimension. The measurement derives either from
individual particles or as a property of the collection of particles that is often expressed as a diameter of sorts. Measurement of a single individual particle can have m a n y different
"diameters" depending on the direction and m e t h o d of view.
Particle characterization, therefore, m a y involve determining
the rate of a particle's travel through a fluid (either under the
influence of gravity or while being subjected to angular acceleration due to rotation), its actual surface area, its ability to
pass through a screen of square or r o u n d holes, or its ability
to scatter light of various wavelengths in various directions.
It is convenient to use the term "equivalent diameters"
when comparing sizes. The value so determined for a given
collection of irregular particles will vary somewhat depending on the technique used (i.e., the size-dependent variable
being measured). The definition of some of these "diameters"
are presented in Table 2 along with their mathematical representation. Table 3 lists some of the methods, the nominal
particle-size range, and the size measured. The methods
310
Symbol
Name
Defufition
d~
Volume diameter
ds
Surface diameter
dsv
Surface volume
diameter
dd
Drag diameter
dr
Free-falling
diameter
dst
Stokes' diameter
da
Projected area
diameter
dp
Projectedarea
diameter
de
Perimeter
diameter
dA
Sieve diameter
dr
Feret's diameter
dM
Martin's diameter
dn
Unrolled
diameter
Formula
~" 3
V = - dv
6
S = Ird2
dv3
dsv d2
V2
F~ = C~.p~-
Fo = 31rdarlv
Re < 0.2
d3
dst 2 -
da
A = -~ d~
4
E(de) = - fo ~ dndOR
'IT
Sedimentation (Stokes') E . S . D . - - t h e d i a m e t e r of a s p h e r e of
t h e s a m e d e n s i t y as t h e p a r t i c l e a n d h a v i n g t h e i d e n t i c a l freefall v e l o c i t y of t h e particle.
Volume E . S . D . - - t h e d i a m e t e r of a s p h e r e h a v i n g t h e s a m e
v o l u m e as t h e particle.
311
Size Determined
Mean
Mean
Mean
>10
2-74
Passing through
minimum opening
Microscope
Optical
Electron
0.5-500
0.002-15
Martin's, Feret's, or
equivalent circle diameter
Zone sensing
Resistivity
Optical
0.05-500
Volume or area
Gas Permeability
Gas Adsorption
Brownian Motion
Sieving
Dry
Wet
1-500
Elutriation
Laminar flow
Cyclone
3-75
8-50
Equivalent spherical
diameter (E.S.D.)
0.5-50
E.S.D.
Mercury intrusion
0.01-200
E.S.D.
Centrifugal sedimentation
Mass accumulation
Photo extinction
X-ray
0.05-25
0.5-100
0.01-5
Gravity sedimentation
Pipettes & hydrometers
Photo extinction
X-ray
1-100
0.05-100
0.1-130
Centrifugal classification
E.S.D.
Hydrodynamic chromatography
Packed column
Capillary column
0.03-2
Cascade impactor
0.05-30
Aerodynamic diameter
,t---.-- Martin's
Diameter
n ~ 2.'%':5.,~:.~:x-.',::,~
Equivalent
"~-Diameter'-~
Feret's
Diameter
E.S.D,
0.1-60
DIAMETER DEFINITIONS
|-
E.S.D.
=1
Area of a sphere = ~D 2
(4)
(5)
These relationships alIow d e t e r m i n a t i o n of the m e a n particle d i a m e t e r if the specific surface (area) is known, Particlesize c h a r a c t e r i z a t i o n s t h a t e m p l o y surface a r e a techniques in
the size d e t e r m i n a t i o n yield average diameters. The surface
a r e a of a p o w d e r m a y be d e t e r m i n e d from gas a d s o r p t i o n
experiments. By a s s u m i n g uniform-size n o n p o r o u s a n d
spherical particles, the m e a n particle size m a y b e d e t e r m i n e d
from the surface a r e a data. The F i s h e r subsieve sizer is an
example of an i n s t r u m e n t of this type (Fig, 6). The "specific
surface" o b t a i n e d equals the d e t e r m i n e d surface a r e a divided
b y the p r o d u c t of the particle v o l u m e and density. W i t h app r o p r i a t e units conversion,
D = 6/[oA]
(6)
312
313
Silica ~--Cap
Helix~,.~ ~=~.,
"--': ITo~--~ I'I ] ~Water JaCv::~um
Adsorption of Gases
This method is based on determining the number of gas
molecules that will adsorb as a monomolecular layer on the
surface of the particles. Knowing the area occupied by one
molecule and the number of molecules, the specific surface
area of a specimen of pigment may be calculated from
s
where
E =
n =
N =
A --
nNA
11
~
(7)
Sample
Mercury
Manometer
314
Hutto-Davis Method
This approach is primarily a means for separating or fractionating a quantity of pigment into portions according to
particle size rather than providing a value of the sizes separated. Size determinations may then be made on the separated fractions. The technique has utility in evaluating the
influence of pigment and filler particle size on the properties
of the formulated product. After standardizing operating conditions for a material and measuring sizes by an independent
method, approximate size distribution may be estimated for
additional material.
air
t nlet
sorew clamp
ao iurt
oo.I
valve
//
/]
//
/ /
//
/ /
//
//
//
//
//
//
//
//
//
//
//
//
//
ample-/
plusJ
diffuser
/
/
/
/
t~bes
back a
f r o n t aria
/~
~P---levoliN
l~re samva r e ~ d a t o ~
tube
<
.L
Sievieg
Finerparticles
passthrough
sieve
EIMdatlen f
Largerparticles
tend to settle
Felvation
This method [30] combines elutriating and sieving for fractionating fine powders. The basic apparatus (Fig. 10) consists
of a column about 4 in. (10 cm) in diameter and 24 in. (61 cm)
in height. The specimen is placed in the narrow tube at the
right. Fluid is introduced and allowed to pass through at a
relatively low rate. The powder soon becomes fluidized in the
conical base of the column. The flow of the liquid is increased
gradually. The smaller particles reach the sieve and pass
through it. The throttling action of the sieve increases the
flow through it. Hence, particles that have passed through do
not fall back and clog the screen. Eventually, particles just
larger than the sieve openings reach the sieve, but they do not
block the screen as they reduce the flow around them and
then tend to fall from the sieve.
The sieve functions only as a gage. It does not support the
powder. Highly accurate electroformed sieves are used, but,
because of their small size (1 in. (2.5 cm) in diameter), their
cost is reasonable. Beside being economical, the method is
Flow from
reservoir
Powderto be
f " fractionated
'% Coarse
wire screen
Flu|dizatiee
Powderfluidizedby flow
FIG. 10-Felvation. Fractionating powders into different sizes
by a combination of fluidization, elutriation, and sieving. (Courtesy of Chemical and Engineering News.)
Individual Particle S e n s i n g
In this technology, individual particles are separated from
each other by a diluted suspension in either air (by fluidization followed by entrainment in a flowing stream) or a constantly stirred conductive solution. The particles are then
forced to pass through the sensing zone. In one air-fluidized
instrument, the time of flight between two precisely placed
laser light sources and detectors is used to calculate size. In
another, the attenuated light as detected by a photodiode is
used to calculate a size. In the liquid suspension instrument,
a change in the established electrical resistivity through an
electrolytecircuit is measured as a particle passes through a
small orifice.
An instrument based on aerodynamic time-of-fight technology was developed by Dahneke [31]. The measurement
range is reported to be from 0.2 to 200/xm, with 150 channels
per decade and a count rate of up to 100 000 particles per
second. Output may be reported in either geometric or aerodynamic diameter. In this instrument, a gas (usually air for
pigment particles) is used to break down agglomerate material and entrain them in a controlled flow; a specially designed "pulse-jet dispenser" is used where a controlled flow of
air is directed down onto a sample placed into a small cup
(Fig. 11). Depending on the nature of the sample, the operator
sets the computer values for particle count rate, flow pressure, and pulse pressure. The disperser flow pressure controlling the carrier gas usually remains constant. The disperser
316
PULSE
JETDISPERSER
~~..~
TM
It~J/~/I
heath
Toroidal
Swirl
Pulse Jet
FIG. 11-A diagram of the operation of the dry-powder pulse jet disperser. (Courtesy of Amherst Process Instruments, Inc.)
pulse pressure determines the number of particles fed
through the analyzer.
Measurements are made over 2-s intervals to ensure that
the minimum count rate is met. Should the count rate fall
below the predetermined count rate, the pressure is increased. Should the count rate exceed the maximum allowed,
the pressure is dropped by a factor of 2, thus maintaining the
number of counts between the allowed maximum and minimum.
Electrical Resistance
FIG. 12-Schematic of the aerosol beam generator and detection mechanism. (Courtesy of Amherst Process Instruments,
Inc.)
COULTER PRINCIPLE
A CURRENT
sieves in the U.S. Series. Especially useful for sizes under 100
/zm is a sieve made by a photoengraving and electroplating
process [39]. Such sieves are intended to serve mainly as
primary reference standards [see ASTM Specification for Precision Electroformed Sieves (Square-Opening Series) (E161)].
PULSEDETECTION, ~
ELECTROLYTE~
WITHDISPERSED
PARTICLES
~.
317
ION
\\
. ~ ' ~ 1 1
\\ / > - ~ J l l
~ / "
J
Hand Sieving
If the sieves are used singly, the following directions that
appear in several ASTM test methods, among them D 546,
Sieve Analysis of Mineral Filler for Road and Paving Materials, may be used.
After transferring the specimen to the sieve, "Hold the
sieve, with pan and cover attached, in one hand in a
slightly inclined position so that the specimen will be
well distributed over the sieve, and at the same time
gently strike the side about 150 times per minute against
the palm of the hand on the upstroke. Turn the sieve
every 25 strokes about one sixth of a revolution in the
same direction each time. Continue the operation until
not more than 0.05 g passes through the sieve in 1 minute
of continuous sieving."
Sources of error in hand sieving are operator fatigue and
casual attention to directions. While machine sieving eliminates these errors, some specifications still require hand sieving unless it can be shown that machine sieving gives the
same results.
Machine Sieving
Machine sieving has the advantages of uniformity of treatment and saving time since the operator is free to perform
other tasks while the machine is working. Several types of
machines are available. The conventional ones impart an
oscillating or rotating motion (or both) to the sieve, with
regular tapping. None appear to reproduce the motions of
hand sieving.
Ro-Tap Sieve Shaker--This machine [37] (Fig. 14) manipulates a series of sieves, graduated with respect to mesh size, so
as to permit separation of a specimen into sizes. As the name
implies, the sieves are given a special rotary motion accompanied at regular intervals by a tap. The nature of the specimen
dictates the size of the sieve openings and the timing cycle.
This type of machine is recommended in ASTM Test Method
for Particle Size or Screen Analysis at No. 4 Sieve (4.75-mm)
and Finer for Metal Bearing Ores and Related Materials (E276).
Sonic Sifter--In the Allen-Bradley sonic sifter [40] (Fig.
15), the sieves are stationary, and agitation is imparted to the
particles by an oscillating column of air. Sieve wear and
particle attrition are said to be minimal. The sonic sifter
consists of a sieving chamber, a diaphragm at the top vibrating at 60 Hz, and a motor with the necessary controls. The
amplitude of vibration is adjustable to the nature of the specimen. A determination may require no more than 60-s operation of the machine.
To make an analysis, the sieves, in descending order from
top to bottom, are assembled in the holder, and the specimen
(not more than 30 g or 10 mL) is transferred to the top sieve.
The cone, coupling unit, and the diaphragm are added, and
the stack is latched within the chamber. The complete assembly is positioned in the machine, the power level and the time
interval are set, and the operation is started. After the sift
318
P A I N T A N D COATING T E S T I N G M A N U A L
Lock
Air C0h
Sieve S
Light
upport
m
6 Standat
or 3 Dee
older
M(
P~
I
[tude
flitude
~ot
Di'.
FIG. 1 5 - D i a g r a m of the Allen-Bradley sonic 'sifter.
(Courtesy of Allen-Bradley Co.)
.
Direct M i c r o s c o p i c M e a s u r e m e n t
Microscopes, both optical and electron as well as automated image analyzers, are used to measure particle size
directly. Optical techniques suffer somewhat from an inability to focus on the "edge" of a particle at very high magnifications due to a depth of field problem. The lower limit is set by
its resolving power and the upper limit by its depth of focus.
The microscope is especially useful for measurement of platelike and needle-shape particles that do not obey Stokes' law,
on which the sedimentation methods are based. Disadvantages of the method are that it is slow and laborious. Hence, it
is used chiefly for the calibration of the more rapid relative
methods. ASTM Practice for Particle-Size Analysis of Particu-
320
-~)
where
D -- diameter of sphere,
/z = medium viscosity,
v = velocity of fall under influence of gravity,
g = gravitational constant,
pp -- sphere density, and
p = medium density.
Most often, the particles are not exactly spherical. Because
of this, it is difficult to relate a particle's dimensions directly
to the observed settling rate. The usual procedure is to use
Stokes' equation to determine the values for d from the sedimentation distance and its corresponding time. The value so
determined is then the "Stokes' diameter" of the particle. The
definition then becomes "the diameter of a sphere that has
the same density and free falling velocity (in a given fluid) as
the particle being investigated (within the range of Stokes'
law)."
This practice avoids the problem of variations in free fall
velocities caused by shapes which differ from being a sphere.
The assumption holds and permits useful comparisons of the
size distributions when similar types of materials are evaluated. The size distribution of particles of different shapes may
he compared provided that the phenomenon being studied is
dependent on its behavior in the fluid.
While the concept of the Stokes' diameter is useful, it is
necessary to appreciate its limitations. One should not equate
the Stokes' diameter to a sphere of equal volume or other
related quantity. Two types of errors may be introduced. In
the first case, errors arise when the particle's movements
depart from Stokes' law and, in the second case, errors are
introduced by the experimental technique itself.
Departure from Stokes' law can occur when flow conditions are not met. Stokes' equation is valid under laminar
flow only. Consequently, there is an upper limit to the size of
a particle that can be evaluated in a given liquid. Large particles can experience too high a velocity in the liquid and create
turbulent flow. Vortexes in the liquid in the vicinity of other
particles also introduce errors. Laminar flow is determined
by the Reynolds number experienced by the particle/fluid
system at the fall rate. The Reynolds number, Re, is defined as
Re - vdp
FIG. 19-The use of an internal standard of known size. (Courtesy of Stan Duke.)
(8)
(9)
Gravity Sedimentation
The analysis of particles by sedimentation is possible because of Stokes' law, which states that the time of fall of a
particle through a viscous medium is proportional to the
particle's density (the difference between it and the medium)
and its diameter. Of course, if the density of the medium were
greater than the particle, the particle would float. Another
requirement is that all of the particles must have a common
density. This rules out mixtures of different minerals and
pigments having different densities since they cannot be determined together.
Because of the time required for sedimentation to occur,
the simple gravimetric method and the photometric method
appear to be limited to pigments of sizes above 0.5 to 1.0/~m.
Cadle [53.1] and Orr and Dallavalle [54] have reviewed the
many variations of the method. Gravity settling was first proposed by Oden [55,56]. Calbeck and Harner [57] were among
the first to use the technique for paint pigments; Jacobsen
and Sullivan [58] brought the method to a higher degree of
refinement by using an analytical balance with one of the
pans replaced with a cup submerged in the suspension.
Hydrometer Method--The density of a dispersion is proportional to the concentration of the dispersed material, and
methods for particle-size analysis based on the use of the
hydrometer have been developed. One such method is ASTM
Method for Particle-Size Analysis of Soils (D 422). Another,
321
Centrifugal Sedimentation
The centrifuge is used to provide an accelerating force for
sedimentation analysis. Configurations exist using rotating
disks with "see-through" ports as well as holders of small seethrough cells.
Disk Centrifuge--The technique for the disk centrifuge was
developed by Atherton et al. [63]. The apparatus might be
considered to be a direct descendant of the single cell centrifuge of Donoghue [64] and the scratch start technique of
Marshall [65]. The range is from 0.01 to 0.5/~m.
The apparatus consists of a centrifuge unit, a sampling
unit, and an electronic control unit [66]. The rotor of the
centrifuge is a cell (hollow disk) of plastic or glass that rotates
on a horizontal axis (Fig. 20). The back wall is attached to the
shaft of the rotor. The front wall has a hole in the middle that
serves as an access port. The inside diameter of the standard
cell is 10 cm, and the width is 1 cm. In operation, the cell
takes liquid up to a minimum radius of 2.3 cm. The speed
ranges from 500 to 8000 rpm.
The sampling unit (Fig. 21) consists of a probe connected to
collection flask and a clock motor. The probe is an L-shape
thin-wall steel tube arranged to rotate about the axis of one
arm. The other arm terminates in a sharp bevel for scooping
up the contents of the cell in a manner analogous to that of an
inside cutter in a lathe. The center of rotation of the probe lies
below the center of the rotor.
To make a test, an appropriate volume of "spin fluid,"
typically a 4% sucrose solution, is transferred to the rotating
cell. After swirling stops (20 to 30 s), the specimen--usually
0.5 mL of a 0.5% dispersion--is expelled from a syringe
against the back wall near the center of rotation. The specimen flows outward over the wall unit it reaches the free
surface of the spin fluid, where it forms a band about 1 mm
thick. The spin fluid and the dispersion do not mix because of
the higher density of the former. Thus, zero time for the
measurement is defined rather accurately.
After the desired time, spin fluid is withdrawn from the cell
with the probe, which is driven by a clock motor at 1 rpm.
With the pickup end of the probe in the 12 o'clock position,
the motor is started automatically. All but 5 mL of the spin
fluid is removed for measurement of the undersized fraction
of the dispersed powder.
The development of detector systems must consider the
action on a transmitted light beam. Light-scattering theory
dictates that when light of intensity I0 attempts to pass
through a dilute suspension (i.e., no multiple scattering) of
particles, it is lost or extinguished to an extent that It makes it
322
FLUID
SAMPLE LAYER
ENTRY PORT
MOTOR SHAFT
i, ' f
i~!~ii~~"i
BOSS
9
i 84
,pf~
~ P E R S P E X
ROTOR
FIG. 20-Diagram illustrating the principle of the disk centrifuge. (Courtesy of Joyce, Loebl
& Company, Ltd.)
tBE PIVOT
PATH DESC
BY PROBE "
LE
FINAL COLLECTION POINT
FIG. 21-Relationship of disk and probe of disk centrifuge sampling. (Courtesy of
Joyce, Loebl & Company, Ltd.)
(10)
by
323
ing of the reference cell, the sample cell, and the rotor speed
(Fig. 23). Data are displayed in real time on a built-in CRT as
well as printed out on tape after the analysis for a permanent
record. Graphs are presented indicating the absorbance versus time, frequency distribution, and cumulative distribution
(either percent undersize or percent oversize).
Light A t t e n u a t i o n a n d S c a t t e r i n g T e c h n i q u e s
Otext = N C e x t
(11)
a = Cext/Qext
(12)
N 1rd2Qext
4
(13)
Spectrophotometric Techniques
Gamble and Barnett [71] developed a method for measuring particle-size distribution by the scattering of light in the
near infrared. The pigment is dispersed in low concentration
and placed in a transmission cell for spectrophotometric
measurement. From the shape of the spectrophotometric
curve, the relative size and size distribution characteristics of
an unknown pigment are obtained in terms of calibrated
samples (Fig. 24).
Bailey [72] also developed a spectral transmission method
using infrared wavelengths from 0.4 to 2/~m. The spectrophotometric curve was related to size by graphic comparison
with specimens of known sizes.
Atherton and Peters [73] measured light scattering by
polydispersed system of spherical particles. The size distribution curves for the materials compared favorably with direct
measurement with the electron microscope.
Leobel [74] used a spectrophotometer to obtain the effect
of wavelength on turbidity in the determination of the size of
latex particles. The sizes of particles used for calibration were
determined from electron micrographs.
Light-Scattering Techniques
When solid particles pass through a light beam, the light
will interact with the particles in one or more ways. It can
either be reflected, refracted, diffracted, or adsorbed and reradiated. This is shown schematically in Fig. 25. The scattered radiation will present a pattern that is dependent on the
shape and size distribution of the particles. By evaluating the
scattered radiation detected at different locations relative to
the beam direction and in different positions, much can be
learned about the scattering media. Figure 26 depicts some of
the angular intensities of scattered light produced by particles of various size. With low-cost computers and stable de-
324
SYSTEM DIAGRAM
PHOTOCELLS
1.SYNCHRO-SIGNAL(REF)
2.ANALOG-SIGNAL
3.SYNCHRO-SIGNAL(SAMPLE)
;;;
,~~2OCELL
(REFERENCE)
(OPTION)
(OPTION)
The CAPA-700 system is comprised of an optical system, a centrifuge, computation circuitry and input/output functions. The rotating disc in the horizontally mounted centrifuge is connected directly to the motor to minimize gravitational effects, and electronic
control keeps the rotational speed stable at the set value. The CPU monitors and controls
automatic checking for fluctuations in rotational speed, computation formulae and
deterioration of the light source and detector, assuring precision data at all times. In the
optical system, a reference cell guarantees both optical and mechanical balance for each
revolution, which, after CPU processing, gives even higher precision particle size distribution analysis.
LO
z0
80
~- 40
DZ
~cg ao
0
LO
a.o
3.o
4.0
325
Reflected
Absorbed and
Reradiated
>
~"
~'-
Refracted
Diffracted
FIG. 2 5 - P o s s i b l e interactions w h e n light strikes a particle.
ture in the housing for the tube. The radii of the optical
inhomogeneities range from 0.1 to 100/~m. Modern diode
array detectors are now available to do similar tasks without
the movement.
Diffraction of Laser Light--Instruments using diffraction of
single-wave-length laser light have been made possible by the
development of low-cost, highly stable lasers and diode array
detector technology. By fluidizing the particles in a stream of
air, they are directed through a cell being illuminated by a
laser source. The He-Ne laser, emitting a coherent beam of
632.8-nm wavelength is often used. To increase the crosssectional area of the beam, expanders are often employed
(Fig. 27).
The diffraction pattern that is seen by the detector is a
pattern of rings varying in darkness depending on the size
distribution of the passing particles. On-board computers use
both the Fraunhofer diffraction and Mie scattering theories
to calculate the particle-size distribution of the sample. These
methods allow the determination of size distribution based
Incident
Beam ~
~---=--:..~_~.~_
~-~---~,,,.~
-'~"
~ ; ,~, . ,~~, .,~-~-
Incident
Beam
~'~2
~-
X-Ray Scattering
Beam
-~---~-.-
'
Sphere
. " - - ~ - ~
larger than t h e
,, L '..2__
Light Wavelength
326
sampleparticle
/
diffracted lightpattern
He-Nelaser
beamexpander
condenser
lens
I) photo-cell
Ycletector
Principle of Operation
The He-hie laser emits a beam of 632.8 nm whose flux is enlarged by a beam expander and radiated upon the particles suspended in the liquid. After it has been
diffracted and dispersed by the particles, the laser beam passes through the
condenser lens and its image is formed at the photo-cell detector located at the
focal point of the lens.
The diffraction pattern that appears at the detector is a pattern of light and dark
concentric rings that corresponds to the particle size distribution of the sample.
Now, using both of the Fraunhofer diffraction and Mie scattering theories, the
intensity values are used to calculate the particle size distribution of the sample.
tungstenlamp
He-Nelaser
~ r -
filter
sampleparticle
~ condenser detector
I\
lens
[~
--- ",~......... - ~
rear
detector
scatteredlightpattern
~side
detector
detector
FIG. 27-Schematic layout for the large-particle system. (Courtesy of Horbia Instruments, Inc.)
are not ground but are only wet out and dispersed to their
"primary" size. This primary size is the smallest possible size
supplied from the producer.
327
Flow Schematics
reservoir unit (option)
.......................
-~
I
l
i
auto-sampler (option)
.........................
"I
I
===
!
,=,,,
printer
light
soure~...~",",,J,'~:',T':
......
_lL'-e
Y II I ~/~_ultra-sonicl'~ J ~
/
II ~
mirror
;'H-/-Nelase
He
jH'
"
",,'T'
,,
II
' detector
scattered light
~""~:.
-I"I ' I
ainnal
IA/D converter
flow cell
circulation
[ _
lens / /
.....CPU
+ra,
I
tecto,
valve
II
ouoo
RS-232C
mouse
I
drain
FIG 28-Schematic
Instruments, Inc.)
"'",',"', . . . . . . "1"". . . . . .
J],"l"~. ~_~y~" / ~ I I ~
....
m'~or~
9
I.
,at>
panel keys
Fineness-of-Dispersion Gages
Drawdown tests for the detection of oversize particles led
to development of fineness-of-dispersion gages, or, as first
called, fineness-of-grind gages. The gage is a steel block in
which is cut a wedge-shape channel, tapering usually from 4
mils at the deep end to zero at the other end, though other
depths and different widths and lengths of the channel are
available. Some gages have twin channels. An excess of the
sample is placed in the deep end of the channel, and the
excess is drawn to the shallow end with a scraper. At some
point along the channel, coarse particles or agglomerates
become visible. The results are interpreted by reference to
standard reference patterns. The addition of slow-evaporating solvents may be required to thin down the system to allow
more time for reading the gage without experiencing volume
loss by evaporation.
328
fresh material each time. The first drawdown allows accommodation to the light source and a rough estimate of the
dispersion pattern and the end point. Subsequent readings
may then he made within 3 or 4 s. ASTM directs viewing the
drawdown with the line of vision at a right angle to the long
dimension of the channel and at an angle between 20 and 30 ~
with the face of the gage in a light that renders the pattern
readily visible. Diffuse subdued light is preferred.
/
MILS
4-
3-
MICRONS
-I00
- 80
-60
2-40
I-
-20
J
FIG. 30-ASTM dispersion gage and scraper.
CHAPTER 32--PARTICLE-SIZE
4--
329
where
microns
mils
MEASUREMENTS
--I00
- 80
3--
--60
2
- 40
[
0 ---J
;Piiil --
4 0 microns
1.6 mils
FIG. 31-Typical pattern produced by a dispersion gage.
Vr
_ _
(14)
Carefully prepared particles of known size and composition have become an important part of testing for emulsions,
powders, film, and processes. When properly used, reference
particles are an important factor in demonstrating compliance with standards such as ISO-9000, FDA Good Manufacturing Practices and various military specifications [91]. In
the past two decades, the need for instrument calibration has
prompted the establishment of several businesses specializing in the production and supply of reference particles,
which are available in assortment of materials of various
sizes, densities, and grades.
A brief discussion of some typical applications will illustrate the usefulness of these test reference particles. They are
used for instrument calibration, filter checking, flow tracing,
and evaluation of processes such as blending, cleaning, and
spraying, to name a few.
Instrument calibration and checking covers two broad
classes: (1) particle-size analyzers and (2) particle contamination analyzers. Both types of instruments are calibrated or
controlled by spherical particle-size standards, primarily
polystyrene microspheres, which are normally measured and
calibrated by methods traceable to the National Institute of
r
f
>
330
REFERENCES
[1] Thompson, G. W., "The Classification of Fine Particles According to Size," Proceedings, American Society for Testing and Materials, Vol. 10, Part II, 1910, p. 601.
[2] Oden, S., "A New Method for Determination of Particle Size in
Suspension," Kolloid Zeitschrift, Vol. 18, 1916, p. 33.
[3] Oden, S., "Sedimentation Analysis and Its Application to the
Physical Chemistry of Clays and Precipitates," Colloid Chemistry, J. Alexander, Ed., Chemical Catalog Co., New York, 1926,
Vol. 1, p. 861.
[4] Stutz, G. F. A. and Pfund, A. H., "A Relative Method for Determining Particle Size of Pigments," Industrial and Engineering
Chemistry, Vol. 19, 1927, p. 51.
[5] Gamble, D. L. and Barnett, C. E., "Scattering in the Near Infrared; A Measure of Particle Size and Size Distribution," Industrial
and Engineering Chemistry, Analytical Edition, Vol. 9, 1937, p.
310.
[6] Atherton, E. and Peters, R. H., "Light Scattering Measurements
on Polydispersed Systems of Spherical Particles," British Journal of Applied Physics, Vol. 4, 1953, p. 344.
[7] Bunce, E. H., "Zinc Oxide in Exterior Mixed Paints," Scientific
Section Circular, National Paint, Varnish, and Lacquer Association, No. 319, 1927, p. 541.
[8] Eide, A. C., "Properties of Zinc Oxide Influencing the Weathering of Paints," Official Digest, Federation of Paint and Varnish
Production Clubs, Vol. 7, 1935, p. 164.
[9] Morris, H. H., "Titanium Dioxide, Lithopone, and Leaded Zinc,"
Official Digest, Federation of Paint and Varnish Production Clubs,
Vol. 6, 1934, p. 8.
[10] Nelson, H. A., "Zinc Sulfide Pigments for Interior Paints,"
Official Digest, Federation of Paint and Varnish Production Clubs,
Vol. 7, 1935, p. 177.
[11] Jacobsen, A. E., "Significance of Pigment Particle Size and
Shape," Canadian Chemical Process Industries, Vol. 33, 1949, p.
124.
[12] Pigment Index, National Paint, Varnish, and Lacquer Association, Washington, DC.
[13] Allen, T., Particle-Size Measurement, 4th ed., Chapman and Hall,
New York, 1990, p. 5.
[14] Allen, T., Particle-Size Measurement, 4th ed., Chapman and Hall,
New York, 1990, p. 9.
[15] Allen, T. and Khan, A. A., Chemical Engineering, Vol. 238, 1970,
pp. 108-112.
[16] HORIBA: PARTICLE SIZING SEMINAR, Notes and Workbook,
Horiba Instruments, Inc., (714) 250-4811, Irvine, CA, 1992, p. 5.
[17] Fries, R., "The Determination of Particle Size by Adsorption
Methods," Particle-Size Measurement, STP 234, American Society for Testing and Materials, Philadelphia, 1958, p. 259.
[18] Brunauer, S., Emmett, P. H., and Teller, E., "Absorption of
Gases in Multimolecular Layers," Journal, American Chemical
Society, Vol. 60, 1938, p. 309.
[19] Emmett, P. H., "A New Method for Measuring the Surface Areas
of Finely Divided Materials and for Determining the Size of
Particles," Particle Size Determinations in the Subsieve Range,
STP 51, American Society for Testing and Materials, Philadelphia, 1941, p. 95.
[20] Nelsen, F. M. and Eggersten, F. T., "Determination of Surface
Area. Adsorption Measurement by Continuous Flow Method,"
Analytical Chemistry, Vol. 30, 1958, p. 1387.
[21] Beresford, J., Carr, W., and Lombard, G. J., "Surface Area of
Pigments," Journal of the Oil and Colour Chemists' Association,
Vol. 48, 1965, p. 293.
[22] McBain, J. W. and Bahr, A.M., "A New Sorption Balance,"
Journal of the American Chemical Society, Vol. 48, 1926, p. 690.
[23] Ewing, W. W., "Specific Surface of Pigments by Adsorption from
Solution," Particle Size Deternzination in the Subsieve Range, STP
51, American Society for Testing and Materials, Philadelphia,
1958, p. 259.
[24] Maron, S. H., Elder, M. E., and Ulevitch, I. W., "Surface Area
and Particle Size of Synthetic Latex Containing Fatty Acid
Soap," Journal of Colloid Science, Vol. 9, 1954, p. 89.
[25] Brodnyan, J. G. and Brown, G. L., "The Soap Titration of Acrylic
Emulsions," Journal of Colloid Science, Vol. 15, 1960, p. 75.
[26] Gooden, E. L. and Smith, C. M., "Measuring Average Particle
Diameter of Powders," Industrial and Engineering Chemistry,
Analytical Edition, Vol. 12, 1940, p. 479.
[27] Hutto, F. B., Jr. and Davis, D. W., "An Improved Air Permeability
Apparatus," Official Digest, Federation of Paint and Varnish Production Clubs, Vol. 31, 1959, p. 429.
[30] Anonymous, "Felvation Speeds Powder Fractionation," Chemical and Engineering News, 6 March 1967, p. 50.
[31] Dahneke, B. E. and Cheng, Y. S., "Properties of Continuum
Source Particle Beams. L Calculation Methods and Results,"
331
332
[82] Pigments Division, duPont Co., White Pigments for Paint, Sec-
[83] St. Louis Paint and Varnish Production Club, "Effects of Wetting Agents upon Pigment Dispersion," Scientific Section
Circular, National Paint, Varnish, and Lacquer Association, No.
471, 1934, p. 429.
MNL17-EB/Jun. 1995
33
by Richard R. Eley I
G~ Plateau m o d u l u s
G* Complex s h e a r m o d u l u s
G' Storage m o d u l u s
G" Loss m o d u l u s
K Consistency in p o w e r law model; c o n s t a n t in viscosity-molecular weight equation
L Capillary tube length
M w Weight-average p o l y m e r m o l e c u l a r weight
M c Critical (entanglement) p o l y m e r m o l e c u l a r weight
P Pressure
Q Volumetric flow rate
R Capillary tube radius; particle radius; air b u b b l e radius
T Absolute t e m p e r a t u r e
Tg Glass t r a n s i t i o n t e m p e r a t u r e
a Curvature p a r a m e t e r in Eq 15; a m p l i t u d e of coating
surface striations
a0 Time-zero a m p l i t u d e of coating surface striations
e Base of the n a t u r a l l o g a r i t h m i c scale = 2.718 28
f Frequency, Hertz
g Gravitational acceleration
h Film thickness
k B o l t z m a n n ' s constant; general rate c o n s t a n t
l Length
m Kinetic energy correction t e r m for capillary tube
flow, Eqs 72 a n d 73
n Power law exponent
t Time
v Velocity
x Coordinate parallel to substrate
y Coordinate n o r m a l to substrate
Nomenclature
ap
a
/3
7
~w
8
T0
~/|
~d
Tie
~l
"Or
~'
[~]
0
)t
v
p
tT
(r0
~r
~%
Zs
%
the
thin
tO
A
De
F
Fg
G
Fluidity integral, Eq 64
Rate of decay of r o u g h n e s s amplitude, s- l
Time c o n s t a n t characteristic of a critical shear rate, s
Dimensionless shear strain
S h e a r strain rate, s-1
Wall s h e a r rate in t u b e flow, s 1
Phase shift; thickness of a d s o r b e d p o l y m e r layer
Extensional (Hencky) strain, dimensionless
Extensional (Hencky) strain rate, s-1
Coefficient of viscosity
Zero-shear viscosity
H i g h - s h e a r limiting N e w t o n i a n viscosity
Dispersion viscosity
Extensional viscosity
Liquid-phase viscosity
Relative viscosity, ~d/~t
D y n a m i c viscosity
Intrinsic viscosity (limiting viscosity n u m b e r )
Angle of inclination with respect to the vertical
Wavelength of coating surface striations; elastic
stress relaxation t i m e c o n s t a n t
K i n e m a t i c viscosity
Ratio of c i r c u m f e r e n c e of a circle to its d i a m e t e r
Density
Surface tension; generalized stress
Initial i m p o s e d stress
Tensile stress
Shear stress; viscosity-kinetic time constant for drying, wicking, or t h i x o t r o p y
Yield stress
Tangential surface s h e a r stress
Wall s h e a r stress
Volume fraction of internal (dispersed) p h a s e of a
dispersion
Effective volume fraction for a d i s p e r s i o n
M a x i m u m packing fraction of a dispersion, where
~r ---~ ~
Angular frequency ( = 2wf)(rad/s)
Area of s h e a r face
D e b o r a h n u m b e r ( )t/t )
Force
Force of gravity
Shear modulus
INTRODUCTION
THE VALUEOF RHEOLOGICALSCIENCEis increasingly being realized in the coatings laboratory. One r e a s o n is economic: As
m u c h as half the cost of new p r o d u c t d e v e l o p m e n t c a n be
c o n s u m e d in solving rheology-related p r o b l e m s of m a n u f a c ture or p e r f o r m a n c e . Moreover, the rheology of an established p r o d u c t can go a w r y due to r e f o r m u l a t i o n or a r a w
m a t e r i a l or process change, a n d such p r o b l e m s are generally
in urgent need of solution. Rheological analysis can be a costeffective aid to the coatings f o r m u l a t o r in u n d e r s t a n d i n g a n d
solving p r o d u c t a n d process difficulties.
Traditionally, m e a s u r e m e n t of the viscosity or "consistency" of p a i n t s a n d coatings h a d b e e n b a s e d on a n u m b e r of
test m e t h o d s having certain perceived virtues: They were
www.astm.org
334
undemanding in operator skill, required inexpensive equipment, and the result was usually a single number requiring no
interpretation. These tests proved useful enough, especially
as tools of the experienced formulator or bench chemist. This
was partly because, in the times when many industrial coatings were solvent-borne and relatively low in solids, the product rheology was seldom far from Newtonian. In the latter
case, any test serves as well as any other. The advent of
environmentally compliant technologies, such as waterborne, higher solids, and powder coatings, changed this situation. With the new formulations, non-Newtonian, time-dependent, and viscoelastic behaviors were encountered. Here,
the traditional methods were inadequate for the reasons that
many of the latter tests yield only a single-point measurement, use arbitrary (rather than absolute) viscosity units, or
use a flow field which is "nonviscometric. "2 Any of these
shortcomings render a method inappropriate for non-Newtonian materials.
A recurrent failing in product viscosity testing is the employment of methods not relevant to the performance property in question. This deprives the test of any analytical or
predictive power relative to paint performance. Thus, for example, a low-shear viscosity measured using a spindle viscometer, paddle viscometer, or orifice cup bears no relation
to the performance of a paint during application, generally a
high-shear process. Part of the aim, therefore, is the development of tests which are related specifically to the critical
processes paints must undergo.
Rheological factors play a key role in all stages of a coating's lifetime, from manufacture to the final career of a protective, decorative film. The many processes embodied in that
history involve broad aspects of the science of rheology. Table
1 lists some coatings processes, each process having associated with it several distinct deformation characteristics. For
each deformation type, a specific rheological test is required
to measure its effect on the process. Many of these measurement quantities are independent, i.e., they cannot be inferred
from another rheological property. Obviously, if one were to
measure only steady-shear viscosity, and over a limited range
of shear rate at that, the real cause of a performance problem
may be missed. Thus, the characterization necessary for complete understanding of rheology-controlled behavior may require the use of more than one instrument and technique.
Notwithstanding, many problems can be solved from shear
viscosity and viscoelastic data alone provided the experiments performed are well designed and the results properly
interpreted.
In order to take full advantage of the capabilities built into
the sophisticated rheological instruments now being widely
used in the coatings industry, more than a passing knowledge
of the subject of rheology is required. This chapter is therefore somewhat tutorial in style, endeavoring to provide the
novice an entry point to the discipline. Certain concepts are
discussed at some length because of their importance or
complexity. One of these is viscoelasticity. It is worth the time
because (a) it is established that viscoelasticity exerts control
over coating processes when present, and (b) a number of
2"Viscometric" shear flow requires that the flow be "everywhere
indistinguishable from steady simple shear" [1].
Deformation (Strain)
A deformation is a change in shape and/or volume of a
material in response to an applied stress. The equivalent
engineering term is strain. During the lifetime of a coating,
the deformation history may be complex (see Table 1), with
the most important components being simple shear and extension. For purposes of definition, we will limit our discussion to simple shear. Simple shear deformation is exactly
analogous to the spreading of a deck of playing cards, each
card representing a thin volume element (or shear plane)
displaced relative to its nearest neighbor (Fig. 1). If a force F
is applied to the uppermost volume element (thickness dy),
the material will deform by the displacement of adjacent volume elements by a distance dx. The total thickness is Ay, and
the total displacement is Ax. The shear strain, % is the ratio of
the net displacement, Ax, to the distance of separation of the
confining surfaces, Ay.
V-
Ax
ay
(1)
Strain Rate
In order to measure the viscosity, or resistance to flow, of a
fluid, we must know not only the extent, of deformation
(strain), but also the rate of deformation (strain rate). The
strain rate is the change in strain per unit time, or the time
CHAPTER
33--RHEOLOGY
AND
VISCOMETRY
335
Rheological
Property
Roll Coating
Squeezing flow
Stretching flow
Shearing flow
High strain rate
Large accelerations
Large decelerations
Surface area transients
Drying
Spray
Flash-off
Brushing/rolling
Shear viscosity
Extensional viscosity/elasticity
Dynamic surface tension
Leveling/sagging
Curtain coating
Extensional flow
Surface area transients
Shear (pumping,
extrusion)
Extensional viscosity/elasticity
Dynamic surface tension
Shear viscosity
Process
F
A
Ax
Ay
Viscosity (~/) =
Wicking
Drying
dv
Stress
dy
7
"it
r -
dv = dx/dt
Non-Rheological
Effects
F
A
(3)
A
~y
EXx
"
At
At
_ A(~/At______) _ A v
Ay
(2)
Ay
Viscosity
The viscosity of a fluid characterizes its resistance to flow.
The resistance to flow is, in turn, a m e a s u r e of the friction
b e t w e e n the flow units of the fluid (e.g., molecules) o r m a y
also be a m e a s u r e of the attractive forces b e t w e e n the flow
units. Thus, a "viscous" fluid (one reluctant to flow) m a y be so
b e c a u s e of high m o l e c u l a r weight (as in m o t o r oil) o r be of
relatively low m o l e c u l a r weight, b u t having strong i n t e r m o lecular interactions (e.g., h y d r o g e n bonds, as b e t w e e n sugar
molecules in honey).
The s e p a r a t i o n of molecules in flow dissipates energy,
chiefly as frictional heat. Flow, therefore, is a process w h i c h
costs energy, of w h i c h the viscosity is a measure. F o r the case
of s h e a r d e f o r m a t i o n , the viscosity, a?, is calculated as the
ratio of s h e a r stress to s h e a r rate. The viscosity, therefore, is
the energy p e r unit volume dissipated to a t t a i n a unit velocity
gradient.
T
rl = -7
Y
(4)
336
Modulus
Materials c o m p l y with an a p p l i e d stress b y deforming, o r
u n d e r g o i n g strain. F o r ideal H o o k e a n materials, the strain
will be p r o p o r t i o n a l to the a p p l i e d stress. The m o d u l u s is the
p r o p o r t i o n a l i t y constant b e t w e e n the stress a n d strain. F o r
example
C -
(s)
Units
Various systems of units for rheological variables are in use
a n d m a y be e n c o u n t e r e d in the literature. Until recently, the
m o s t c o m m o n system of units for rheological t e r m s was the
cgs (centimeter-gram-second), o r "smaLl metric" system.
However, m a n y technical p u b l i c a t i o n s a n d scientific j o u r n a l s
n o w specify that Systeme Internationale (SI) units be a d h e r e d
to. The SI system is b a s e d on the "large metric," o r MKS
(meter-kilogram-second) units, with s o m e a d d i t i o n a l n a m e d
units. The units associated with the above variables, according to the various systems, are given in Table 2.
CLASSES OF RHEOLOGICAL B E H A V I O R
Newtonian
Fluids
(6)
r = n~/
(7)
or
Non-Newtonian Fluids
Of m a t e r i a l s e n c o u n t e r e d in the coatings industry, only
dilute o r low-molecular-weight p o l y m e r solutions or stable
dispersions of low c o n c e n t r a t i o n are likely to be Newtonian.
In general, p o l y m e r solutions, colloids, dispersions, a n d suspensions of particulate solids will be non-Newtonian. F o r
n o n - N e w t o n i a n materials, the viscosity is no longer a material constant, b u t is called a m a t e r i a l f u n c t i o n - - i n this case, a
"function" of the s h e a r rate (or s h e a r stress). F o r non-Newt o n i a n fluids, a viscosity m e a s u r e d at a single s h e a r rate is not
an a d e q u a t e r e p r e s e n t a t i o n of the rheology of the system.
C L A S S E S OF N O N - N E W T O N I A N B E H A V I O R
In the following sections, the various types of non-Newt o n i a n flow behavior will be outlined. At the s a m e time,
several m a t h e m a t i c a l expressions which can describe nonN e w t o n i a n flow will be introduced. M a t h e m a t i c a l m o d e l s are
useful for s u m m a r i z i n g flow b e h a v i o r quantitatively. To be
sure, m a t e r i a l s m a y be evaluated by qualitative c o m p a r i s o n
of flow curves (e.g., b y visual inspection), b u t the m a t h e m a t i cal analysis of a flow curve has significant value. F o r one
thing, the m o d e l constants m a y have physical significance.
F o r example, s o m e of the m o d e l s contain a yield stress t e r m
(see P l a s t i c (Yield) B e h a v i o r ) as a fitted p a r a m e t e r . The
m a g n i t u d e of this p a r a m e t e r m a y be coupled to sag o r
leveling p e r f o r m a n c e [2]. A later section of this chapter,
LEVELING, gives examples of h o w sagging can be p r e d i c t e d
for n o n - N e w t o n i a n fluids using constants from m o d e l s discussed below. F u r t h e r m o r e , the values of m o d e l p a r a m e t e r s
m a y be associated with f o r m u l a t i o n variables, allowing one,
in principle, to o p t i m i z e rheology b y adjusting c o m p o s i t i o n
in a rational way.
It should be u n d e r s t o o d t h a t the models a b o u t to be discussed are actually idealizations a n d therefore limited in
their ability to r e p r e s e n t the b e h a v i o r of real materials. The
models can describe real b e h a v i o r at least over a limited
range of stress or strain rate. Thus, a second use of m a t h e matical m o d e l s of flow is to m a k e p r e d i c t i o n s of flow behavior, b e a r i n g in m i n d that it is d a n g e r o u s to extrapolate the
m o d e l s b e y o n d their range of validity.
As m e n t i o n e d above, the simplest flow m o d e l is the Newt o n i a n expression, which has only one constant, the coeffi-
TABLE 2--Units.
Variable
CGS
Strain
Strain rate
Stress
Viscosity
Dimensionless
s- ~
Dyne/cm2
Poise (P)(= 1 dyne 9 s / c m 2 )
or centipoise (cP) (1 cP
= 0.01 P = 1 mPa 9 s)
dyne/cm 2
Modulus
MKS
SI
. . . . . .
s- 1
sN/M 2
Pascal (Pa)( = 1 N/M z)
...
Pa - s (= 10 P) or
millipascal-second
(mPa 9s)(= 1 cP)
N/M2
Pa
CHAPTER 3 3 - - R H E O L O G Y A N D V I S C O M E T R Y
337
rl
~p
Shear-Dependent Viscosity
Materials in w h i c h the viscosity falls with increasing shear
rate 3 are d e s i g n a t e d shear thinning. S i m p l e shear t h i n n i n g
b e h a v i o r w i t h o u t either t i m e d e p e n d e n c e (see u n d e r T i m e D e p e n d e n t Fluids) o r a yield stress (see u n d e r Plastic
(Yield) B e h a v i o r ) is termedpseudoplastic, a c o m m o n type of
n o n - N e w t o n i a n b e h a v i o r in coatings systems. Viscosity rising
with increasing rate of s h e a r is called shear thickening. The
t e r m dilatancy (see u n d e r Shear Thickening Fluids) is often
a p p l i e d to s h e a r thickening behavior, although this refers
strictly to s h e a r thickening a c c o m p a n i e d b y a v o l u m e increase, as the t e r m implies. Figure 2 shows curves illustrating
viscosity-shear rate relationships for N e w t o n i a n a n d nonN e w t o n i a n fluids.
As stated, N e w t o n i a n b e h a v i o r is the simplest of all a n d is
described b y Eq 4. The viscosity, 4, is a m a t e r i a l c o n s t a n t
i n d e p e n d e n t of s h e a r rate (Contour N, Fig. 2). More complicated viscosity-shear rate b e h a v i o r requires a m o r e c o m p l e x
expression to m o d e l it. The first level of complexity is to a d d
yield b e h a v i o r (see u n d e r P l a s t i c (Yield) B e h a v i o r ) to the
N e w t o n i a n model, resulting in the B i n g h a m equation [3]
,r-
r0
= 4//
(8)
"1"1/2 =
41~:,/2' 1/2
(9)
(10)
which is somewhat surprising since few paints utilize rodshaped particles as fillersor pigments. In fact, this author's
experience is that frequently the Casson model does not represent paint flow as well as certain other models (see below).
In Eqs 9 a n d 10, q~, s o m e t i m e s called the Casson viscosity, is
not truly an "infinite-shear viscosity," b u t is a limit t h a t is
a p p r o a c h e d , c o r r e s p o n d i n g to s o m e u n k n o w n high shear
rate. The value o b t a i n e d for the Casson viscosity will d e p e n d
on the m a x i m u m e x p e r i m e n t a l s h e a r rate. As with all such
models, the u s e r m u s t be a w a r e that the constants resulting
3Any definitions or descriptions of shear rate-dependent behavior
may likewise be stated in terms of shear stress dependence.
41n the Bingham expression and in other models incorporating a
yield stress term, it is important to note that the equations describe
flow behavior only when r > %. When r -< %, 5' = 0 (i.e., "q = co),and
there is no flow.
~HB
N
PL (n> 1)
PL (n< 1)
from a Casson analysis are not necessarily true m a t e r i a l constants. F o r example, b e c a u s e the analysis of flow d a t a is simply curve-fitting, a finite yield stress will generally be o b t a i n e d
w h e t h e r o r not the m a t e r i a l really possesses yield behavior.
The next c o m p l i c a t i o n we will i n t r o d u c e is to let the exponent of the s h e a r rate in the N e w t o n i a n law be other t h a n
unity. In o t h e r words, the s h e a r stress now will d e p e n d on
s o m e p o w e r of the s h e a r rate
' r = K * '~
(11)
(12)
(13)
338
TESTING
MANUAL
= ~ + K'~, "-1
This expression is known as the Sisko model [9] and includes Regions II and III of Fig. 3.
Of several proposed models encompassing Regions I, II,
and III inclusively, two in particular have perhaps found
wider acceptance and utility in the literature. These are the
Cross and Carreau models. Hieber et al. [10] recently wrote a
general form of which the Cross and Carreau models are
special cases (here modified to include Region III)
~/0
log "17
I[I
log "Y
FIG. 3-Generalized equilibrium flow curve: rio is the zeroshear viscosity (random structure, maximum disorder); ~q| is
the high-shear limiting viscosity (maximum order). Region I is
the first Newtonian plateau; Region II the power law regime;
Region III the second Newtonian plateau; Region IV the shearthickening regime. (Adapted from Ref 6.)
"qo -- "r/~
= ~ -~ (1 + [/37],)(,-,)/a
(15)
/3
(16)
(17)
Shear-Thinning Fluids
The term pseudoplastic has been applied t o fluids which
decrease in viscosity with increasing shear rate (or shear
stress) and implies shear-thinning behavior without yield
stress. However, the term is passing out of use in favor of the
more general description shear thinning. Particulate dispersions, polymer colloids, and polymer solutions can display
this behavior above a certain concentration threshold.
Viscosity is a measure of the dissipation of energy or the
"energy cost" to flow. Shear thinning behavior, therefore,
implies that an increase of shear rate causes a structural
change in the fluid that allows it to flow more efficiently,
consequently with less energy loss. The mechanism 6 involves
a shear-induced increase in order, or anisotropy, within the
system. Thermal (Brownian) motion tends to keep systems
disordered (of random order). Shear forces work against this,
tending to impose orderliness. If shear rates are low, the
randomizing forces win out and the viscosity does not change
for small increases of shear rate (Point a to Point b in Fig. 3).
Since the structure is no less random anywhere in Region I
than at zero shear rate, the viscosity equals ~?o,the zero-shear
value. As the shear rate approaches a critical magnitude (see
Shear-Dependent Viscosity), the competition of thermal
randomizing and shear ordering starts to favor ordering
(Point c in Fig. 3). In the case of polymers in solution, randomly coiled polymer chains tend to stretch in the direction
of shear, partially uncoil, and align in more or less parallel
fashion depending on the strength of the shear field. The
particles of a dispersion tend to line up like "strings of pearls"
(Fig. 4) and eventually in ordered planes perpendicular to the
shear gradient [18-20]. The result is a steadily decreasing
viscosity with increasing shear rate as the degree of order
increases. Ultimately, if the shear rate is high enough, the
maximum amount of shear ordering possible is attained and
the viscosity again becomes independent of shear rate (Newtonian).
Figure 3 shows the overall way in which viscosity varies
with shear rate for systems such as those described above
where Region I is the low-shear Newtonian regime (where
Brownian motion controls structure). Region II is the shearthinning segment of the flow curve (where shear forces control the structure). It is found that the viscosity decreases
exponentially with shear rate here; hence, it is often referred
to as the "power law" regime. Region III is the high-shear
Newtonian regime. Here, the maximum degree of shear ordering has been attained; thus, the viscosity is once again
independent of shear rate. The high-shear limiting Newtonian viscosity is usually given the symbol ~ . Region IV is a
shear-thickening region which is occasionally seen, especially with concentrated dispersions. In actuality, shear thickening in dispersions may occur at virtually any magnitude of
6The following discussion applies strictly to "stable" systems, i.e.,
those in which the net force between flow units is repulsive and
therefore which do not flocculate. The shear-thinning mechanism for
unstable systems (net interparticle force attractive) is discussed in
the subsection entitled Mechanism of Thixotropy.
339
Shear-Thickening Fluids
We have seen above that shear thinning involves a shearinduced increase in order of a system. This allows the elements of a fluid to move or flow with minimum expenditure
of energy. Conversely, shear thickening evidences that shear
has caused a decrease in order of a system. The resulting
disordered system dissipates more energy during flow and
hence is more viscous. An example of this is provided by the
catastrophic increase in viscosity observed by Hoffrnan [19],
resulting from the "buckling" or "log-jamming" of ordered,
layered arrays of particles.
One frequently encountered type of shear thickening behavior is dilatancy. Properly, dflatant behavior is shear thickening accompanied by an increase in volume of the fluid. It is
most commonly observed in relatively concentrated disperse
systems. In a dilatant system, the disperse phase particles are
"wetted" with the minimum amount of liquid continuous
phase. Furthermore, at rest, the particles of the disperse
phase are in a random close-packed structure for which the
interstitial volume is relatively minimal (Fig. 6). If the dispersion moves only slowly, adequate time exists for the meager
liquid phase to flow sufficiently to maintain the dispersed
phase in a "wetted" state, and the system is able to maintain
its close-packed structure. Faster or more forceful motion
causes a liquid-starved condition because the interstitial volume increases when the system is deformed or made to flow
(Fig. 6). There is no longer enough liquid to lubricate the
system. The particles are, therefore, incompletely wetted, and
forced flow would ultimately create microscopic voids, leading to fracture of the material. The surface of a dilatant
material may appear dry when stressed due to the withdrawal
of surface liquid into the increased interstitial volume. This is
seen when walking on wet sand on the beach. The resistance
to deformation of the material can increase tremendously
with increased deformation rate due to these effects.
During the course of a pigment grind operation, a fairly
sudden maximum in viscosity is often seen and is an indication that a good grind (i.e., to primary particles) has been
achieved. In fact, the surge in viscosity and power draw result
9O
o
o
9
Q
o
oO
O0
0
0
0
Oo
9
o
ooooo0
ooo
ooo
o
o
ooooo
o~
9 o
O0
0Ooooo
ooo
oooo
o
o
~)
~)
o~
oo0oOOOOO o
oooo
oor
(c)
(d)
FIG. 4-Dilute suspension of glass spheres in a polymer solution confined between glass plates with small plate
separation: (a) just after loading, particles are randomly distributed; (b)-(d) after being sheared in a side-to-side
direction at both increasing duration and shear rate. (By permission from J. Michel, R. P~tzold, and R. Donis,
R h e o l o g i c a Acre, Vol. 16, 1977, p. 317. Cited in Ref 20.)
permit flow under even very low stresses. For this reason,
paints in a dilatant state may suffer from rapid settling and be
difficult to redisperse. For most coatings operations, dilatancy is, in fact, undesirable. Pumping of dilatant dispersions may result in high back-pressure in lines, excessive
03
~X
\\
\\
log "~
X\
\n \
Dilatant Behavior
\\
log
FIG. 5-Flow curve seen for unstable (flocculating) dispersions is indicated by the ascending curve going toward infinite
viscosity at low shear rate.
from the grind having become dilatant. The dilatancy is desirable here because it facilitates energy transfer throughout the
grind. Thus, dilatancy is frequently an indicator of achievement of a stable dispersion to primary particles. Dilatant
systems, in general, are not also thixotropic and therefore
random
close-packed
under shear
Time-Dependent Fluids
Time-dependent fluids are those whose viscosity is a function of both shear rate (or shear stress) and time. The most
common such behavior encountered in coatings is time-dependent shear thinning or thixotropy [23]. At constant shear
rate and temperature, the viscosity of thixotropic fluids will
fall, eventually reaching a constant value. If the shear rate is
changed, the viscosity will approach a new equilibrium value
at a characteristic rate. This behavior is illustrated in Fig. 7,
showing the way viscosity changes for a time-dependent system when the imposed shear rate (or shear stress) is changed
in steps. Initially, the shear rate is zero, and the viscosity is
very high or infinite for a thixotropic system. As a shear rate
greater than zero is imposed (%), the viscosity drops exponentially, reaching a constant value. Increasing the shear rate
to ~/2 decreases the viscosity further to a new equilibrium
value. A decrease of the shear rate to % results in an exponential rise of viscosity to a higher equilibrium value. If, instead
of a multiple steady-shear experiment, just described, we
were to carry out a shear rate (or shear stress) ramp experiment (Fig. 8a), the time dependence would result in a loop
(Fig. 8b). The explanation of the loop is given below, but has
to do with the fact that in a ramp experiment the equilibrium
structure is never attained. The circuit in Fig. 8b is called a
thixotropic loop. Roughly bisecting the loop is the equilibrium-structure curve generated from the equilibrium viscosity data of Fig. 7. The analogous time-dependent behavior for
"Y--o
>4,1
"YI>0
r/
Time
FIG. 7-Time-dependent fluid behavior. At ~, = 0, viscosity is
high (or infinite), Imposing ~'1 > 0 causes viscosity to fall exponentially, reaching new equilibrium value. Subsequent changes
in ~, result in re-equilibration of structure, hence viscosity.
antithixotropy.
"Thixotropic Index" Test
We emphasize that the most important characteristic of
thixotropic behavior is not shear thinning alone, but time
dependence. The relatively slow change of Viscosity provides
a means of control of flow behavior and is the reason
thixotropy is formulated into coatings. Hence, it is important
to correctly characterize the time-dependent aspect of the
behavior. For this reason, the so-called "Thixotropic Index"
test is of limited benefit for characterization of such systems.
We will digress for a moment to discuss the Thixotropic
Index test since it is very widespread in practice. This
misnamed test determines the ratio of viscosities measured at
arbitrary high- and low-shear conditions. ASTM Test Method
D 2196 specifies taking the ratio of viscosities measured on
the Brookfield Synchro-Lectric viscometer at two speeds, representing a ten-fold speed ratio. Since only equilibrium viscosities are measured, the test yields no information about
time dependence and should be called the "Shear-Thinning
Index" instead (it is so termed in ASTM D 2196). Its value,
like many quality-control tests, is in its simplicity and "quickand-easy" character, requiting no interpretation. As long as a
given coating formulation changes little, so that the hidden
kinetic factor would be expected to change little, the "Thix
Index" can reveal when something has gone awry (i.e., can be
useful as a gross indicator whether a formulation error has
occurred). However, it is always possible that the recovery
kinetics of the system have changed, which would go completely unnoticed if the "Thix Index" were the only test used to
evaluate the rheology. Below, we will present test methods
which can be virtually as simple as the "Thix Index," but
which give more useful, relevant, and complete information
about thixotropic systems.
Mechanism of Thixotropy
Thixotropy is formally defined as an isothermal, reversible
sol-gel (fluid-solid) transformation [24]. As stated, it is experienced as a viscosity which is both time- and shear-dependent.
Its origin is the breakdown, under shear, of internal fluid
structure to smaller flow units or the reassembly of structure
from smaller units when shear is relaxed.
The mechanism of shear thinning in thixotropic (time-dependent) systems is different from pseudoplastic (time-independent) systems. In pseudoplastic systems, shear thinning is
the consequence of order externally imposed by shear [14]. In
thixotropic systems, an internally imposed, viscosifying
structure exists at rest, and the viscosity falls because of the
collapse of that structure under shear. (Flocculated systems
possess extra mechanisms of energy dissipation [25]; therefore, their viscosity will be higher than that of a deflocculated
dispersion of the same composition.) A further important
difference between the two is in the amount of time the
structure requires to respond to changes in shear rate. In the
case of time-independent systems, rapid structural equilibration quickly accommodates to changes in shear rate. The
accommodation process essentially is particle diffusion,
which is quite rapid for submicron particles (see Shear-Dependent Viscosity). The viscosity (a measure of structure)
342
T
T
OT
o,T
gRLr~ C~'Vr
Time
~1 ~p
time
FIG. 8-(A) Shear rate or shear stress ramp experiment. Shear rate or stress increases linearly
(sometimes logarithmically, optionally) to preselected maximum over a selected sweep time
period, resulting in a given acceleration gradient (~) or stress rate (~-); (B) Thixotropic loop.
Equilibrium structure curve (approximately bisecting loop) corresponds to data from an experiment like that in Fig. 7.
thus always "keeps up" with changes in shear rate for such
systems. For thixotropic systems, the rate of structural reorganization is slower than the experimental rate of change of
shear rate (~) or slow with respect to the time of observation
at constant shear rate. In a "shear rate ramp" experiment (see
below), the structural breakdown always lags behind the
ever-increasing shear rate, so that the viscosity on the "up"
r a m p will be higher than the equilibrium viscosity at a given
shear rate. On the "down" side of the ramp, the rebuilding
structure lags behind the rate of reduction of shear rate, so
that the measured viscosity is always lower than the equilibrium value. Thus, a "thixotropic loop" is seen, the size of
which should be proportional to the structural time constant
for a given r a m p time. Holding the shear rate constant, as in
the description above, allows the structure breakdown process to "catch up." The viscosity then continues to change
until an equilibrium between structural breakdown and recovery rates is achieved (see Fig. 7).
+--o
')'1> 0
~t2< ~1
f f
--~/00
7
Time
FIG. 9-Step-shear method for thixotropic recovery. High
shear rate ~'1 simulates application process, followed by low
shear rate ~'2, emulating film after application. Viscosity recovers from zero-time value ~1(o)with a characteristic time constant 7, eventually reaching final level ~(|
test (Fig. 9). In it, a high shear rate (order of 104 s -1 desirable) is applied to the material, allowing time for the viscosity
(hence, structure) to reach equilibrium; then the shear rate is
suddenly reduced to a very low value (order of 1 s-1). The
equilibrium a m o u n t of structure which can exist at the lower
shear rate is greater than at the previous high shear rate, so
reassembly of fluid structure occurs, accompanied by an approximately exponential rise of viscosity. Meaningful physical constants can be extracted from the data by fitting the
following equation to the recovery curve
-q(t) = ~/(0) + [~(o0) - n(0)] [1 - e -t/v]
(18)
CHAPTER 3 3 - - R H E O L O G Y AND V I S C O M E T R Y
~, s
r/(00),p
~(~)/~,
P/s
Thix
Index
Sag?
With additive
Without additive
8.9
18.2
116
97.3
13
5.4
4.04
4.24
No
Yes
343
Small-Amplitude
Viscoelastic Measurement
Time
FIG. lOa-Viscoelastic characterization of structural recovery
by step-shear method using small amplitude oscillatory strain
for recovery phase.
ts
r--t
E
q
S
v
2
o
O
O~
O3
cY
CL
<
I
~-3
o
O
0.0
I
2.5
I
5.0
7.5
TIME (minutes)
FIG. lOb-Experimental curves of G' (elastic modulus, []) and
G" (viscous modulus, O) versus time for a viscoelastic stepshear experiment.
344
[25,33].
Yield Stress Test M e t h o d s
Startup-of-flow methods include the use of penetrometertype instruments such as a thermomechanical analyzer,
where increasing force is applied to a standard probe. The
yield stress is determined as the break point of a forcepenetration curve [34].
In recent years, a new type of instrument known as a
controlled-stress rheometer has become commercially available that is well-suited to measurement of yield stress and
other properties of structured materials. For this instrument,
the shear stress is the independent (or controlled) variable,
while the dependent (or measured) variable is the shear rate.
This allows an experiment to be done whereby the stress is
gradually increased from zero or a very low value, registering
zero shear rate (i.e., infinite viscosity) until the applied stress
reaches the yield value, whereupon the viscosity becomes
finite. The instrument reports this value as the measured
yield stress. Another recent method employs a special vaned
rotor to remedy problems of slip with yield-stress materials
[35-37]. The vaned rotor consists of rectangular blades or
vanes fixed to a rotating shaft. Advantages of this geometry
are: (1) there is little disturbance of the sample when this type
of probe is inserted, and (2) when the rotor turns, the material moves as a solid "cylinder." Thus, the shear surface is
within the material itself, avoiding problems of wall slip.
Fg = 4 7rR3(pp _ Pl)g;A
4~rR2
~- = -~ (pp - p~)g
where R is the particle radius, pp the particle density, and Pl
the liquid density.
For a titanium dioxide particle of radius 0.2 m m and density 4 g/cm 3, the shear stress due to gravity acting on the
particle is about 0.2 dyne/cm z. To prevent settling of such a
particle, the surrounding m e d i u m need only resist with an
opposing stress of greater than 0.2 dyne/cm z. Even this, alas,
is impossible for a Newtonian liquid, be it water or honey,
since it will flow under all stresses no matter h o w slight (it is
only a question of how slowly). A pigment particle will inevitably settle out of such a fluid, especially for viscosities of
practical magnitudes. However, if the suspending m e d i u m
possesses a yield stress equal to or greater than the particle
shear stress, the particle "thinks" it is suspended in a solid
and will be suspended indefinitely. This a r g u m e n t assumes
more or less ideal yield behavior, which, as described above,
m a y rarely be encountered. A m e d i u m with a measured yield
stress of apparently sufficient magnitude m a y or m a y not
permit the particle to settle over long periods of time due to
the possibility of viscous flow below the apparent yield point.
Therefore, to ensure adequate practical stability, one should
build in a higher yield value than that calculated from the
above.
CHAPTER 33--RHEOLOGY
tural relaxation time (see below) is measurably long. This
structure, and particularly the destruction and rebuilding
process that occurs during and after coating application, can
have great consequences for application and film formation
processes. An example of this is the influence of elasticity on
leveling of an applied coating [38] (see also Massouda [39]
and Glass [40]).
As the term implies, viscoelasticity refers to a material
response which is a combination of viscous and elastic behavior. Viscous flow superimposed on elastic strain results iia the
"relaxation," or gradual disappearance, of stress within the
strained object. This is manifested as an imperfect, or fading,
stress memory. Figure 11 illustrates the material response to
an applied elongational stress for a material with permanent
stress m e m o r y (e.g., rubber band) and one with fading stress
m e m o r y (e.g., "bouncing putty").
The Viscoelastic P a r a m e t e r s a n d Their M e a s u r e m e n t
A convenient way of experimental characterization of viscoelastic materials is by alternating the direction of strain (or
stress). Most often, a sinusoidal deformation is employed
(Fig. 12). The strain amplitude must be kept small so that the
material response remains in the linear viscoelastic region
where stress and strain are linearly related. 8 In perfectly elastic behavior (Hookean spring), the stress and strain are "in
phase" with each other, that is, u p o n deformation, the maxim u m stress and m a x i m u m strain occur at the same instant in
time. If there is any viscous (energy-loss) component in the
material response, the stress and strain maxima will not be
coincident, but will be "out of phase." This happens because
viscous flow relieves the stress within the material, causing
the stress m a x i m u m to occur before the strain maximum.
That is, as the rate of strain decreases near the m a x i m u m (or
m i n i m u m ) of the strain sine wave, stress relaxation "catches
up" and overtakes the stress-building effect of the strain. The
separation in time of the stress and strain maxima is called
the phase shift (orphase angle, the fraction of a complete cycle
in degrees or radians that the phase shift represents). The
phase shift is often given the symbol g. The faster the viscous
stress-relaxation process, the earlier in the cycle the stress
m a x i m u m will occur, i.e., the larger the phase shift will be.
The limiting value of the phase angle for purely viscous liquids is 90 ~ (see Fig. 12). The reason is that, for sinusoidal
deformation, the m a x i m u m strain rate (maximum slope of
the strain sine wave) occurs 90 ~ ahead of the m a x i m u m
strain, and that, for Newtonian liquids, the stress is proportional to strain rate. Therefore, the m a x i m u m stress must
occur at the m a x i m u m strain rate, which corresponds to a
phase shift of 90 ~.
The derivation of viscoelastic parameters from a sinusoidal
shear experiment begins with the calculation of the complex
shear modulus, G* (refer to Fig. 13). This is simply the ratio of
the m a x i m u m stress, ~o, to the m a x i m u m strain, 70 (G* =
%/70). F r o m G* m a y be separated G', the modulus of elasticity (storage modulus), and G", the viscous modulus (loss modulus). Figure 13 demonstrates the geometric relationship of
G* to its in-phase and out-of-phase components, G' and G",
governed by the phase angle, 6. It is obvious from geometry
8This is a requirement because the equations used are valid only in
the linear viscoelastic region.
AND VISCOMETRY
345
rubber band
oB
viscoelastic material
time
FIG. 11-Viscoelastic stress-memory loss: stretch-force experiment. Rubber band is cross-linked polymer, does not relax
stress ((rE) when stretched. Viscoelastic material can accommodate to strain by molecular motion (viscous flow), allowing
elastic stress to decay.
6=o ~
Stress response,
elastic solid
6=90 c
Stress response,
viscous liquid
Time
FIG. 12-Phase shift/~ for ideal viscous and elastic bodies.
(19)
(20)
346
out-of- T
phase axisl
G'
in-phaseaxis
"
Complex
G* = s h e a r stress
modulus
shear strain
Storage
modulus
G' = G ' c o s
Loss
modulus
G"
G'sin
Dynamic
viscosity
O0
-
'YO
(~
I!
'J~'--
(21)
[96]
o-* = % cos 8 cos cot - o-0sin 8 sin cot
(22)
o-osin 8
.
.
~o
o-o sin 8
.
.
Y0co
G* sin 8
G"
co
co
(23)
Viscoelastic Models
It turns out that viscoelasticity can be r a t h e r realistically
m o d e l e d b y simple m e c h a n i c a l analogues. These are useful
not only as an aid to c o n c e p t u a l i z a t i o n of viscoelastic behavior, b u t also in helping to u n d e r s t a n d the e l e m e n t a r y m a t h e matics of viscoelasticity. As we have said, viscoelasticity is a
o-Elastic =
O-Vi . . . . .
( = O-0)
(24)
and
o"T = 6-e = ou
\
\
\
\
\
(25)
CHAPTER 33--RHEOLOGYAND
VISCOMETRY
347
Stress
a0
(26)
oE _
d0-/dt
a0
(27)
(28)
X (='r//e)
TEe
relaxation
time constant
FIG. 15-Stress relaxation (constant strain) experiment. initial elastic stress r o relaxes viscously with a
time constant ,1 ( = ~q/G). A corresponds to the point
where stress has fallen to a value ~role.
rearranging
1 + 602)i 2
do"_
G dt
0-v
(29)
and
G~2,~. 2
(30)
(31)
G' - -
1 + ~o2h 2
(32)
from w h i c h
tan 6 -
G"
G'
~0h
(33)
(34)
(35)
348
\
\
\
\
\
71
72
II
G1
FIG. 18-Burgers model. Symbol definitions same as Fig. 13.
Subscript 1 refers to the Voigt element, 2 to the Maxwell element.
FIG. 16-Kelvin-Voigt
same as Fig. 14.
tan 6 = toh
(36)
(37)
~2
(38)
3'
retarded spring
motion:
"Y(t)= ~0 (l_e-t/X)
Time
FIG. 17-Kelvin-Voigt creep (constant stress) experiment. At
constant applied stress ~ro,strain increases exponentially with
time constant A ( = -q/G).
A
t
(39)
CHAPTER
33--RHEOLOGY
AND VISCOMETRY
349
Strain,
3'
t viscous
flow:
O~QO
.y
t/x)
instantaneous O0 {
strain:
77 =
or,
"Y(t)= ~t
G22
Time
FIG. 19-Burgers creep (constant stress) experiment. Under applied stress ~0, the
Burgers model undergoes instantaneous deformation equal in magnitude to (rolG. In
next segment of curve ("retarded spring motion") strain increases exponentially
with time. Finally, spring is fully extended and viscous flow occurs with a constant
strain rate.
viscous
relaxation:
"Y0G2e-t/x2
_~ unrelaxed stress:
oGi
time
FIG. 20-Burgers model stress relaxation (constant strain). Stress generated by
initial strain ~'o decays exponentially governed by the relaxation time ~ ( = ~/~G2).
Voigt element contributes unrelaxed stress ~r| = ~'oG1.
34.5
0,020
7.75
0.09
0.972
0.67
0.0997
6.95
0.02
34.7
0.01
69.3
As stated before, the process consequences of viscoelasticity stem partly from the stabilization of otherwise unstable
liquid structures by the elastic "extra stress." Thus, liquid
fibers and "webs" which would ordinarily collapse by surface
tension are stabilized, producing, for example, excessive
rollcoat spatter (or "misting") and ribbing, and inhibiting atomization of sprayed materials. The importance of viscoelasticity for a particular process is gauged, using the Deborah
number, by the ratio of the stress-relaxation time constant to
the time duration of the process stress. Of course, both the
magnitude and lifetime of the elastic stress will be important,
for together they will govern the degree of stabilization.
The analysis of the problem is complicated by the fact that
m a n y processes, particularly of coatings application, involve
strain magnitudes outside the range of linear viscoelasticity.
Approaches to nonlinear viscoelasticity exist, but are beyond
the scope of this chapter. Quantitative prediction of viscoelas-
350
tic effects would require the use of a model for the fluid
behavior, or viscoelastic constitutive equation, also outside
the scope of this presentation. However, it is often possible to
build experimental correlations between coating elasticity
and performance problems, so that guidance may be provided for formulation efforts to solve them.
For most modern coatings, in particular, the origin of elasticity is likely to be an associated structure built up from a
dispersed phase rather than polymeric entanglement. Such
particulate flocs are generally shear-sensitive and are reduced
or destroyed by high-shear application processes. The elastic
modulus G' will be seen to decrease with increasing strain
and strain rate outside the linear regime. Thus, in most cases,
G' is a measure of structure that has its greatest effect at low
strain and strain rate (unless the elastic character is highpolymeric in origin). Therefore, under most conditions of
application, structure (therefore elasticity) is destroyed and
must rebuild in the applied film. Herein, it is seen that
thixotropy and viscoelasticity are kindred phenomena.
EXTENSIONAL RHEOLOGY
The other important deformation occurring in coatings
besides simple shear is extensional (or elongational) deformation. Extensional or "stretching" deformation causes an
increase in length and decrease in cross section of an object.
In a simple shear field, particles or polymer coils (i.e., the flow
units) rotate with a velocity ~/2. The rotational motion lessens
the friction between the solvent and solute particles. In an
extensional flow, this rotational accommodation to the flow
field is not possible because there is no velocity gradient normal to the flow direction. The separation of flow units is thus
more costly in terms of energy dissipation due to friction.
Thus, the viscosity of a Newtonian fluid in extension turns out
to be three times greater than its viscosity measured in shear
(Trouton rule).
The extensional viscosity (~e) is calculated as the ratio of
tensile stress to extensional deformation rate
l dt
(40)
~e -
d(lnl)
dt
(41)
E x t e n s i o n a l V i s c o s i t y in C o a t i n g s P r o c e s s e s
(42)
DISPERSION
RHEOLOGY
a~d
It is reasonable that the viscosity of a liquid will be augmented by a factor equal to the product of the particle intrinsic viscosity and the concentration of particles.
(43)
(44)
~z
~~
high-molecular-weight, water-soluble polymers are used
as thickeners. However, they are used at low levels, and their effects
on rheology are mainly colloidal/osmotic rather than as solution
polymers.
351
n,
+ [n]~'
(45)
1 + 2.5~b
(46)
(47)
1 - g-~!
(48)
[6,14].
It should be noted here that, although the dispersion rheology is controlled by the disperse-phase volume fraction, (b,
the effect of the particle phase on the rheology may be greater
than expected on the basis of the volume of material added to
make up the dispersion. This is because the disperse-phase
volume may be augmented by various effects tending to increase the effective particle radius. It is the "hydrodynamically effective" particle volume that determines the
rheology. Thus, the rheological behavior will be found to
scale with the "effective" volume fraction, ~e, rather than with
352
TESTING
[]
MANUAL
]
/
1
~-
~.
o
Lt~ ~
~[
0.00
:
0.15
I
0.30
Volume
I
0.45
I
0.60
0.75
Fraction, ~o
the formulated volume fraction, 4~. The effective particle radius can be increased in a number of ways, often as a consequence of employing various methods of achieving stabilization of dispersions. Adsorption of a polymeric stabilizer
onto the surface of a particle adds the thickness of the stabilizer layer to the particle radius. This layer prevents the close
approach and flocculation of particles by steric interactions
between stabilizer layers, resulting in steric stabilization. If
the thickness of the steric stabilizing layer on the particle is 6,
the effective volume fraction is [63]
~e= q~[1-t- ( ~ ) 3 1
(49)
where R is the original particle radius. Quantitative viscomettic methods have been developed for inferring the adsorbedlayer thickness [63,64].
Aqueous dispersions are often stabilized by association of
repulsive electrical charge with the particle, known as electrostatic stabilization. The charge may be due to adsorption
of ions, anionic or cationic surfactants or polyelectrolytes, or,
in the case of polymer colloids, to the presence of ionizable
groups which are part of the polymer molecules. (In the case
of functionalized polymer latexes, such groups tend to migrate to the particle surface.) The surface ionic charge propagates an electrical potential field into the aqueous phase,
depending on the ionic strength of the medium. In the presence of dissolved counterions, an ionic "atmosphere" develops around the charged particle. These phenomena are the
origin of the so-called electroviscous effects, which have to do
with the way the electrical field surrounding the particle
affects the effective volume fraction or collision cross section,
and the nature of the hydrodynamic interaction between
particle and surrounding liquid [57,65]. Dispersion rheology
can be greatly altered as a consequence of these effects, as the
solution ion concentration or pH are varied. Krieger and
Eguiluz showed the ~/r of a dispersion of uniform polystyrene
latex spheres (4 = 0.4) decreased from 106 to 10 for a twoorders-of-magnitude increase in concentration of electrolyte
[66]. In that study, the low-electrolyte latexes exhibited apparent yield stress behavior, a consequence of the increase of
the effective volume fraction of the latex particles due to the
expansion of the repulsive electrostatic field. The effect is so
great that the particles are actually "locked" into crystalline
arrays that can diffract light, producing striking iridescent
colors. As the electrolyte concentration is increased, the
counterion "cloud" both shrinks the electrostatic field and
shields particle fields from each other. Consequently, the viscosity drops dramatically (remember that the volume change
depends on the cube of the radius change).
Rheology is particularly useful for dispersion characterization because of its sensitivity to microstructure. Dispersion
rheology has two broad aspects: (1) the dependence of viscosity on the concentration of the dispersed phase, and (2) the
dependence of viscosity on shear stress and shear rate, discussed in CLASSES OF NON-NEWTONIAN BEHAVIOR.
To the foregoing are added effects of particle shape, rigidity,
particle size and particle size distribution, and interparticle
forces, both attractive and repulsive. All these factors combine to determine the microstructure of the dispersion and
hence its rheology.
Dispersions can exhibit the full range of rheological behavior mentioned previously, including Newtonian, shear-dependent, time-dependent, plastic, and elastic behavior. A
dispersion of noninteracting spherical particles will be Newtonian up to about q~ = 0.2 [15]. Above this point, onset of
non-Newtonian character begins due to particle interactions
and hydrodynamic factors. Mechanisms for these effects are
discussed in the section entitled Shear-Thinning Fluids.
SAGGING
A coating layer on any but a horizontal surface will experience a tangential shear stress due to gravity of magnitude
"r = pgh cos 0
(50)
(51)
(52)
\
\
T = p g h cosO
x j,
\
\
\
\
T = pg(h-y)
cosO
~-h~
FIG. 22-Sagging, driven by gravitational shear stress.
inner layers. For a coating with a large yield stress, the load
necessary to cause yield and flow is greater. Therefore, the
yield plane moves deeper into the coating layer, leading to a
phenomenon known as slumping. Slumping, therefore, is diagnostic of the presence of a significant yield stress. Figure 23
illustrates the effect of a yield stress on sagging, leading to
plug flow (slumping). Croll [67] showed direct evidence of
plug flow in a sagging coating possessing a yield stress.
The surface velocity of a sagging Newtonian liquid is
v-
pgh 2
(53)
27
(Wu [68] gives sagging velocity expressions for various nonNewtonian rheologies.) Sagging transmits substrate imperfections to the surface and amplifies them [69]. This is because any surface irregularity causes fluctuations in the
effective local coating thickness normal to gravity and therefore in the local sagging shear stress. Furthermore, any local
variations in film thickness due to application or to substrate
features (e.g., a hole or a corner) can produce local accelerations of sagging in which thicker elements overtake thinner
elements. This is a self-accelerating process, leading to drips,
"tears," runs, or "curtaining" [70]. Such undesired flows can
be minimized by proper characterization and control of rheology [71].
xl /
z0
Pg
~-hq~
FIG. 23-Slumping (plug flow), caused by the presence of a
yield stress, ~o-
The sagging of a coating is similar to the problem of drainage of a liquid layer from an inclined surface. The difference
between the two is that, in sagging, the coating layer is assumed infinite in extent; hence, sagging causes no change in
the local coating thickness. If this assumption is not pertinent, then gravitational flow will result in thinning of the
coating layer at the top and thickening at the bottom of a
finite substrate. The distinction between the two processes
may be useful for those desiring to calculate, for example, the
degree of "wedging" on a dipcoated part as against simply
calculating a sag length or sagging velocity. Again, in the case
of sagging, h is assumed constant and a sagging distance x
may be calculated, whereas, for drainage, the thickness h
varies with distance x down the substrate. The equations
describing the flow are otherwise identical and interchangeable. By a derivation similar to that of Wu [68, 72] for sagging,
the expressions below, describing drainage, can be obtained.
For a Newtonian liquid, the thickness at time t at a distance
x down from the upper edge of the liquid layer is given by
h = ~/
fix
pgt cos 0
(54)
The angle 0 is as defined above. Most coatings are non-Newtonian, however, which will have great impact on the drainage behavior. For example, shear thinning fluids will drain to
a much more uniform film thickness than Newtonian fluids.
The gravity drainage of a power law fluid (see Shear-Dependent Viscosity) is given by
The constants n, K, and % are obtained by fitting the Herschel-Bulkley flow model to the experimental flow curve (see
Shear-Dependent Viscosity).
As with leveling, a realistic description of sagging must
include not only non-Newtonian effects, but also effects of
drying, geometry of the applied film, and the instantaneous
rheological state of the applied film. A recent review, analysis,
and experimental study of sagging examines these effects
[67].
l~Note that t = 0 is excluded, since h = ~.
354
o
hf)
o ~--4
hO
ufactured by Leneta) spreads paint stripes of graduated thicknesses over a nonabsorbent substrate. Sag is rated according
to the thickest stripe that does not show sag (Fig. 25). A
similar but somewhat simpler test involves the use of a wire
device that scribes two lines, of 1//8 and 1/4 in. (0.32 and
0.64 cm) width across a 3-wet-mil paint stripe, which is then
hung vertically, and sagging is visually evaluated on the dry
paint film. 12The method is illustrated in Patton [73]. Another
device which has apparently met with some success is the socalled "sagging balance" [74], which uses an electronic balance to measure the shift in mass accompanying drainage of
a coating applied to an inclined plate.
Sagging is, of course, driven by gravitational shear stress.
The sagging shear stress magnitude depends entirely on the
wet film thickness and density (Eq 50). The resulting shear
rate of sagging is determined by the rheology profile of the
paint in question. It is imprecise to attempt to predict sagging
from viscosity measurements at an arbitrary "sagging shear
rate" and may lead to incorrect estimates of relative sagging.
The proper way to predict relative sagging tendency is to plot
viscosity as a function of shear stress rather than shear rate.
Shear stress levels corresponding to the desired wet film
thickness can be calculated, and the magnitude of the viscosity controlling sagging (~sag) determined from the graph. Figure 26 compares two paints in this manner, with indicated
gravitational shear stress levels corresponding to wet film
thicknesses of 3, 6, and 12 mils film thickness indicated. Figure 27 shows flow curves for the same two paints plotted as a
function of shear rate, with the calculated sagging shear rates
at 3, 6, and 12 mils indicated ( ~ / s a g = T s a g / ' / J s a g ) 9 The solid line
in Fig. 27 indicates approximately the shear rate of the
Stormer TM paddle viscometer. The ratio of the viscosities of
the two paints at the Stormer TM shear rate is less than 2,
whereas the ratio computed at the true sagging shear rates is
as high as 6. Clearly, comparison of viscosities measured at
an arbitrary shear rate can lead to incorrect predictions of
relative sagging behavior, particularly if flow curves should
cross over.
LEVELING
.;
FIG. 24-(a) Drainage behavior for Newtonian fluid is represented three-dimensionally as film thickness versus vertical
height versus time. Note that thickness varies strongly with
height, known as "wedging"; (b) Drainage behavior for nonNewtonian (shear thinning) fluid is represented three-dimensionally as film thickness versus vertical height versus time.
Note that thickness is nearly constant with height, showing that
shear thinning rheology can achieve improved film uniformity
in dip coating.
Measures of Sagging
A number of laboratory methods for evaluating sagging
have been used, some of which measure some rheological
property related to sagging behavior [80] and some of which
measure sagging directly. Among the latter are ASTM
D 4400, in which a drawdown blade with multiple slots (man-
i ..... 3ii II
....
i J
c~
9 9149
i 84 84 :
::
: .....
~:
I ......
9 :
:~i
....
! :!:ii ..... i
0~
o
v
o
0~
~>
O
9i
i
O
Shear
R a t e ( s e c -1)
: "
......
i............
101_1J J JJJHIIoJO-~
J JIIJJ{lOJ 1 I J I~HIIIoI2
Shear Stress
I , JlllllloI3
J l iJlJl
[0 4
(dyne/em 2)
FIG. 26-Viscosity versus shear stress for two paints, together with lines indicating sagging shear stress acting on
films of 3, 6, and 12 wet mils thickness. Relative sagging behavior is indicated by the ratio of viscosities at the appropriate film
thickness. From this, #sag = %ag/~sag.
356
Ao
-0
Ax
-AP
AP
u~0
Ax
= a 0" '"'
Ao
-0
Ax
AP
-0
Ax
sumed to be small relative to the roughness wavelength. Assuming a single sinusoidal wavelength (which is a reasonable
approximation since the leveling behavior will be dominated
by the longest wavelength), the Orchard equation is
In at a0
16~4h3trt
3)t40
(57)
2n+--n-l~
s
where o(t) is some time function of viscosity relating effects
of thixotropy, drying, wicking, etc. The effect of time-dependent viscosity on leveling is dramatic, as shown in Fig. 29.
Here, for two different paints, the decay of surface amplitude
is calculated using Eq 58 (Curves A) and Eq 59, together with
an experimentally determined expression for the increase of
viscosity with time due to drying (Curves B). Camina [76]
reported that the viscosity of a drying paint increases exponentially in the initial stages. Therefore, an expression such
as the following would fit drying-viscosity data
o(t) = ooekt
(60)
(61)
CHAPTER 3 3 - - R H E O L O G Y AND V I S C O M E T R Y
357
0
x
0
~a
~d
k.---I
<~
~c5
mS
I
40
o 0
I
120
8 0
I
160
TIME (see)
FIG. 29-Calculated brushmark leveling for two paints, with and without effects of
drying. Curves calculated using Eqs 59 and 60: FI--Paint A, with drying; OmPaint A,
without drying; A--Paint B, with drying; 0 rePaint B, without drying.
for solvent loss through wicking (%ick) and for viscosity increase due to thixotropy (Tthix) (see Thixotropy Test Methods).
Quach [84] has discussed and summarized the shortcomings of various laboratory methods of leveling evaluation. As
noted by Quach, much work on leveling has been done without adequately taking into account the numerous interacting
subprocesses whose final result is the dried film profile. An
additional important factor recently dealt with experimentally and theoretically is the influence of surface tension
gradient-driven flows (Marangoni flows) [78,88,90]. Surface
tension gradients may arise due to a number of causes during
film formation and when present can have consequences for
the course of film leveling, among other things. Figure 30
illustrates the mechanism of surface tension gradient-driven
flow, which can result in the deleveling of an initially level
liquid layer. Local surface tension gradients may develop due
to differential evaporation or to temperature gradients (or
other causes). This results in a surface flow from regions of
low surface tension toward regions of high, in an attempt to
reach surface equilibrium. The moving surface "drags" subsurface liquid along, creating a bulk flow. This is the
Marangoni effect. The driving force for Marangoni flow in the
case of differential evaporation is a shear stress tangent to the
film surface, %, proportional to the strength of the dependence of surface tension on solvent concentration, Oo'/O[S],
and to the magnitude of the solvent concentration gradient,
O[S]/Ox (x is the film coordinate). Hence
~s -
O~r a[S]
-
o[s] Ox
O~r
-
Ox
(62)
the surface tension gradient Oo'/Ox drives the flow. For the
case of Marangoni flow driven by thermal surface tension
gradients, replace O[S] by OT in the above. Persistence of
surface tension gradients until the film is incapable of reflow
+ Ao
-Ao
+ 4o
'
4o
Ax
'
1
~'-
-'*
4k
AP
,1~
Ax
--0
1
f
AO
Ax
AP
Ax ~0
FIG. 30-Deleveling by Marangoni (surface tension gradientdriven) flow. Surface tension gradient (~r/Ox ~ 0) drives surface flow, resulting in bulk flow and deleveling of initially level
surface.
will result in an appearance defect. Overdiep [78] demonstrated (for solvent-based paints) that Marangoni flows initially enhance the leveling rate, but can produce a "rebound"
effect that ultimately worsens film roughness. Wilson [90]
358
recently modeled this behavior by a linear perturbation analysis. Other authors have discussed the importance of
Marangoni flows for waterborne, cosolvent-containing coatings [79,89].
The role of viscoelasticity in leveling has been a subject of
some debate, with some authors concluding that elasticity
enhances leveling [91] and some that it retards leveling
[38, 92]. The evident link between elasticity and the underlying structural rheology for coatings (see Viscoelasticity
a n d Industrial Processes) suggests the presence of a gel-like
structure of some sort in systems possessing significant elasticity. Such a structure would be expected to inhibit flow at
low stress levels so that coatings which exhibit elasticity
should also show poorer leveling. In any case, the leveling
behavior of viscoelastic systems has been modeled by Keunings [38] and the presence of viscoelastic relaxation shown to
retard leveling. The leveling rate, a, as a function of the Newtonian leveling rate, O/Newt, was shown to be
O/ --
O/Newt
(63)
1 + ~tffNewt
the best rheological test for leveling should most closely simulate the application experience of the paint. This means: (1)
the paint should experience shear rates/stresses of similar
magnitude and duration to those of the application process;
(2) the shear rate/stress should then be step-changed to values
representative of the leveling process; (3) the change of viscosity with time should then be followed under the latter
conditions. This protocol is essentially identical to the "stepshear" method of characterizing thixotropic recovery described in Thixotropy Test Methods. This kind of procedure
is most easily accomplished by employing a rheometer capable of "job streaming" or "linked methods." However, the
foregoing method still suffers from the limitation that the
effect of drying on viscosity during the leveling period is
neglected. Figure 29 demonstrates that this can be a very
significant effect. Paints "A" and "B" were commercial formulas which differed markedly in leveling performance. The
increase of viscosity with time during drying of a film of
typical applied thickness was measured for both and found to
obey Eq 60. The latter expression was then inserted into Eq
59 as the time-integral function for viscosity (as described in
the previous section) and the leveling curves in Fig. 29 were
calculated. There are two curves for each paint, one showing
how the paint levels without the effect of drying, and one
calculated taking the increase of viscosity due to drying into
account. The effect of drying is most dramatic on Paint B,
where the reduction of surface roughness achieved after 3
min decreases from 50 to 10%.
It is established that leveling shear stress decays exponentially as leveling progresses [80]. A controlled-stress
rheometer with programmable logarithmic stress ramps offers the ability to simulate the variation of viscosity with
realistic shear-stress decay using variable ramp times.
Leveling efficiency might then be judged by numerically integrating the fluidity over the "leveling" period.
Measures of Leveling
|
do~
(64)
RHEOLOGY INSTRUMENTATION
There are a great many instruments that have been devised
to measure viscosity or "consistency." However, a number of
them have in common a serious limitation in their design
15ATISystems, Inc., P.O. Box 71460, 32355 Howard Street, Madison Heights, MI 48071.
CHAPTER 3 3 - - R H E O L O G Y AND V I S C O M E T R Y 3 5 9
which makes them generally unsuitable for measurements of
non-Newtonian fluids. The importance of this issue becomes
apparent when it is realized that the majority of coatings and
coatings components are non-Newtonian, yet m a n y laboratories continue to use methods which are not suited for such
materials. The difficulty with m a n y of the "traditional" laboratory viscometers is that the "flow field" (the total description of the trajectories of the fluid elements) is complex and
not subject to practicable mathematical description. The resuit is that an accurate strain rate cannot be calculated.
Therefore, even if the stress is known, the true viscosity cannot be obtained. Furthermore, the shear field is often so nonuniform that, for non-Newtonian materials, the viscosity of
the material itself varies within the test sample. For complex
flow fields, such an error cannot be corrected. The measurement error will be in proportion to the deviation from Newtonian character. Nevertheless, such instruments have been
in use throughout the industry for decades and no doubt will
continue to be used for the foreseeable future. The approximate measurement given is s o m e h o w related by the practitioner to something believed relevant to the performance.
One suspects that when the result is contradictory, as is probably often the case, it is either ignored or "worked around."
We shall refer to this type of device as a "Q/C (quality control)
instrument" or a "qualitative viscometer." It should be emphasized that these instruments are accurate for Newtonian
or near-Newtonian materials and are generally useful as Q/C
test devices even when the measurement is approximate.
However, the practitioner should be alert to situations where
their deficiencies can be of significance.
In years past, m a n y coating fluids were nearly Newtonian,
which accounts in part for the success of Q/C-type instruments. As alluded to before, it is very easy to characterize a
Newtonian fluid. Virtually any type of flow measurement device m a y be used to obtain accurate information on the viscosity of such a material provided the device used is
calibrated with known standard fluids and the temperature is
controlled. It is not even necessary to know the shear rate of
the measurement since Newtonian fluid viscosity is independent of the shear rate. Consequently, Newtonian viscosity
measured by any test is valid for all process conditions (except turbulent flow). Even instruments which measure viscosity according to some arbitrary scale m a y be used since
they m a y be calibrated in absolute units using Newtonian
standard fluids.
A requirement for an instrument to measure non-Newtonian fluids properly is that the flow field within the test fluid
be viscometric, defined as "everywhere indistinguishable
from steady simple shear" (or other ideal deformation) [1].
Instruments which measure under such well-controlled conditions we will call "research instruments." Nonviscometric
flows such as tube flow can be used for non-Newtonian fluids
when necessary corrections are applied.
Q/C INSTRUMENTS
These are of three types: (1) efflux devices, (2) rotational
devices, and (3) obstructed-flow devices (following Barnes
et al. [94]).
Rotational Devices
Stormer TM Viscometer
The widely-used Stormer 16Viscometer was one of the earliest controlled-stress rotational viscometers. Rotors of various
geometries are available, but the "paddle" rotors, in which
two paddles are attached in offset fashion to a rotating shaft,
are exclusively used for the measurement of the consistency
of paints. During a measurement, the rotation is driven by a
16The name "Stormer" is a trademark of the Thomas Scientific
Company.
360
ICI Rotothinner
10
15
20
25
Measurement Number
FIG. 31 -Ford cup viscosity data taken with and without temperature control of the cup. Test temperature was 130~ (54~
free-falling weight attached to a string and pulley arrangement, the string being wound around a drum. The shear
stress is varied by use of different weights. A counter tallies
up the number of revolutions as the weight falls. After the first
ten revolutions, the time required for the next 100 is measured. (Stroboscopic timers are available.) The apparent viscosity is calculated from a plot of applied torque versus rotor
rpm. The measurement is also made in terms of the weight,
W, required to achieve a rotational speed of 200 rpm. The
viscosity is obtained according to an arbitrary scale called
"Krebs Units" (KU). A conversion table of W versus KU is
supplied. As with any viscometer whose measurement geometry is complex, an absolute viscosity (i.e., in engineering
units of poise or pascal-seconds) cannot be calculated with
this instrument for non-Newtonian fluids. The Stormer viscometer is specified in a number of standard test methodsJ 7
For its purpose, i.e., to measure the in-can "feel" of paint,
the Stormer is a very good viscometer, that is, the Stormer
measures while stirring the paint with a constant force, just
as the consumer would. Thus, the instrument satisfies the
criterion of measuring under conditions closely approximating those of the process. This justifies the use of an arbitrary measurement scale, in this case, and makes the Stormer
a valuable component of the paint laboratory. The only caveat would be not to violate the above-mentioned principle by
attempting to use Stormer data to predict paint performance
17Testmethods include ASTMD 115,D 562, D 816, D 856, D 1084,
D 1131, D 1337, D 1338, and Federal Test Methods 3011.1, 3012,
3018, 3019, 3022, and 4281.
Obstructed-Flow Devices
These are gravity-driven instruments in which flow is due
to density differences between the test fluid and a falling
object (falling ball viscometer, falling needle viscometer) or a
rising bubble (bubble tube viscometer). In each case, the fluid
has to flow around the moving object; hence, they are classed
as obstructed-flow devices. In the falling ball and rising bubble instruments, the flow field is complex with the conse18The Thomas-Stormer ETS-1000 is available from the Cannon
Instrument Company.
(Ps - P,)gd2
18U=
(65)
Rising-Bubble Viscometers
If certain flow field assumptions are made for a rising air
bubble in a liquid, the viscosity of the liquid can be calculated
from [42]
-
1 pgR 2
3 v
(66)
361
RESEARCH
RHEOMETERS/VISCOMETERS
Instruments
362
~A0-1) _ ~A(T2)
(67)
%(r
_ "~o,8
~/B(T)
~0.~
(68)
Inertia Correction
It can be p a r t i c u l a r l y i m p o r t a n t for r o t a t i o n a l r h e o m e t e r s
of the controlled-stress type to correct the d a t a for inertia
error. If the test fluid is low in viscosity, and/or the test r o t o r
has a large m o m e n t of inertia, a n d / o r the acceleration is too
high (short r a m p time), a significant p o r t i o n of the applied
torque is dissipated not viscously, b u t in the acceleration of
the rotor. A c o r r e c t i o n for this e r r o r has been p u b l i s h e d by
Krieger [100]. S o m e c o m m e r c i a l controlled-stress instrum e n t s n o w feature on-line inertia correction.
Brookfield Viscometers
Brookfield Synchro-Lectric
The Brookfield Synchro-Lectric v i s c o m e t e r utilizes a set of
spindles o r disks as the rotor/sensor, w h i c h are r o t a t e d in the
test fluid at selected rpm's, so that the a p p a r e n t viscosity m a y
be m e a s u r e d at several s h e a r rates to o b t a i n a flow curve. Its
advantages include low cost, simplicity of use, ease of cleaning, a n d durability. The i n s t r u m e n t is in wide use t h r o u g h o u t
the i n d u s t r y a n d is the basis for a n u m b e r of ASTM test
methods. 22 It is i n c l u d e d here in the list of "research quality"
viscometers b e c a u s e the viscosity can be r e p o r t e d in absolute
units over a range of s h e a r rate, a l t h o u g h often it is not (see
below). Its limitations include the latter fact, plus that tem21This would also hold true of the Burgers correction to the parallel-plate viscosity of non-Newtonian fluids for the same reason.
22These include ASTM D 115, D 816, D 1076, D 1084, D 1286,
D 1337, D 1338, D 1417, D 1439, D 1638, D 1824, D 2196, D 2364,
D 2393, D 2556, D 2669, and Federal Test Method 4287.
ICI cone and plate viscometer, but represents an improvement in that it is capable of variable shear rate m e a s u r e m e n t
(to 24 000 s - 1). It also provides a digital display of viscosity
and temperature as well as a data interface to a personal
c o m p u t e r or data logger with applications software.
Falling-Needle V i s c o m e t e r
This is an "obstructed-flow" device which utilizes a long,
slender needle as the falling object. In so doing, it overcomes
the objections to the falling ball viscometer while retaining
the latter's simplicity of operation and relatively low cost
[103]. The needle is hollow (allowing a wide range of needle
densities) with hemispherically capped ends. E n d effects due
to the finite needle length are mathematically correctable.
This geometry produces a well-behaved flow field known as
"annular-ducted flow," with the central tube (needle) moving
at constant velocity. Because of the well-defined flow field, the
true velocity gradient between the needle and container wall
can be obtained, and the instrument therefore is suitable for
measurements of non-Newtonian fluids [104]. The fallingneedle viscometer m a y be especially useful for determination
of very low shear stress or shear rate behavior of non-Newtonian fluids, for example the zero-shear viscosity (Region I
of Fig. 3) and measurement of yield stresses [105]. 23
Capillary V i s c o m e t e r s
Capillary tube flow is a classical viscometric method which
is useful for coatings in two main ways. Capillary viscometry
is the method of choice for measurement of intrinsic viscosity
(ASTM Method D 445) (see also D I S P E R S I O N R H E O L OGY) and also the measurement of very high shear rate
rheological properties (see below).
For fluid flowing through a tube, the shear stress at the tube
wall is
rw -
APR
2L
(69)
363
~/w -
4Q
~rR3
(70)
rw
Tw
r
- - 8LQ
(71)
which is the well-known Hagen-Poiseuille equation. For applied pressure-driven capillary flow, particularly for highshear measurements, a correction to Eq 71 is required because the fluid undergoes a large acceleration as it enters the
capillary. Therefore, part of the energy loss represented by
the pressure drop Ap is in accelerating the fluid. This would
result in a calculated viscosity which is too high and so
necessitates a subtractive term or kinetic energy correction
23A new ASTM method for falling-needle viscometry is D 5478.
364
n - - -
(72)
m =
(4n + 2)(5n + 3)
(73)
~q
p
(74)
l d ( l o g ~ a ) ] -1
-4 d(log %) d
(75)
Manufacturgr/
Vendor~
Price
Rangeb
Viscosity
RangC (mPa.s)
Shear Rate
RangC (s-l)
Test
Geometrya
Temperature
Range, ~
ACA S y s t e m s Oy
1-55 000
to 106
Tube flow
20-90
Bohlin
Instruments
Bohlin
Instruments
Brookfield
Engineering
Brookfield
Engineering
TA I n s t r u m e n t s
Mettler
Mettler
0.1 - 1011
10 - 3_ 104
CP,PP,CC
- 150- 350
0.1-108
10 5-104
CP,PP,CC
1- l06
ca. 1-102
CP,CC
5 0 - 3 0 000
150-24 000
CP
- 15-250
RT-400
RT
RT-300 f
5-75
E
E
C
0.1 - 109
10 3_ 10 s
3 - 3 7 800
10- 6_ 10 4
10- 4-260
26-1290
CP,PP,CC
CC
CC
- 100-400
0-150
0-80
Mettler
0.6-106
0.06-10 500
CP,CC
-10-400
Haake/Fisons
Haake/Fisons
Haake/Fisons
Haake/Fisons
Stony Brook
Scientific
E
E
E
D
B
0.1 - 107
0.1-108
0.1-6 108
1-107
0.3 - 10 4
0.01 - 103
1-40 000
10-2-3000
4-6000
10- 4_ 103
CC
CP,PP,CC
CP,PP,CC
CP,CC
A n n u l a r flow
5-95
-50-300
-50-350
- 30-200
- 40-150
Paar-Physica
0.8-107
102-106
T u b e flow
-20-150
Paar-Physica
C-D
1-3
107
0 . 1 - 5 0 000
CP,PP,CC
-60-500
Paar-Physica
D-E
1-3
1012
CP,PP,CC
- 60-500
Tube flow
0.4-95
Bohlin
Instruments
TA I n s t r u m e n t s
0.005-5000
10- 3_
50 000
0.1-1000
1-10 la
10 4_ 104
CP,PP,CC
- 100-500
Brookfield
Engineering
Pen-Kern
0.6-750
CP
- 15-100
...
250 h
10-60
Rheometrics
D-E
0.1-109
10 5-104
Acoustic
wave
CP,PP,CC
Rheometrics
Rheometrics
E
D
1- 10 s
30-106
10 2_ 104
10- 2_ 104(~)
1-105(~)
CP,PP,CC
O p p o s e d jets
a n n u l a r flow
-40-150
RT-350
0-100
0-100
from the signal transit time and used to calculate the shear
elastic modulus according to
G' = pv2
APPENDIX
(76)
366
(609) 655-4447
Brookfield Engineering Laboratories, Inc.
240 Cushing Street
Stoughton, MA 02072
(617) 344-4310 o r 344-4313
C. W. B r a b e n d e r I n s t r u m e n t s , Inc.
50 E. Wesley Street
P.O. Box 2127
S o u t h Hackensack, NJ 07606
(201) 343-8425
BYK-Gardner, Inc.
1100 East-West H i g h w a y
Silver Spring, MD 20910
(301) 589-4747
(800) 343-7721
Cannon Instrument Company
P.O. Box 16
2138 High Tech R o a d
State College, PA 16804-0016
(800) 533-6232
Haake/Fisons, Inc.
53 W e s t Century R o a d
P a r a m u s , NJ 07652
(201) 265-7865
Kayeness, Inc.
115 T h o u s a n d Oaks Blvd.
Suite 101, P.O. Box 709
Morgantown, PA 19543
(215) 286-9396
Mettler I n s t r u m e n t C o r p o r a t i o n
Princeton-Hightstown Road
Box 71
Hightstown, NJ 08520-0071
(609) 448-3000
Paar-Physica USA, Inc.
400 R a n d a l W a y B-207
Spring, TX 77388
(713) 350-3576
Pen Kem, Inc.
341 A d a m s Street
Bedford Hills, NY 10507
(914) 241-4777
Rheometrics, Inc.
One P o s s u m t o w n R o a d
Piscataway, NJ 08854
(201) 560-8550
S h e e n I n s t r u m e n t s Ltd.
Sheendale R o a d
Richmond, Surrey
E n g l a n d TW9 2JL
S t o n y B r o o k Scientific
914 F i l l m o r e Rd.
Norristown, PA 19403
(215) 584-9632
TA I n s t r u m e n t s , Inc.
109 Lukens Drive
New Castle, DE 19720
(302) 427-4000
T h o m a s Scientific
99 High Hill R o a d
P.O. Box 99
Swedesboro, NJ 08085-0099
(609) 467-2000
(800) 345-2100
REFERENCES
[1] Dealy, J. M., Rheometers for Molten Plastics, Van Nostrand
Reinhold Co., New York, 1985.
[2] Smith, N. D. P., Orchard, S. E., and Rhind-Tutt, A. J., Journal
of the Oil and Colour Chemists Association, Vol. 44, 1961, p.
618.
[3] Bingham, E. C., U.S. Bureau of Standards Scientific Paper No.
278, 1916.
[4] Casson, N., in Rheology of Disperse Systems, C. C. Mill, Ed.,
Pergamon Press, New York, 1959.
[5] Asbeck, W. K., Official Digest, Federation of Societies for Paint
Technology, Vol. 33, No. 432, 1961, p. 65.
[6] Krieger, I. M., "Rheology of Polymer Colloids," Polymer Colloids, R. Buscall, T. Corner, and J. F. Stageman, Eds., Elsevier
Applied Science, New York, 1986.
[7] Choi, G. N., "Rheology of Sterically-StabilizedModel Colloidal
Dispersions," Ph.D. thesis, Case Western Reserve University,
Cleveland, OH, 1982.
[8] Lapasin, R. and Torriano, G., "Rheological Models Suitable for
Application in the Paint Field," Proceedings, 18th FATIPEC
Congress, Venice, Vol. 4, 1986, p. 1.
[9] Sisko, A. W., Industrial and Engineering Chemistry, Vol. 50,
1958, p. 1789.
[10] Hieber, C.A. and Chiang, H.H., "Shear-Rate-Dependence
Modeling of Polymer Melt Viscosity," Polymer Engineering and
Science, Vot. 32, No. 14, 1992, p. 931.
[11] Sorbie, K. S., Clifford, P. J., and Jones, E. R. W., Journal of
Colloid and Interface Science, Vol. 130, No. 2, 1989, p. 508.
[12] Laven, J. and Stein, H. N., Journal ofRheology, Vol. 36, No. 3,
1992, p. 497.
[13] Jenekhe, S. A., Polymer Engineering and Science, Vol. 23, No.
15, 1983, p. 830.
[14] Mewis, J. and D'Haene, P., "Prediction of Rheological Properties in Polymer Colloids," Makromolecular Chemistry, Macromolecular Symposium, Vol. 68, 1993, p. 213.
[15] Krieger, I. M. and Dougherty, T. J., "A Mechanism for NonNewtonian Flow in Suspensions of Rigid Spheres," Transactions of the Society of Rheology, Vol. 3, 1972, p. 137.
[16] Boersma, W. H., Baets, P. J. M., Laven, J., and Stein, H. N.,
Journal ofRheology, Vol. 35, No. 6, 1991, p. 1093.
[17] Toussaint, A., "Choice of Rheological Model for Steady Flow,"
Progress in Organic Coatings, Vol. 21, 1992, p. 255.
[18] Petit, L. and Noetinger, B., Rheologica Acta, Vol. 27, 1988, p.
437.
[19] Hoffman, R. L, Transactions of the Society of Rheology, Vol. 16,
1972, p. 99.
[20] Boger, D. V. and Waiters, K., Rheotogical Phenomena in Focus,
Elsevier, New York, 1993, p. 147.
[21] Cheng, D. C.-H., "Viscosity-Concentration Equations and Flow
Curves for Suspensions," Chemistry and Industry, 17 May 1980,
p. 403.
Industrial & Engineering Chemistry Product Research & Development, Vol. 24, No. 3, 1985, p. 412.
[49] Soules, D. A., Fernando, R. H., and Glass, J. E., "Dynamic Uniaxial Extensional Viscosity Effects in Roll Application I. Rib
and Web Growth in Commercial Coatings," Journal of Rheology, Vol. 32, No. 2, 1988, p. 181.
[50] Soules, D. A., Dinga, G. P., and Glass, J. E., "Dynamic Uniaxial
Extensional Viscosity: Response in Spray Applications," ACS
Symposium Series, 1991, No. 462, Chap. 20, p. 323.
367
368
[99] Gleigle, W., "Rate- or Stress-Controlled Rheometry," Techniques in Rheological Measurement, A. A. Collyer, Ed., Chapman & Hall, New York, 1993.
[I00] Krieger, I. M., "The Role of Instrument Inertia in ControlledStress Rheometers," Journal ofRheology, Vol. 34, No. 4, May
1990, p. 471.
[104] Park, N. A. and Irvine, T. F., Jr., Reviews of Scientific Instruments, Vol. 59, No. 9, 1988, p. 2051.
[105] Park, N. A., Irvine, T. F., Jr., and Gui, F., Proceedings, Xth
International Congress on Rheology, Sydney, Australia, Australian Society of Rheology.
[106] Maron, S. H. and Krieger, I. M., Rheology: Theory andApplications, F. R. Eirich, Ed., Vol. 3, Academic Press, New York,
1960, p. 127ff.
[107] Krieger, I. M. and Dodge, J. S., Society of Petroleum Engineers
Journal, September 1967, p. 259.
BIBLIOGRAPHY
Collyer, A. A., Ed., Techniques in Rheological Measurement, Chapman
& Hall, New York, 1993.
Collyer, A. A. and Clegg, D. W., Eds., RheoIogical Measurement, Elsevier Applied Science, New York, 1988.
Eirich, F. R., Ed., Rheology: Theory and Applications, Academic Press,
Inc., New York, VoL 1, 1956, Vol. 2, 1958, Vol. 3, 1960, Vol. 4, 1967,
Vol. 5, 1970.
Lee, L. H. and Copley, A. L., Proceedings, Fourth International Conference on Rheology, Providence, 1963, Parts 1-4, Wiley-Interscience, New York, 1965.
Onogi, S., Ed., Proceedings, Fifth International Congress on Rheology, Kyoto, 1968, Vols. 1-4, University Park Press, Baltimore,
1970.
Ross, S. and Morrison, I. D., Colloidal Systems and Interfaces, John
Wiley & Sons, New York, 1988.
Strivens, T. A., "An Introduction to Rheology" and "The Rheology of
Paints" Paint and Surface Coatings: Theory and Practice, R.
Lambourue, Ed., Halsted Press (J. Wiley & Sons), New York, 1987.
Walters, K., Ed., Rheometry: Industrial Applications, Research Studies Press (J. Wiley & Sons), New York, 1980.
MNL17-EB/Jun. 1995
Surface Energetics
by Gordon P. Bierwagen 1
NOMENCLATURE
a
A
b
c
c~
Cio
D
%
f
g
G
h
h
i
k
l
l
n
n
n
n,
0
p
p
pr
Q
q
r
r
R
RI, R 2
s
L
X
V
v
V
W
7
F, Fi
8f
A
~1
A
/xi
~r
0
O
INTRODUCTION
SURFACES ACT AND PERFORM differently from bulk materials
because they have two distinct properties that are not true of
bulk materials. First, because of unbalanced forces on molecules or atoms at a surface as compared to the bulk, those in
the surface have an excess free energy [1] (i.e., they are in a
higher state of potential energy). This excess energy per unit
area is the t h e r m o d y n a m i c cost of forming a new surface and
has the units of energy/area, or force/length. These latter
units are those of tension, and the surface excess free energy
is often known as surface tension and can be measured for
liquids as such. (A more detailed discussion of this excess free
energy identified with a surface, including the thermodynamic definition of surface tension, is given below.) Second,
there is a preferred direction normal to the surface that can
be defined in the mechanical definition [2] of surface tension.
This directional effect of surfaces can be observed in molecular directionality in adsorption phenomena, surface area
minimization by surface tension effects, and molecular ordering in Langmuir-Blodgett films deposited from ordered
mono-molecular layers (monolayers).
Surfaces occur only when there is an energetic cost to
creating an interface between two dissimilar materials or
phases. Thus, there are no stable interfaces between gases,
between supercritical fluids, nor a m o n g phases in a material
above its critical point. However, surfaces can occur between
gas and liquid (g/l), liquid and liquid (1/1), gas and solid (g/s),
liquid and solid (l/s), and between solid and solid (s/s). An
example of a gfl interface is the surface of a pool of water, and
so forth. Liquid surface energy p h e n o m e n a can be analyzed
directly by equilibrium thermodynamics because a liquid
369
Copyright9 1995 by ASTM International
Velocity
Volume
Weight
Liquid surface tension
Surface excess concentration, of i th species
Final film thickness in dip coating
Difference
Dielectric constant
Viscosity
Wavelength
Chemical potential of species i
3.141 59
Contact angle
Density
www.astm.org
370
TESTING
MANUAL
SURFACE T H E R M O D Y N A M I C S ~ B A S I C S
where G, T, S, V, p, P-i and ni are the thermodynamic quantities Gibbs free energy. Temperature, entropy, volume, pressure, chemical potential of component i, and the number of
moles of component i, respectively, and 7 and A are the surface tension and surface area. The other equations of thermodynamics can be similarly modified. As can be seen, the
energetic cost of expanding a liquid surface is the 7dA term.
As pointed out above, this use of 3' is valid only for liquid
interfaces. Another equation for 7 is the mechanical definition of Ref 2, also discussed by Adamson [1] and reviewed by
Burshtein [7] and Navascues [8] as
v=f_~a(p- pr)dn
(3)
(4)
- "~,iridl.J,i
(5)
where Fi is the surface excess concentration value for component i [11]. This equation gives the relationship between the
surface tension of a fluid interface and the amounts of surface
active materials (hereafter referred to as surfactants) in the
solution (component i). The surface excess concentration F i
is the difference between the actual and bulk concentrations,
c~ and ci0, of component i and can be calculated in a manner
analogous to Eq 3 as
ri
Liquid Surfaces
(2)
f_a
(Ci - Cio) dx
(6)
CHAPTER 3 4 - - S U R F A C E E NE R G E T IC S
371
iiii)Vapor
]ii i!i i i i!i i i i i i i i i i i !i i i i l~
~+a::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::l I:) I
n-direction
'
TangentialPressure Jiiiiiiiiiii!~iiiiiiiiiiiiiiiiililili~i~~
I
aegionby Interface ii i i i!!i!i ii i i i i i i i i i i!!ii i i i i ii i i i i i i i i i:::
iiLiquidiiiiiiiiiiiiiiiii!!iiiiiiiiiiiiiiiii!iiiiiiiiiiiiiiiiiiiiiiii
~,-ffl~-#)an
FIG. 1-Schematic of local pressure changes at surface giving surface tension.
It
Interracial Layer
0
n
Q
nc(x)
t
r
t
i
0
n
i<
Overlying Fluid
Bulk Liquid
%
x
> +
372
dv _
dlnA
dv
dlnF
(7)
CMC
%=
- (d~,/d In F)
[1 + (h/2)(dc/dF)]
Angles
3_SurfaceTension
~N~4-Equlval.entvlty
~
C C
Surfaotant Concentration
FIG. 3-Schematic of physical property changes in surtactant
solution at critical micelle concentration (CMC).
(10)
where %t, %v, and 7zv are the solid/liquid, solid/vapor, and
liquid/vapor surface tensions, respectively, and O is the contact angle formed between the liquid and solid [9,22]. This is
shown in Fig. 4 and discussed extensively in the references
given above. The contact angle between a liquid and a solid is
in some ways a measure of the difference in surface energies
of the solid and liquid. If a liquid "wets" a solid, the contact
angle is zero, and the liquid spreads spontaneously over the
surface of the solid, displacing air in contact with the solid
surface. If the contact angle is greater than zero, a liquid will
not wet and spread on a solid. An extreme example of this is
found with Teflon TM, which is of such a low surface energy
that it is wet by few pure liquids or solutions. In general, pure
2-OsmoticPressure
Property
(9)
J
Physioal
(8)
CHAPTER 3 4 - - S U R F A C E E N E R G E T I C S
hydrocarbon and fluorocarbon interfaces that are nonpolar
in nature have very low surface energies and are difficult to
wet, while polar materials such as metals and metal oxides
have high surface energies and are easily wet. Oils or other
impurities on the surface of a polar substrate will cause the
material to act as a low surface energy solid, making it difficult to wet. There is extensive qualitative discussion in the
literature concerning polar and nonpolar contributions to
surface energetics, much of it of value only in a qualitative
sense as a guide to interpreting the wetting behavior of pure
liquids. Good and Fowkes have both published extensively in
this area (see Refs 1 and 23 for a more complete listing of
these citations), and the literature is full of equations of
arguable theoretical value invoking empirical relations between composition and surface energetics, including acidbase interactions [23]. In coatings application, it is very crucial to have the liquid coating wet the substrate. Substrate
cleaning and the use of surfactants to depress the liquid
coating surface tension and reduce the contact angle to zero
are two of the most common steps to achieve this. It is
essential to have this wetting of the substrate to obtain good
adhesion of the coating to the substrate, hence the importance of proper surface preparation for coatings use.
Rough surfaces tend to have lower contact angles than
smooth surfaces of the same composition [24]. This is why
sanding or other surface roughening will give better wetting
of a material by a coating. There is also often a difference in
the contact angle measured by an advancing drop and a
receding drop, the advancing angle being the larger. This is
often due to surface roughness, causing a hysteresis in the
contact angle [25]. Surface compositional differences and
their scale have also been shown to give hysteresis, both by
themselves and together with surface roughness [26]. These
literature references, plus many others (see Ref I for a more
complete discussion), indicate the difficulties in obtaining
completely unambiguous contact angle measurements, especially when considering both advancing and receding drops
on solid surfaces. Zisman and coworkers have also shown
that there is a "critical surface tension" characteristic of a
given surface [27]. This is determined by plotting the cosine
of the contact angle O versus surface tension and extrapolating to cos O = 1 (zero contact angle) and determining the
surface tension at this value. This is often used to determine
the relative surface energy of a solid and the surface tension
required of a wetting liquid for that surface. Pure liquids can
be used as test liquids for the measurement of critical surface
tension, or surfactant solutions can be utilized [13,28]. Some
precautions need to be taken on the choice of test liquids as
the polarity of the test liquid may influence measurements
and thus the extrapolation procedure used to estimate the
critical surface tension (see Ref 1 for further details).
Exposure to exterior weathering has been noted to decrease contact angles of organic coatings and other polymeric
films [29]. Similar effects are noted when these surfaces are
modified by corona or flame treatment, and these treatments
are often used to give wetting and adhesion of coatings to
hard-to-wet plastic substrates such as polyethylene and polypropylene. In addition to these surface treatments, it has been
found that certain chlorinated olefinic polymers improve the
wetting and adhesion of coatings to polyolefin plastics [30].
373
D Y N A M I C P R O P E R T I E S OF LIQUID
SURFACES
When fresh surfaces are formed in a liquid solution, such
as in coatings application processes, manufacture, etc., the
surface tension and composition of the fresh surface of a
solution will be different from the equilibrium value. At the
time of new surface creation, the surface tension of the liquid
will be nearly equal to the surface tension of the pure solvent
at the instant of the surface formation. The surface tension
then decreases as the surfactant in the solution diffuses to the
interface. The dynamics of the diffusion from bulk to interface, or vice versa in the case of surface compression, has
been well studied, initially by Ward and Tordai [31] and later
by Sutherland [32], Hansen [33], Joos [34], and others. There
are also possible complicating effects if the adsorbing material is polymeric, for which case additional time-dependent
changes in the surface tension may occur as the polymer
molecules relax to their equilibrium conformation at the surface, or if there is an energy barrier to adsorption of the
material [35,36]. Special methods have been developed to
measure dynamic surface tension, and these are discussed
below, along with static surface tension measurement methods. It is especially important to consider and eliminate dynamic surface tension effects if one is trying to measure the
equilibrium value of ~7(t) for t --~ o0],meaning for example, a
Wilhelmy plate rather than a Du Nuoy ring is the appropriate
measurement for systems that are other than pure liquids.
These dynamic effects are especially important in coating
application processes and all coating operations that generate fresh surfaces [37]. There are also dynamic effects in the
wetting of surfaces that must be considered for coating application operations. The first is the dynamics of wetting in thin
film spreading as discussed by de Gennes [38]; the other is the
dynamics of contact angles on moving substrates [39].
M E A S U R E M E N T OF T H E S U R F A C E
T E N S I O N OF L I Q U I D S
Introduction
There are many ways of measuring surface tension, but in
essence, they are all related to two effects of capillarity. The
first effect is the excess pressure due to surface tension at a
curved interface. This is described by the Young-Laplace
equation as
Ap -= T(1/R, + 1/R2)
(11)
Ap = 2T/r
(12)
(13)
374
<--r
i _ _
Du Nuoy Ring
Applying Eq 13 to the case where the object is a ring being
pulled from the surface of a liquid, one has
Static Surface T e n s i o n M e a s u r e m e n t s
W = Wnng + 41r?R
(16)
Capillary Rise
There will be a pressure on a liquid in a small capillary tube
relative to the pressure on a large vessel of the liquid. Using
Eq 12 and allowing for the contact angle between the liquid
and the capillary, we have at equilibrium between the force of
gravity and the capillary pressure
/
/
/---/
/-/
/_--_/
/
/ - - /
//
-/-_-/
/-/
/ -/-/-/
-
Apgh - 2 ? c o s O
r
(14)
--
/
/
/
/
/
/ -- /
/--1
/--I
/_--/
/-- I
/--/
~--~_<z~
Drop Weight
The weight of a drop when it is formed slowly is the weight
just to exceed the force of surface tension times the radius of
the capillary tip from which it is formed, with a correction
factor required for the formation of small satellite drops.
Thus, one has
W--
2r
(15)
375
To a force m e a s u r i n g
balance
Wilhelmy Plate
If one uses a thin plate instead of a ring a n d m e a s u r e s the
force exerted on the plate just touching the surface of a liquid,
one has
W
~---
(17)
(17a)
To Force
Balance
-]
I
_~_. . . . . .
376
///.
f///
i/.-/~
i-//~ I
~
~ ._____ _
P e n d a n t drop profile
FIG. 9-Schematic of sessile and pendant drop methods of measuring surface tension,
To
Pressure Tranducer
37b2~
~1 + 2 - - ~ ]
(18)
3'app =
6rh 2 (1 + 5w2ral3h
2 ]
where p is the liquid density, vis the velocity of the jet, h is the
wavelength of the oscillation, r is the sum of the minimum
and maximum diameters, and b is their difference [1]. This
dynamic measurement of 3' has been considered by Vijian
and Ponter [46], who give references to the earlier work of
Rayleigh, Bohr, Sutherland, Hansen, and others.
gas
FIG. 10-Schematic of maximum bubble pressure
method of measuring surface tension.
flow
_~h
Oscillating Jet
377
I_
Falling Curtain
In an analysis of curtain coating, Brown [47] observed that
the angle O in the falling curtain formed by the break around
a small, nonwettable obstacle could be used to measure surface tension as
sin O - 27
Qu
(19)
where Q is the mass flow rate per unit orifice slit length in the
curtain and u is the velocity of the liquid. This can enable one
to calculate the dynamic surface tension in the falling film at
the point where the obstacle intersects the falling curtain if
the velocity u is greater than the "bursting velocity" of the
falling sheet. A schematic of this method is given in Fig. 13.
This has been considered further by Van Havenburgh and
Joos [48]. Antoniades et al. [49] reconsidered the work of
Brown and suggest that Eq 19, when derived correctly,
should be written as
sin 2 0 - 27
Qu
(19a)
Capillary Waves
The properties of capillary waves, small wavelength waves
on the surface of a liquid with the dominant restoring force
being surface tension, can be studied to provide a measurement of surface tension, surface elasticity, and other dynamic
surface properties. For clean surfaces of an inviscid liquid,
Kelvin [50] determined that on a liquid of density p, waves of
frequency 0~, and wave number k, the surface tension is given
for small wavelengths
Pc~
(20)
7 - - k3
378
P A I N T AND COATING T E S T I N G M A N U A L
(22)
Rate o f Penetration
CONTACT ANGLE M E A S U R E M E N T S
Optical Measurement Methods
Contact angles are often measured by some form of optical
measurement technique, either directly by a contact angle
goniometer, by a measurement on a photograph of a drop
shape, or digitally on a video image of the drop. A diagram of
a contact angle goniometer is given in Fig. 14. This measurement often is done with the aid of a microscope. [57]. One can
also calculate the contact angle from the dimensions of a drip
on a solid surface. The corrections and information given in
sessile drop, etc., measurement descriptions inherently contain information on the drop profiles, including the contact
angle [38,39]. A more complete discussion of contact angle
measurements is given by Neuman and Good [58], and
Adamson [1] also surveys these measurements. Sell and
Renzow [59] have reviewed the application of contact angle
studies to pigments and give comments on the measurement
of contact angles in pigments. The relation of wetting and the
thermodynamics of liquid-solid interfaces to adhesion are
discussed in some detail in the monograph edited by Lee [60].
(21)
S O M E SPECIFIC APPLICATIONS OF
S U R F A C E E N E R G E T I C S TO ORGANIC
COATINGS
Coatings Application and Defects
Flow phenomena, and their control, at surfaces are very
important to coatings film application technology [6, 63]. The
creation of uniform thin films at high speeds involves many
problems that are determined by a combination of the application geometry, the velocity of the substrate relative to the
liquid coating, the physical properties of the liquid coating,
especially the energetics of the surface of the liquid coating,
the surface of the substrate, and the new liquid/solid and gas/
G0ni0meter
Microscope
Eyepiece
Op/ties
~//r
(23)
Syringe
Therm0statted Cell
~-, ~/
Light Filter
Liquid 11~
~//
Drop
ii
~.+Lilht~ourco_.
CHAPTER 34--SURFACE
liquid interfaces created in the application processes. Analysis of several application techniques is given below to illustrate the importance of the use of concepts discussed in the
prior portion of this chapter.
8f =
0.946
(7/2)2/3
(24)
As described above in the section on measurement of dynamic surface tension, analysis of the curtain coating process
379
has yielded a measurement method for dynamic surface tension. In the analyses of this problem, Brown [45] and Havenburgh and Joos [46] both modeled curtain coating by a
falling liquid film held in place by two vertical wires (see Fig.
16). The flux Q of falling liquid is
Dip Coating
Dip coating is a coating method in which a sheet of material is constantly withdrawn vertically from a coating liquid
bath at constant velocity, producing a constant film thickness
coating adhering to the sheet, which is usually then dried or
cured to produce the final coating on the sheet (see Fig. 15).
This problem was originally analyzed by Landau and Levich
[64], and its solution has been given in modern form by
Probstein [65]. Only the solution of the problem will be given
here, but it is representative of the problems identified by
chemical engineers as coating flows. In these cases, the geometry of the coating device, the relative velocity, v, of the object
to be coated, and the physical properties of the coating fluid
(surface tension, -/; viscosity, ~1;density, p; and acceleration of
gravity, g) fix the solution to the coating flow problem. In this
case, the limiting film thickness, 8f, at large distances from
the coating bath surface, is given by
ENERGETICS
Q = voho
(25)
(26)
where g is the acceleration of gravity. Since the flux of material is constant through the slot, we know that
Q = voh o = hv
(27)
and therefore
h(x)
Q
-
(28)
k / ~ o + 2gx
(29)
(30)
380
SUMMARY
The concepts of surface energy, surface tension, and wetting and contact angle p h e n o m e n a are of exceptional importance to the science and technology of organic coating. Their
understanding is vital for the proper formulation and application of coating. Many of the features of the final organic
coating/substrate system are controlled by proper understanding of the surfaces of the liquid coating and the substrate, as well as creation of a proper coating/substrate
interface. Both the static and dynamic aspects of liquid surface properties should be considered and the dynamic aspects properly accounted for in coating production and
application. These concepts have been reviewed, and references to further reading in this important area of organic
coatings science have been given.
REFERENCES
[1] Adamson, A. W., Physical Chemistry of Surfaces, 5th ed., Wiley,
New York, 1990, Ch. II-III.
[2] Bakker, G., "Kapillarit~t und Oberflachenspannung," Handbuch
der Experimentalphysik, Vol. VI, Akadem, Verlag, Leipzig, 1928.
[3] Wolf, D. E., Griffiths, R. B., and Tang, L., "Surface Stress and
Surface Tension for Solid-Vapor Interfaces," Surface Science,
Vol. 162, 1985, p. 114.
[4] Walton, J. P. R. B., Tildesley, D. J., and Rowlinson, J., Molecular
Physics, Vol. 50, 1983, p. 1357.
[5] Braun, J. H., "Titanium Dioxide's Contribution to the Durability
of Paint Films," Progress in Organic Coatings, Vol. 15, 1987, pp.
249-260.
[6] Bierwagen, G. P., "Surface Defects and Surface Flows in Coatings," Progress in Organic Coatings, Vol. 19, 1991, pp. 59-68.
[7] Burshtein, A. I., "Simple Liquid Surface Structure and Surface
Tension," Advances in Colloid Interface Science, Vol. 11, 1979,
pp. 315-374.
[8] Navascues, G., "Liquid Surfaces: Theories of Surface Tension,"
Reports of Progress in Physics, Vol. 42, 1979, pp. 1132-1186.
[9] Rowlinson, J. S. and Widom, B., Molecular Theory of Capillarity,
Clarendon Press, Oxford, UK, 1982, Ch. 2-4.
[10] Guggenheim, E. A., Journal of Chemical Physics, Vol. 13, 1945,
p. 253.
[111 Pitzer, K.S. and Brewer, L., Thermodynamics, 2nd ed.,
McGraw-Hill, New York, 1961, Ch. 29.
[12] Meyers, D., Surfactant Science and Technology, VCH Publishers,
1988, Ch. 3.
[13] Rosen, M. J., Surfactants and Interfacial Phenomena, Wiley &
Sons, New York, 1978.
[14] Tanford, C., The Hydrophobic Effect, Wiley & Sons, New York,
1980.
[15] Rusanov, A. I. and Krotov, V. V., "Gibbs Elasticity of Liquid
Films, Threads, and Foams," Progress in Surface and Membrane
Science, Vol. 13, J. Danielli, Ed., Academic Press, New York,
1979.
[16] Lucassen-Reynders, E. H., Lucassen, J., Garrett, P. R., Giles, D.,
and Hollway, F., "Dynamic Surface Measurements as a Tool to
Obtain Equation-of-State Data for Soluble Monolayers," Ch. 21,
Advances in Chemistry Series, No. 145, American Chemical Society, Wash., DC, 1975, pp. 275-285.
CHAPTER 3 4 - - S U R F A C E E N E R G E T I C S
[17] Hansen, R. S. and Mann, J. A., "Propagation Characteristics of
Capillary Ripples," Journal of Applied Physics, Vol. 35, 1964, pp.
152-158.
[18] Hansen, R. S., Lucassen, J., Bendure, R. L., and Bierwagen,
G. P., "Propagation Characteristics of Interfacial Ripples," Journal of Colloid and Interface Science, Vol. 26, 1968, p. 198.
[19] Lucassen, J. and Hansen, R. S., Journal of Colloid and Interface
Science, Vol. 22, 1966, p. 32.
[20] Lucassen, J., "Dynamic Properties of Free Liquid Films and
Foams," Ch. 6, E. H. Lucassen-Reynders, Ed., Physical Chemist~ of Anionic Surfactants, Vol. 6 in Surfactant Science, series, M.
Schiff, Ed., Marcell Dekker, New York, 1981.
[21] Benney, D. J., Gutoff, E. B., and Foley, J. A., "The Effect of
Surface Elasticity on the Stability of Flow Down an Inclined
Plane," Pre-Print 3544, Session on Fundamental Research in
Fluid Mechanics, 72nd Annual Meeting, American Institute of
Chemical Engineering, San Francisco, 25-29 Nov. 1979.
[22] Adamson, Ref. 1, Ch. X.
[23] Lee, L.-H., Ed., Fundamentals of Adhesion, Plenum Press, New
York, 1991, Chapters 2 and 3.
[24] Huh, C. and Mason, S. G., "Effects of Surface Roughness on
Wetting (Theoretical)," Journal of Colloid and Interface Science,
Vol. 60, 1977, pp. 11-38.
[25] Bracke, M., De Bisschop, F., and Joos, P., "Contact Angle Hysteresis due to Surface Roughness," Progress in Colloid and Polymer
Science, Vol. 76, 1988, pp. 251-259.
[26] Joanny, J. F. and de Gennes, P. G., "A Model for Contact Angle
Hysteresis," Journal of Chemical Physics, Vol. 81, 1984, pp.
552-562.
[27] Zisman, W. A., Advances in Chemistry Series, Vol. 43, American
Chemical Society, Wash., DC, 1964.
[28] Liao, W.-C. and Zatz, J. L., "Surfactant Solutions as Test Liquids
for Measurements of Critical Surface Tension," Journal of Pharmaceutical Science, Vol. 68, 1979, pp. 486-488.
[29] Croll, S. G., Progress in Organic Coatings, Vol. 15, 1987, pp.
223-248.
[30] Lawniczak, J., Greene, P., Evans, R., and King, G., "WaterReducible Adhesion Promoters for Coatings on PolypropyleneBased Substrates," Proceedings, 19th Water-Borne, Higher-Solids, and Powder Coatings Symposium, R. Storey and S. Thames,
Eds., New Orleans, 26-28 Feb. 1992, Univ. of Southern Mississippi, pp. 63-74.
[313 Ward, A. F. H. and Tordai, L., Journal of Chemical Physics, Vol.
14, 1946, p. 453.
[32] Sutherland, K. L., "The Kinetics of Adsorption at Liquid Surfaces," Australian Journal of Scientific Research A5, 1952, pp.
683-696.
[33] Hansen, R. S., Journal of Physical Chemistry, VoL 64, 1960, p.
637.
[34] Joos, P. and Rillaerts, E., "Theory on the Determination of the
Dynamic Surface Tension with the Drop Volume and Maximum
Bubble Pressure Methods," Journal of Colloid and Interface Science, Vol. 79, 1981, pp. 96-100.
[35] Bois, A. G., Baret, J. F., and Roux, R., "Adsorption at the OilWater Interface: Both Energy Barrier and Diffusion Controlled
Kinetics," Kolloid Zeitschrift und Zeitschrift fi~r Polymere, Vol.
249, 1971, pp. 1144-1147.
[36] Borwankar, R. P. and Wasan, D. T., "Equilibrium and Dynamics
of Adsorption of Surfactants at Fluid-Fluid Interfaces," Chemical Engineering Science, Vol. 43, I988, pp. 1323-1337.
[37] Bierwagen, G. P., "Surface Dynamics of Defect Formation in
Paint Films," Progress in Organic Coatings, Vol. 3, 1975, p. 101,
and Bierwagen, Ref 5.
[38] de Gennes, P. G., "The Dynamics of Wetting," Ch. 5, Fundamentals of Adhesion, L.-H. Lee, Ed., Plenum Press, New York, 1991.
381
[39] Ishimi, K., Hikita, H., and Esmail, M., "Dynamic Contact Angles
on Moving Plates," American Institute of Chemical Engineering
Journal, Vol. 32, 1986, pp. 486-492.
[40] Lyons, C. J., Elbing, E., and Wilson, I. R., "The Rod-in-Free
Surface Technique for Surface-Tension Measurement Using
Small Rods," Journal of Colloid and Interface Science, Vol. 101,
1984, pp. 292-294.
[41] Ugarcic, Z., Vohra, D. K., Atteya, E., and Hartland, S., "Measurement of Surface Tension Using a Vertical Cone," Journal of
Chemical Society, Faraday Transaction I, Vol. 77, 1981, pp.
49-61.
[42] Girault, H. H., Schiffrin, D. J., and Smith, B. D. V., "Drop Image
Processing for Surface and Interracial Tension Measurements,"
Journal of Electroanalyticat Chemistry, Vol. 137, 1982, pp.
207-217.
[43] Seeto, Y. and Scriven, L. E., "Precision Spinning Drop Interracial Tensiometer," Review of Scientific Instruments, VoL 53,
1982, pp. 1757-1761.
[44] Bendure, R. L., "Dynamic Surface Tension Determination with
the Maximum Bubble Pressure Method," Journal of Colloid and
Interface Science, Vol. 35, 1971, pp. 238-248.
[45] Shork, F. J. and Ray, W. H., "On-Line Measurement of Surface
Tension and Density with Applications to Emulsion Polymerization," Journal of Applied Polymer Science, Vol. 28, 1983, pp.
407-430.
[46] Vijian, S. and Ponter, A. B., "Dynamic Surface Tension Studies
Using an Oscillating Jet," Indian Journal of Chemical Engineering, VoL 14, 1972, pp. 26-32.
[47] Brown, D. R, "A Study of the Behaviour of a Thin Sheet of
Moving Liquid," Journal of Fluid Mechanics, VoL 10, 1961, pp.
297-305.
[48] Van Havenburgh, J. and Joos, P., "The Dynamic Surface Tension
in a Free Falling Film," Journal of Colloid and Interface Science,
Vol. 95, 1983, pp. 172-182.
[49] Antoniades, M. G., Goodwin, R., and Lin, S. P., Journal of Colloid and Interface Science, VoL 77, 1989, p. 583.
[50] Kelvin, Lord (W. Thomson), Philosophical Magazine, Vol. 42,
1871, p. 368.
[51] Hansen, R. S. and Ahmad, J., Progress in Surface and Membrane
Science, Vol. 4, Academic Press, New York, 1971.
[52] Lofgren, H., Neuman, R. D., Scriven, L. E., and Davis, H. T.,
"Laser Light-Scattering Measurements of Interracial Tension
Using Optical Hetrodyne Mixing Spectroscopy," Journal of Colloid and Interface Science, Vol. 98, 1984, pp. 175-183.
[53] Delay, R. and Hommeln, J., "II. Measurement of Dynamic Surface Tensions of Aqueous Solutions by the Falling Meniscus
Method," Journal of Colloid Science, Vol. 14, 1959, pp. 401-410.
[54] Lunkenheimer, K., Serrien, G., and Joos, P., "The Adsorption
Kinetics of Octanol at the Air Solution Interface Measured with
the Oscillating Bubble and Oscillating Jet Methods," Journal of
Colloid Interface Science, Vol. 134, 1990, pp. 407-411.
[55] Montgomery, D. D. and Anson, F. C., "Time-Resolved Measurement of Equilibrium Surface Tensions at the Electrified Mercury-Aqueous NaF Interphase by the Method of Wilhelmy,"
Langmuir, Vol. 7, 1991, pp. 1000-1004.
[56] Jho, C. and Burke, R., "Drop Weight Technique for the Measurement of Dynamic Surface Tension," Journal of Colloid and Interface Science, Vo]. 95, 1983, pp. 61-71.
[573 Farnarier, C., Capo, C., Balloy, V., Benoliel, A.M., and
Bongrand, P., "Simple Microscopical Measurement of Contact
Angles on Transparent Substrates," Journal of Colloid and Interface Science, Vol. 99, 1984, pp. 164-167.
[58] Neuman, A. W. and Good, R. J., "Technique of Measuring Contact Angle," Ch. 2, Surface and Colloid Science, Vol. H
Experimental Methods, R. J. Good and R. R. Strornberg, Eds.,
Plenum Press, New York, 1979.
382
[59] Sell, P.-J. and Renzow, D., "Bestimmung des Benetzungsverhaltens von Pigmenten," Progress in Organic Coatings,
[68] Richardson, C. B., Pigg, A. L., and Hightower, R., "On the Stability Limit of Charged Droplets," Proceedings of the Royal Society of London, A, Vol. 422, 1989, pp. 319-328.
[69] Schweitzer, J.W. and Hanson, D.N., "Stability Limit of
Charged Droplets," Journal of Colloid and Interface Science, Vol.
35, 1971, pp. 417-423.
MNL17-EB/Jun. 1995
|
Solubility Parameters
by Charles M. Hansen 1
NOMENCLATURE
C Dispersion cohesion energy from Fig. 2 and Fig. 3
D Dispersion cohesion (solubility) p a r a m e t e r - - i n tables and computer printouts
D M Dipole m o m e n t - - D e b y e s
~k~d Dispersion cohesion energy
AEp Polar cohesion energy
AEh Hydrogen bonding cohesion energy
AEv Energy of vaporization ( = ) cohesion energy
AG M Molar free energy of mixing
H Hydrogen bonding cohesion (solubility) paramet e r - i n tables and computer printouts
Molar heat of vaporization
d~"l v
A H M Molar heat of mixing
P Polar cohesion (solubility) p a r a m e t e r - - i n tables
and computer printouts
R Gas constant (1.987 cal/mole-~
R~ Distance in Hansen space
R0 Radius of interaction sphere in Hansen space
RED Relative energy difference, R,/Ro
AS M Molar entropy of mixing
T Absolute temperature
1; (Normal) boiling point
L Critical temperature
v,,, Molar volume
Ar Lydersen critical temperature group contribution
O/
Thermal expansion coefficient
~d Dispersion cohesion (solubility) parameter
~h Hydrogen bonding cohesion (solubility) parameter
Polar cohesion (solubility) parameter
8r Total cohesion (solubility) parameter
6, Volume fraction of component "i"
X Polymer-liquid interaction parameter (FloryHuggins)
INTRODUCTION
SOLUBILITYPARAMETERSAREUSEDin the coatings industry to
select solvents. Liquids with similar solubility parameters
will be miscible, and polymers will dissolve in solvents whose
solubility parameters are not too different from their own.
The basic principle is "like dissolves like." Solubility parameters help put numbers into this simple qualitative idea.
~FORCE Institute, Division for Mechatronic and Sensor Technology, Park Alle 345, DK-2605 Broendby, Denmark.
383
Copyright9 1995 by ASTM International
www.astm.org
384
PAINT
AND
COATING
TESTING
MANUAL
HILDEBRAND PARAMETERS
The term solubility parameter was first used by Hildebrand
and Scott [1,2]. The solubility parameter is the square root of
the cohesive energy density
8 = (c.e.d) 112
v l l / 2] ( c a ] / c m 3 ) l / 2 o r M P a l / 2
\( ~VM
(1)
A G u = z3J4M - T A S M
82)2
(3)
H A N S E N SOLUBILITY P A R A M E T E R S
A widely used solubility parameter approach to predicting
polymer solubility is that proposed by the author. The basis
of these so-called Hansen solubility parameters is that the
total energy of vaporization of a liquid consists of several
individual parts [ 7 - 1 1 ] . Needless to say, without the work of
Hildebrand and Scott [1,2] and others not specifically referenced here such as Scatchard, this postulate could never have
been made. The total cohesive energy, A E t, can be measured
by evaporating the liquid, i.e., breaking all the cohesive
bonds. It should also be noted that these cohesive energies
arise from interactions of a given solvent molecule with another of its own kind. The basis of the approach is, therefore,
very simple, and it is surprising that so many different applications have been possible over the past 25 years. A number
of applications are discussed below. A lucid discussion by
Barton [12] enumerates typical situations where problems
occur when using solubility parameters. These are most often
where the environment causes the solvent molecules to interact with or within themselves differently than when they
make up their own environment, i.e., as pure liquids.
Materials having similar (Hansen) solubility parameters
have high affinity for each other. The extent of the similarity
in a given situation determines the extent of the interaction.
The same can not be said of the total or Hildebrand solubility
parameter [1,2]. Ethanol and nitromethane, for example,
CHAPTER
35--SOLUBILITY
PARAMETERS
385
-~- z~kEh
(4)
Dividing this by the molar volume gives the square of the total
(or Hildebrand) solubility parameter as sum of the squares of
the Hansen D, P, and H components.
AE~ _ AEd + AEp + AEh
v~
v~
v~
(5)
v~
St= 82 + 82 + 82
(6)
= D 2 + p2 + H 2 (computer printouts)
M E T H O D S AND P R O B L E M S IN T H E
D E T E R M I N A T I O N OF PARTIAL
SOLUBILITY P A R A M E T E R S
The best method to calculate Hansen solubility parameters
depends to a great extent on what data are available. Hansen
originally adopted an essentially experimental procedure and
established numbers for 90 liquids based on solubility data
for 32 polymers [7]. This procedure involved calculation of
the nonpolar parameter according to the procedure outlined
386
(7)
387
phenomena based on specific interactions among the components of the mixtures. Barton has recently discussed some of
these situations and points out that Hildebrand or Hansen
parameters must be used with particular caution where the
extent of donor-acceptor interactions, and in particular hydrogen bonding within a compound, is very different from
that between compounds [12]. Amines, for example, are
known to associate with each other. Pure component data
can not be expected to predict the behavior in such cases.
Still another reason for difficulties is the large variation of
dipole moments reported for the same liquid. The dipole
moment for some liquids depends on their environment, as
discussed below. A given solvent can be listed with different
values in files to keep these phenomena in mind.
Large data sources greatly enhance searching for similar
materials and locating new solvents for a polymer based on
limited data, for example. Unfortunately, different authors
have used different group contribution techniques, and there
is a proliferation of different "Hansen" parameters for the
same chemicals in the literature. This would seem to be an
unfortunate situation, but may ultimately provide benefits. In
particular, partial solubility parameter values found in Hoy's
extensive tables [3, 31] are not compatible with the customary
Hansen parameters reported here. Hoy has provided an excellent source of total solubility parameters. He independently arrived at the same type division of cohesion energies
as Hansen, although the methods of calculation are quite
different.
Many solvent suppliers have also presented tables of solvent properties and/or use computer techniques using these
in their technical service. Partial solubility parameters not
taken directly from earlier well-documented sources should
be used with caution. In particular it can be noted that the
Hoy dispersion parameter is consistently lower than that
found by Hansen. Hoy subtracts estimated values of the polar
and hydrogen bonding energies from the total energy to find
the dispersion energy. This allows for more calculational
error and underestimates the dispersion energy since the Hoy
procedure does not appear to fully separate the polar and
hydrogen bonding energies. The Van Krevelen dispersion parameters appear too low. The author has not attempted these
calculations, being completely dedicated to the full procedure
described here, but values estimated independently based on
the Van Krevelen dispersion parameters are clearly low. A
comparison with related compounds, or similarity principle,
gives better results than those found from the Van Krevelen
dispersion group contributions.
In the following, calculational procedures and experience
are presented according to the procedures found most reliable for the experimental and/or physical data available for a
given liquid.
CALCULATION OF T H E D I S P E R S I O N
SOLUBILITY P A R A M E T E R , 8,~
The 8d parameter is calculated according to the procedures
outlined by Blanks and Prausnitz [6]. Figures 1, 2, or 3 can be
used to find this parameter depending on whether the molecule of interest is aliphatic, cycloaliphatic, or aromatic. These
figures have been inspired by Barton [3], who converted
40.0
66.0
=F 2 twin d
~ F 3 triplet d
30.0
62.0
97.2
--Br
=Br 2 twind
~ B r 3 triplet d
(6.7)
NH2 a m i d e
Same
Same
Same
Same
32.0
Same
Same
Same
Same
Same
(31.4)
Same
Same
123.0
74.6
35.5
109.2
70.0
34.0
73.9
60.0
28.0
78,0
48.0
22.0
Same
350
820
1180
1125
Alkane
160
175
...c
1150 225
1050 300
3000 -+ 600
1600 850 a
1770 _+ 450
3350 300
...c
950 _+ 300
1050 -+ 450 a
1370 ~_ 500
3550 250
0
2350 400
2200 250 a
1500
250
250
Same
Same
Same
Same
Cyclo
...c
5500 _+ 3 0 0 a
2350 250 ~
5800 _+ 400 a
4300 _+ 300 a
1950 + 300 a
4750 _+ 300 a
3650
1400 + 100
..-
. . . . . .
800 100
875 + 100
850 _+ 100
. . . . . .
71.4
Same
Same
Same
Same
Same
Same
Same
Aromatic ~
Parameter,
AV6~ ( c a l / m o l )
London
125
150 _+ 150 ~
2550
1870 _+ 600
3600 400
...c
550 _+ 275
2800 325
4200 + 300 a
2000 _+ 250 a
3500 300 a
1650 _+ 140
3100 _+ 175 a
1300 +- 100
250
...
7530
Same
Same
Same
Same
150
150 a
150
100
(81 0 0 0 + 10%)/V
100 50
600 200
3600 + 600
4000 + 800 a
1500
700 + 200
500 _+ 150
2100 + 200
500
800 _+ 250 a
1250 + 100
350
800 _+ 250 a
1250 100
300 _+ 100
800 _+ 150
1250 + 100
700 -+ 250 ~
60 _+ 10
18 5
25 + 10
solubility
100
150
600 + 350 a
1100 x 300
300 + 50
3000 500
1000 300
600
1350 _+ 100
1700 _+ 150
1450
Cyclo
Polar Parameter,
AV8 2 ( c a l / m o l )
to partial
Alkane
1000
contributions
Aromatic
1--Group
100
150 ~
150 a
800 200
1750 + 100
3750 _+ 300 a
800 _+ 150
750 350
2750 _+ 2 0 0
950 _+ 300
4 5 0 _+ 150
400
575 + 100
400 +_ 150 a
800
400
800 + 100
500 -+ 250 ~
700 +_ 100
...
50 -+ 25
Aromatic
parameters.
150
3000 500
2700 550 a
750 200
1350 200
400 -+ 50 b
500 200 b
9000 600
4650 400
2750 _+ 250
1250
1000 200
800 250 b
450 _+ 25
1650 2 5 0 a
1000 200 a
1500 300 a
825 2 0 0 ~
500 100
350 -+ 250 a
165 _+ 10a
100 20 a
---
180 _+ 75
180 75
180 75
Aliphatic
10 a
100
125 a
100 a
2250 _+ 200 b
350 + 50 a
400 _+ 125 a
9300 + 600
4650 _+ 500
2250 250 ~
475
750 _+ 150
400
1200
1800 _+ 250 a
1000 200 a
800 _+ 250 a
500 + 100
180
Same
...
50 50 a
Aromatic
Electron Transfer
Parameter,
AV~ 2 (cal/mol)
aBased on very limited data. Limits shown are roughly 95% confidence; in many cases, values are for information
only and not to be used for computation.
blncludes unpublished
infrared data.
C U s e f o r m u l a i n A V g p2 c o l u m n t o c a l c u l a t e , w i t h V f o r t o t a l c o m p o u n d .
dTwin and triplet values apply to halogens on the same C atom, except that AV~2 also includes those on adjacent C atoms.
~These values apply to halogens attached directly to the ring and also to halogen attached to aliphatic double-bonded
C atoms.
fFrom R. F. Fedors [25].
28.0
4.5
)PO 4 ester
19.2
NHz amine
24.0
--NO 2
>NH 2 amine
24.0
--CN
adjacent
26.0
10.0
~ ( O H ) 2 twin o r
28.5
OH
18.0
COO-ester
--COOH
(23.2)
CHO
3.8
10.8
>CO ketone
~ I 3 triplet d
--O--ether
66.6
111.0
=I 2 twind
31.5
81.9
~ C I 3 triplet d
52.0
~C12 twin d
24,0
18.0
--F
CI
16
C-6 r i n g
(saturated)
C-5 r i n g
16
-5.5
> C = olefin
13.5
- - C H = olefin
Phenyl .
28.5
- 19.2
C H 2 = olefin
>C<
- 1.0
16.1
CH<
33.5
CH2<
Aliphatic
CH~-
Group
Functional
Molar Volumef
AV (cm3/mol)
TABLE
4300 e
5 400
(7 000)
(5 850)
2 000
3 000
7 000
4 150
10 440
7 120
6 600
4 300
(4 050)
4 150
800
11 700
Same
Same
Same
Same
(4400)
Same
Same
Same
Same
Same
Same
Same
(1650 +- 150)
9350 e
6400 e
6100 e
3600 e
7 650
4 550
8 000
4700 e
5 900
2960 ~
3670 e
4 600
3 700
1315 e
2200 e
1 650
2 760
800 e
1360 e
250
-..
7630
1 700
250
250
Same
Same
Same
Same
Same
Same
Same
Aromatic
1 000
...
1 030
1 030
1 030
350
820
1 180
1 125
Aliphatic
Total Parameter
AV,52 ( c a l / m o l )
(.~
00
O0
389
nED kJ/mol
i/
50
40
ss-
,_~ I 0;,;~~
~.~"
i'"
,,,s
.-
~.s "'~
30
L...~
20
io
///,/~
50
100
150
200
250
V, ~mS/mo l
FIG. 1-Energy of vaporization for straight chain hydrocarbons as a function of molar volume and reduced
temperature.
85o
. . . . . . -I o.~
. . . . . . .
600
600 -
,. . . . . . .
- ~
o. o
0.60
0.65
0.70
80
70
80
90
V,
100
110
120
0.65
~50-
50
4 0.50
130
em~/mol
FIG. 2-Cohesive energy density for cycloalkanes as a function of molar volume and reduced temperature.
i
80
90
,
100
110
j
120
, - - ~ o.,o
~
130
140
150
160
170
V, c m ~ / m o l
390
P A I N T A N D COATING T E S T I N G M A N U A L
Tb/Tr = 0.567 + s
(EAT)2
(8)
and
T~ = T/T~
(9)
(i.e., its homomorph), and it has a higher dispersion solubility parameter without any special need for corrections.
The careful evaluation of the dispersion cohesive energy
may not have major impact on the value of the dispersion
solubility parameter itself because of the taking of square
roots. Larger problems arise because of Eq 4. Energy assigned to the dispersion portion can not be reused when
finding the other partial parameters using Eq 4 (or Eq 6). This
is one reason group contributions are recommended in some
cases below.
8p - ( ~ ) ~ d (DM)
(10)
CHAPTER
TABLE 2 - - L y d e r s e n
group
Aliphatic,
AT
Cyclic,
AT
>C<
~CH2
0.020
0.020
0.012
0.000
0.018
...
0.013
0.012
- 0.007
---
=CH--
0.018
0.011
=C<
~CH
=CH
0.000
. .
. .
Group
CH3
CH 2
>CH--
aromatic
aromatic
--O->O epoxide
--COO->C~O
--CHO
--COzO
0.021
. .
0.047
0.040
0.048
. .
--OH--~
--H-o
--OH primary
--OH sec .
.
--OH tert.
--OH phenolic
.
.
.
.
.
.
.
...
0.033
...
. . . . . .
.
.
.
.
0.082
.
.
.
9. . . . .
0.035
--NH 2
--NH->N---C~-~N
0.031
0.031
0.014
0.060
--NCO
HCON<
--CONH .
--CON<
--CONH2
--OCONH .
.
.
.
.
.
.
.
...
...
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.015
0.015
- - C I 1~
--C1 2 ~
C12 t w i n
C1 a r o m a t i c
0.017
9. . . . .
. . . . . .
. . . . . .
...
--Br
--Br
0.010
. .
..-
--F
--I
.
.
.
4
5
6
7
.
.
.
.
.
.
.
Ortho
Meta
Para
.
.
.
Bicycloheptyl
Tricyclodecane
.
.
ring
ring
ring
ring
...
. .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.0175
0.0267
0.0497
0.0400
0.0445
0.0863
0.16
. .
0.47
0.29
0.33
. .
0.0343
0.0077
0.0493
0.0440
0.0593
0.0060
0.06
. .
. .
. .
. .
- 0.02
0.0318
.
.
0.018
0.012
Conjugation
c is double bond
trans double bond
Member
Member
Member
Member
0.227
0.227
0.210
0.210
0.198
0.198
0.198
. . .
. . .
0.0345
0.0274
0.0093
0.0539
0.008
.
.
Cyclic,
b5'
0.0226
0.0200
0.0131
0.0040
0.0192
0.0184
0.0129
0.0178
0.0149
...
0.184
0.192
0.154
--0.154
0.154
.
.
.
.
.
.
0.12
.
...
0.02
...
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
...
0.095
0.135
0.17
0.36
0.0539
0.0546
0.0843
0.0729
0.0897
0.0938
--S---SH
aromatic
.-.
0.024
0.007
...
. .
. .
.
. .
. .
.
Aliphatic,
AP
Aer
0.014
PARAMETERS
constants.
0.011
.
.
35--SOLUBILITY
.
.
.
.
.
.
.
.
.
.
.
.
...
0.09
0,13
...
.
.
.
.
.
.
0.27
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.24
0.0311
0.0317
0.0521
0.0245
0.320
. . .
. . .
. . .
.
.
.
.
.
.
.
.
.
0.0392
0.0313
0.50
. .
0.006
0.224
0.83
-..
...
.
...
...
0.0035
0.0010
0.0020
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.0118
0.003
0.0035
0.0069
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.0015
0.0010
0.0060
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.0034
0.0095
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
391
392
(12)
d(8,,) _
dT
d(~a) _
dT
1.25 a8 d
(13)
d(Sp) _
dT
0.5 asp
(14)
~h (1.22 x 10 -3 + 0.5 ~)
(15)
CHAPTER 3 5 - - S O L U B I L I T Y PARAMETERS
where the parameters for the given liquids were desired with
a high degree of accuracy. The procedure is to enter solvent
quality, good or bad, into the program for a reasonably large
number of polymers where the solubility parameters and
appropriate radius of interaction for the polymers are known.
The program then locates that set of 6d, 8p, and ~h parameters
for the solvent which best satisfies the requirements of a
location within the spheres of the appropriate polymers
where solvent quality is good and outside of the appropriate
spheres where it is bad.
An additional aid in estimating the Hansen parameters for
many compounds is that these parameters can be found by
interpolation or extrapolation, especially for homologous seties. The first member may not necessarily be a straight line
extrapolation, but comparisons with related compounds
should always be made where possible to confirm assignments. Plotting the parameters reported in Table 3 for homologous series among the esters, nitroparaffins, ketones,
alcohols, and glycol ethers will aid in finding the parameters
for related compounds.
Table 3 contains Hansen solubility parameters for a large
number of liquids and plasticizers. These are given in SI
units.
393
APPLICATIONS
There are many applications documented in the literature
where solubility parameters have aided in selection of solvents, understanding and controlling processes, and, in general, offered guidance where affinities among materials are of
prime importance. To find the optimum solvent for a polymer
using solubility parameters, it is most desirable to have the
solubility parameters for the polymer. Matching the parameters of an already existing solvent or combination of solvents
can be done, but does not necessarily optimize the new situation. The optimum depends on what is desired of the system.
A solvent with highest possible affinity for the polymer is both
expensive and probably not necessary.
Most coatings applications involve solvents safely within
the solubility limit with a maximum of cheaper hydrocarbon
solvent. Some safety is advised because temperature changes,
potential variations in production, etc. can lead to a situation
where solvent quality changes in an adverse manner. Balance
of solvent quality on evaporation of mixed solvents is also
necessary. Here again computer approaches are possible.
An oxygenated solvent frequently added to hydrocarbon
solvent and which has been cost effective in increasing the
very important hydrogen bonding solubility parameters has
been n-butanol. The mixture of equal parts xylene and
n-butanol can be used in conjunction with many polymers,
but a third solvent, such as a ketone or ester, is often included
in small amounts to increase the polar parameter/solvency of
the mixture. Glycol ethers can also be added to hydrocarbon
solvents with advantage, and the polar and hydrogen bonding
parameters are higher than had n-butanol been added to the
same concentration. There are many possibilities, and a solubility parameter approach is particularly valuable in quickly
limiting the number of candidates.
Coalescing solvents in water-reducible coatings are often
those with somewhat higher hydrogen bonding parameters
than the polymer, which also means they are water soluble or
have considerable water solubility. The distribution between
the water phase and the dispersed polymer phase depends on
the relative affinities for water and the polymer. Solvents
which are not particularly water soluble will preferentially be
found in the polymer phase. Such coalescing solvents may be
preferred for applications to porous substrates, making certain they are where they are needed. Otherwise a water-soluble coalescing solvent would tend to follow the aqueous phase
penetrating the substrate and not be available to do its job in
the film itself.
When water evaporates the solvent must dissolve to some
extent in the polymer to promote coalescence. This can be
determined and adjusted by either increasing or decreasing
the affinity for the polymer.
Amines are frequently added in water-reducible coatings to
neutralize acid groups in polymers, thus providing a watersolubilizing amine salt. Amine in excess of that required for
total neutralization acts like a solvent. Such amine salts have
been characterized separately to demonstrate that they have
higher solubility parameters than either (acetic) acid or organic bases [42]. These salts are hydrophilic and have very
little affinity for coatings polymers, which means they are to
be found in a stabilizing role in interfaces in the aqueous
394
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
Solvent
Acetaldehyde
Acetic acid
Acetic anhydride
*Acetone
Acetonitrile
*Acetophenone
Acrylonitrile
Allyl alcohol
Amyl acetate
Aniline
Anisole
Benzaldehyde
*Benzene
1.3-Benzenediol
Benzoic acid
Benzonitrile
Benzyl alcohol
Benzyl butyl phthalate
Benzyl chloride
Biphenyl
Bromobenzene
Bromochloromethane
Bromoform
1-Bromonaphtalene
Bromotrifluoromethane
Butane
1.3-Butanediol
*l-Butanol
2-Butanol
*Butyl acetate
Sec-butyl acetate
Butyl acrylate
Butylamine
Butyl lactate
Butyraldehyde
Butyric acid
*Gamma butyrolactone
Butyronitrile
Carbon disulfide
*Carbon tetrachloride
*Chlorobenzene
1-Chlorobutane
Chlorodifluoromethane
*Chloroform
3-Chloro- 1-propanol
m-cresol
Cyclohexane
*Cyclohexanol
Cyclohexanone
Cyclohexylamine
Cyclohexylchloride
Cis-decahydronaphthalene
Trans-decahydronaphthalene
Decane
1-Decanol
*Diacetone alcohol
Dibenzyl ether
Dibutyl phthalate
Dibutyl sebacate
Dibutyl stearate
*o-dichlorobenzene
2.2-Dichlorodiethyl ether
Dichlorodifluoromethane
1.1-Dichloroethane
1.1-Dichloroethylene
Di-(2-chloro-isopropyl) ether
Dichloromonofluoromethane
1.2-Dichlorotetrafluoroethane
Di-iso-butyl carbino]
Diethanolamine
Diethylamine
Dispersion
Polar
Hydrogen
Bonding
Molar
Volume
14.7
14.5
16.0
15.5
15.3
19.6
16.4
16.2
15.8
19.4
17.8
19.4
18.4
18.0
18.2
17.4
18.4
19.0
18.8
21.4
20.5
17.3
21.4
20.3
9.6
14.1
16.6
16.0
15.8
15.8
15.0
15.6
16.2
15.8
14.7
14.9
19.0
15.3
20.5
17.8
19.0
16.2
12.3
17.8
17.5
18.0
16.8
17.4
17.8
17.2
17.3
18.8
18.0
15.7
17.5
15.8
17.3
17.8
13.9
14.5
19.2
18.8
12.3
16.5
17.0
19.0
15.8
12.6
14.9
17.2
14.9
8.0
8.0
11.7
10.4
18.0
8.6
17.4
10.8
3.3
5.1
4.1
7.4
0.0
8.4
6.9
9.0
6.3
11.2
7.1
1.0
5.5
5.7
4.1
3.1
2.4
0.0
10.0
5.7
5.7
3.7
3.7
6.2
4.5
6.5
5.3
4.1
16.6
12.4
0.0
0.0
4.3
5.5
6.3
3.1
5.7
5.1
0.0
4.1
6.3
3.1
5.5
0.0
0.0
0.0
2.6
8.2
3.7
8.6
4.5
3.7
6.3
9.0
2.0
8.2
6.8
8.2
3.1
1.8
3.1
10.8
2.3
11.3
13.5
10.2
7.0
6.1
3.7
6.8
16.8
6.1
10.2
6.7
5.3
2.0
21.0
9.8
3.3
13.7
3.1
2.6
2.0
4.1
3.5
6.1
4.1
0.0
0.0
21.5
15.8
14.5
6.3
7.6
4.9
8.0
10.2
7.0
10.6
7.4
5.1
0.6
0.6
2.0
2.0
5.7
5.7
14.7
12.9
0.2
13.5
5.1
6.5
2.0
0.0
0.0
0.0
10.0
10.8
7.3
4.1
4.1
3.5
3.3
5.7
0.0
0.4
4.5
5.1
5.7
0.0
10.8
21.2
6.1
57.1
57.1
94.5
74.0
52.6
117.4
67.1
68.4
148.0
91.5
119.1
101.5
89.4
87.5
100.0
102.6
103.6
306.0
115.0
154.1
105.3
65.0
87.5
140.0
97.0
101.4
89.9
91.5
92.0
132.5
133.6
143.8
99.0
149.0
88.5
110.0
76.8
87.3
60.0
97.1
102.1
104.5
72.9
80.7
84.2
104.7
108.7
106.0
104.0
113.8
118.6
156.9
156.9
195.9
191.8
124.2
192.7
266.0
339.0
382.0
112.8
117.2
92.3
84.8
79.0
146.0
75.4
117.6
177.8
95.9
103.2
CHAPTER 3 5 - - S O L U B I L I T Y P A R A M E T E R S
395
TABLE 3 - - H a n s e n solubility parameters for selected liquids. The solvents in alphabetical order.
No.
Solvent
Dispersion
Polar
Hydrogen
Bonding
Molar
Volume
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
2-(Diethylamino)ethanol
Para-diethylbenzene
Diethyl carbonate
*Diethylene glycol
Diethylene glycol butyl ether acetate
Diethylene glycol hexyl ether
Diethylene glycol monobutyl ether
Diethylene glycol monoethyl ether
Diethylene glycol monomethyl ether
Diethylenetriamine
*Diethyl ether
Diethyl ketone
Diethyl phthalate
Diethyl sulfate
Diethyl sulfide
Di(isobutyl) ketone
Di(2-methoxyethyl) ether
N.N-dimethylacetamide
*Dimethylforrnamide
1.1-Dimethylhydrazine
Dimethyl phthalate
Dimethyl sulfone
*Dimethyl sulfoxide
Dioctyl phthalate
* 1,4-Dioxane
Dipropylamine
*Dipropylene glycol
Dipropylene glycol methyl ether
Dodecane
Eicosane
Epichlorohydrin
Ethanethiol
*Ethanol
*Ethanolamine
*Ethyl acetate
Ethyl acrylate
Ethyl amyl ketone
Ethylbenzene
Ethyl bromide
2-Ethyl- 1-butanol
Ethyl butyl ketone
Ethyl chloride
Ethyl chloroformate
Ethyl cinnamate
Ethylene carbonate
Ethylene cyanohydrin
Ethylenediamine
Ethylene dibromide
*Ethylene dichloride
*Ethylene glycol
Ethylene glycol butyl ether acetate
*Ethylene glycol monobutyl ether
*Ethylene glycol monoethyl ether
Ethylene glycol monoethyl ether acetate
*Ethylene glycol monomethyl ether
Ethylene glycol monomethyl ether acetate
Ethyl formate
2-Ethyl hexanol
Ethyl lactate
*Formamide
Formic acid
Furan
Furfural
Furfuryl alcohol
Glycerol
Heptane
Hexadecane
Hexamethylphosphoramide
*Hexane
Hexylene glycol
Isoamyl acetate
14.9
18.0
16.6
16.6
16.0
16.0
16.0
16.1
16.2
16.7
14.5
15.8
17.6
15.7
16.8
16.0
15.7
16.8
17.4
15.3
18.6
19.0
18.4
16.6
19.0
15.3
16.5
15.5
16.0
16.5
19.0
15.7
15.8
17.0
15.8
15.5
16.2
17.8
16,5
15.8
16.2
15,7
15.5
18.4
19.4
17.2
16.6
19.2
19.0
17.0
15.3
16.0
16.2
15.9
16.2
15.9
15.5
15.9
16.0
17.2
14.3
17.8
18.6
17.4
17.4
15.3
16.3
18.5
14.9
15.7
15.3
5.8
0.0
3.1
12.0
4.1
6.0
7.0
9.2
7.8
13.3
2.9
7.6
9.6
14.7
3.1
3.7
6.1
11.5
13.7
5.9
10.8
19.4
16.4
7.0
1.8
1.4
10.6
5.7
0,0
0,0
10.2
6.5
8.8
15.5
5.3
7.1
4.5
0.6
8.0
4.3
5.0
6.1
10.0
8.2
21.7
18.8
8.8
3.5
7,4
11.0
4.5
5.1
9.2
4.7
9.2
5.5
8.4
3.3
7.6
26.2
11.9
1.8
14.9
7,6
12.1
0.0
0.0
8.6
0.0
8.4
3,1
12.0
0.6
6.1
20.7
8.2
10.0
10.6
12.2
12.6
14.3
5.1
4.7,
4.5
7.1
2.0
4.1
6.5
10.2
11.3
11.0
4.9
12.3
10.2
3.1
7.4
4.1
17.7
11.2
0.0
0,0
3,7
7.1
19.4
21.2
7.2
5.5
4.1
1.4
5.1
13.5
4,1
2.9
6.7
4.1
5.1
17.6
17.0
8.6
4.1
26.0
8.8
12.3
14.3
10.6
16.4
11.6
8.4
11.8
12.5
19.0
16.6
5.3
5.1
15.1
29.3
0.0
0.0
11.3
0.0
17.8
7.0
133.2
156.9
121.0
94.9
208.2
204.3
170.6
130.9
118.0
108.0
104,8
106.4
198.0
131.5
107,4
177.1
142.0
92.5
77.0
76.0
163.0
75.0
71.3
377.0
85.7
136,9
130.9
157.4
228.6
359.8
79.9
74.3
58.5
59.8
98.5
108.8
156.0
123.1
76.9
123.2
139.0
70,0
95.6
166.8
66.0
68.3
67.3
87.0
79.4
55.8
171.2
131.6
97.8
136.1
79.1
121.6
80.2
156.6
115.0
39.8
37.8
72.5
83.2
86.5
73.3
147.4
294.1
175,7
131.6
123,0
148,8
396
No.
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
Solvent
Isobutyl acetate
Isobutyl alcohol
Isobutyl isobutyrate
Isooctyl alcohol
Isopentane
*Isophorone
Isopropyl palmitate
Mesitylene
Mesityl oxide
Methacrylonitrile
*Methanol
o-Methoxyphenol
Methyl acetate
Methyl acrylate
Methylal
Methyl amyl acetate
Methyl butyl ketone
Methyl chloride
Methylcyclohexane
*Methylene dichloride
Methylene diiodide
Methyl ethyl ketone
Methyl isoamyl ketone
Methyl isobutyl carbinol
*Methyl isobutyl ketone
Methyl methacrylate
1-Methylnaphthalene
Methyl oleate
2-Methyl- l-propanol
*Methyl-2-pyrrolidone
Methyl salicylate
Morpholine
Naphtha.high-flash
Naphthalene
*Nitrobenzene
*Nitroethane
*Nitromethane
1-Nitropropane
*2-Nitropropane
Nonane
Nonyl phenol
Nonyl phenoxy ethanol
Octane
Octanoic acid
1-Octanol
2-Octanol
Oleic acid
Oleyl alcohol
Pentane
2.4-Pentanedione
1-Pentanol
Perfluoro(dimethylcyclohexane)
Perfluoroheptane
Peiaquoromethylcyclohexane
Phenol
Bis-(m-phenoxyphenyl) ether
1-Propanol ~
2-Propanol
Propionitrile
Propylamine
Propyl chloride
*Propylene carbonate
*Propylene glycol
Propylene glycol monobutyl ether
Propylene glycol monoethyl ether
Propylene glycol monoisobutyl ether
Propylene glycol monomethyl ether
Propylene glycol monophenyl ether
Propylene glycol monopropyl ether
Pyridine
2-Pyrolidone
Dispersion
Polar
Hydrogen
Bonding
Molar
Volume
15.1
15.1
15.1
14.4
13.7
16.6
14.3
18.0
16.4
15.3
15.1
18.0
15.5
15.3
15.0
15.2
15.3
15.3
16.0
18.2
17.8
16.0
16.0
15.4
15.3
17.5
20.6
14.5
15.1
18.0
16.0
18.8
17.9
19.2
20.0
16.0
15.8
16.6
16.2
15.7
16.5
16.7
15.5
15.1
17.0
16.1
14.3
14.3
14.5
17.1
15.9
12.4
12.0
12.4
18.0
19.6
16.0
15.8
15.3
16.9
16.0
20.0
16.8
15.3
15.7
15. l
15.6
17.4
15.8
19.0
19.4
3.7
5.7
2.9
7.3
O.0
8.2
3.9
0.0
6.1
10.8
12.3
8.2
7.2
9.3
1.8
3.1
6.1
6.1
0.0
6.3
3.9
9.0
5.7
3.3
6.1
5.5
0.8
3.9
5.7
12.3
8.0
4.9
0.7
2.0
8.6
15.5
l 8.8
12.3
12.1
0.0
4.1
10.2
0.0
3.3
3.3
4.9
3.1
2.6
0.0
9.0
4.5
0.0
0.0
0.0
5.9
3.1
6.8
6.1
14.3
4.9
7.8
18.0
9.4
4.5
6.5
4.7
6.3
5.3
7.0
8.8
17.4
6.3
15.9
5.9
12.9
O.0
7.4
3.7
0.6
6.1
3.6
22.3
13.3
7.6
5.9
8.6
6.8
4.1
3.9
1.0
6.1
5.5
5.1
4.1
12.3
4.1
4.3
4.7
3.7
15.9
7.2
12.3
9.2
1.8
5.9
4.1
4.5
5.1
5.5
4.1
0.0
9.2
8.4
0.0
8.2
11.9
11.0
5.5
8.0
0.0
4.1
13.9
0.0
0.0
0.0
14.9
5.1
17.4
16.4
5.5
8.6
2.0
4.1
23.3
9.2
10.5
9.8
11.6
11.5
9.2
5.9
11.3
133.5
92.8
163.0
156.6
i 17.4
150.5
330.0
139.8
115.6
83.9
40.7
109.5
79.7
89.7
169.4
167.4
123.6
55.4
128.3
63.9
80.5
90.1
142.8
127.2
125.8
106.5
138.8
340.0
92.8
96.5
129.0
87.1
181.8
111.5
102.7
71.5
54.3
88.4
86.9
179.7
231.0
275.0
163.5
159.0
157.7
159.1
320.0
316.0
116.2
103.1
108.6
217.4
227.3
196.0
87.5
373.0
75.2
76.8
70.9
83.0
88.1
85.0
73.6
132.0
115.6
132.2
93.8
143.2
130.3
80.9
76.4
CHAPTER 3 5 - - S O L U B I L I T Y P A R A M E T E R S
397
TABLE 3 Continued--Hansen solubility parameters for selected liquids. The solvents in alphabetical order.
No.
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
Solvent
Quinoline
Stearic acid
Styrene
Succinic anhydride
1.1.2.2-Tetrabromoethane
1.1.2.2-Tetrachloroethane
Tetrachloroethylene
Tetraethylorthosilicate
*Tetrahydrofuran
Tetrahydronaphthalene
Tetramethylurea
*Toluene
Tributyl phosphate
Trichlorobiphenyl
1.1.1-Trichloroethane
*Trichloroethylene
Trichlorofluoromethane
1.1.2-Trichlorotrifluoroethane
Tricresyl phosphate
Tridecyl alcohol
Triethanolamine
Triethylamine
Triethyleneglycol
Triethylene glycol monooleyl ether
Triethylphosphate
Trifluoroacetic acid
Trirnethylhenzene
2.2.2.4-Trimethylpentane
2.2.4-Trimethyl- 1.3-pentanediol M.I. butyral
Trimethylphosphate
Water
Xylene
o-xylene
Dispersion
Polar
Hydrogen
Bonding
Molar
Volume
19.4
16.3
18.6
18.6
22.6
18.8
19.0
13.9
16.8
19.6
16.7
18.0
16.3
19.2
16.8
18.0
15.3
14.7
19.0
14.3
17.3
17.8
16.0
13.3
16.7
15.6
17.8
14.1
15.1
16.7
15.5
17.6
17.8
7.0
3.3
1.0
19.2
5.1
5.1
6.5
0.4
5.7
2.0
8.2
1.4
6.3
5.3
4.3
3.1
2.0
1.6
12.3
3.1
22.4
0.4
12.5
3.1
11.4
9.9
0.4
0.0
6.1
15.9
16.0
1.0
1.0
7.6
5.5
4.1
16.6
8.2
9.4
2.9
0.6
8.0
2.9
11.0
2.0
4.3
4.1
2.0
5.3
0.0
0.0
4.5
9.0
23.3
1.0
18.6
8.4
9.2
11.6
1.0
0.0
9.8
10.2
42.3
3.1
3.1
118.0
326.0
115.6
66.8
116.8
105.2
101.1
224.0
81.7
136.0
120.4
106.8
345.0
187.0
99.3
90.2
92.8
119.2
316.0
242.0
133.2
138.6
114.0
418.5
171.0
74.2
133.6
166.1
227.4
115.8
18.0
123.3
121.2
398
P A I N T A N D COATING T E S T I N G M A N U A L
TABLE 4 C o n t i n u e d - - S o l u b i l i t y parameters for polymers.
Cellulose acetobutyrate
Cellit BP-300"
12.0
18.2
12.4
6.7 10.2
10.8
4.3
6.9
3.9
5.9
7.4
14.2
11.4
10.5
11.1
9.6
7.2
9.4
6.1
9.0
9.0
13.4
10.7
14.8
13.7
17.7
9.1
7.9
11.7
7.8
14.9
23.8
20.3
24.9
26.9
5.3
6.6
3.1
2.4
16.2 16.1
14.1 9.6
18.7 20.3
18.5 24.0
17.7
19.1
21.1
16.0
20.6
19.4
17.9
18.7
19.9
10.6
12.2
14.6
13.1
7.8
7.4
9.6
9.6
8.1
11.6 9.5
9.9 8.0
12.0 16.2
9.2 11.4
11.6 13.1
6.0 9.8
5.9 8.2
9.9 8.2
6.0 9.8
22.7
19.3
6.4
11.4
8.2 19.4
14.3 12.4
Polyurethane
Desrnophen 651
Desmophen 800
Desmophen 850"
Desmophen 1100
Desmophen 1150
Desmophen 1200
Desmophen 1700
Desmolac 4200
Macrynal SM 510N
Phenolic resins
Super Beckacite 1001~
Phenodur 373 U"
Hydrocarbon resins
Piccolyte S-I00"
Piccopale 110"
Piccoumarone 450 La
16.1
17.2
19.0
0.4
1.2
5.4
2.8
3.5
5.6
8.4
6.4
9.4
17.2
3.3
2.6
6.4
8.6
4.1
9.4
Acrylonitrile-butadiene elastomer
Hycar 1052 a
18.2
Polybutadiene
Buna H~ls B-10"
2.2
3.3
6.2
5.3 10.4
18.1
18.2
3.4
4.7
4.9
2.0
3.6
5.0
19.9
0.0
0.0
9.4
Nitrocellulose
15.1
1/2-sec-Nitrocellulose H 23 a
14.4
17.4
17.4
Chlorinated polypropylene
19.8
Chlorosulfonated polyethylene
Hypalon 20 b
Hypalon 30 b
Cyclized rubber
Alpexb
16.2
1.4
-0.8
14.2
16.9
17.4
19.7
16.1
2.5
2.5
4.3
14.3
3.7
17.2
7.4
Polyvinylchloride
8.2
3.4
21.2
17.2
19.6
19.2
0.9
9.2
5.7
4.6
8.3
14.0
10.7
7.6
15.4
10.4
11.4
10.4
17.0
18.9
20.4
-1.9
9.6
0.4
14.6 7.4
11.1 6.2
14.0 12.9
17.5
17.6
19.7
11.3
10.0
12.9
5.9 8.5
3.7 9.3
12.8 11.4
18.6
20.2
18.2
12.9
11.2
4.3
10.3 8.3
13.3 11.2
12.7 10.4
17.2
16.2
18.6
18.4
18.2
9.4
6.8
10.8
9.4
10.3
3.9 10.4
5.7 9.1
4.1 11.5
6.5 10.7
7.7 8.4
20.5
11.0
9.4 13.4
20.8
5.6
4.2 12.4
Polyamide
Versamid 930"
Versamid 961
Versamid 965
Isocyanate
Desmodur L
Demodur N ~
Suprasec F-5100"
Polyvinylbutyral
Mowithal B 30 H
Mowithal B 60 H
Butvar B 76 a
Polyacrylate
Lucite 2042"
Lucite 2044
Plexigum MB 319
Plexigum M 527
PMMAa
Polyvinylacetate
Polystyrene
9.4
4.6 12.4
4.0 7.2
8.4 7.4
14.7 11.4
7.9 8.9
8.6 11.2
Rosin derivatives
Cellolyn 102a
Pentatyn 255 ~
Pentalyn 830"
Ester Gum 8L~
Polystyren LG~
Polyisobutylene
Vipla KR a
3.8 10.0
3.9 6.1
6.4
Polyisoprene
Lutonal IC/1203 ~
Lutonal I60
Polyvinylbutyl ether
Lignin p o w d e r ~
Modaflow Multiflow
9.5
4.3
Chlorinated rubber
Mowilith 50"
17.1
Cariflex IR 305 a
6.8 9.8
7.9 11.9
Parlon P 10"
14.0
21.3
18.1
17.4
21.0
18.9
23.4
8.3
7.6
5.9
9.9
Epoxy
Versamid
Versamid
Versamid
Versamid
20.0
17.0
Pergut S 5
Allopren R 10
17.9
20.1
Araldite DY 025
Epikote 828
Epikote 1001
Epikote 1004
Epikote 1007
Epikote 1009
Phenoxy PKHH
Cereclor 70
Chlorparaffin 40
7.4
Ethyl cellulose
Ethocel HE 10 ind b
Ethocel Std 20 ind b
Chlorparaffin
16.6
Cellulose acetate
Cellidora Aa
Vinylchloride/copolymers
Laroflex MP 45
Vilit MB 30
Vilit MC 31
Vilit MC 39
Vinylite VAGD
Vinylite VAGH
Vinylite VMCA
Vinylite VMCC
Vinylite VMCH
Vinylite VYHH
Vinylite VYLF
18.4
20.0
20.0
18.4
17.1
16.5
17.7
17.6
17.6
17.4
18.1
8.4
8.3
8.3
7.6
10.4
10.9
11.1
11.1
11.1
10.2
10.3
5.8
6.7
6.7
6.7
6.5
6.4
6.9
6.8
6.4
5.9
4.2
9.0
9.4
9.4
6.8
7.5
7.7
8.7
8.8
8.6
7.8
8.3
CHAPTER 3 5 - - S O L U B I L I T Y P A R A M E T E R S
T A B L E 4 Continued--Solubilityparameters for polymers.
D
10.0
2.2
15.2
13.8
9.3
5.3
1.0
4.6
4.2
I3.1
6.2
9.0
11.6
12.0
13.0
5.0
4.2
7.6
8.1
9.1
6.3
7.6
5.5
7.9
5.8
7.0
4.8
8.5
6.0
7.6
10.4
16.9
18.1
17.1
12.4
11.9
19.0
12.6
9.3
16.8
9.5
10.4
9.0
11.5
11.5
Amino resins
BE 370
Beetle 681
Cymel 300~
Cymel 325
Dynomin MM 9
DynominUM 15
Soamin M 60
Synresen A 560
Plastopal H~
Uformite MX-61
20.7
22.2
19.9
25.5
18.8
19.9
15.9
22.1
20.3
22.7
6.1
-0.4
8.3
15.2
14.0
15.8
8.1
5.0
8.1
2.8
12.7
10.1
10.4
9.5
12.3
13.4
6.5
11.3
14.6
5.4
14.8
18.4
14.4
22.2
10.5
11.7
10.6
15.5
12.4
16.2
Acrylate resins
Uracron 15
Paraloid P 400
Paraloid P 410
Paraloid experimental resin QR 954
19.2
19.2
19.6
18.4
7.7
9.6
9.1
9.8
5.7
9.3
6.8
10.0
10.6
12.2
12.2
12.4
19.4
16.6
9.9
1.9
10.1
8.0
6.9
8.0
Silicone resins
Baysilon UD 125
Wacker 190 F
A d d i t i o n a l S p e c i a l Data
polymers.
B i n d e r s in s o l u t i o n
Alftalat AC 366
Alftalat AM 756
Alftalat AN 896
Alftalat AN 950
Alftalat AT 316
Alflalat AT 576
Mkydal F 261 HS
Alkydal F 41
Durofta] T 354
Dynapol L 812
Dynapol L 850
Plexal C-34a
Soalkyd 1935-EGAX
Vesturit BL 908
Vesturit BL 915
399
20.3
19.5
23.5
18.4
15.4
11.6
17.5
9.4
5.3 15.1
9.3 10.0
16.8 15.6
10.1 7.0
17.0
18.7
17.0
17.4
17.0
16.1
20.5
12.1
7.5
3.4
9.8
4.4
18.5
10.5
10.2
8.9
10.6
14.6
10.6
14.5
12.3
4.1
5.8
5.1
5.1
5.1
9.3
7.3
solubility p a r a m e t e r c o m p o n e n t . Solvent quality can be adjusted by the RED n u m b e r concept or graphically as described above.
A c o m p u t e r search for nearest neighbors for a given single
solvent has b e e n used m a n y times to locate alternates. A
similar application is to predict which other solvents will
Suppliers
Trademarks
Bayer (D)
Hercules (USA)
Ciba-Geigy
Shell (D)
Union Carbide (USA)
Hoechst (D)
Reichhold (CH)
Polymer Corp. (CAN)
Goodrich (USA)
Hills (D)
BASF (O)
Monsanto (USA)
Montecatini Edison (I)
ICI (GB)
Du Pont (USA)
Hagedom (D)
R6hm (D)
Rohm and Haas (USA)
Dynamit Nobel (D)
SOAB (S)
BIP Chemicals (GB)
Dyno Cyanamid (N)
DSM Resins (S)
Reichhold Chemie (CH)
Wacker (D)
Dow Chemical (CH)
Cray Valley Prod. (GB)
W. Biesterfeld (D)
Synres (NL)
American Cyanamide (USA)
Polyplex (DK)
Pennsylvania Industrial
Chemical Corp. (USA)
400
Activity coefficients
Aerosol formulation
Biological materials and compatibility
Chromatography
Coal solvent extraction
Compressed gases
Cosmetics
Cryogenic solvents
Dispersion
Dyes
Emulsions
Gas-Liquid solubility
Grease removal
Membrane permeability and swelling
Paint film appearance
Pharmaceutical
Pigments
Plasticizers, polymers, resins
Plasticization
Polymer and plasticizer compatibility
Printing ink
Reaction rate of radical polymerization
Resistance of plastics to solvents
Rubber blends
Solid surface characterization--organic and inorganic
Solid surface modification
Solvent extraction
Solvent formulation, environmental aspects
Surface tension
Urea-water solutions
Vaporization of plasticizers
Viscosity of polymer systems
Water-based polymer systems, coalescents
Pigment
~p
~p
~h
FIG. 4-Solubility parameter relations for optimum pigment
dispersion stability.
~h
FIG. 5-Solubility relations for polymer mixtures can be quickly evaluated to ensure solution stability. Even mixtures of nonsolvents can
be systematically used to regulate solution behavior,
401
14
3: Dewetting
12
10
~;p
~p
6
4
10 12 14 16
~h
FIG. 6-Schematic representation showing expected miscibility of Polymers A and B with
each other but not with Polymer C.
CONCLUSION
The background and many uses of the solubility parameter
concept have been described in detail. Tables of solubility
parameters for many liquids and polymers have been presented. Systematic use of solubility, swelling, or permeation
402
150 --
"="
"NO="
<am
>alto
[]
BREAKTHROUGH'ro~.
OSTC
OBCN
NONE
Evaluation
uncertain
0.~
BCL
MSO []
OCH^
MM~'~~ c F I
OSTY
_mE'r
u (oL__
100
oN'm
--
;'...., ~'~
~
LE ~-v~"
~,~ ~
"E~zz ~o
BOND ,~c
_~ d~ ___x~L
"OC''r-- _~
~cO~
.02"' "?'~
":_'Z~" ~ci .....\
:Z
. ... . . . .
..... ~ , . ~ x . , ~ - - . .
MICO
ALI.,
0.0
1.0
o~,
-
o~r
rl~.A
CBBO'X
",,00~\
\\ \
50 --
"D
[]
ALN
,~,, \
o"~
'
o,c,
'
O,~c
2.0
3.0
^~00.ME
'
'
4.0
I ~'~
5.0
RED NUMBER
FIG. 8-Effects of molecular size (molar volume) and affinity (RED number) on the breakthrough time of Challenge 5100
[48].
Othmer Encyclopedia of Chemical Technology, Supplement Volume, 2nd ed., A. Standen, Ed., Interscience, New York, 1971, pp.
889-910.
403
31).
[33] McLellan, A. L, Tables of Experimental Dipole Moments, W. H.
Freeman, San Francisco, 1963.
404
MNL17-EB/Jun. 1995
i
36
by Thomas J. Miranda 1
INTRODUC~ON
One of the most critical, and often misunderstood properties of a coating is cure and its measurement. The optimum
physical and chemical properties of a coating depend largely
on proper curing conditions. For example, a thermosetting
acrylic polymer when applied to a panel and dried without
curing will be brittle and have poor solvent resistance and low
hardness. When properly cured, the film properties will
change dramatically and the properties which were designed
into the coating become apparent. Similarly, an oil-based
paint will be soft and tacky and slowly become hard and
scratch resistant as its cure develops. To appreciate the scope
of the material in this chapter, it may be well to review a few
film-forming mechanisms, polymer fundamentals, and some
background into the development of tests and what they
mean.
Polymers
A polymer is a high-molecular-weight interreaction product of related polyfunctional molecules [1 ]. The term polymer
is derived from the Greek poly (many) and met (part). Polymers are formed from monomers (mono -- one) (met -- part)
by a process of polymerization. Polymers consist of long
chains of macromolecules with molecular weights of a few
thousand up to many millions. For example, ultrahigh-molecular-weight polyethylene may have a molecular weight of 4
to 6 million, while alkyds have molecular weights of a few
thousand. The concept of macromolecules was developed by
Herman Staudinger in 1920 [2]. Staudinger's theory was
supported by the work of Wallace Carothers, who introduced
the concept of functionality and the distinction between thermoplastic and thermosetting polymers [3].
There are two types of polymers: addition and condensation. Addition polymers have high molecular weight and are
characterized by fast chain reaction syntheses that are exothermic and initiated by free radical, coordination polymerization, cationic, group transfer, or anionic mechanisms.
Free radical-initiated polymerization is initiated by incorporation of a free radical producer such as benzoyl peroxide
which decomposes with heat to form free radicals, which in
turn initiate polymerization. Coordination polymerization is
Senior Consultant, Consolidated Research, Inc., 16731 Brick Rd.,
Granger, IN 46530.
407
Copyright9 1995 by ASTMInternational
www.astm.org
Lacquers
Lacquers consist of a thermoplastic polymer which is dissolved in a solvent. When the coating is applied, the solvent
evaporates and a thermoplastic film is formed. This is the
type of coating used in certain furniture and automotive
finishes.
(crosslinking)
THERMOSET
CURE MECHANISMS
(no c r o s s l i n k i n g )
l
S
Emulsions
= solvent molecules
= linear polymer
= crosslinked segments
FIG. I-Polymers.
TYPES OF FILMS
As described above, polymers can be classified as thermoplastic and thermoset in nature when derived from addition
and condensation polymerization as well as by their physical
response to heat and solvent action.
Thermoplastic
A long-chain polymer such as polyethylene is considered
thermoplastic since it can be dissolved in certain solvents and
can be repeatedly softened or melted when heated and hardened when cooled.
Thermoset
On the other hand, a polymer prepared, for example, from
a phenol-formaldehyde condensate cannot be liquified and
solidified repeatedly after it is formed. These polymers are
termed thermosetting and tend to degrade if heated repeatedly. The reason for this is that they are cross-linked.
Oxidative Cross-Linking
In oxidative cross-linking, a polymer is prepared from an
unsaturated fatty acid or oil such as castor, tall, soya, linseed,
or tung oil, and a small amount of a siccative (drier) such as
OWOWOWOWOWOWOWOWOWOWOW
W
0000000000OO000000OOOO
O=Polymer
particles
W=Water
Latex
on
surface
Water
evaporates
Fused
film
OOH
R--CH--CH=CH--CH~---CH--R' + .OOH
where R is CH3(CH2) 4 and R' is (CH2)TCO2CH 3.
The initial products are converted to polymers according to:
Initiation:
Propagation
RH
02
) R" + "OOH
R" + 0 2
409
Melamine can be condensed with up to 6 mol of formaldehyde and 6 mol of methanol to form hexamethoxymethyl
melamine (HMMM). The reaction product has the following
structure and is often referred to as MF resin:
N(CH2OCH3)2
/A
N
II
(CH3OCH2)2N--C
C--N(CH2OCH3)2
N
Hexamethoxymethyl melamine
Hexamethoxymethyl melamine can be reacted to contain
from one to six methoxymethyl groups. Methanol is used to
cap the hydroxyl group to prevent premature reaction. Other
alcohols are commonly used, including butanol and isobutanol. In applying a melamine formaldehyde resin, the resin
usually is reacted with a functional polymer such as a thermosetting acrylic or alkyd polymer containing an acid or
hydroxyl group that can react with the MF resin. This can be
depicted in the following manner:
2 Polymer--[- + M--N(CH2OCH3)2
CH2OH
RO0"
Polymer-----[-RO0" + RH
Termination
) ROOH
RO0" + R"
RO0" + ROO"
+ R"
CH2(~
ROOR
/ CH2
M--N
+ 2CH3OH
\
> ROOR + 02
R'+R"
>R--R
Reactive Cross-linking
In this type of cross-linking, a reactive intermediate is
added to a polymer and a further chemical reaction is initiated either by heating alone, heating in the presence of a
catalyst, or by some other form of initiation.
CH~
CH20
Polymer
Urea
Melamine
Melamine formaldehyde condensates are used to cure
a reactive polymer. Melamine is 1,3,5 triamino-s-triazine
and is produced from the condensation of 3 moles of
dicyandiamide:
NH2
II
0
iL
H2N--C
C--NH 2
N
Melamine
N,N' bishydroxymethylurea
and is capable of reacting with hydroxyl groups to produce a
cross-link with the elimination of byproducts as water, alcohol, and formaldehyde.
CH3
/\
/\
CH2--CHz--O--Z--C--Z--O--CHz--CH--CH2
CH3
These epoxy functional groups can react with active hydrogen groups such as amines, hydroxyls, and acids. For example, they can react with acid groups in a thermosetting
acrylic, alkyd, or other polymer and produce a cross-linked
polymer. It is interesting to note that the reaction product of
the epoxy and acid function produce additional hydroxyl
groups which can be reacted with a melamine formaldehyde
or urea formaldehyde adduct to produce improved properties, such as hardness, chemical resistance, or solvent resistance in the cured films. The reaction of two acrylic polymer
chains with an epoxy resin is shown as follows:
[
COOH
0
/\
CH3
COOH
I
Acrylic polymer
l
Acrylic polymer
H
CH~
HN
CH--CH2--O--Z--C--Z--O--CH2--CH
CH3
OH
CH2
t
I
O
C-~O
Acrylic polymer
where Z represents a phenylene group.
Cross-linked acrylic polymer
Isocyanates
O=C--O
(CH2)2
Acrylic polymer
= CH3--C6H
3-
Catalyzed Cross-linking
Phenolics
Phenolic resins are condensation reaction products of phenol or substituted phenols and formaldehyde. Two types of
phenolics are obtained depending upon the catalyst and reaction conditions. Using an acid in its preparation, a thermoplastic, soluble novolac resin is obtained. Under basic conditions, the thermoset product formed is a resole resin which is
cross-linked at the final stages of the reaction. A phenolformaldehyde condensate may have a structure as shown:
~R--N--CqO
L I
H
Alcohol
Isocyanate
NH
CH3
O--C~-~O
CH2--CH--CH2--O--Z--C--Z--O--CH2--CH--CH2Epoxy resin
I
C=O
I
Acrylic polymer
I
I
(CH2)2
CH3
/\
Acrylic polymer
O--CHz--CH3
Urethane
This reaction is used in applying isocyanates to the production of insulation and seating foams, reaction injection mold-
OH
If I
HOH2C--C
C--CH2OH
\//
C
CH2OH
Phenol-formaldehyde (P--F) condensate
411
source for initiation. Electron beam (EB) and ultraviolet radiation is used to cure coating films. These processes induce
either free radical or carbonium ions to initiate polymerization, which occurs rapidly at ambient conditions.
I
/C\~
+ HOH2C--C
C--CH2OH
HEAT
I
II
C C
\//
CH2OH
C
CH2OH
Alk, 'd
Phenol-Formaldehyde Condensate
f
--CH20
H2C--C
C--CH2
II I
C C
\//
C
I
ALKYD
CH2OH
OH2C-- + 2 H20
ALKYD
Cross-linked alkyd
Silicones
These useful polymers are prepared from silicon by chlorination, then subsequent reaction with alkyl or aryl halides
to form alkyl/aryl chlorosilanes. Upon hydrolysis, these produce silicones. The alkyl silicones, such as dimethyl silicone,
CH3
Si
O--]n--
CH3
are low-molecular-weight or cyclic materials used in antifoam applications. The linear forms are specialty elastomers.
Blends of methyl and phenyl silicones have higher-temperature resistance and find use in heat-resistant coatings or polymers. Silicones can be cross-linked when prepared with multi functional silane monomers such as trichloromethyl silane.
Upon hydrolysis, the silicone chains can be cross-linked
through siloxane bridges:
CH3
Si
O--].--
O
[
Si
O--In-
CH3
Cross-linked silicone
Silicones can also be cross-linked by peroxide initiators. In
this case a silicone monomer containing a vinyl or allyl group
is copolymerized to provide an active site along the chain.
When used in a gasket or caulk, a small amount of a peroxide
is added which initiates polymerization and cross-links the
resin system. Silicone reactions are usually catalyzed by 01"gano zinc or tin compounds.
Curing can also be accomplished using radiation as a
CURE MEASUREMENT
It is very important for the user of coatings to know
whether a coating is adequately cured. This can be done
quickly in qualitative testing or in more sophisticated test
methods requiring instrumentation. The rapid methods are
desirable because of time and cost, but in some cases do not
really tell the true story. In some cases, even instrumented
testing only tests a certain range of cross-linking and could
lead to erroneous conclusions. We shall discuss the qualitative methods first, then proceed to the more quantitative.
What should be borne in mind is that we are attempting to
ascertain a molecular process, cross-linking, and its relationship to coating performance.
Many thermoplastic coatings "dry" by simple evaporation
of solvent, and though cure was defined above as the crosslinking of a polymeric system, such drying of lacquers can be
considered a form of curing even though no cross-linking
occurs. This is true for nitrocellulose lacquers, cellulose acetate, and solvent soluble acrylics where no cross-linking takes
place. To measure cure for such coating, the time for either
print-free or tack-free is measured. At some time during evaporation, the coating goes from tacky, to set-to-touch, to tackfree. Upon further drying, the coating becomes print-free,
whereby a thumb print will not be visible on the coating. This
can also be measured by dropping cotton linters onto the
surface and noting the time after which they do not adhere to
the coating. Also see ASTM D 2091, which describes a standard method for print resistance of lacquers.
These tests also apply to coatings which dry by oxidative
cross-linking, for example, alkyds. Here, times are noted for
solvent evaporation, and the coating is monitored for set-totouch, then print-free.
Hardness Measurements
Another way of obtaining information concerning crosslinking is to measure some physical property such as, hard-
412
from:
PFN = L/A = 4L/wd2 = 1.27 L/d 2
where
L = applied load in kilograms,
A = area of projected indentation in mm 2, and
d = diameter of the projected indentation in mm.
Thermal Analysis
Thermal analysis is an important analytical tool for determining the response of material to changes in temperatures.
This method of analysis can be used to monitor the glass
transition temperature, Tg, of a coating, and this can be related to the cross-linking density. For example, a ladder of
paint panels cured at various times or temperatures can be
prepared and then studied by thermal analysis to determine
the change in Tg as a function of bake schedule. From this, the
optimum cure cycle can be determined to insure a quality
finish.
Thermal analysis units have several modes for determining
Te: differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and dynamic mechanical analysis (DMA) are useful tools for obtaining quantitative mea-
KIlN
Sward
Pencil (Brands)
C
3.09
4.33
2.77
2.61
5.81
24
28
24
22
38
5B
4B
5B
3B
2B
6B
6B
6B
4B
2B
5B
6B
5B
5B
2B
6B
6B
4B
4B
2B
4B
4B
3B
3B
HB
1
2
3
4
5
10
25.7
54
2H
12
39.1
40
3H
2H
2H
4H
3H
40
8H
9H
7H
7H
9H
14
Impedance Measurements
Myers [16] s t u d i e d the drying behavior of latex systems
using ultrasonic i m p e d a n c e m e a s u r e m e n t s , I n this work, a
latex coating was cast on a quartz crystal a n d ultrasonic energy was b e a m e d at an 11 ~ angle at the u n d e r s i d e of the
coating a n d reflected to a d e t e c t o r w h i c h m e a s u r e d the attenu a t i o n of the initial b e a m as a b s o r b e d by the drying coatings.
As w a t e r evaporated, there were changes in i m p e d a n c e t h a t
could be c o r r e l a t e d to drying.
414
REFERENCES
[1] D'Alelio, G. F., Fundamental Principles of Polymerization, John
Wiley & Sons, Inc., New York, 1952, pp. 5-22.
[2] Staudinger, H., Uber Polymerization, Vol. 53, 1920, pp. 10731085.
[3] Mark, H. and Whitby, G. S., Eds., Collected Papers of Wallace
Hume Carothers on High Polymeric Substances, Interscience,
New York, 1940.
[4] Paul, S., Surface Coatings, Chapter 1, John Wiley & Sons, New
York, 1985.
[5] Wicks, Z. W., Jr., Film Formation, Federation Series on Coatings
Technology, Blue Bell, PA, June 1986.
[6] Paul, S., Surface Coatings, John Wiley & Sons, New York, 1985,
pp. 452-453.
[7] Brown, W. H. and Miranda, T. J., Official Digest, Vol. 36, No.
475, 1964, p. 92.
[8] Paul, S., Surface Coatings, John Wiley & Sons, New York, 1985,
p. 485.
[9] Sato, K., Progress in Organic Coatings, Vol. 8, No. 1, 1980.
[10] Miranda, T. J., Journal of Paint Technology, Vol. 43, No. 553,
1971, p. 51.
[11] Seymour, R. B. and Carraher, C. E., Jr., Polymer Chemistry, An
Introduction, 3rd ed., Marcel Dekker, New York, 1992, p. 139.
[12] Stevens, M. P., Polymer Chemistry, An Introduction, 2nd ed.,
Oxford University Press, 1990, p. 167.
[13] Miranda, T. J., Mechanical Behavior of Materials, Vol. III, The
Society of Materials Science, Japan 1972, p. 392.
[14] Lambourne, R., Ed., Paint and Surface Coatings, Ellis Horwood
Ltd., 1987, p. 607.
[15] Allcock, H. R. and Lampe, F. W., Contemporary Polymer Chem/stry, 2nd ed., Prentice Hall, Englewood Cliffs, NJ, 1990, p. 427.
[16] Myers, R. R., Journal of Polymer Science, C, Vol. 35, No. 3, 1971.
[17] Anderson, J. L., Root, D. E., and Green, G., Journal of Paint
Technology, Vol. 40, No. 320, 1968.
[18] Rossi, A. G. and Paolini, A., Journal of Paint Technology, Vol. 40,
No. 328, 1968.
MNL17-EB/Jun. 1995
37
T E S T R E Q U I R E M E N T S OF F I L M S
Test requirements come in two classes, appearance and
physical properties. Choice of application method for the film
may affect the appearance in some cases. For instance, the
"multicolor" paints must be applied by dip or spray techniques for laboratory testing, or the appearance does not give
the desired mottle of nearly circular spots. Roller, brush, or
even drawdown bar will cause these spots to become streaks.
Choice of application method for appearance includes drying
technique, as some films require special drying conditions to
attain their desired special appearance. Examples include
leafing aluminum flake "metallic" look paints, hammertones,
and wrinkle finishes.
Choice of application method driven by physical property
testing is also necessary. Think carefully of the three kinds of
stresses (tensile, compression, shear) and recognize that all
are blended in a hardness or adhesion evaluation by indenter,
pencil, mandrel bend, or dart impact test on a coating. Recognizing these stress combinations can make one aware of film
preparation needs. In cases where adhesion is stronger than
cohesion of the film, one should be able to distinguish between adhesive failure and cohesive failure. Film preparation
should not conflict with these objectives.
The physical properties to be tested in specific ASTM methods have a "significance and use" section in the method to
ascribe the relation of the test value to some "in use" perfor~Athey Technologies, P.O. Drawer 7, E1 Cerrito, CA 94530-0007.
Another portion of film influence on the test is film thickness. The presentation by the Technical Committee from
Toronto in the 1990 National FSCT meeting and Paint Show
[1] dealt with hardness measurements in films of varying
thickness. However, the control of film thickness was not as
straightforward as might have been thought. Hardness values
turned out to be dependent on film thickness along with other
equally important variables [2].
Fluid rheology, concentration, and other factors govern the
amount of coating left after the application process. Knowing
the process variables associated with a film-casting technique
are essential to getting what is needed for the ultimate test
and results therefrom. Certain other properties of the film
(opacity, permeability, erosion rate by some attacking mode,
etc.) will depend on the thickness of the film. So, understanding thickness control in the casting process is crucial to
obtaining meaningful results in terms of meeting specifications in reproducibility.
In instances where fluid or gas permeation resistance or
corrosion barrier properties are to be tested, a "pinhole,"
"holiday," or "mudcrack" in the film is a fatal flaw. The film
preparation technique must eliminate (as much as possible)
any such fatal flaw, or the test method should prescribe what
is to be done (for example, replications) in cases where an
unseen fatal flaw is detected by the test.
FILM C A S T I N G T E C H N I Q U E S
Free Films
Free films, that is, films not applied permanently to a substrate, are used for a wide variety of tests and accordingly
vary in thickness and size. The most common castings of free
films are used for permeation or strength and elongation
testing. They can also be used for cold flex tests or moisture/
solvent absorption studies related to permeation. Free film
thickness can be measured as described in ASTM D 1005:
Test Method for Measurement of Dry-Film Thickness of Organic Coatings Using Micrometers.
Probably the most common ~ee film castings are laid down
on a "nonstick" surface, such as the silicone-coated papers
(available through Leneta and other suppliers) or TEFLON TM
or polyethylene sheets. Release substrates are described in
ASTM D 823: Test Methods for Producing Films of Uniform
415
Copyright9 1995 by ASTMInternational
www.astm.org
416
P A I N T A N D COATING T E S T I N G M A N U A L
417
418
Tar =
Twf =
Ot =
0f =
G =
S =
Gardner "Microm"
applicator (also
Hercules-Gardner
adjustable [3])
"Universal" blade
applicator
Design Details
Suppliex~
Reference
P.N. Gardner
P.N. Gardner
[20]
P.N. Gardner
[20]
P.N. Gardner
[20]
P.N. Gardner
[20]
Byk-Gardner
[3]
aThere may be many other suppliers, but only one is cited herein as a space savings technique.
[3]
419
50%
60%
80%
90%
The hand-held drawdown bars are covered in an ASTM specification: Method E in ASTM D 832, Practice for Rubber
Conditioning for Low-Temperature Testing.
A wide variety of drawdown bars are commercially available, though your local machine shop can make special orders of any design, if needed. Table 1 lists a few of the
available types of drawdown bars, with commercial sources
reports on them. Some rectangular design devices have differing gap depths on the sides so one may choose the film
thickness needed for casting (see Figs. 4 and 5).
Stainless steel or aluminum are the preferred materials of
construction, as corrosion can damage the region of the
drawbar controlling thickness of applied film. Good laboratory practice dictates immediate cleaning of the paint contact
surfaces after every usage to minimize the threat of corrosion
or other damage. A caution on marking the drawdown bars,
as some manufacturers label them not with the gap spacing,
but a number half the gap spacing since that is the expected
wet film thickness to be obtained.
Some drawdown bars have film thickness adjustment
choices by micrometers or other techniques (see Table 1 and
Fig. 6). When these are used, the settings should be checked
with feeler gages to make certain user wear has not made
them inaccurate. These also require dismantling and cleaning after every use. If oil is used to inhibit corrosion and make
the mechanics move smoothly, make sure they are rigorously
cleaned of oil prior to usage.
420
sheets, one sheet at a time as the sheets are pulled out from
underneath the device. One such device is the Parks Film-OGraph cylinder. One puts the cylinder on a stack of Leneta
charts or metal panels, fills the cylinder with the coating, and
pulls each sheet from underneath the cylinder. A portion of
the rim edge of the cylinder is milled out to act as the gate to
allow coating at a desired thickness. One may even use it for
very viscous coatings (even putty) by forcing the fluid through
the tube with a loose-fitting plug from the top and wiping the
bottom of the tube over the substrate to be coated.
The second of the devices discussed was the Parks Rapid
coater. Paper sheets were stacked in the bottom of a box with
their ends out of a side slot at the bottom. The box was then
filled with coating fluid, and each sheet was withdrawn individually. Grenko [3] noted this was not a precision device, but
it was adequate for some purposes.
Grenko [3] also described the flat Parks Film-O-Graph,
which used a flat plate with spring clips to hold shims along
the sides of the sheet of substrate. One poured the coating
onto the substrate between the shims and used a bar such as a
ruler or other straight edge to doctor off the excess and make
the coating as thick as the shims. Bending of the scraper bar
by the very slightest amount would make very thin films
almost impossible, but for thick films (for example, roof coatings), this technique worked well.
Some applicators are meant only for the wet film tests. Two
especially useful applicators for these are the sag test devices
and the wet hiding test devices. The latter, most frequently
the Pfund Cryptometers (available from Erichsen [19] and
Byk-Gardner [20]), have black or white glass (ceramic) beds
over which a transparent wedged cover levels the coating film
(see Fig. 9). Although these devices are quite hard, care in
cleaning will assure they do not get scratched. They must be
stored carefully, wrapped, and covered.
The sag test film casters essentially drawdown several narrow films in gradations of film thickness. Many are simply
slotted U-shaped drawdown bars with variations in slot depth
from 1 to 6 mil, 3 to 12 mil, and 14 to 60 mil. However, the
New York Paint Club Technical Committee designed a special "leveling test blade" that had double slots for each depth
with a wide space between each set of double slots [21]. Their
slots are 1, 2, 4, 8 and 16 rail in depth (see Fig. 10).
As paint film drip or sag depends on the rheological characteristics, the thickness of the coating that first sags may be
related to the gravity-applied shear stress by the outer elements furthest away from the substrate on that film. Other
rheological factors (high shear viscosity, ca. 10 000 s-1, for
instance) are also important in sag and leveling. Sag test
devices complying with ASTM D 3730, Guide for Testing
High-Performance Interior Architectural Wall Coatings, and
several federal specifications and the New York leveling test
blades are available from P.N. Gardner [20] and BykGardner [18].
Wire-Wound R o d s
For very thin films, the wire-wound rods are quite useful
for quickly and easily applying films. The wire-wound rods
are simple rods of 12 or 16-in. (30 to 40-cm) length, of I/4, 3/8,
or 1/2 in. (0.63, 0.45, or 1.27 cm) diameter, with a sprial wind
of wire tight about 75 to 80% of the rod. Table 2 shows a
selection of wet film thicknesses obtained from the rods with
different wire diameter.
The film laid down with a wire-wound rod is almost exactly
a tenth the thickness of the wire winding. Strictly speaking, as
the film has the rod depart, there are ridges in the film in the
direction of travel of the rod. However, these collapse to make
a quite smooth film unless there is rheological inhibition in
the formulation or the coating is very fast drying. This technique is quite effective to simulate paper or can coating end
products. There are industrial production systems that era-
Wire
Diameter (in.)
0.0025
0.003
0.0035
0.004
0.0045
0.005
0.0055
0.006
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
6.4
7.6
8.9
10.2
11.4
12.7
14.0
15.2
25.4
50.8
76.2
101.6
127.0
152.4
177.8
203.2
228.6
421
Spray Outs
S p r a y application, including b y weight on a panel h a n g i n g
on a b a l a n c e in a spray booth, can be done with good precision. Good s p r a y out a p p l i c a t i o n on panels can be done by
those skilled in the art. To control the weight a p p l i e d in a
s p r a y booth, a triple b e a m b a l a n c e m a y be a t t a c h e d to a b e a m
5 o r 6 ft. (1.5 o r 1.8 m) above the floor, a n d a hanger-wire
panel h o l d e r is h u n g from it as the s p r a y target. A c a r d b o a r d
shield over the b a l a n c e will keep off overspray. Tare the balance a n d p r e s e t weight n e e d e d to apply. Take off a few tenths
of a g r a m to give a p o i n t e r i n d i c a t o r w a r n i n g w h e n the s p r a y
has a l m o s t r e a c h e d the desired weight. S p r a y quickly to minimize evaporation.
There are a u t o m a t e d s p r a y devices. Grenko [3] related the
a u t o m a t e d spray device design from Bell Labs [23] to M e t h o d
A of ASTM D 823. The Bell Labs design has the gun travel
over s t a t i o n a r y panels, while an alternative design has the
panels on a moving belt u n d e r a s t a t i o n a r y s p r a y gun, s i m i l a r
to a design r e p o r t e d from Battelle [24]. I n either case, the
a m o u n t of coating a p p l i e d to the panel is controlled by the
speed of the moving belt a n d by nonvolatile content of the
s p r a y e d fluid. G r e n k o [3] notes the s a m p l e panels on the
moving belt m a y be held to the belt with m a g n e t s or suction
cups. Erichsen [19], G a r d n e r [20], a n d others offer autom a t e d spray a p p l i c a t o r s for lab s a m p l e p r e p a r a t i o n (see Figs.
12 a n d 13).
The s p r a y technique is p a r t i c u l a r l y i m p o r t a n t , b u t p r e c a u tions are necessary to assure evenness of coating on the
substrate. The spray p a t t e r n should extend b e y o n d the edges
of the substrate w h e n the nozzle is a i m e d at the center of the
target. The s p r a y p a t t e r n - - b e it flat, fan, o r c i r c u l a r - - h a s less
p a i n t at the edges t h a n at the center. Moving the s p r a y nozzle
across the target or the target u n d e r the center of the nozzle
m a k e s the d e p o s i t i o n m o r e likely to be consistent in thickness.
Dip Coating
422
Spin Coating
Grenko [3] described the work of Walker and Thompson
[27] attaching a panel to a turntable and rotating for I min at
300 rpm to obtain a 25-/zm varnish film thickness. He also
described the Sward-Gardner [28] relation of film thickness
(F) to viscosity (V, in poise) and nonvolatiles, % N, as
F = O . 4 N + V4 + 3
where spin rate was 290 rpm for 60 s. Their work had a
precision of 5 to 10%, and corrections for time or rpm variations were offered. Parker and Siddle [29] suggested modifying the method by adjusting viscosity to equivalence for all
fluids to be compared and using volume solids rather than
weight percent nonvolatiles. Plots of film thickness versus
volume percent nonvolatile were straight lines for nonthixotropic fluids, but curvature existed for thixotropic fluids.
A commercial lab spin coating device is currently available
from Erichsen [19]. There are two versions, one with 600 rpm
speed set, and another adjustable from 50 to 2000 rpm (see
Fig. 14).
FIG. 12-Single setting lab spray applicator,
(Courtesy of Erichsen GMBH & Co.)
CONCLUSION
How the film is prepared for testing can have a d r a m a t i c
effect o n the test results. The thought p u t into film preparation prior to p r e p a r a t i o n a n d the care used in casting can he
crucial factors in o b t a i n i n g m e a n i n g f u l a n d reproducible results.
REFERENCES
[1] Toronto Society for Coatings Technology Technical Committee
presentation, 1990 National Paint Show Voss/APJ Competition
presentation, available from the Federation of Societies for
Coatings Technology, 492 Norristown Rd., Blue Bell, PA 194222350.
[2] Athey, R. D., Jr., "Coating Tests--Hardness of the Film," European Coatings Journal, Vol. 92, No. 10, December 1992, p. 461.
[3] Grenko, C., "Preparation of Films for Test," ASTM STP 500,
Paint Testing Manual, G. G. Sward, Ed., American Society for
Testing and Materials, Philadelphia, 1972.
[4] Sager, T. P., "The Preparation of Thin Films," Industrial and
Engineering Chemistry, Analytical Edition, IENAA, Vol. 9, 1937,
p. 156.
[5] Brightwell, E.P., "An Optical Method for Measuring Film
Thickness of Paint Films," Official Digest, Federation of Paint and
Varnish Clubs, ODPFA, Vol. 28, 1956, p. 412.
[6] Bayor, E. H. and Kempf, L., "Preparing Fragile Paint and Varnish Films," Industrial and Engineering Chemistry, Analytical
Edition, Vol. 9, 1937, p. 49.
[7] Clarke, G. L. and Tschentke, H. L., "Physicochemical Studies on
the Mechanism of Drying of Linseed Oil. 1. Changes in Density
of Films," Industrial and Engineering Chemistry, IECHA, Vol. 21,
1929, p. 621.
MNL17-EB/Jun. 1995
38
Measurement of Film
Thickness
by C. M. Wenzler 1 and J. F. Fletcher I
O N E OF T H E MAJOR R E Q U I R E M E N T S OF PAINT a n d
coating testing
is the m e a s u r e m e n t a n d control of film thickness. E n s u r i n g
that a specification is achieved is i m p o r t a n t in l a b o r a t o r y
tests, p a i n t application, a u t o m a t i c spraying, a n d o t h e r coating a p p l i c a t i o n methods.
A n u m b e r of test m e t h o d s are available, a n d the choice is
d e p e n d e n t on: (1) the l o c a t i o n - - l a b o r a t o r y o r site; (2) the
m a t e r i a l c o a t e d - - m e t a l (ferrous o r nonferrous), wood, plaster, b r i c k a n d plastic; (3) the c o n d i t i o n of the c o a t i n g - - w e t o r
dry; a n d (4) the c o n d i t i o n of the s u r f a c e - - r o u g h or smooth,
flat o r shaped, thick or thin, etc.
t = D2/16R
where
D = diameter, m m , of spot, a n d
R = r a d i u s of curvature, m m , of the lens.
Table 1 gives film thickness a n d the c o r r e s p o n d i n g spreading rate in square feet p e r gallon for spots from 3 to 38 m m in
diameter.
It has been observed that a substantial p r o p o r t i o n of p a i n t s
do n o t obey the 1 to 1 relationship. The actual thickness,
o b t a i n e d by i n d e p e n d e n t methods, m a y be several times, o r
only a fraction of, the thickness calculated b y the equation. A
small a m o u n t of t h i n n e r a d d e d to a p a i n t m a y increase t h e
d i a m e t e r of the spot on the lens a n d give a c o r r e s p o n d i n g
increase in the calculated thickness. This p h e n o m e n o n has
been a s c r i b e d to the effects of surface tension. Hence, for b e s t
results, a correction factor should be established for each
type of p a i n t b a s e d on the k n o w n thickness of a freshly prep a r e d film m e a s u r e d b y the I n m o n t gage.
R e p r o d u c i b i l i t y is within a b o u t 2% for films 2 mils ( 5 0 / z m )
thick, decreasing to a b o u t 10% for films 5 mils (125/zm)
thick, then b e c o m i n g better as thickness increases.
(1)
www.astm.org
425
ECCENTRICINNERWHEEL
WETF~M I
Needle Micrometer
This method was used to study the relationship between
the clearance of a doctor blade and the thickness of the wet
film left by the blade [1]. A needle is attached vertically to the
objective holder of a microscope. The barrel is lowered until
the needle just touches the film that has been spread on a
plain metal panel. The contact is observed through a horizon-
r,
426
Diameter
of Spot,
mm
mm
Mils
Ft/Gal
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
32
34
36
38
0.002 25
0.004 00
0.006 25
0.009 00
0.012 25
0.016 00
0.020 25
0.025 00
0.030 25
0.036 00
0.042 25
0.049 00
0.056 25
0.064 00
0.072 25
0.081 00
0.090 25
0.100 00
0.110 25
0.121 00
0.132 25
0.144 00
0.156 25
0.169 00
0.182 25
0.196 00
0.210 25
0.225 00
0.256 00
0.289 00
0.324 00
0.361 00
0.089
0.157
0.246
0.354
0.482
0.630
0.805
0.985
1.19
1.42
1.66
1.93
2.21
2.52
2.84
3.19
3.55
3.94
4.34
4.76
5.20
5.67
6.15
6.65
7.18
7.72
8.28
8.96
10.08
11.38
12.76
14.21
18 088
10 175
6 512
4 522
3 321
2 543
2 009
1 628
1 345
1 130
963
830
723
636
563
502
450
407
369
336
307
282
260
241
223
207
193
180
158
141
125
113
Thickness
CHAPTER 3 8 - - M E A S U ~ M E N T
OF FILM THICKNESS
427
428
Microscope for F i l m T h i c k n e s s
Classical Method
To use a microscope to assess film thickness, a section is
prepared and the width of the coating is measured using a
graticule in the eyepiece of the microscope. For an approximate assessment, a flake of the coating can be used, but for
best results from this method the specimen should be prepared as follows.
The specimen is mounted in a block of wax. The face of the
mount is cut or ground to a smooth surface. The prepared
specimen is then inspected under the microscope. ASTM
Method for Microscopic Measurement of Dry Film Thickness
of Coatings on Wood Products (D 2691-88) is based on this
method; however, as paints are often hard and brittle, a
grinding and polishing method is preferred to the blade
method indicated in D 2691.
This method does not require removal of a chip and elaborate mounting and preparation. A tiny furrow is made in the
film or a small chip is removed. A prism or ribbon of light is
projected on the selected area at an angle of 45 ~. The distortion of the beam is examined with a microscope equipped
with a micrometer eyepiece. Apparatus for this is available in
the Schmaltz optical surface analyzer (Carl Zeiss).
The apparatus is calibrated by measuring known depths
milled in a smooth metal block. The ribbon of light is focused
on line A, and the filar micrometer reading is recorded. The
procedure is repeated on line BC. The difference multiplied
by the calibration factor equals the thickness of the film.
Table 2 compares results by this method with results with a
micrometer.
Dial Micrometer
0.39
0.46
0.71
0.98
0.4
0.5
0.8
1.0
1.51
2.28
3.58
1.4
2.1
3.5
1.30
1.3
[4]
This gage (shown in Fig. 6) provides for estimating the
thickness of a film from the geometry of a V-groove cut in the
film by a special tool. With the aid of a x 50 illuminated
magnifier equipped with a reticle in the eyepiece, the operator measures the lateral distance from the top edge of the cut
and the projection of the intersection of the cut and the substrate. To make a measurement, a "bench mark" of ink applied to the surface of the film serves to make the top edge of
the cut readily visible. A short cut is then made at a right angle
to the bench mark with the selected cutting tip. Film thickness is then obtained by counting the scale divisions as described previously.
The relationship among the tips is summarized in Table 3.
Tip
Maximum
Coating
Thickness,mils
Precision of
Thickness
Determination
Represents,mils
One
Division on
Reticle Scale, mils
1
x2
x 10
50
20
3
_+0.25
_+0.13
-+0.025
1.0
0.5
0.1
Saberg Drill
This method is similar to the Tooke inspection gage
described in the previous subsection; however, a circular drill
is used to penetrate the film. The hole can then be inspected
using the x 50 magnifier with graticule, and the width of the
cut from the outer edge to the print where the drill penetrates
to the substrate is a measure of the coating thickness. For the
instrument kit supplied by Elcometer Inc., Rochester Hills,
M148309 (Model 195), the calculation of coating thickness is
as follows:
1. For measurement in mils, multiply graduations by 0.79.
2. For measurement in micrometers, multiply graduations by
20.0.
3. This method is now described in ASTM Test Method for
Measurement of Dry Film Thickness of Protective Coating
Systems by Destructive Means (D 4138).
D R Y FILM T H I C K N E S S
(NONDESTRUCTIVE METHODS)
Permanent Magnet Thickness Gages
Permanent magnet coating thickness gages can be used to
determine the thickness of films applied to magnetic substrates such as steel, iron, magnetic stainless steel, etc., providing that the coating is nonmagnetic. Materials such as
nickel and cobalt, that are naturally magnetic have to be
treated with care, while paints containing magnetic particles,
such as some ferrous micaceous iron oxide (MIO), can cause
errors when using magnetic gages.
Simple magnetic coating thickness gages or mechanical
gages use the principle that the attractive force between a
permanent magnet and the magnetic metal substrate is inversely proportional to the distance between them.
The principal limitations are (1) the film must be sufficiently hard to prevent indentation, and (2) the film must not
be tacky causing the magnet to be held by the surface of the
coating.
Electronic magnetic coating thickness gages are also available, but these will be described in a separate section entitled
Electromagnetic Thickness Gages; however, this section
Magne-Gage [5]
This instrument (Fig. 7) consists of a small permanent bar
magnet, 2 mm in diameter, suspended from a horizontal
lever arm. The arm is actuated through a spiral spring by
turning a dial. The tip of the magnet is brought into contact
with the paint film (on iron or steel), and the dial is then
turned until the magnet is detached. The attractive force between the magnet and the film support is indicated on the
dial, and the thickness of the nonmagnetic paint film is obtained from a calibration curve relating thickness to dial
reading.
The gage can be used to measure coatings on convex and
concave surfaces as well as on flat ones provided the radius of
the curvature is not too small. Unless special calibrations are
made, cylinders should not be less than 1/2 in. (1.27 cm) in
diameter, spheres not less than 3/4 in. (1.9 cm), and fiat pieces
should be at least 3/4 in. (1.9 cm) square.
Magnets for thicknesses in the following ranges are available: 0.0 to 0.002, 0.002 to 0.007, and 0.007 to 0.025 in.
ASTM Method for Nondestructive Measurement of Dry
Film Thickness of Nonmagnetic Organic Coatings Applied to
a Ferrous Base (D 1186) has standardized the operation on
the magne gage.
430
ELCOMETER
111 INSPECTOR
MAGNETIC ATTRACTION
OUTER CASE
, BALANCEWEIGHT
~'--'J~
\ TENSION SPRING
!
' ~ --~\
~
SCALE
_..~ "--"-'-'~, ~
BALANCEARM
~.
( . . ~
,....~"k% " \ /
MAGNET
--
,/COATING
,!
FIG. lO-Magnetic coating thickness gage principle.
ELCOMETER
FERRITE MEASUREMENT
FERRITECTOR TYPE 1581
ELCOMETER
MAGNETIC RELUCTANCE PRINCIPLE
SCALE
PERMANENT MAGNET
NOgEA#'ggus
\
--
~;~
t:.;iil
MAGNETIC LINES
OFFORCE
SENSING ELEk
WELD SEAM
,STAINLESS STEEL
I:ERRITE
432
E l e c t r o m a g n e t i c T h i c k n e s s Gages
The electromagnetic induction method for measuring film
thickness is based on the effect of a magnetic metal substrate
on the balance of the alternating magnetic field in the probe
tip, generated in the probe (Fig. 13) by a signal applied to the
central coil.
When the probe is away from the influence of the substrate
(free air condition), the net voltage output from the two outer
coils tends to zero. As the substrate is brought towards the
tip, the field is increasingly out of balance between the two
outer coils until, with the uncoated substrate in contact with
the tip, the net voltage output from the coils tends toward V
max.
ELCOMETER
ELECTROMAGNETIC
INDUCTION PRINCIPLE
ELECTROMAGNETIC
FIELD
DETECTIONCOILS
:!: i:
mlm[:!:|!:|l
ELECTROMAGNETIC
SUREMENTS.
= m l i:!t:!
==ml t tl
atoll ili|ll
~i
m]
mum
~
:i: i:
~
I
1 ~
ENERGISECOIL
PROBE BALANCED
~l:f :1:l:ir~i"
/PROBE
TIP
TO FERROUS SUBSTRATE
433
434
E F F E C T S OF S U R F A C E F I N I S H ,
CURVATURE, AND SUBSTRATE
COMPOSITION ON ELECTROMAGNETIC
AND EDDY CURRENT MEASUREMENTS
The accuracy of coating thickness measurements carried
out using the methods described in the last two subsections
depends on the technique used in calibrating the instruments. The three major influences on the calibration are
435
profile. This is achieved b y using a thin foil 1.0 mil (25 p.m)
over the profile to set the lower c a l i b r a t i o n p o i n t a n d a thicker
foil 5.0 mils (125/zm) o r 10.0 mils (250/zm) to set the u p p e r
value over the profile. The i n s t r u m e n t will t h e n indicate the
thickness over the peaks for the coating b e t w e e n the values of
foil chosen.
This m e t h o d is m o s t a c c u r a t e a n d r e p r o d u c i b l e w h e n 15 to
20 readings are t a k e n on each c a l i b r a t i o n foil to establish a
m e a n value a n d the m e a n value is t h e n reset to the correct
value of the foil. Trials have shown that the m e a n of 15 to 20
readings taken over a n a r e a of coating give a m e a n value
within a few p e r c e n t of the actual value over p e a k s determ i n e d by sectioning.
The m e t h o d does not, however, take into a c c o u n t situations w h e r e access to the s u b s t r a t e is not possible for
c a l i b r a t i o n purposes. In this case, the m e t h o d d e s c r i b e d in
SSPC PA2 w h e r e a c o r r e c t i o n factor is a p p l i e d to r e a d i n g s
taken using a s m o o t h surface c a l i b r a t i o n in the i n s t r u m e n t is
m o r e a p p r o p r i a t e . I n either case it is i m p o r t a n t to agree w i t h
the m e t h o d before m e a s u r e m e n t s start to avoid discrepancies
in reporting.
Curvature
Surface Finish
A variety of surface finishes are to be f o u n d on m e t a l to
w h i c h a protective or decorative coating is to be applied. In
s o m e cases the coatings u s e d require an a n c h o r p a t t e r n of
profile d e p t h w h i c h forms a p a r t of the specification. C o m p a rators such as the K e a n e - T a t o r Surface Profile C o m p a r a t o r or
the I n t e r n a t i o n a l S t a n d a r d s O r g a n i z a t i o n ISO 8503 are u s e d
to d e t e r m i n e the surface finish after shot o r grit blasting. Also
Testex Tape a n d the E l c o m e t e r Surface Profile Gage can be
used to m e a s u r e p e a k to valley heights of profiles. These
i n s t r u m e n t s are shown in Fig. 20 along with the p h o t o g r a p h i c
s t a n d a r d s for cleanliness ASTM Pictorial Surface P r e p a r a tion S t a n d a r d s for Painting Steel Surfaces D 2200-1989 a n d
SSPC-VIS1.
Surface finish also influences c a l i b r a t i o n as the q u a n t i t y of
m e t a l directly b e n e a t h the p r o b e is r e d u c e d by the effects of
shot a n d grit blasting as the p r o b e tip sits on the highest
peaks. This has the effect of increasing the value of thickness
i n d i c a t e d using a gage c a l i b r a t e d on a s m o o t h surface by as
m u c h as 1.5 mils (35/~m) at 4 mils (100/~m) coating thickness for the highest values of profile.
It is possible to use a r o u g h surface c a l i b r a t i o n t e c h n i q u e to
eliminate this e r r o r a n d m a k e the i n s t r u m e n t r e a d the correct
value of coating thickness over the peaks by using the statistical p o w e r of the m i c r o p r o c e s s o r type gages to calibrate on the
Substrate Composition
In the case of e l e c t r o m a g n e t i c i n d u c t i o n probes, m o s t are
insensitive to the m a j o r i t y of steel specifications in general
engineering use. However, w h e n h i g h - c a r b o n steels are
coated, the c a r b o n content sufficiently alters the m a g n e t i c
p r o p e r t i e s of the steel to cause the n o r m a l c a l i b r a t i o n curve
a p p l i e d within the i n s t r u m e n t s to be in e r r o r with respect to
linearity. Thus, a n i n s t r u m e n t c a l i b r a t e d at zero a n d say 5
mils (125/~m) m a y have an e r r o r at 2 mils (50 ~ m ) of m o r e
t h a n 0.2 rail (50 ~m) or 10%. A similar effect can be seen with
s o m e cast irons.
This e r r o r can be o v e r c o m e b y calibrating as for the r o u g h
surface d e s c r i b e d in the section earlier in this c h a p t e r entitled
Surface Finish. F o r best accuracy, choose a foil just b e l o w
the expected coating thickness value for the lower c a l i b r a t i o n
436
437
Coating
Chromium
Cadmium
Copper
Nickel
Nickel-phosphorous
Zinc
Zinc-nickel
Gold
Rhodium
Palladium
Silver
Tin
Titanium nitride
Ferrous oxide
Substrate
Steel, copper
Steel, copper
Steel, zinc, brass
Steel, copper, Kovar, aluminum, Alloy 42,
inconel
Steel, copper, Kovar, aluminum, Alloy 42
Steel, copper, brass
Steel
Nickel, aluminum, Kovar
Nickel, gold
Nickel
Steel, copper, Kovar
Steel, copper, Kovar, aluminum
Steel
Aluminum, plastic
S T A T I S T I C S IN FILM T H I C K N E S S
MEASUREMENT
As m a n y r a n d o m variations c a n be expected in a coating
process, it is a p p r o p r i a t e to classify the thickness of the
coating using a statistical analysis. In fact, m a n y n a t i o n a l
specifications utilize a statistical a p p r o a c h in r e c o g n i t i o n of
these variations, e.g., SSPC PA2.
The sources of these variations are many, a n d only a few
examples can be cited h e r e - - o p e r a t o r e r r o r in taking the
m e a s u r e m e n t , recording error, variation due to surface o r
curvature or composition, local variation in substrate due to
local heat t r e a t m e n t o r due to f o r m i n g o r working the metal,
inclusions in the metal or in the coating, etc.
The influence of these factors can be greatly r e d u c e d by
taking a statistically significant n u m b e r of r e a d i n g s for each
a r e a of the coating to be tested. This g r o u p of readings can
then be s u m m a r i z e d using m e a n a n d either s t a n d a r d deviation or range to show the average a n d the s p r e a d of r e a d i n g s
a b o u t the average.
A statistically significant n u m b e r of readings w o u l d be 20
to 50; however, if the process is u n d e r statistical control as
defined, five readings in each g r o u p o r s u b g r o u p is sufficient.
Many of the m i c r o p r o c e s s o r - b a s e d coating thickness ins t r u m e n t s are capable of calculating a n d r e c o r d i n g m e a n
REFERENCES
[1] New Jersey Zinc Co., "Leaves from a Paint Research Note Book,"
No. 1, 1937, p. 33.
[2] Brightwell, E. P., "An Optical Method for Measuring Film Thickness of Paint Films," Official Digest, Federation of Paint and Varnish Production Clubs, ODFPA, Vol. 28, 1956, p. 412.
[3] Stoppel, E. A., "Measurement of Thickness of Varnish Films,"
Proceedings, American Society for Testing and Materials, ASTEA,
Vol. 23, Part 1, 1923, p. 286.
[4] Tooke, R., Jr., "A Paint Inspection Gage," Official Digest, Federation of Societies for Paint Technology, ODFPA, Vol. 35, 1963, pp.
691-698.
[5] Brenner, A., "Magnetic Method for Measuring the Thickness of
Non-magnetic Coatings on Iron and Steel," Journal of Research,
National Bureau of Standards, JRNBA, Vol. 2, 1938, p. 357.
[6] Stebel, M. D. and Silvermann, W. M., "XRF Programmable Plating Thickness Measurement Instrumentation," Proceedings of the
International Coil Winding Association, November 1984.
MNL17-EB/Jun. 1995
39
Drying Time
by Thomas J. Sliva 1
PREPARATION OF S P E C I M E N S
Substrate Preparation
It is essential that the substrate to be used and the applied
wet film thickness be agreed upon in advance, preferably to
conform to the intended use of the coating. Flat glass panels
are typically the substrate of choice. Ground and polished
glass plates are more suitable for low-viscosity coatings that
may tend to crawl. All panels must be thoroughly cleaned,
dried, and placed in a horizontal position on a level surface.
Application
The test coating should be filtered to remove any dirt or
contamination. Test films are typically prepared, in duplicate, using a drawdown or doctor blade adjusted to obtain a
uniform film thickness. Films should be drawn down at a
uniform rate of application to avoid drag on the coating. It is
recommended that all test films should be prepared and
tested by one operator properly skilled in the method to be
used and that a control (known) coating be run alongside the
test coating. All testing should be done within an area, any
point of which is not less than 1/2 in. (15 mm) from the edge of
the test film.
Table I can be used as a general guide for film application
when nothing more specific is agreed upon between the purchaser and seller. The dry film thicknesses shown in Table 1
are suggested.
Other methods of application, such as spraying, dipping, or
flood coat, may be used provided the film thickness obtained
is consistent with that recommended under actual usage.
Other substrates, such as metal, may be used provided they
are smooth and flat.
ENVIRONMENT
When determining drying time, a controlled environment
is essential. Variations in temperature, relative humidity, and
circulation of air and light will have an effect on the drying
time of a coating. The typical standard environment used for
determining the drying time of air dry coatings is a temperature of 73.4 ~ +_ 3.6~ (23 ~ _ 2~ and a relative humidity of 50
+__ 5% under diffuse daylight (about 25 fc).
Relative humidity should be strictly controlled for moisture-cure and two-package urethane coatings since their cure
is greatly affected by the existing relative humidity. The effect
of variation in temperature was discussed by Algeo and Jones
[1], who observed a difference of 4 h for a particular paint
dried at 73 and 77~ (22.7 and 25~
both at 50% relative
humidity.
All testing should be conducted in a well-ventilated room
free from direct drafts and dust. Airflow is important in determining drying time. For films that dry by oxidation, the rate
of drying is a function of the concentration of oxygen at the
interface. Since oxygen can reach the surface only by diffusion, the rate of drying is a function of the thickness of the
stationary air layer. For films that dry by solvent evaporation,
the continuous removal of solvent-laden air hastens drying.
TEST M E T H O D S
ASTM D 1640: Test Methods for Drying, Curing,
or Film Formation o f Organic Coatings at Room
Temperature
Method D 1640 is the most commonly used method to determine the various stages and rates of film formation in the
drying of organic coatings normally used under conditions of
ambient room temperature. The method describes eight
stages of the drying process:
I. Set-To-Touch Time
The test film is lightly touched with the tip of a clean finger,
and the fingertip is immediately placed against a piece of
clean, clear glass to determine when the film does not
adhere to the finger or transfer to the glass.
2. Dust-Free Time
439
Copyright9 1995 by ASTMInternational
www.astm.org
440 P A I N T A N D C O A T I N G T E S T I N G M A N U A L
TABLE 1--Recommended film thickness of materials to be tested.
Material
Oil paints
Enamels
Drying oils
Water-based paints
Varnishes
Lacquers, resins solutions
+ 0.2
+ 0.1
_+ 0.1
_+ 0.1
_+ 0.1
_+ 0.1
I
I
'J
!
3. Tack-Free Time
The test film is c o n s i d e r e d to be tack free when no stickiness is observed u n d e r m o d e r a t e pressure. This can be
m e a s u r e d by either of two methods:
a. Paper Test Method
A special p a p e r (K-4 Power Cable Paper) [3] is placed on
the test film u n d e r a weight of 2 psi (13.8 kPa). After 5 s,
the weight is r e m o v e d a n d the test film inverted. If the
p a p e r d r o p s off within 10 s, the film is c o n s i d e r e d tackfree.
A variation of the above m e t h o d is used to test the tackfree time of insulating varnishes. The varnish is considered tack free w h e n the p a p e r is placed on the test film
u n d e r a weight of 1 lb (450 g) for 1 m i n and tested as
above.
b. Tack Tester
This is a m e c h a n i c a l device w h i c h consists of a strip of
metal 1 in. (25 ram) wide, 3 in. (75 m m ) long, a n d 0.016
to 0.018 in. (0.41 to 0.46 m m ) in thickness. It is b e n t to
form a base 1 in. (25 m m ) square a n d a vertical length 1
by 2 in. (25 b y 50 ram) angled at 135 ~ The b o t t o m of the
base of the tester is covered with a l u m i n u m foil [4] (Fig.
1). A 300-g weight is placed on the center of the base a n d
allowed to set for 5 s. The test film is tack free w h e n the
tester tips over i m m e d i a t e l y after the weight is removed.
Occasionally, tack-free t i m e m a y be longer t h a n dryh a r d or d r y - t h r o u g h t i m e due to the inclusion of external
plasticizers in the coating.
4. Dry-To-Touch Time
The test film is c o n s i d e r e d dry-to-touch w h e n no m a r k is
left w h e n the film is t o u c h e d by a finger. The following
variations are used:
a. Drying Oils--The film is c o n s i d e r e d dry-to-touch w h e n
it does not r u b u p a p p r e c i a b l y w h e n a finger is r u b b e d
lightly across the surface.
b. Lacquers (and S e a l e r s ) - - T h e film is c o n s i d e r e d dry-totouch w h e n no p r o n o u n c e d m a r k s are left by a finger
touching the film. Sealers are generally tested on w o o d
o r o t h e r p o r o u s substrates.
5. Dry-Hard Time
'
CHAPTER 3 9 - - D R Y I N G TIME
touch. However, it includes a test for free-from-after-tack.
This test is applicable to coatings w h e r e tackiness persists
beyond, o r r e a p p e a r s at, the t h r o u g h - d r y stage. It is similar to
the P a p e r Test Method, discussed earlier in this chapter,
except that a 2.8-kg (6.2-1b) weight is used.
ISO Standard
1. Through-Dry State
This state defines the c o n d i t i o n of a film in w h i c h it is d r y
t h r o u g h o u t its thickness as o p p o s e d to that c o n d i t i o n in
w h i c h the surface of the film is dry b u t the b u l k of the
| iii
I
Plunger
Ball-joint
..-- Plunger head
~-. Baseplate
\
IIIIIIIII
Clip
Rod for rotating
- plunger head
~L~auze
Rubber disc
441
Double-faced
adhessive tape
442
DIN 53 150: D e t e r m i n a t i o n o f D r y i n g T i m e o f
Paints
Drying time is determined in this method by the adherence
or nonadherence of sand or paper to the film under various
loadings. Stage I is determined with sand (0.16 to 0.315 mm)
or glass beads (ballotini). The sand is allowed to remain on
the film for 10 s. The remaining stages are determined using
disks of typewriter paper (22 mm in diameter and weighing
about 60 g/m 2) and various loads ranging from 5 to
5000 g/cm 2. Interposed between the load and the test disk is a
soft rubber cushion. The load remains on the disks for 60 s.
The criteria for the seven stages are as follows:
1.
2.
3.
4.
but film is
but film is
but film is
hut film is
CHAPTER 3 9 - - D R Y I N G TIME
443
MECHANICAL DEVICES
In an attempt to improve the accuracy and reproducibility
of the drying time test procedure, various mechanical devices
have been developed. The following sections outline these
devices and the procedures used in determining drying characteristics.
444
I . C . I . D r y i n g T i m e Recorder
This i n s t r u m e n t consists of a m e t a l box p l a t f o r m w h i c h will
a c c o m m o d a t e flat panels, usually m a d e of glass. A gantry
moves between a n d parallel to the long d i m e n s i o n of the flat
panels [8]. This g a n t r y will c a r r y up to three d e t a c h a b l e
devices for each panel. These include a flock dispenser, a s a n d
hopper, a b a n d a g e roller, a n d a ball-pointed needle. These
can be used in any c o m b i n a t i o n to test up to six coatings,
three on each panel.
The different stages in drying w h i c h can be m e a s u r e d , dep e n d i n g on the device used, are dust free, surface dry, a n d dry
through.
N O PICK-UP T I M E TRAFFIC P A I N T R O L L E R
This device is d e s c r i b e d in ASTM S t a n d a r d D 711: Test
M e t h o d for No-Pick-Up Time of Traffic Paint.
The a p p a r a t u s consists of a steel cylinder weighing 11 lb,
14 oz (5385 g) with two O-rings [6]. It is rolled along a drying
film of traffic p a i n t w h i c h has b e e n a p p l i e d on a glass plate.
The p a i n t is d r y w h e n no p a i n t adheres to the O-rings (Fig. 6).
REFERENCES
FIG. 6-No pick-up time traffic paint roller. (Courtesy of
BykoGardner.)
at elevated t e m p e r a t u r e s [up to 500~ (260~
The compactness of the i n s t r u m e n t allows the u s e r to place it in an
oven at a specified t e m p e r a t u r e .
MNL17-EB/Jun. 1995
ii
an object, it is an important characteristic of any paint. Appearance, of which color is a part, is one quality of a product
that every customer can judge for himself. No matter how
good the physical properties of a paint, if its color does not
meet the expectation of the customer, the finished product
will be rated as unsatisfactory.
Color, often thought to be a property of the paint itself,
depends on three objective aspects: (1) the spectral composition of the light in which the paint is viewed, (2) the spectral
reflectance of the paint, and (3) the spectral response of the
eye of the observer. The subjective interpretation of the response to these aspects by the brain is also an essential part of
color. Describing the color of a paint or other material requires consideration of all of these and not merely the spectral character of the material. The three objective aspects of
color are considered in sections entitled LIGHT SOURCE,
REFLECTION AND TRANSMISSION, and THE EYE. The
sciences involved include chemistry, physics, physiology, and
psychology. These are broad subjects, and only enough discussion is included to provide a background for understanding the development of test methods. Readers desiring to
pursue these subjects in detail should consult an appropriate
text [1-6].
LIGHT SOURCES
Light is electromagnetic radiation weighted by the response of the normal h u m a n eye. It occupies a small portion
of the electromagnetic spectrum between ultraviolet and infrared radiation. Its wavelength range is approximately 380
to 780 nm (Fig. 1).
Illuminants).
TERMINOLOGY
Incandescent Sources
To understand this chapter and to make the best use of it,
the reader should be familiar with the terminology of appearance. The precise definition of terms is becoming increasingly important in today's world community. The paint terminology standard, ASTM Definitions of Terms Relating to
Paint, Varnish, Lacquer, and Related Products (D 16), is the
primary source of terms and definitions relating to paint, but
it contains very few appearance terms. The reader should
refer to ASTM Terminology of Appearance (E 284) for terms
and definitions relating to color and other appearance attributes. All significant terms used in this section are defined in
ASTM E 284.
An important international source of appearance terms is
the International Lighting Vocabulary [7], published jointly by
the International Commission on Illumination (CIE) and the
~Color consultant, 1294 Garner Avenue, Schenectady, NY 123095746.
2Consulting scientist, BYK-Gardner, Inc., 2435 Linden Lane, Silver
Spring, MD 20910.
Other light sources must replace daylight when appropriate. For use in homes, incandescent lamplight is generally
preferred because it imparts a soft, mellow effect similar to
that of candlelight.
Fluorescent Sources
In stores and offices, fluorescent lamps can provide high
levels of illumination with low power consumption and heat
generation. The most commonly used fluorescent lamp,
known as cool white, has a spectral distribution consisting of
a relatively smooth curve throughout the visible spectrum.
This arises from the fluorescent emission from a phosphor
coated on the inside of the lamp tube. The fluorescence is
excited by ultraviolet radiation from mercury vapor inside
the tube. This lamp is, however, deficient in power in the red
end of the visible spectrum. Modifications of it, known as
deluxe and super-deluxe versions, have been designed to
overcome this deficiency. Fluorescent lamps have also been
447
Copyright9 1995 by ASTM International
www.astm.org
448
700
400
Green
Blue
Red
\
\
\
/
Frequency, Hz
I
i
!I
I
Cosmic
rays
I
I
I
1020
I
X
1016\~
"1rand X
rays
i
1024
I
1012
I
~/I
10-4
104
Ultra-high frequency
and radio broadcast
:l OV ! Infrared
104
10s
10 8
1012
Wavelength, nm
FIG. 1-Electromagnetic spectrum showing the relatively small portion that the visible
spectrum occupies.
designed with phosphors emitting only in three rather narrow regions of the spectrum. When these three bands are
selected to peak near 450, 530, and 610 nm, light is provided
that is especially pleasing to the eye and energy efficient.
The color-balance and color-rendering properties among
the various types of commercial fluorescent lamps can be
vastly different one from another.
Other Sources
Other light sources have been developed for special purposes. They include arc lamps (sodium, mercury, neon,
xenon), metal halide lamps, and high-intensity discharge
(HID) lamps. None of these lamps has been adopted as standard for use in color measurement.
Color-Matching Booths
Because of the variation in spectral composition of different natural and artificial sources, it is essential that visual
color matching be done under standardized illumination,
such as that provided by a color-matching booth. This device
allows the colorist to compare the colors of specimens under
controlled and standardized illumination. Carefully manufactured and maintained light booths permit a colorist to
make a visual match with confidence that the illumination
duplicates that used at another time or place. However, the
spectral power distribution of daylight illumination in colormatching booths is not the same as that of natural daylight.
CHAPTER
100%
WHITE
40--COLOR
AND LIGHT
449
Fluorescence
PERCENT
REFLECTANCE
O~
4OO
700
WAVELENGTH, NANOMETERS
FIG. 2-Spectrophotometric curves typical of those measured on paint films. Note the sharp drop in the curve for rutile
titanium dioxide (white) as the violet end of the spectrum is
approached. The drop continues in the ultraviolet, where this
pigment absorbs light strongly. (Based on Ref. 2.)
Geometry (E 1331), ASTM Test Method for Color and ColorDifference Measurement by Tristimulus (Filter) Colorimetry
(E 1347), ASTM Test Method for Transmittance and Color
by Spectrophotometry Using Hemispherical Geometry
(E 1348), and ASTM Test Method for Reflectance Factor and
Color by Spectrophotometry Using Bidirectional Geometry
(E 1349). 3
Some materials have the property of fluorescing when irradiated by ultraviolet or short-wavelength visible radiation.
They emit radiation at longer wavelengths in the visible range
or even in the near-infrared. The effect of fluorescence is to
increase the apparent reflectance since the eye responds to
the sum of the fluoresced and the reflected energy. This sum
may even exceed the amount of light reflected by an ideal
white material at the wavelengths of maximum fluorescent
emission. Many fluorescent pigments have relatively poor
lightfastness in outdoor applications.
Most modern colorimeters and spectrophotometers are designed to evaluate properly the colors of fluorescent materials, although many do not have light sources adequately
simulating the ultraviolet content of natural daylight. In such
a case the instrument will not produce the same amount of
fluorescence as would daylight.
Two ASTM standards apply to the measurement of fluorescence. ASTM Test Method for Identifying Fluorescence in
Object-Color Specimens by Spectrophotometry (E 1247) provides two instrumental methods to supplement simple visual
examination of the specimen under ultraviolet light to detect
the presence of fluorescence. ASTM Practice for Color Measurement of Fluorescent Materials (E 991) specifies the instrument geometry required for the measurement and shows
how to assess the performance of daylight-simulating instrument light sources.
Retroreflection
Retroreflection is defined in ASTM E 284 as "reflection in
which the reflected rays are preferentially returned in directions close to the opposite of the direction of the incident
rays . . . . "It is important in paints and coatings used for signs
viewed at night, pavement and pedestrian markings, and
other safety devices. The measurement of retroreflection requires special instrumentation and special test methods for
the determination of daytime and nighttime colors of
retroreflecting materials. Among the ASTM standards dealing with this subject are: ASTM Practice for Describing
Retroreflection (E 808), ASTM Practice for Measuring Photometric Characteristics of Retroreflectors (E 809), ASTM
Practice for Measuring Colorimetric Characteristics of
Retroreflectors under Nighttime Conditions (E 811), ASTM
Test Method for Coefficient of Retroreflection of Retroreflective Sheeting (E810), ASTM Test Method for
Retroreflectance of Horizontal Coatings (D 4061), ASTM
Guide to Properties of High Visibility Materials Used to Improve Individual Safety (F 923), and ASTM Specification for
Nightime Photometric Performance of Retroreflective Pedestrian Markings for Visibility Enhancement (E 1501).
450
THE EYE
Perception
Temporal
side
stalline
lens
rI
/
Vitreous
humor
Blind
Optic
nerve
Cornea"
Nasal side
FIG. 3-Cross-sectional diagram of the eye showing features of most interest for
color vision [9].
"~- -1
.>_
rr
(9
(I)
(9
9>-- "2
HUE
2
S
o}
CHROMA
FIG. 5-Arrangement of the hue, lightness, and chroma axes
in the usual cylindrical representation of color space.
-3
\
-4
400
500
600
7o0
Wavelength, nm
FIG. 4-Spectral curves showing the relative sensitivities of
the three types of cones in the eye, peaking in the short (S),
medium (M), and long (L) wavelength regions (based on Ref 10.)
Colored Lights
When we deal with colored lights instead of objects, two
changes need to be made in the above system: Lightness is
replaced by brightness and chroma by saturation. Brightness
in this sense is defined as the attribute by which an area
appears to emit more or less light.
Color Constancy
As previously noted under Perception, color constancy is
the general tendency of colors to remain constant in appearance when the color of the illumination is changed. Note that
this term refers to what happens to the color of a single
specimen when the illumination is changed.
Metamerism
Of greater concern to the colorist, because it is of industrial
importance and largely under his control, is what happens to
the relationship of two colors when the illumination is
changed. Suppose, for example, that two colors, matching in
452
/--J ,%.,
(Green)
a (Red)
(Blue)
0 = Black
FIG. 6-Arrangement of the lightness, rednessgreenness, and yellowness-blueness axes in the
usual opponent-color representation of color space
[I].
C O L O R I M E T R Y A N D T H E CIE S Y S T E M
Colorimetry is defined as the science of color measurement. Its modern development began in 1931, when, in the
interest of standardization and to focus attention on the
properties of material objects such as paint films, international standards and recommendations were established by
the International Commission on Illumination (Commission
Internationale de l'l~clairage, CIE). These recommendations
[12] define standard lights and observers and a methodology
for combining their properties with those of the objects to
describe color and related appearance parameters.
CIE Standard Sources and Illuminants
Here it is necessary to note two conventions of CIE terminology [7] reflected in ASTM E 284. A source is defined as a
real emitter of light, whereas an illuminant is defined as a
60
=~ 40
O
e-
r
C
20
......
tO
,!
0
I
0
tO
C,
Wavelength, nm
FIG. 7-Spectrophotometric curves of two highly metameric paint films. To most
observers, the films match visually and are a dull green color in daylight, but Sample
A shifts color to a strong reddish brown in incandescent lamp light while Sample B
exhibits color constancy for this change of illumination.
The data for the CIE 1931 Standard Observer were obtained with a visual colorimeter in which the field of view
subtended an angle of only 2~ at the eye of the observer. This
was selected to correspond to the size of the fovea, that part of
the retina containing only cones used in color vision. Later,
the CIE studied color vision in a 10~ field, with the central 2 ~
portion disregarded. This corresponds to sample sizes more
like those used in commerce, but for which the spectral
sensitivity of the eye is somewhat different from that for the
2~ field. With the newer data, the CIE established the
1964 Supplementary Standard Observer [12,15]; see also
ASTM E 308. Where confusion might result, quantities referring to the 1964 Supplementary Standard Observer are given
the subscript 10; for example, its color-matching functions
are :~jo(4), 3~1o(4), and 21o(4).
Fluorescent Illuminants
In 1986, the CIE defined [12], but did not recommend as
standard illuminants, a series of twelve spectral power distributions representative of various types of fluorescent lamps,
including cool white, lamps simulating daylight well, and
three-band lamps. These data should be used when calculations involving fluorescent lamps are required.
454
250
CIE Illunlinmits
200
. . . .
065
150
i,.
I
II t'",~... I
I
.'>_
m
o
r162
""~.~.,,.,,...~_.~../
I/
100
":
# /
1""4
....
i I
il
+,..,.~.^~ %
\
i,
/;
.,,.j]
50
o"
i/
: ~,'7"-
i/
300
t"
,,#
I
350
&00
~,50
500
550
600
650
700
Wavelentjfh(nm)
FIG. 8-Relative spectral power distributions of CIE standard Illuminants A (incandescent lamp light), C (north-sky daylight), and D65 (actual daylight) [6].
1.50
"~ 1.00
0,50
0
400
~
500
600
700
Wavelength, nm
FIG. 9-The color-matching functions of the CIE 1931 standard observer; they are
the tristimulus values of the colors of the spectrum [1].
spectrum locus. For purple colors where the line would end at
the purple locus, it is extended back through the white point
to the spectrum locus, and the wavelength at that point is
designated as the complementary wavelength of the sample.
The fractional distance from the white point to the sample
point relative to the distance to the spectrum or purple locus
is called the (excitation) purity of the sample. Dominant
wavelength correlates well with the hue of the sample, but
purity does not correlate well with any perceived quantity
and is little used today.
456
P A I N T A N D COATING T E S T I N G M A N U A L
0.6
o65.f4. ooK
Z2:~
0.2
0.4
0.8
0.6
Z
FIG. 10-The CIE 1931 x,y chromaticity diagram showing the various features
described in the text [I].
U n i f o r m Color S p a c e s
From almost the beginning of the CIE system, it was recognized that distances in the CIE space did not correlate well
with visual estimates of the magnitudes of color differences.
Many proposals have been made for deriving quantities that
are more uniformly visually spaced. In 1976, the CIE recom-
500
[(S/Xn)
1/3 -
(y/y.)l,3]
457
- 100
-80
-60
-
Ir,~
-40
0.8
0.6
0.4
Y
0.6
u0
FIG. 11 - A three-dimensional representation of CIE color space with the luminance
(lightness) axis Y rising above the chromaticity diagram [1].
use of the equations for very small values of X, Y, or Z described in the references cited above.
Because CIELAB does not have tristimulus values or chromaticity coordinates as defined for the 1931 and 1964 CIE
systems in Chromaticity Coordinates and Diagram, it does
not have a chromaticity diagram.
An alternative set of CIELAB coordinates retains L* but
combines a* and b* to give chroma C* and hue angle h
(measured in degrees):
C* -= (a .2 + b*2) 1/2,
h = tan -1 (b*/a*)
COLOR
ORDER
SYSTEMS
Dating from the early 1900s, the Munsell system is accepted by most users as the standard for equal visual spacing.
It is described in ASTM Test Method for Specifying Color by
the Munsell System (D 1535). Its color solid is like that of Fig.
5 with the sole exception that lightness is called value in the
Munsell system. Munsell Hue is designated by position
around the hue circle in a notation combining letters designating five major hues (red, yellow, green, blue, purple) and
their pairs (R, YR, Y, GY, G, BG, B, PB, P, RP) with numbers
from 1 to 10. Munsell Value, to which CIE lightness L* is a
good approximation, runs from zero for black to 10 for white.
Munsell Chroma, which expresses the degree of departure of
the color from the gray of the same lightness, starts at zero
and is open-ended. To describe a color in the Munsell system,
the hue, value, and chroma are noted in a prescribed sequence, as for example, 8R 4/10. This designation indicates
that the hue is red (toward yellow-red), the value is 4, and the
chroma is 10.
The Munsel[ Book of Color is available in two collections of
painted color chips. The glossy finish collection contains approximately 1600 removable chips, the matte collection ap-
458
v0
0.2
0.4
0.6
0.8
FIG. 12-Lines of constant Munsell Hue and closed curves of constant Munsell
Chroma, at Munsell Value 5 plotted on the ClE 1931 chromaticity diagram [19].
ISCC-NBS System
In the 1950s the Inter-Society Color Council (ISCC) a n d the
N a t i o n a l B u r e a u of S t a n d a r d s (NBS) developed the ISCCNBS M e t h o d of Designating Colors [20] b a s e d on the Munsell
system b u t g r o u p i n g s i m i l a r colors to p r o d u c e a s m a l l e r n u m b e r (267) of categories. These are d e s i g n a t e d by descriptive
color names, for example, d a r k r e d d i s h orange for the group
c o n t a i n i n g 8R 4/10.
W
6~e ~
~C~ a ~
~0~ /
~
caL~
e ~
Full
color
ea
Series with
same white
content
.
Furl
color
">'<
B
FIG. 13-Two opposing constant-hue pages in the Ostwald system [1].
Ostwald S y s t e m
This system [21], which is not illustrated by any set of
samples now commercially available, consists of 24 charts of
approximately constant hue containing sets of chips having
nearly constant chroma but different lightnesses. The chips
are arranged (Fig. 13) on each chart in a triangular array, as
shown. The most important atlas based on the Ostwald system in the United States was the Color Harmony Manual,
available in the 1940s and 1950s [22].
DIN S y s t e m
The DIN Color System is the official German Standard
Color System [23]. Its coordinates are hue (for which dominant wavelength is used), saturation (like chroma except representing difference from black instead of from gray of the
same lightness), and relative darkness. Contours of constant
DIN hue and saturation, applicable to all lightness levels, are
shown on the 1931 CIE x, y diagram in Fig. 14. From time to
time, atlases of DIN samples have been available in glossy
and matte finish and in transparent films. In the former two,
chips are arranged on pages of constant hue, similar to the
Munsel] arrangement.
OSA-UCS System
Natural Color S y s t e m
Developed in the late 1960s and 1970s, the Natural Color
System (NCS) [24] is the national standard color order system in Sweden and several other European countries. It is
based on an entirely different principle from that of the other
systems discussed, namely the resemblances of colors to six
imaginary elementary colors, unique red, yellow, green, and
blue, and black and white. The four hues are placed 90 ~apart
on the hue circle. This does not lead to visually equal hue
spacing. Two opponent-type axes result, perpendicular to the
black-white lightness axis. The third variable of the system is
chromaticness.
In terms of resemblances, hue is defined as the resemblance of a color to the two nearest chromatic elementary
460
PAINT AND
COATING
TESTING
MANUAL
0.8
0.,
///,,,
sgo
! l/l
.,' A _ / _ f / / ' , 2
490~ @
i90tO7110
0.2:
0.1
~
'
0.1 " o , i o 02
0.3
0.,
0.5
0.e
0.T
FIG. 14-Lines of constant DIN hue and closed curves of constant DIN saturation on
the CIE 1931 chromaticity diagram. The figure applies to all DIN darkness levels
modified from 23].
[16,
Colorcurve System
This new color order system was introduced in the United
States in 1989. It is based on a color space similar to CIE 1964
tristimulus space [27]. Aim points are laid out according to
additive mixing (see subsection later in this chapter entitled
Additive Mixing of Lights) of CIE 1964 tristimulus values
Xlo, Yl0, Zlo for Illuminant D65, starting from eight specified
CIELAB points. The CIELAB lightness axis L* (designated
only as L) is retained, but coordinates along the CIELAB-type
opponent axes are replaced by a simple numbering system
giving the sample location in terms of the number of lattice
steps between it and the neutral axis in the directions of two
Printed Systems
For each of the color order systems described above, atlas
samples consist of painted chips individually matched to the
CHAPTER 40--COLOR
0.6
'1
AND LIGHT
~
4
eo
0.5
./
.',: .
9
x~,0
,,:
/-~.,.....',"
Ylo
o_ ~
9
~e/"
080
0,3-
. /
/~"#
.r~--~
,
4
/ ,t --4
f
0,2
(,Jc-, 10
0.:'
S
FIG. 15-Arrangement of colors on a constant-hue
page in the NCS system. They are located according
to their resemblances to ideal white (W), ideal black
(B), and the imaginary Color C having 100% chromaticness [24].
0.3
0.4
(15
O.S
Xlo
FIG. 17-Section of the CIE 1964 Xlo, Ylo diagram showing the
locations of points on the L = 0 plane of the OSA system
(ASTM E 1360, from Ref 3).
and it is especially difficult to reproduce the samples accurately in subsequent printings or editions. Their cost is, however, relatively low.
+L
0-20
,~o
0.4
",'."
L-O
.//'\~
/ Vx./,,
/ 9
,..
oJ," ,,"
P~
/"k.'//"
.,
461
,,,7 g
~+j
.....
.g"
I~
-I1-1
-L
FIG. 16-Cuboctahedron around the center point of the OSA
system showing its three axes, _+L (lightness), +_j(yellownessblueness), and _ g(greenness-redness). There are twelve nearest neighbors around the center point, with the L,j,g coordihates shown. The entire OSA space is formed by extending this
figure in all directions [16].
4(0.847Z - Y)
The first term is the luminance, Y, which approximates perceived lightness, and the second term is a measure of departure from white toward yellow. The CIE has defined a whiteness index [12] as
W = Y + 800(x. - x) + 1700(y. - y)
where x and y are the 1931 chromaticity coordinates of the
sample with lightness Y, and x . and y. are the values for the
462
Yellowness Indices
Indices of departure from achromatic toward yellow are
formulated similarly to the second term in the ASTM
E 313 WI equation given above. The indices start at zero and
increase as yellowness increases. In ASTM E 313, the yellowness index YI is given by
YI = 100 (1 - 0.847Z/Y)
A similar equation, given in ASTM Test Method for Yellowness Index of Plastics (D 1925), includes the effect of
change in tristimulus value X as well as Y and Z
I N D U S T R I A L COLOR M E A S U R E M E N T
Instruments Using the Eye as Detector
The eye is the ultimate arbiter in color evaluation because,
of course, it passes the final judgment on the acceptability of
a color. The first color-measuring instruments used the eye as
detector, and this practice is still followed when use of a
simple color comparator suffices, as in many of the test
methods for single-number color scales described in the pre-
ceding paragraph. But there are many factors, such as fatigue, poor color memory, and subjectivity, as well as the
perceptual phenomena described earlier under Perception,
that make the eye at least suspect for close color evaluation
work. Therefore the use of the eye as detector has been almost
entirely replaced by the use of two types of photoelectric
instruments developed since the 1940s for color measurement.
Spectrophotometers
Spectrophotometers provide detailed information on the
color properties of specimens, in the form of spectral reflectances (or transmittances), required for the calculation of
CIE tristimulus values and derived color coordinates, as described earlier under Colorimetry a n d the CIE System and
in ASTM E 308. Spectrophotometers are described here and
their abridgments in the form of tristimulus (filter) colorimeters in the next section.
When radiation strikes a sample, it may be reflected, absorbed, or transmitted. Each of these can be measured by
most spectrophotometers. All spectrophotometers consist of
a light source, a monochromator, arrangements for illuminating and viewing the sample, a photodetector, and an output device. In modern instruments, the latter consists of a
computer that processes the signals from the detector and
provides for the calculation of tristimulus values and a wide
variety of other color-related quantities. Each of these components is described briefly.
Light Source
In most cases the exact nature of the light source in a
spectrophotometer is of little importance as long as it has
adequate power and stability at all wavelengths in the visible
spectrum. Incandescent lamps or xenon flash tubes are
widely used. When fluorescent samples are measured (see
earlier under Fluorescence), the source must illuminate the
sample directly and may be filtered to simulate a standard
source, such as CIE daylight D65. Most color measuring
spectrophotometers are designed with these features.
ASTM E 991 provides more information on the measurement of fluorescent samples.
Spectroradiometers
Instruments closely related to spectrophotometers but
made to measure light incident from external sources are
known as spectroradiometers. They could be used in the
paint industry when, for example, the specimen must be
sensed remotely after illumination external to the instrument. Methods for making such measurements are described
in ASTM Practice for Obtaining Spectroradiometric Data
from Radiant Sources for Colorimetry (E 1341) and ASTM
Practice for Obtaining Colorimetric Data from a Visual Display Unit Using Colorimeters (E 1455).
Spectrocolorimeters
Some spectrophotometers are designed so that the measured spectral reflectances or transmittances cannot be accessed for examination; only the resulting tristimulus values
and other color coordinates can be printed out. Such instruments are designated spectrocolorimeters.
464
of Materials (E 805) address this topic. They should be consulted, if possible, before the purchase of a new instrument.
The user of any color-measuring instrument must give regular attention to its calibration. Appropriate calibration standards, available from instrument manufacturers and, in
some cases, national standardizing laboratories, should be
obtained, maintained in good condition, and used at frequent
intervals in an established routine [30]. A collaborative reference program [31] is available by means of which a user's
instrument performance can be compared to that obtained
for the same samples by the color community as a whole and
by national standardizing laboratories.
With proper calibration and maintenance, modern colormeasuring instruments are capable of a repeatability and
reproducibility far greater than the repeatability with which
the samples themselves can normally be prepared for industrial measurement. Thus, special care must be taken to establish a highly reproducible method of paint sample preparation and to establish by careful measurement and periodic
verification the uncertainties associated with this step in the
measurement process. ASTM standards that deal with these
matters are E 1164, E 1331, ASTM Practice for Reducing the
Effect of Variability of Color Measurement by Use of Multiple
Measurements (E 1345), E 1348, and E 1349. See also ASTM
Practice for Selection of Coating Specimens and Their Preparation for Appearance Measurements (D 3964) and Standard
Guide for the Preparation, Maintenance, and Distribution of
Physical Product Standards for Color and Geometric Appearance of Coatings (D 5531).
The following two subsections apply mainly to spectrophotometers.
Precision
The modern age of computer-interfaced color measuring
spectrophotometers began in the mid-1970s. By then it had
been clearly demonstrated that such instruments could surpass the eye in the precision of color measurement. Repeatability of instrumental color measurement is about 0.1
CIELAB unit of color difference [32] (see later in this chapter
under Color Difference Calculations). The average reproducibility within a group of similar instruments is about 0.2
CIELAB units [33]. Note that 0.5 CIELAB unit is approximately the smallest difference that can be detected visually.
Repeatability and reproducibility values are published in the
Precision and Bias section of ASTM E 1164.
Bias
This quantity, the difference between a measured result for
a standard sample and the result when it is measured in a
reference laboratory, is difficult to quantify in the color field
where there are no "absolute" values. It is usual to accept the
results obtained in a national standardizing laboratory as the
reference. On this basis, when instruments are selected to
minimize differences in measuring geometry and are properly calibrated and used, the average bias for a group of
standard samples can be as low as 0.5 CIELAB unit [34]. In
addition, the differences between the two sets of measurements can be utilized effectively to model and correct the
systematic spectrophotometric errors leading to the bias [35].
C o m m e r c i a l Instruments
Instrument design changes have been so frequent in recent
years that published information in a manual such as this
would almost certainly become obsolete by the time the manuscript is printed. For this reason, detailed information on
suppliers and their instrumentation is not included. Such
information, including types of instruments manufactured
and their design features and performance characteristics,
can best be found by first consulting buyers' guides [36,37]
that are revised annually. Another useful source of information is the lists of exhibitors at paint shows, such as the
descriptions published annually in the Journal of Coatings
Technology. In contacting suppliers of instrumentation, the
user might request that they send literature, measure samples
sent them, or have a representative visit the user to demonstrate the instrument. Another procedure is to negotiate a
rental-purchase contract. While some suppliers are reluctant
to negotiate such contracts, the procedure provides users the
opportunity to evaluate the instrument with their own operators at their own facilities. Most major manufacturers currently in the field supply both spectrophotometers and colorimeters meeting the descriptions given earlier under
C H A P T E R 4 0 - - C O L O R AND L I G H T
this chapter under Instrumental and Computer-Aided
Color Matching) are today finding extensive use at pointof-purchase locations such as retail paint stores.
465
Color-Difference Calculations
Color Tolerances
In the 1931 and 1964 CIE systems, equal distances in different parts of color space do not represent equally perceived
color differences. Although many proposals for more uniform color spaces have been made, an ideally uniform space
has not been and may not ever be devised. However, modern
color-measuring instruments compute sets of color coordinates that correlate better with perceived color differences
than do CIE tristimulus values.
Among the many modifications of CIE tristimulus values
that have been proposed for more uniform color spaces,
those proposed by Hunter [29], MacAdam [38-40], and the
CIE [12] are preferred for use in the paint industry and are
given in ASTM Test Method for Calculation of Color Differences from Instrumentally Measured Color Coordinates
(D 2244). The most widely used of these is the CIE 1976
L*a*b* (CIELAB) space discussed earlier in the subsection
entitled Uniform Color Spaces. Omitting subscripts ab
throughout for convenience, the total CIELAB color difference, AE*, is given by
Tolerance Charts
Color-tolerance charts are usually enlarged sections of a
nearly visually equally spaced diagram, such as the CIELAB
a*, b* diagram. A color-tolerance chart is set up with the
coordinates of the standard at the center, and the differences
Aa* and Ab* of production batches are entered as they are
made (Fig. 18a). The process is described in ASTM Practice
for Establishing Color and Gloss Tolerance (D 3134). As experience is gained, it should be possible to draw a tolerancelimit curve enclosing most, if not all, of the acceptable
batches and excluding most, if not all, of the unacceptable
batches. Because no known diagram is perfectly visually uniform, the tolerance limit figure may not be a circle or an
ellipse and may not be centered on the location of the standard.
Lightness differences between the standard and batch
must also be taken into account. This can be done by use of a
separate tolerance for AL*, but better practice is to use a
second chart (Fig. 18b), in which AL* is plotted against either
Aa* or Ab*, depending on the data. The batch readings should
fall within the tolerance figure on both charts.
It must be emphasized that the final criterion for acceptance of a color is always its visual appearance, to which
instrumental measurements, color differences, and tolerance
466
AL*
2
O
L3y~rld:
X Accelml~Match
B Border~e~
O
~Color
Ab*
I
o
-!
8
0
0
-!
'
-2
II
-
I
0
I
I
Aa"
2z
,
.,
,,
,
,
~ Aa*
2
(b) ~
Tolerances
FIG. 18-Color tolerance charts plotted in the CIELAB system: (a) chromaticity tolerance figure on a Aa*, Ab* diagram; (b)
lightness tolerance figure on a AL*, Aa* diagram. In this case, a plot of AL* versus Ab* would have served as well. (Based on
ASTM D 3134.)
charts provide only clues. Instrument malfunctions, miscalibrations, miscalculations, and operator errors can be revealed only by use of confirming visual observations.
Indices
of Metamerism
COLOR MIXING
area of the card, produce white again (Fig. 19). In this area,
the reflected lights from the three sources add together. These
three lights are called the additive primaries. By adjusting the
intensities of each of the three lights, a wide range of colors
can be produced.
The procedure just described can provide an analytical tool
for color measurement. If an adjacent spot on the white card
is illuminated by light of an unknown color, it could be
matched visually, in principle, with the three-light combination by adjusting their intensities. This is the basis for color
matching by addition of lights. The additive principle is used
to produce the colors in television [45].
The analytical device described above is also a simple version of the visual colorimeter used to generate the tristimulus
values of the spectrum colors that form the basis for the CIE
Standard Observers (see earlier in this chapter under CIE
S t a n d a r d Observers). At each wavelength, the total light
reflected is the sum of the power reflected from each of the
three primary lights. Since tristimulus values are obtained by
adding such sums across the spectrum, they too are produced
by additive mixing. It is not necessary to know the spectral
nature of the additive primaries to predict the resulting
colors.
Subtractive
Mixing in T r a n s p a r e n t Films
RED
GREEN
YELLOW
MAGENTA A
CYAN
Pigment M i x i n g
BLUE
CYAN
YELLOW
Most paint films contain, in addition to three colored pigments (one of which may be black), a white pigment used as
an opacifier. The mixing of colors produced in this way is
more complex than simple subtractive mixing in transparent
films because of the scattering of light caused by the white
pigment (and by opaque colored pigments as well). Again, it
is necessary to know the spectral character of all the colorants present. The Beer's law calculation of the transparent
case is replaced by the Kubelka-Munk relation: For opaque
films, as is usually the case in the paint industry, this is a
simple equation relating the reflectance R(h) of the film at
each wavelength to the~ratio of two constants describing what
happens to the light in the film
K(A)/S(A) = [1 - R(A)]2/2R(A)
where K(A) is the Kubelka-Munk absorption coefficient, and
S(~t) is the Kubelka-Munk scattering coefficient. Here R(X)
must be expressed as a fraction, not the usual percentage. The
quantities K(X) and S(X) refer to the mixture of pigments in
the paint film. These are calculated by adding the separate
contributions of each pigment, using its K(X) and S()t)
weighted by its concentration C in the mixture
K(A)MIXTUR E --
C~KI(A) + C2K2(A) + 9 9 9
S(X)MIXTURE
C l S l ( X ) -b C282()k) -{- 9 . .
GREEN
COLOR MATCHING
RED
BLUE
MAGENTA
468
REFERENCES
[1] Billmeyer, F. W., Jr. and Saltzman, M., Principles of Color Technology, 2nd ed., Wiley, New York, 1981.
[2] Hunter, R. S. and Harold, R. W., The Measurement of Appearance, 2nd ed., Wiley, New York, 1987.
[3] Wyszecki, G. and Stiles, W.S., Color Science: Concepts and
Methods, Quantitative Data and Formulae, 2nd ed., Wiley, New
York, 1982.
[4] Hunt, R. W. G., Measuring Colour, 2nd ed., Ellis Horwood,
Chichester, England, 1991.
[5] McDonald, R., Ed., Colour Physics for Industry, Society of Dyers
and Colourists, Bradford, England, 1987.
[6] McLaren, K., The Colour Science of Dyes and Pigments, 2nd ed.,
Adam Hilger, Bristol, England, 1986.
[7] CIE-IEC International Lighting Vocabulary, Publication CIE No.
17.4, Central Bureau of the CIE, Vienna, 1987.
[8] ASTM Standards on Color and Appearance Measurement, 4th ed.,
ASTM, Philadelphia, 1994.
[9] Burnham, R. W., Hanes, R. M., and Bartleson, C. J., Color: A
Guide to Basic Facts and Concepts, Wiley, New York, 1963.
[10] Boynton, R.M., Human Color Vision, Holt, Rinehart and
Winston, New York, 1979.
[1t] Hurvich, L. M., Color Vision, Sinauer, Sunderland, MA, 1981.
[12] Colorimetry, 2nd ed., Publication CIE No. 15.2, Central Bureau
of the CIE, Vienna, 1986.
[13] ClE Standard on Colorimetric Illuminants, Publication CIE No.
$001 (ISO IS 10526), Central Bureau of the CIE, Vienna, 1986.
[14] A Method for Assessing the Quality of Daylight Simulators for
Colorimetry, Publication CIE No. 51, Central Bureau of the CIE,
Vienna, 1981.
[15] CIE Standard on Colorimetric Observers, Publication CIE No.
$002 (ISO IS 10527), Central Bureau of the CIE, Vienna, 1986.
[16] Billmeyer, F. W., Jr., "A Survey of Color Order Systems," Color
Research and Application, Vol. 12, 1987, pp. 173-186.
[17] Agoston, G. A., Color Theory and Its Application in Art and Design, 2nd ed., Springer, New York, 1987, Chaps. 8-10.
[18] Newhall, S. M., Nickerson, D., and Judd, D. B., "Final Report of
the O. S. A. Subcomnqittee on the Spacing of the Munsell
Colors," Journal, Optical Society of America, Vol. 33, 1943, pp.
385-418.
[19] Judd, D. B., Color in Business, Science and Industry, 1st ed.,
Wiley, New York, 1952.
[20] Kelly, K. L. and Judd, D. B., "Color: Universal Language and
Dictionary of Names," NBS Special Publication 440, U.S. Government Printing Office, Washington, 1976.
[21] Jacobson, E., Basic Color." An Interpretation of the Ostwald System, Paul Theobald, Chicago, 1948.
[22] Granville, W. C., "Color Harmony Manual, a Color Atlas Based
on the Ostwald Color System," Color Research and Application,
Vol. 19, 1994, pp. 77-98.
[23] Richter, M. and Witt, K., "The Story of the DIN System," Color
Research and Application, Vol. 11, 1986, pp. 138-145.
[25] MacAdam, D. L., "Uniform Color Scales," Journal, Optical Society of America, Vol. 64, 1974, pp. 1691-1702.
[26] Nickerson, D., "Uniform Color Scales Samples: A Unique Set,"
Color Research and Application, Vol. 6, 1981, pp. 7-33.
[27] Stanziola, R., "The Colorcurve System| '' Color Research and
Application, Vol. 17, 1992, pp. 263-272.
[28] Johnston, R.M., "Colorimetry of Transparent Materials,"
Journal of Paint Technology, Vol. 43, No. 553, 1971, pp. 42-50.
[29] Hunter, R.S., "Photoelectric Tristimulus Colorimetry with
Three Filters," Journal, Optical Society of America, Vol. 32, 1942,
pp. 509-538.
[30] Carter, E. C., Billmeyer, F. W., Jr., and Rich, D. C., "Guide to
Material Standards and Their Use in Color Measurement," ISCC
Technical Report 89-1, Inter-Society Color Council, Princeton,
NJ, 1989; see also Carter, E. C. and Billmeyer, F, W., Jr., "Material Standards and Their Use in Color Measurement," Color
Research and Application, Vol. 4, 1979, pp. 96-100.
[31] Color & Appearance Interlaboratory Testing, Collaborative Testing Services, Inc., Herndon, VA 22070.
[32] Billmeyer, F. W., Jr. and Alessi, P. J., "Assessment of Color-measuring Instruments," Color Research and Application, Vol. 6,
1981, pp. 195-202.
[33] Stanziola, R., Momiroff, B., and Hemmendinger, H., "The Spectro Sensor--A New Generation Spectrophotometer," Color Research and Application, Vol. 4, 1979, pp. 157-163.
[34] Billmeyer, F. W., Jr. and Hemmendinger, H., "Instrumentation
for Color Measurement and its Performance," Golden Jubilee of
Colour in the C1E, Society of Dyers and Colourists, Bradford,
England, 1981, pp. 98-112.
[35] Berns, R. S. and Petersen, K. H., "Empirical Modeling of Systematic Spectrophotometric Errors," Color Research and Application, Vol. 13, 1988, pp. 243-256.
[36] Optical Industry and Systems Purchasing Directory, Optical Pubfishing Co., Pittsfield, MA, annually.
[37] Modern Paint and Coatings Paint Red Book, Communications
Channels, Inc., Atlanta, annually.
[38] MacAdam, D. L., "Visual Sensitivities to Color Differences in
Daylight," Journal, Optical Society of America, Vol. 32, 1942, pp.
247-274.
[39] Chickering, K.D., "Optimization of the MacAdam-Modified
1965 Friele Color-Difference Formula," Journal, Optical Society
of America, Vol. 57, 1967, pp. 537-541.
[40] Chickering, K. D., "FMC Color-Difference Formulas: Clarification Concerning Usage," Journal, Optical Society of America, Vol.
61, 1971, pp. 118-122.
469
[41] S~ve, R., "New Formula for the Computation of CIE 1976 Hue
Difference," Color Research and Application, Vol. 16, 1991, pp.
217-218.
[46] Longley, W. V., "A Visual Approach to Controlling Metamerism," Color Research and Application, Vol. 1, 1976, pp.
43-49.
[47] Winey, R. K., "Computer Color Matching with the Aid of Visual
Techniques," Color Research and Application, Vol. 3, 1987, pp.
165-167.
[48] Kumar, R., Billmeyer, F. W., Jr., and Saltzman, M., "Identification of Organic Pigments in Paints," Journal of Coatings Technology, Vol. 57, No. 720, 1985, pp. 49-54; see also Billmeyer, F. W.,
Jr., Saltzman, M., and Kumar, R., "Identification of Organic
Pigments by Solution Spectrophotometry," Color Research and
Application, Vol. 7, 1982, pp. 327-337.
[49] Kuehni, R. G., Computer Colorant Formulation, D.C. Heath,
Lexington, MA, 1975.
[50] Judd, D. B. and Wyszecki, G., Color in Business, Science, and
Industry, 3rd ed., Wiley, New York, 1975.
[51] Allen, E., "Colorant Formulation and Shading," Chap. 7 in Color
Measurement, F. Grum and C. J. Bartleson, Eds. Academic, New
York, 1980, pp. 290-336.
[52] Billmeyer, F. W., Jr. and Abrams, R. L., "Predicting Reflectance
and Color of Paint Films by Kubelka-MunkAnalysis," Journal of
Paint Technology, Vol. 45, No. 579, 1973; Part I, pp. 23-30; Part
II, pp. 31-38.
[53] Mudgett, P. S. and Richards, L. W., "Kubelka-Munk Scattering
and Absorption Coefficients for Use with Glossy, Opaque Objects," Journal of Paint Technology, Vol. 45, No. 586, 1973, pp.
43-53.
[54] Phillips, D. G. and Billmeyer, F. W., Jr., "Predicting Reflectance
and Color of Paint Films by Kubelka-Munk Analysis. IV.
Kubelka-MunkScattering Coefficient," Journal of Coatings Technology, Vol. 48, No. 616, 1976, pp. 30-36.
[55] Rich, D. C., "Computer-Aided Design and Manufacturing of the
Color of Decorative and Protective Coatings," Journal of Coatings Technology, Vol. 67, No. 840, 1995, pp. 53-60.
MNL17-EB/Jun. 1995
Gloss
by Harry K. Hammond 1111 and Gabriele Kigle-Boeckler2
Specular Gloss
Specular gloss is defined in ASTM E 284 [3] as the "ratio of
flux reflected in specular direction to incident flux for a specified angle of incidence and source and receptor angular apertures" (Fig. 4). This aspect of gloss has been measured most
frequently because it is the one for which an instrument is
most easily constructed. In practice the divergence angles of
source and receptor are precisely specified in ASTM Test
Method for Specular Gloss (D 523) [4] as are the directional
angles of incidence and reflection. Tolerances are specified
for all angles. For simplicity, glossmeter geometries are identified by reference to the incidence angles, most frequently
20, 60, and 85~. However, the associated source and receptor
aperture angles and their tolerances play a vital role in determining the reproducibility of instrument readings.
Sheen
A S P E C T S OF GLOSS A N D T H E I R
DEFINITION
The simple term "gloss" is defined in an ASTM standard,
Terminology of Appearance (E 284) [3] as "angular selectivity
of reflectance, involving surface-reflected light, responsible
for the degree to which reflected highlights or images of
objects may be seen as superimposed on a surface." To indicate specific types of "angular selectivity," such as those involving specular gloss, sheen, or haze and to illustrate the
difference between an evaluation where the focus is on the
surface and one where the focus is on the reflected image, the
complexity of the phenomenon "gloss" is illustrated in Fig. 3.
By focusing on the reflected image of an object, an observer
obtains information on how distinctly the object is reflected
by the surface. A reflected light source may appear brilliant or
diffuse depending on the specular gloss of the surface. The
outline of a reflected object may appear distinct or blurred
depending on image clarity. A halo surrounding the image of
the reflected object is an indication of haze. Focusing on the
surface of an object provides information on the size, depth,
and shape of surface structures contributing to such things as
waviness or directionality of brush marks.
~Consulting scientist, BYK-Gardner USA,2435 Linden Lane, Silver
Spring, MD 20910.
2Technical marketing manager, gloss, BYK-Gardener USA, 2435
Linden Lane, Silver Spring, MD 20910.
Haze
Haze in coating films is often designated "reflection haze"
because in plastics there is encountered a near-forward scattering in transmission that is designated transmission haze.
ASTM E 284 [3] defines haze in reflection as "percent of
reflected light scattered by a specimen having a glossy surface
so that its direction deviates more than a specified angle from
the direction of specular reflection."
Image C l a r i t y
This aspect of gloss has often been referred to as "distinctness of image." It is essentially independent of haze or change
in specular gloss. ASTM E 284 [3] defines distinctness-ofimage gloss as "the aspect of gloss characterized by the
sharpness of images of objects produced by reflection at a
surface." During visual observation, the sharpness of the
light-dark edge of a reflected object can be observed. Image
470
Copyright9 1995 by ASTMInternational
www.astm.org
CHAPTER 4 1 - - G L O S S
471
/
m
Waviness
One obvious type of waviness is designated "orange peel."
ASTM E 284 [3] defines orange peel as "the appearance of
irregularity of a surface resembling the skin of an orange." A
surface m a y be described as exhibiting orange peel when it
Directionality
ASTM E 284 [3] defines directionality, perceived, as "the
degree to which the appearance of a surface changes as the
O
\t....O O0
472
appearance
I
I !
focus on surface
focus on reflected
Image
waviness
=': II
(OOI)
tl
I
i
distinctnessof image
II
VISUAL G L O S S EVALUATION
Early investigations of gloss were carried out by observing
differences in the characteristics of images reflected in the
surfaces of specimens. In 1932, the Detroit Paint and Varnish
Production Club [5] reported on investigations carried out
with their distinctness-of-image gloss comparator. In 1936,
Hunter [6] reported an investigation where reflected images
of a target pattern were observed.
FIG. 4-Reflected light flux distribution from a semigloss surface is depicted by a broken
curve. Three lines are shown proceeding from the specimen surface. The center one depicts
the specular direction, the image of a ray reflected from a mirror-like surface. The two other
rays represent the range of angles passing through the aperture (AP) to the detector (shown
as a rectangle).
CHAPTER 4 1 - - G L O S S
473
FIG. 5-"Landolt Rings." Broken rings of bvarious sizes are used to provide a
scale for visual evaluation of the distinctness of surface-reflected images?
474
FIG. 6-Schematic diagram of a gloss meter. Source is on left, detector on right. Lenses are
used to provide beam control. Source aperture is designated AP1, receptor aperture AP2.
INSTRUMENTAL MEASUREMENT
TECHNIQUES
Specular Gloss Measurement
The design of many gloss meters is based on the precise
measurement of the specular component of reflected light. A
light source, usually a small filament incandescent lamp, is
placed at the focal point of a collimating lens. The axis of the
collimated beam is set to the desired angle of illumination. A
receptor lens with an aperture in the focal plane followed by
an illumination detector completes the basic optical design
(Fig. 6 and Fig. 7). The size of the receptor aperture and the
size of the source image in that aperture are the elements that
complete the optics and that determine the high, low, and
intermediate gloss scale readings. The specular angle largely
determines the magnitude of the reflected light. However, the
tolerances assigned to the source and receptor apertures are
what determine the accuracy and reproducibility of measurements made with instruments having the same angles of
illumination and view.
Periodic calibration or verification of instrument performance requires the use of calibrated gloss standards. For permanence they should be made of glass or ceramic material.
ASTM D 523 recommends the use of a primary standard of
polished black glass of known refractive index for which the
Fresnel (specular) reflectance [11] has been computed for
the angle of incidence of the geometry for which the instrument is designed. Since about 1990, national standardizing
laboratories have preferred a primary reference stan-
CHAPTER 41--GLOSS
FIG. 7-Photograph of a modern miniature glossmeter. Note size of the hand holding the
instrument?
FIG. 8-Diagram depicting the positions of source and receptor for the three geometries of
ASTM D 523.
SApparatus designated "micro-TRLgloss," available from BYKGardner USA, Silver Spring, MD.
475
476
/'--- PHOTOT/JBE
"~
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N
.SOURCE
/x,..-.~. ~
VIEW/N(; ,BEAM
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.NI.,~-~
l_
Lt,~S
"~'~
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7"
BEAM
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OBJECTLENS
1
Goniophotometry
Gonio means angle, and photometer means light; so a
goniophotometer is an instrument for measuring the angular
distribution of reflected or transmitted light. This type of
instrument is used regularly in the research laboratory to
investigate the distribution of light flux (Fig. 9). A goniophotometer with appropriate apertures can also be used
to provide gloss data for a wide variety of angles and apertures. When goniophotometric measurements are desired,
SPECULARGLOSS
RECEIVERWINDOW
-L""~/AZERECEIVERWINDOW
FIG, 1 0 - S c h e m a t i c diagram of an instrument for reflection
haze measurement,
.CHAPTER 4 I - - G L O S S
SPECIMEN
SOURCE OBJECT L E N S - ~
477
//~
"'/I
~
--
5o SLIT
20 SLIT
'D/I SLIT
Rs SLIT
reference should be m a d e to ASTM Practice for Gon i o p h o t o m e t r y of Objects a n d Materials (E 167) [18], Analysis of g o n i o p h o t o m e t r i c curves was t r e a t e d by Nimeroff [19].
7Apparatus designated "Dorigon," available from Hunter Associates Laboratory, Inc., Reston, VA.
surface.
478
Profile Amplitude
.................,~--T.~F.-.+
@
I E : Dis,anc.
Light Intensity @ ~} @
--I i
@|
Distance
@@@
FIG. 14-Schematic diagram of the measurement principle for evaluation of orange
peel.
CHAPTER 4 1 - - G L O S S
REFERENCES
[1] Hunter, R. S., "Methods of Determining Gloss," NBS Research
Paper RP 958, Journal of Research, National Bureau of Standards, Vol. 18, No. 77, January 1937, p. 281.
[2] Lex, K., "Die erweiterte Glanzmessung und die Messung von
Oberflaechenstrukturen," Pruftechnik bei Lackherstellung und
Lackverarbeitung, Vincentz Verlag, Hannover, Germany 1992,
pp. 70-74.
[3] ASTM Standard E 284, Terminology of Appearance, Annual
Book of ASTM Standards, Vol. 06,01, American Society for Testing and Materials, Philadelphia, PA, 1994.
[4] ASTM Standard D 523, Test Method for Specular Gloss, Annual
Book of ASTM Standards, Vol. 06.01, American Society for Testing and Materials, Philadelphia, PA, 1994.
479
480
[24] Matsuta, M., Kito, K., and Kubota, T., "New Portable Orange
Peel Meter for Paint Coatings," Proceedings, Williamsburg Conference, 8-11 Feb. 1987, pp. 25-28.
[25] Ladstaedter, E. and Gessner, N., "Die quantitative Erfassung
yon Reflexionsvermoegen, Verlaufsqualitaet und Glanzschleier
MNL17-EB/Jun. 1995
42
Hiding Power
by Leonard Schaeffer 1
1. CONCEPTS, RELATIONSHIPS,
TERMINOLOGY
a. Opacity
When light enters a paint film, some or all of it is absorbed
or reflected by the film before reaching the substrate, thereby
hiding the substrate to a lesser or greater degree. The light
that reaches the substrate is partly absorbed by it and partly
reflected back in conformance with the substrate's visual pattern. Reflection from the substrate eventually emerges from
the film carrying the substrate reflectivity information perceived as visibility or lack thereof and referred to as hiding.
Opacity m a y he qualitatively defined as the property of a
paint film that enables it to prevent the passage of light and
thereby to hide the substrate on which it has been applied.
Note that opacity is a film property, whereas hiding power is a
property of the whole paint. Hiding is a more general term
used frequently to refer to either opacity or hiding power.
L Contrast Ratio
The extent to which a paint film obscures or hides the
contrasting features of the test substrate on which it is uniformly applied is the measure of its opacity. This is expressed
photometrically as the ratio of the luminous (CIE-Y) reflectance over the darker to that over the lighter area of the
substrate, which is referred to as the contrast ratio (CR). The
Y-reflectance is employed because this CIE parameter is designed to match the sensitivity of the h u m a n eye. The CR and
the reflectance are expressed as a percentage or as a decimal
fraction, the latter to be assumed unless otherwise indicated.
A CR value of unity indicates that too little light has reached
the substrate for the substrate reflectance characteristics to
have a measurable effect on the emergent light flux; thus,
there is complete absence of contrast, or complete hiding.
Lesser CR values define intermediate levels of contrast, or
incomplete hiding. The contrast ratio of a given paint film
varies with substrate reflectances and therefore has significance only with respect to a known substrate and primarily to
a standard black-and-white substrate as defined in 1.e. In
practice, the white area of a commercially available blackand-white substrate normally deviates somewhat from the
ideal reflectance of 8 0 % whereas the black area is normally
1% or less, which has no measurable effect on test results and
is therefore treated mathematically as having zero reflec-
b. Light Absorption
If most of the light is absorbed by the film before reaching
the substrate, the film is dark in color and hides the substrate
well, in which case hiding has been produced by light absorption.
c. Light Scattering
If most of the light entering the film is reflected back and
reemerges without having reached the substrate, the film is
white or light in color and hides the substrate well. The
reflection mechanism of the film involves multiple internal
refractions and reflections that scatter the light to produce a
net reversal in its direction. Hiding in this case is produced by
light scattering.
d. Incomplete Hiding
In all cases, the light-absorbing and light-scattering properties of the film act together to produce its opacity. If the film is
low in both light-absorption and light-scattering ability,
m u c h of the light reaches the suhstrate. Such a film therefore
hides poorly and is characterized as being low in opacity.
481
Copyright9 1995 by ASTM International
www.astm.org
482
WR0(1 - 0.80R0)
(1)
R o ( W - 0.80) + 0.80Rw(1 - WRo)
WCw(1 - 0.80R0)
(2)
Cw(W - 0.80) + 0.80(1 - WRo)
h. Film Thickness
This is usually expressed in t h o u s a n d t h s of an inch (mils)
o r in m i c r o m e t e r s (~m). A liquid p a i n t usually contains a
s u b s t a n t i a l q u a n t i t y of volatiles, so that its d r y film thickness
(DFT) is substantially less t h a n the original wet film thickness
(WFT). The W F T of a r c h i t e c t u r a l p a i n t s a p p l i e d in the field
are typically in the n e i g h b o r h o o d of 3 to 4 mils (75 to
100/~m). W i t h o t h e r coating types, it m i g h t b e as low as 1 mil
(25/~m) or as high as 60 mils (1500/zm). W i t h volatile-free
liquid coatings, the W F T a n d DFT are the s a m e except for a
possible small increase in density d u r i n g curing. W i t h powd e r coatings, for w h i c h film f o r m a t i o n a n d curing are concurrent, the t e r m W F T is i n a p p l i c a b l e a n d DFT r e d u n d a n t , so
t h a t it is a p p r o p r i a t e to refer simply to film thickness.
(3)
(4)
(5)
(6)
(2) M e t r i c U n i t s 6
H(mZ/L) x T(p~m) = 1000
(7)
(8)
(9)
(10)
(3) U . S . - - M e t r i c Unit C o n v e r s i o n s
n (ft2/gal) = H (mZ/L) 40.746
H (ft2/lb) = H (m2/kg) 4.8882
(11)
(12)
(13)
(14)
(4) D r y V e r s u s W e t F i l m R e l a t i o n s h i p s 7
ND = N~cl
(15)
t = N~T
(16)
T = td + ND
(17)
2. D E F I N I T I O N OF H I D I N G P O W E R ( H P )
i. Spreading Rate
W h e n p a i n t is applied, w h e t h e r for test p u r p o s e s o r in
actual usage, the a r e a covered p e r unit q u a n t i t y of p a i n t is
called the s p r e a d i n g rate (SR) for that p a r t i c u l a r application.
W h e n the q u a n t i t y of coating is expressed volumetrically, as
is usual with liquid paints, the SR is usually expressed in
square feet p e r gallon (ft2/gal) o r square metres p e r litre
(m2/L). W h e n the quantity is expressed gravimetrically, the
3Derived from Eq 39 by equating to W = 0.80.
Qualitatively, h i d i n g p o w e r is the p r o p e r t y of a p a i n t t h a t is
m a n i f e s t e d as o p a c i t y in its films. Quantitatively, it is the
4Note that WFT and SR, when the latter is expressed by volume,
are inverse ways of stating the same information.
5Refers to films containing no air or hypothetically compressed to
exclude air.
6The following metric notations are identities: kg/L = g/mL =
g/cm 3 = g/cc.
7These are applicable to both common and metric units since the
units all cancel.
3. T H E R O L E OF P I G M E N T S I N H I D I N G
POWER
a. Binders and Pigments
A typical paint binder, by itself, forms a transparent and
virtually colorless film that neither absorbs nor scatters light
to any appreciable degree and therefore makes no contribution to the hiding power of the coating of which it is a part.
This task resides entirely in the pigment constituent of the
paint. Pigments are fine-particle-size, insoluble, and usually
crystalline solids that when dispersed in paint vehicles contribute to the various properties of the mixture, among which
are the optical properties of color and hiding power. Pigments that absorb light strongly over the entire visible spectrum are black; those that are optically selective, absorbing
strongly in parts of the visible spectrum and poorly in other
parts, are colored, viz. blue, red, yellow, etc., corresponding
to the spectral region of nonabsorption. Those that absorb
poorly over the entire visible spectrum are white.
b. White Pigments
When dispersed in a paint binder, some white pigments
scatter light strongly and thereby contribute to hiding, while
others scatter very poorly and make little if any contribution.
On that basis white pigments are classified as hiding pigments
or as extenders. White hiding pigments in a paint formulation
are sometimes called "prime pigments" as distinguished from
the nonhiding "extender" types. The latter are also referred to
as "inerts" in view of their apparent passivity with regard to
both light absorption and scattering. The difference in scattering behavior between hiding and extender pigments is a
function of their refractive indices.
c. Refractive Index
Most pigments are crystalline in nature. If a single crystal
of white pigment were grown sufficiently large, it would be
perceived as shiny and transparent like glass, and objects
observed through it would look bent and distorted as when
observed through a glass prism. This is due to the change in
direction, referred to as refraction, that occurs when light
passes between media in which it has different velocities, as
illustrated in Fig. 1. The relationship between the angles in
this figure is expressed by Snell's law of refraction
n = sin//sin r
(18)
of
I
FIG. 1-Bending of a light ray by refraction towards the normal as it enters a medium of lower light velocity (higher
refractive index).
484
P A I N T A N D COATING T E S T I N G M A N U A L
d. White Hiding P i g m e n t s
A r o u g h i n d i c a t i o n of the relative hiding p o w e r of a white
p i g m e n t can be calculated from its refractive index using the
Fresnell equation of reflectivity (Ref 2, p. 1),
F%-
( n - nm) 2 100
(n + rim) 2
(19)
['~
(n + 1.5) 2
100
(20)
Refractive
Index
Relative HP,
F%a
2.76
2.55
2.40
2.37
2.19
2.02
2.01
1.93
1.84
8.8
6.7
5.3
5.0
3.5
2.2
2.1
1.6
1.0
~Calculatedfrom Eq 20.
Refractive
Index
Relative HP,
F%a
Barium sulfate
Calcium sulfate
Calcium carbonate
Magnesium silicate
Aluminum silicate
Silica
1.64
1.59
1.57
1.57
1.55
1.55
0.20
0.08
0.05
0.05
0.03
0.03
(n -- 1.5) 2
e. E x t e n d e r P i g m e n t s
Pigments in this category have low refractive indices in the
n e i g h b o r h o o d of 1.5. In the form of a powder, with the surr o u n d i n g m e d i u m being air with a refractive index of 1.0, the
difference in the two indices p r o d u c e s substantial light scattering, so that extender p i g m e n t s look white. But d i s p e r s e d in
p a i n t binders, w h i c h like themselves typically have a value of
a b o u t 1.5, they scatter light very p o o r l y and are virtually
transparent. This is i n d i c a t e d by the low HP values listed for
t h e m in Table 2 as c o m p a r e d with the white hiding p i g m e n t s
in Table 1. Although extender p i g m e n t s are also referred to as
"inerts," the latter t e r m is s o m e w h a t of a m i s n o m e r . They
have an indirect b u t strong influence on light scattering a n d
hiding p o w e r t h r o u g h p h e n o m e n a referred to as "crowding"
and "dry hiding." They also have i m p o r t a n t effects on o t h e r
physical p r o p e r t i e s of paints such as consistency a n d gloss.
f. Colored P i g m e n t s
If a p i g m e n t a b s o r b s s o m e wavelengths of light m o r e
strongly t h a n others, it reflects b a c k a higher p r o p o r t i o n of
the weakly a b s o r b e d wavelengths a n d is perceived as having
the color of the latter (e.g., red, blue, yellow, etc.). Light
a b s o r p t i o n of this n a t u r e is referred to as "selective." Colored
p i g m e n t s can vary greatly in hiding p o w e r d e p e n d i n g on their
light a b s o r p t i o n a n d light-scattering abilities. W i t h r e g a r d to
light scattering, as with white p i g m e n t s this is a function of
the refractive index or m o r e specifically the difference in refractive index b e t w e e n the p i g m e n t a n d s u r r o u n d i n g medium. Refractive indices of colored p i g m e n t s vary widely
with wavelength, ranging from 1.3 to 2.7. These variations
cause such p h e n o m e n a as bronzing, dichroism, color change
with film thickness, a n d differences in u n d e r t o n e u p o n dilution with white p i g m e n t s (Ref 4, p. 22).
485
4. EARLY VISUAL H I D I N G P O W E R
METHODS
a. Brushouts
The earliest methods for determining hiding power employed the practical procedure of brushing the paint uniformly onto combination black-and-white test substrates,
increasing the amount of paint in small increments until
reaching the point of essentially complete hiding at which the
amount of visual contrast was considered negligible. The
quantity of paint was determined by weighing the container
and brush in grams before and after painting. The corresponding spreading rate (SR) is the hiding power (HP) by
definition and was calculated from the equation
SR (ft2/gal) =
Test Area (ft2) Paint Density (lb/gal) x 454
Weight of Paint (g)
(21)
SRpaint (ftZ/ga])
(22)
Pigment Concentration (lb/gal)
486
II
II
Ii
i
II
504540353025201510
'
i
j
Di
SRTestPaint X 100
(23)
SRstd. Paint
CHAPTER 4 2 - - H I D I N G P O W E R
TABLE 3--Hiding power (m2/kg) of some colored pigments
487
f. Hallet H i d i m e t e r
White Glass
...
..29
72
106
51
129
187
188
101
167
181
62
98
154
202
150
91
130
23
31
44
17
29
66
75
65
36
137
224
160
41
35
105
41
-..
...
--.
-..
...
...
...
.....
..--.
...
...
...
...
..-..
27
34
56
20
.-.
-..
...
...
...
...
...
...
...
...
Lampblack
Carbon Black
Chromic oxide
Prussian blue
Chinese blue
Blue toner
Light green
Medium green
Deep green
Light green
Medium green
Deep green
Light green
Medium green
Light green
Medium green
Deep green
Green toner
Green toner dark
Chrome yellow
Hansa yellow
Lt. chrome orange
Med. chrome orange
Dk. chrome orange
Lithol toner
Lithol toner
Maroon toner
Madder lake
Toluidine toner
Light para toner
Deep para toner
Light para toner
Deep para toner
[12] was one of the very early devices for evaluating HP. The
objective of a regular microscope is replaced by a long tube
fitted with a plain g r o u n d glass objective; the eyepiece is
replaced with a small hole. The principle of the device is the
light-diffusing property of g r o u n d glass. If a contrast substrate is viewed t h r o u g h a plate of g r o u n d glass, the contrast
b o u n d a r i e s b e c o m e more b l u r r e d as the distance b e t w e e n
plate a n d substrate increases. If a liquid p a i n t sample is
sandwiched b e t w e e n them, it blurs the b o u n d a r y further, a n d
the distance required to make the b o u n d a r y disappear decreases. Since that distance is the thickness of the intervening
p a i n t film, it is a m e a s u r e of the hiding power of the paint.
This m e a s u r e m e n t is essentially comparative because it cannot be translated into regular hiding power units.
5. E A R L Y P H O T O M E T R I C H I D I N G P O W E R
METHODS
a. Pfund P r e c i s i o n Cryptometer
I n this device (Fig. 8) a photoelectric cell is used to m e a s u r e
the reflectance of p a i n t c o n t a i n e d in a wedge-shaped layer
[13]. The base plate consists of black-and-white areas B a n d
W, whose b o u n d a r y is parallel to the length of the plate
instead of perpendicular as with the visual cryptometer. The
photoelectric device is shifted until a position is f o u n d where
the reflectance of the p a i n t over the black area is 98% of that
over the white area. The film thickness a n d HP calculations
are the same as with the visual cryptometers described in
section 4.e.
This cryptometer eliminates the uncertainties of the visual
type, as there is n o sliding of the top plate over the base plate
a n d no need to estimate visually the appearance a n d disappearance of a n indistinct line. However, it retains the disadvantage of p e r m i t t i n g only wet hiding m e a s u r e m e n t s a n d has
therefore b e e n superseded by other photometric devices a n d
methods that p e r m i t the m e a s u r e m e n t of dry hiding power.
b. H a n s t o c k M e t h o d
!
!
I'
~%\\\ ~\\\"/////////,~,~:~v////////////,,;
r
,,x~\x~
,:;:.:/"...(///,/~",;,k4/;
1,4
Hanstock [14] studied the relationship of light transmission through free p a i n t films to opacity a n d HP o n a blackand-white substrate. For his t r a n s m i s s i o n work, he employed
a flicker p h o t o m e t e r a n d f o u n d that p a i n t films were perfectly
diffusing a n d that films having the same degree of light transm i s s i o n had approximately equal opacity. He further showed
the correspondence b e t w e e n refractive index, the Fresnel relationship, a n d HP.
The p r o b l e m with the t r a n s m i s s i o n concept is that m o d e m
paints have so m u c h opacity it is difficult to m e a s u r e accurately the t r a n s m i s s i o n of films of c o m m e r c i a l thickness.
Moreover, HP is concerned in practice with p a i n t in i n t i m a t e
contact with opaque surfaces a n d not as a free film. Consequently, m e a s u r e m e n t of light t r a n s m i s s i o n t h r o u g h p a i n t
films is done today only for very specialized research.
488
P A I N T A N D COATING T E S T I N G M A N U A L
"1
I
i f "
....-;,,/K
t ~, i ," i7.) L~
W
',,ii/4.-
,,,
I le , / . ,I;.'.&
W P
..z'~'~"'v
bY'z
G
i,.j..'i;.L' ................... 1 F
Detail of Plate.
~"x"
"
P~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .r~
.
I Wl
FIG. 8-Pfund precision cryptometer. Uses a photoelectric cell instead of the eye to
measure reflectance.
c. Use o f t h e Fell E q u a t i o n
An e m p i r i c a l relationship b e t w e e n spreading rate (SR) a n d
c o n t r a s t ratio (CR) was f o u n d b y Fell a n d r e p o r t e d by S a w y e r
[15] in the following form
l o g ( C R x 10) = m SR + b
(24)
w h e r e m a n d b are e x p e r i m e n t a l constants.
Since the g r a p h for this equation is a straight line, it is a
simple m a t t e r after d e t e r m i n i n g m a n d b from m e a s u r e m e n t s
at two CR levels to find the SR required for any desired CR.
This p r o c e d u r e was a d a p t e d b y M a r c h e s e a n d Z i m m e r m a n to
d e t e r m i n e the hiding p o w e r of p a i n t s at a c o n t r a s t ratio of
0.98, a n d the m e t h o d was used for m a n y years by the Titan i u m Pigment Co. (Ref 4, p. 24). Experience has s h o w n that
r e a s o n a b l y satisfactory results can be o b t a i n e d if the equation 'is used for i n t e r p o l a t i o n b e t w e e n points close to the
desired c o n t r a s t ratio. But, as p o i n t e d out by Switzer [16],
e x t r a p o l a t i o n of results can lead to serious errors. He further
p o i n t e d out that the Fell equation m e t h o d allows only a single
estimate of HP from at least two test applications, thus re-
(25)
489
6. G E N E R A L H I D I N G P O W E R
METHODOLOGY
a. Film Application
The objective is to determine the spreading rate at a specified level of dry film opacity, which is usually full hiding as
perceived visually or corresponding to the contrast ratio: C =
R0/R0,0 = 0.98. The basic experimental procedure is to apply
a uniform film on a suitable test substrate, to observe its
opacity either visually or photometrically, and to determine
its spreading rate. Since it is not possible to apply a film with
precision at a predetermined dry opacity, several such applications need to be made over a range of spreading rates and
their results plotted graphically or otherwise interpolated to
the desired hiding power end-point. This laborious procedure
is exemplified in the visual methods discussed in 4.a and 4.d
and in the contrast ratio (CR) methods discussed in 5.e and
5.f. The Fell equation and NYPC methods (5.c and 5.d) attempt to reduce the workload to only two spreading rate determinations by plotting SR against CR or log CR and finding
the hiding power end-point graphically on the basis of perceived empirical straight-line relationships. Kubelka-Munk
theory (see Section 8) shows how the end-point can be calculated with just one spreading rate determination.
104M (g)
A (cm2)-N.D (kg/L)
(26)
(27)
490
A (cm2).N
10M (g)
(28)
c. P h o t o m e t r i c M e a s u r e m e n t s
The CIE-Y reflectance is measured because this function
defines the human eye's quantitative response to the luminous character of light across the visual spectrum. This is
valid for chromatic as well as nonchromatic colors, as reported by Tough [19], who found good correlation in a large
series of colored paints between visual hiding power measurements and contrast ratio values based on CIE-Y measurements with a spectrophotometer. The end-point of 0.98 CR is
effective with colors, although it appears that other endpoints, for example CIELAB color difference: AE = 1.5,
would make some difference in the relative HP of various
colored paints [20]. However, the simplicity of the 0.98 endpoint and its history of validity and general agreement among
various workers make it the best choice regardless of color
(Ref 4, p. 31). CIE-Y measurements can be made with the
green filter of a tri-stimulus colorimeter or with a spectrophotometer. When properly standardized, results with the two
instrument types should be the same. As a precaution, there
should be coordination between correspondent laboratories
with regard to instrumentation. In all cases, reflectance measurements must be made excluding surface reflection, which
is implicit for instruments designed with 00/45~geometry and
optional with most other instrument types.
c. Glass Panels
Individual black and white glass panels are used to take
advantage of the superior levelness of glass for casting of
uniform films and because the hard, smooth surface permits
rapid wet film thickness measurements with an ASTM-type of
wet-film thickness gage (5.d). The same information is obtained less rapidly but with much better precision by scraping
off and weighing a defined area of dry film and calculating as
described in Section 6.b. In some tests, contrast ratios are
calculated on the questionable assumption that separate film
applications on black and white glass panels are identical in
film thickness.
a. Paperboard Charts
Substrates of this type are described in 4.d. Their employment with baking finishes is limited because of distortion and
Panels of this type are generally used with coatings that are
applied by spraying and cured by baking. The weight of the
applied film is determined by weighing the panel before the
coating is applied and again after drying. The spreading rate
or film thickness is then calculated as described in 6.b. If
desired, the dry film thickness can be determined without
weighing, though with considerably less precision, by direct
measurement with a magnetic or an eddy current thickness
gage. Black-and-white panels are used for contrast ratio measurements or for visual observation of opacity. The use of allblack panels is described by Mitton for measuring the hiding
power of baking enamels [21].
CHAPTER 42--HIDING
Subscripts
x indicates an experimentally d e t e r m i n e d value, e.g., Tx, Hx,
Px.
c indicates a value calculated for a specified c o n t r a s t r a t i o
C,e.g.,Pc, Hc.
0.98 indicates a value calculated for C = 0.98, e.g., H0.98,
T0.98.
H indicates a value p e r t a i n i n g to a s p r e a d i n g rate, e.g., Cn,
PH, s..
T indicates a value p e r t a i n i n g to a film thickness, e.g., C~,
S T.
a a n d b are simplifying functions of R=, defined by
(29)
b -= V2 (1/R= - R=)
(30)
b. Equation
Symbols
C~ = Ro/R~,
C0.s0 = the c o n t r a s t ratio over a s t a n d a r d black-and-white
substrate, thus C0.80 = Ro/Ro.so.
C = a b b r e v i a t i o n for C0.s0; the two are used interchangeably, thus C = C080 = Ro/Ro.ao.
T = the film thickness in any stated unit, e.g.,/zm, mils.
491
Introduction
POWER
(31)
2 - 1) ~/2
(32)
[eZbe+l~
U = f(P, R=) -- b ~e2bf _ 1 ] = b coth bP
(33)
a n d the converse of Eq 33
P = f ( U ' R = ) = ~---bln ( U + b~ = b C ~
(34)
in w h i c h
In = sign of n a t u r a l logarithms, viz., log ~x = In x,
coth = sign of hyperbolic cotangents, defined b y coth x
eZ~+ 1,
- - and
e 2~ - 1
c o t h - 1 = sign of inverse hyperbolic cotangents, defined b y
coth-J x = - In
.
2
\ x - 11
Values of n a t u r a l l o g a r i t h m s a n d hyperbolic functions are
available in p u b l i s h e d tables a n d in calculators. Since the
492
t a n h - 1 1Ix
c. O r i g i n a l K - M E q u a t i o n s
e. G e n e r a l K-M H i d i n g P o w e r M e t h o d
G - R= + (1/R=
G)e
(1/R= -
R=)ST
(35)
F o r o p a q u e films
R= = f(K/S) = I + K/S - (K2S 2 + 2K/S) 1/2
(36)
(37)
d. S c a t t e r i n g C o e f f i c i e n t a n d S c a t t e r i n g P o w e r
1 -G(a-U)
a+U-G
R~ +
R~
-W--Ro
(39)
a n d from Eq 32:
1(
(38)
R = = a - (a z -
1) 1/2
(40)
(2) D e t e r m i n a t i o n o f R 0 a n d H x
This requires the a p p l i c a t i o n of a u n i f o r m film at a spreading rate (or film thickness) such that the c o n t r a s t ratio Cw is
within the range of 0.96 to 0.985. These limits are established
b e c a u s e too low a CR requires excessive e x t r a p o l a t i o n to the
C = 0.98 end-point, a n d h i g h e r CR values b e c o m e increasingly insensitive to s p r e a d i n g rate (or film thickness) variations. If the initial a p p l i c a t i o n is outside that range, the
a p p l i c a t i o n is r e p e a t e d at a h i g h e r o r lower film thickness, as
required.
TABLE 4--Unit conversion equations for scattering coefficients.
S (mZ/L)
"
"
"
S (mZ/kg)
"
S (m2/L)
= S (ft2/gal) + 40.746
= S (mil 1) X 39.37
= S(/~m -1) 1000
= S(mm 1) 1
= S (ft2/lb) + 4.888
= S (crnZ/g) + 10
= S (mZ/kg) D (kg/L)
R o ( l - 0.80Ro)
R 0 + 0.80 (1 - 2aR0)
(41)
ND
H (m2/L) - - t (/~m)-d
(42)
P = f(U, R~)
which are solved sequentially to give
Pc = f (C, R~)
(46)
S/P c w h e r e C = 0.98.
Calculation steps (a) t h r o u g h (d) can be c o m b i n e d into a
single c o m p u t e r p r o g r a m to r u n as follows
INPUT: R0, Hx, R~, C--OUTPUT: S, H c
(47)
(48)
or
U~ = f(PH, R~)
H (m2/kg) =
and
1000 N
(43)
t (/~m).d (kg/L)
CH = f(UH, R~) =
where
N = the nonvolatile fraction by weight (NVW) of the test
paint,
D = the density of a liquid paint,
d = the density of the d r y (or cured) film, and
t = the thickness of the d r y (or cured) film.
R--~-o-~j (44)
Pfl~.
Uo = f(C, R~) =
and Eq 34
[(
1 -C12-1]
a + 1.60 C]
(49)
C , = f(Pm R~)
(50)
(52)
A basic defect of this a n d other m e t h o d s that e m p l o y contrast ratio as the c r i t e r i o n of HP is that CR values are only
c o m p a r a t i v e as o p p o s e d to spreading rates, w h i c h have intrinsic a n d practical significance.
1 - RoR=
a + U - 0.80
(a + U)[1 - 0.80(a - U)]
from
493
1/2-1- 1 - C
1.60C
(45)
f. Judd Graph
Prior to the availability of m o d e r n c o m p u t e r s , K-M equations were m u c h too complex for a practicable hiding p o w e r
test m e t h o d . J u d d [24] therefore l a b o r i o u s l y w o r k e d out a
general solution to Eq 35 in the form of a g r a p h r e p r o d u c e d in
Fig. 9. The g r a p h relates the four variables Ro, Co.8o, R~, a n d P
so that from any two of t h e m the o t h e r two can be determined. It consists of two families of curves for c o n s t a n t
values of R~ a n d P, plotted on the c o o r d i n a t e s R 0 and Co.so,
494
.95
ARoo= .95
DIAGRAM SHOWING INTERRELATION
15.0
12.0
OF REFLECTANCE Ro
P = 10.0
9.0
REFLECTIVITY - Roo CONTRAST RATIO - Co,8o
8.0
i
.90"
.85-
,Roo= .85
P=4.0
.80,
=.90
,Roo= .80
3.5
P=3.0.
.75'
Ro
,Roo= .75
2.5A
= .70
.70,
P=2.0
,Roo= .65
.65.
1.5
.60
,Roo= .60
.55J, P =, 1.0
.50.
.60
.65
.70
.75
.80
.85
.90
1.00
.95
m a y be d e m o n s t r a t e d as follows: S u p p o s e a p o r t i o n of p a i n t
for w h i c h R~ -- 0.85 is tinted with a black c o l o r a n t to a n R~
value of 0.78 a n d the u n t i n t e d a n d tinted paints are a p p l i e d at
the s a m e thickness such that P -- 5.0. F r o m Fig. 9, o r m o r e
accurately from Fig. 10, it can be d e t e r m i n e d that the color a n t a d d i t i o n has increased the c o n t r a s t ratio to 0.965 from
its original value of 0.945, r e p r e s e n t i n g a c o n s i d e r a b l e increase in visual film opacity. To d e t e r m i n e w h a t this a m o u n t s
to in t e r m s of p h o t o m e t r i c hiding power, the P values of the
u n t i n t e d a n d tinted p a i n t s at the intersection of their R=
curves with the vertical line C = 0.98 are f o u n d to be 7.5 a n d
6.0, respectively. Since S is unaffected by tinting, the spreading rate change at C = 0.98 is calculated thus
/-/tinted
Huntinted
-- Puntinted __ 7 . 5
Printed
1.25
6.0
CHAPTER 4 2 - - H I D I N G P O W E R
.95
=.95
.90
.~= .90
.85
< = .85
.80
,o = .80
495
.75
90
9,5
1(30
o~
= .75
C O N T R A S T R A T I O - - C0eo
//o.98 (mE/L) --
S (m2/L).A0.98 _ S (m2/L)
1604.2
P0.98
At a later date Mitton commented that graphical and tabular aids for Kubelka-Munk calculations had become unnecessary with the advent of inexpensive programmable calculators [28]. Nevertheless, the Mitton graph and table
continue to be used in a number of important test methods,
and both the Judd and Mitton graphs are useful for instructional purposes.
Hpigment(m2/kg)
Hcoating (m2/L)
(ma/kg) =
1
Scoating(ma/L)
Pigment Conc. (kg/L)
Spigrnen t
496
P A I N T A N D COATING T E S T I N G M A N U A L
i. Theoretical P r o b l e m s a n d Practical
Considerations
The validity and usefulness of the Kubelka-Munk equations
in hiding power calculations are predicated on the constancy
of the scattering coefficient S over a suitably wide film thickness range. Judd [24] studied this question in connection
with water-borne paints and vitreous white enamels and con-
497
498
Semi-Gloss
White
0.8798
8.510
0.8679
8.I58
7.706
129.8
65.58
0.0656
8.330
120.0
67.95
0.0680
Flat
White
Gloss
Gray
0.9119
9.436
Gloss
Orange
Gloss
Yellow
Gloss
Green
0.5654
3.394
0.3910
2.150
0.6682
4.436
0.6940
4.759
10.32
19.71
96.92
50.74
98.39
66.89
0.0984
0.0669
U.S. Units
420.4
803.0
3.816
1.998
4009
2725
2.499
1.699
15.48
64.60
33.28
0.0333
8.629
115.9
38.28
0.0383
13.57
73.7
64.58
0.0646
630.8
2.543
1356
0.8455
351.6
4.562
1560
0.9723
Metric Units
Ho.9s (mZ/L)
To.98 (~m)
S (mZ/L)
S (~m 1)
/-/o.98 (ft2/gal)
To.9s (mils)
S (ft2/gal)
S (mil- 1)
314.0
5.109
2672
1.665
339.4
4.726
2769
1.726
552.8
2.902
2631
1.640
Light Gray
0.8234
7.011
Orange
0.6860
4.655
0.4389
2.449
Metric Units
Ho.9s (m2/kg)
Density (kg/L)
To.gs (/zm)
S (m2/kg)
18.09
1.60
34.55
126.8
20.22
1.66
29.79
94.13
10.26
1.41
69.12
25.13
98.7
13.85
1.17
459.5
50.1
11.77
2.72
122.7
K2=K 1 +XK,
(a)
XKt = K2 - K,
(b)
from which
U.S. Units
//o.98 (fta/lb)
Density (lb/gal)
T0,98 (mils)
S (~t2/lb)
88.3
13.35
1.36
619.2
0.91
9.5
Zinc
Oxide
Zinc
Sulfide
Anatase Rutile
TiOz
TiO2
. . . . . . . . . . . .
. . . . . . . . . . . .
Metric Units
//o.98 (m2/kg)
S (m2/kg)
3A
29
4.1
39
11.9
113
23.5
223
30
285
U,S. Units
//0.98 (ftE/lb)
S (ft2/lb)
15
140
20
190
58
550
115
1090
147
1390
j. C a l c u l a t i o n o f H i d i n g P o w e r f r o m T i n t i n g D a t a
Initially the S a n d R~ values of a s t a n d a r d white p a i n t are
d e t e r m i n e d in accordance with the procedure described in
8.e. The K value of the p a i n t can then be calculated from Eq
37: K/S = (1 - R~)2/2R~.
F r o m 8.d, S a n d K can be considered as concentrations of
"scattering" a n d "absorption" per u n i t weight or volume, The
(c)
in which
K,
X
K~
/s
S
=
=
=
=
=
the
the
the
the
the
(d)
499
:5200!
p-
rr
UJ
2800
CL
2400
/|
/e
2000
1"
LU
1600
"1"
/@
/
1200
0r r
CURVE IF PERFECT
CORRELATION (i.e. 45 ~ CURVE)
ii
806
S = 106(TS) - 162
r = 0.997
E
(3
40C
Z
U~
UJ
i
400
t
800
1
~200
1
~600
t
2000
t
2400
l,,
2800
t
3200
t
3600
S B / S A = ( K A 2 / S A - K A 1 / S A ) -~- ( K B 2 / S B - K B I / S B )
(c)
(d)
(a)
(b)
XKt/S A
KA2/S A
- -
for Paint B:
9. FACTORS A F F E C T I N G W H I T E H I D I N G
POWER
As shown in Tables 1 and 7, futile titanium dioxide is by far
the most effective of the white hiding pigments in producing
light scattering and hiding power, which is true on a cost as
well as a weight basis. This fact has effectively eliminated the
use of other white hiding pigments except for special properties or considerations. The important variables that determine the scattering and hiding efficiency of a titanium
dioxide pigment in a paint are: (1) its mean crystal and particle size, (2) the state of pigment dispersion, (3) its concentration in the paint film, and (4) film porosity.
500
c. Pigment Concentration
b. Pigment Dispersion
The process of obtaining a satisfactory dispersion involves
the wetting of the pigment by the dispersion medium to
displace air, breakdown of larger particles by milling, and
stabilization after the dispersion has been obtained. With
alkyd media, standard grades of titanium dioxide disperse
easily and develop full hiding with very little milling. Thus,
the main reason for milling alkyd dispersions is to reduce or
eliminate oversize particles that effect the appearance of the
film. With latex paints, milling can have an important effect
on opacity depending on the grade of pigment employed [33],
but the appearance factor is also an important consideration,
particularly with semigloss and gloss finishes.
A major factor affecting the efficiency of TiO 2 in the completed formulation is the phenomenon referred to as "flocculation," which is the formation of large particle groups or
"floccules" due to weak forces of cohesion. Floccules are
easily broken down but can spontaneously and quickly recur
in the wet paint or drying paint film. Despite their weak
bonding, floccules have the optical effect of increasing the
mean particle size, thereby decreasing the scattering efficiency of the pigment. An auxiliary phenomenon related to
increased particle size is the preferential scattering of longer
wavelengths. Balfour and Hird took advantage of this phenomenon to quantify pigment flocculation by measuring
back-scattered infrared radiation (wavelength 25/.m) from a
dried paint film to obtain what they refer to as a "flocculation
gradient" [34,35].
Mean
Crystal Size,
/*m
0.24
0.20
0.16
(53)
(54)
(55)
(56)
d. Film Porosity
The preceding relationships pertain to pigment concentrations at which there is sufficient binder to wet the pigment
completely and form a continuous phase, which means below
the critical pigment volume concentration (CPVC). Above the
CPVC, the dried film becomes porous, containing entrapped
air that increases pigment-scattering efficiency by' effectively
lowering the refractive index of the surrounding medium.
The air itself, as particulate matter in contact with the higher
refractive index binder, contributes to light scattering. Thus,
if the curves of Fig. 14 were extended to a sufficientlv high
PVC, the hiding power of the film would begin to rise again
CHAPTER 42--HIDING
POWER
501
I000
oO
E3
/
O9
tl.I 9
900
80O
ft. rr
g
3:
ILl
LL
UJ
tr"
<
:3
o
0r~
60O
50(1
I
15
I
20
I
25
!
30
I
35
1
40
I
45
I
50
IZ
LU
_~
18o
fiLL
e.I. = 1 -
o 160
c3
z
o
Rutile
(57)
The low-cost hiding power obtained from porosity is unfortunately accompanied by a deterioration in the quality of the
film as manifested by poor scrub, soilant, and stain resistance. This is due to an insufficiency of binder, resulting in an
air phase continuum that gives ready capillary access to
staining materials.
140
tr
uJ
Q.
120
W
LL
LU
rr
<
CPVC (1 - PVC)
PVC (1 - CPVC)
I00
O9
(,)
_z
-----r
ao
10. M I C R O V O I D S F O R W H I T E H I D I N G
POWER
6o
40
i0
i
?.0
,I
30
,i
40
50
60
FIG. 1 5 - H i d i n g power
levels.
Ho.gs(ft2/Ib)
502
11. F O R M A L H I D I N G P O W E R M E T H O D S
a. A S T M M e t h o d s
SPREADING RATEDRYENDVOINX
SPREADING RATEwETENDPOINX
The equation assumes that, for any one drawdown, the
ratio of clearance to WFT for the several notches does not
deviate appreciably. On that basis WFT variations due to
application technique or paint theology would not affect the
final test result. This is not a precision test but provides
significant information of a practical nature with minimal
effort.
i'- BB~
~Notchclearances
are not drawn to scale
24
28
8.56 217
7.04 179
48
2.65 67
TmV~.==
CHAPTER 4 2 - - H I D I N G POWER
503
FIG. 17-Large gray scale chart (6 ft, 2 5575 cm 2) for roller application tests per
ASTM D 5150.
504
m i n a l wet film thicknesses of 40, 50, a n d 60 txm c o r r e s p o n d ing to SRs of 25, 20, a n d 16.67 m2/L. After drying, the CR
values are m e a s u r e d a n d the SR values d e t e r m i n e d b y a
typical weight-area-density m e t h o d as discussed in 6.b. The
d r y film weight is d e t e r m i n e d as the difference between the
p a i n t e d a n d u n p a i n t e d chart, with considerable p r e c a u t i o n s
taken, as discussed in 7.a to avoid error due to n o n u n i f o r m
chart weight. A g r a p h of CR versus SR is p r e p a r e d on squareruled p a p e r from which the CR at exactly 20 mZ/L is determ i n e d by interpolation. The m e t h o d is restricted to paints
with a reflectance value of at least 25%. Weaknesses of this
m e t h o d are: (a) it fails to correct for possible variations in the
reflectance of the white substrate, as discussed in 1.f; (b) the
specified SR of 20 mZ/L c o r r e s p o n d s to a wet film thickness of
only 5 0 / z m (2 mils), at w h i c h thickness irregularities in the
surface of p a p e r test charts can have an a p p r e c i a b l e effect.
Part D6. Contrast Ratio at 20 m2/L Using Polyester Film-This m e t h o d is technically identical with ISO 3906-1980
(11.c).
Part DZ True Hiding Power (SR at C = O.98) by the KubelkaMunk Method--This m e t h o d is technically identical with ISO
6504 (11.c) a n d in a c c o r d a n c e with early versions of ASTM
D 2805 a n d the general K-M hiding p o w e r m e t h o d d e s c r i b e d
in 8.e.
fore a n d after application, with a specified volume being delivered to the c h a r t surface by syringe. W i t h d r a w d o w n s ,
p r e s u m e d l y identical a p p l i c a t i o n s are m a d e on glass a n d
charts a n d the W F T d e t e r m i n e d on glass by m e a n s of a n
I n t e r c h e m i c a l (ASTM D 1212) wet film thickness gage. F o r
the test p a i n t to pass, the dry p a i n t film is r e q u i r e d to completely obscure the c o n t r a s t p a t t e r n of the chart.
REFERENCES
[1] Gardner, H. A. and Sward, G. G., Physical and Chemical Examination of Paints, Varnishes, Lacquers and Colors, 9th ed., May
1939, p. 10.
[2] Simpson, L. A., "Measuring Opacity, Part I," Paint, Pigments and
Coatings Journal, Vol. 179, February 1989.
[3] Mitton, P.B., Vejnoska, L.W., and Frederick, M., "Hiding
Power of White Pigments: Theory and Measurement--I," Official Digest, Federation of Paint and Varnish Production Clubs,
Vol. 33, 1961.
[4] Mitton, P. B., Paint Testing Manual, ASTM STP 500, Chap. 1.3:
Hiding Power, "Physical and Chemical Examination of Paints,
Varnishes, Lacquers and Colors," 13th ed., 1972.
[5] Gardner, H. A., Sward, G. G., and Levy, S. A., "Hiding Power
and Tinting Strength of Pigments and Paints," Scientific Section
Circular, National Paint, Varnish, and Lacquer Association, No.
362, 1930.
[6] Kraemer, E. O. and Schupp, O. E., "Determination of Hiding
Power of White Paints," unpublished paper presented at the
Washington, DC meeting of the American Chemical Society,
March 1933.
[7] Pfund, A. H., "Hiding Power of White Pigments and Paints,"
Journal, Franklin Institute, Vol. 188, 1919, p. 675.
[8] Pfund, A. H., "Hiding Power Measurements in Theory and Application," Proceedings, American Society for Testing Materials,
Vol. 30, Part II, 1930, p. 878.
[9] Sward, G. G. and Levy, S. A., "An Instrument for Hiding Power
Determinations," Scientific Section Circular, National Paint,
Varnish, and Lacquer Association, No. 433, 1933.
[10] Brodgen, D., "The Precision of the Pfund Black and White Cryptometer," Official Digest, Federation of Paint and Varnish Production Clubs, Vol. 33, 1961, p. 1297.
505
[12] Hallet, R. L., "An Instrument for Measuring the Hiding Power of
Paints," Proceedings, American Society for Testing and Materials, Vol. 20, Part II, 1920, p. 426.
[13] Pfund, A. H., "Hiding Power Measurements in Theory and Practice," Proceedings, American Society for Testing and Materials,
Vol. 30, Part II, 1930, p. 882. Pfund, A. H., "The Photoelectric
Cryptometer," Proceedings, American Society for Testing and
Materials, Vol. 31, Part II, 1931, p. 876.
[14] Hanstock, R. F., "The Opacity of Paints," Journal, Oil and Colour
Chemists' Association, Vol. 20, 1937, p. 5.
[15] Sawyer, R. H., "Hiding Power and Opacity," Symposium on
Color, ASTM STP 50, American Society for Testing Materials,
Philadelphia, 1941, p. 22.
[16] Switzer, M. H., "Critical Analysis of the Fell Hiding Power Relationship," American Paint Journal, Vol. 40, No. 13, 1955, p. 72.
[17] Mitton, P. B., "A Mathematical Analysis of the Precision in Determining Hiding Power," American Paint Journal, Vol. 30, 1958,
p. 156.
[18] Van Eyken, W.W. and Anderson, F.T., Jr., "An Improved
Method of Hiding Power Determination," American Paint Journal, Vol. 43, No. 31, 1959, p. 78.
[19] Tough, D., "The Use of Contrast Ratio in the Measurement of
Hiding Power," Journal, Oil and Colour Chemists' Association,
Vol. 39, 1956, p. 169.
[20] Gall, L., "On the Hiding Power of Colored Pigments in Paints
and Printing Inks," Farbe und Lack, Vol. 72, 1966, p. 1073.
[21] Mitton, P. B., "Measuring Hiding Power of Baked Coatings on
Metal," Metal Finishing, Vol. 72(G), 1974, p. 44.
[22] Kubelka, P. and Munk, F., "Ein Beitrage zur Optik der
Farbenstriche," Zeitschrift fur Technische Physik, Vol. 12, 1931,
p. 593.
[23] Steele, F. A., "The Optical Characteristics of Paper," Paper Trade
Journal, Vol. 100, No. 12, 1935, p. 37.
[24] Judd, D. B., Harrison, W. N., Hickson, E. F., Eickhoff, A. J.,
Shaw, M. B., and Paffenbarger, G. C., "Optical Specification of
Light-Scattering Materials," Journal of Research, National Bureau of Standards, Vol. 19, p. 287.
[25] Kubelka, P., "New Contributions to the Optics of Intensely Light
Scattering Materials--Part I," Journal, Optical Society of America, Vol. 38, 1948, p. 448.
[26] Switzer, M. H., "Equation for Calculating Hiding Power Index
and Spreading Rate of Paints," ASTM Bulletin, American Society
for Testing and Materials, No. 181, 1952, p. 75.
[27] Mitton, P.B., "Easy, Quantitative Hiding Power Measurements," Journal of Paint Technology, Vol. 42, 1970, p. 159.
[283 Mitton, P. B. to Weaver, J. C., personal communication, 1977.
[29] Mitton, P. B., Madi, A. J., and Rode, J. W., "Development of a
Test Method for Hiding Power," Journal of Paint Technology,
Vol. 39, 1967, p. 536.
[30] Hallett, R. L., "Hiding Power and Tinting Strength of White
Pigments," Proceedings, American Society for Testing and Materials, Vol. 30, Part II, 1930, p. 895. "Hiding Power of Pigments,"
Proceedings, American Society for Testing and Materials, Vol.
26, Part II, 1926, p. 538.
[31] Titanium Pigment Company, "The Handbook," 1956.
[32] Mitton, P. B. and Jacobsen, E. E., "Reflectometry Method for
Measuring Tinting Strength of White Pigments," Official Digest,
Federation of Paint and Varnish Production Clubs, Vol. 34,
1962, p. 704.
[33] Simpson, L. A., "Measuring Opacity, Part II," Paint, Pigment &
Coatings Journal, Vol. 179, March 1984.
[34] Balfour, J. G. and Hird, M. S., Journal of the Oil and Color
Chemists Association, Vol. 58, 1975, p. 331.
506
P A I N T A N D COATING T E S T I N G M A N U A L
MNL17-EB/Jun. 1995
im
DEFINITIONS
9
The mass color (MC) of a coating is defined in ASTM Terminology Relating to Paint, Varnish, Lacquer, and Related
Products (D 16) as:
"the color, when viewed by diffuse reflected light, of a
pigment-vehicle mixture of such thickness as to obscure
completely the background. Sometimes called over-tone
or mass-tone."
9
9
that m a y contain more than one pigment but are tested and
used as if they contain only a single pigment.
Saturation is "the attribute of a visual sensation that permits a judgment to be made of the proportion of pure
chromatic color in the total sensation." Saturation can also
be described in a mathematical m a n n e r as in ASTM E 284.
Scattering is "the process by which light or other electromagnetic radiant flux passing through matter is redirected
over a range of angles."
Shade is "a color produced by a dye or pigment mixture
including black dye or pigment."
Tint is "a color produced by the mixture of white pigment
or paint with a chromatic pigment or paint."
Tristimulus values are "the amounts of three specified stimuli required to m a t c h a color." In the CIE system, these
stimuli are assigned the symbols )2, Y, and Z.
TINTING STRENGTH
Tinting strength is a measure of the effectiveness with
which a unit quantity of a colorant changes the color of a
material (ASTM E 284). It m a y be thought of as a pigment's
"coloring power." For those colorants that both scatter and
absorb, the scattering and absorption tinting strengths must
be specified. ASTM D 284 defines scattering tinting strength
as "the relative change in the scattering properties of a standard black material (with no scattering colorant present)
when a specified a m o u n t of a white or chromatic scattering
colorant is added to it" and absorption tinting strength as the
relative change in the absorption properties of a standard
white material when a specified a m o u n t of an absorbing
colorant, black or chromatic, is added to it."
Pigment concentration is important to coating strength
and cost, and therefore tinting strength can be an important
relative economic value factor in selecting one paint over
another. There is no particular value of tinting strength that
can be stated as desirable unless an end use is stated. In
certain cases a high value is desirable and in others a low
value is needed to achieve a desired color/strength effect. In a
general sense, tinting strength is determined by dilution of a
test paint and a reference paint with a standard "mixing white
paint" in the case of chromatic paints or a standard "tinting
color" in the case of white paints, drawing down the resulting
pastes on a suitable substrate, and then instrumentally measuring tristimulus values or visually comparing the specimens. The latter comparison technique has lower precision
than the former. Details for the preparation of a standard
507
Copyright9 1995 by ASTM International
www.astm.org
508
Chromatic Paints
ASTM Test Method for Determining the Relative Tinting
Strength of Chromatic Paints (D 4838) is a method used for
determining the absorption tinting strength of a chromatic
(define) test paint relative to that of a paint of the same
chemical type. The method is intended for comparison of
paints that contain the same chemical type vehicle (acrylic,
alkyd, or oil) and single-pigment colorants of the same Colour
Index name and number. Knowledge about the amount of
pigment and other components of the paint is not necessary.
The color measuring instrument can be either a spectrophotometer that provides 1931 CIE tristimulus values X, Y, Z
for CIE standard illuminant C, or a tristimulus colorimeter
providing either such tristimulus values or colorimeter readings R, G, B. Other related test methods useful in following
ASTM D 4838 are ASTM Test Method for Computing the
Colors of Objects by Using the CIE System (E 308) and ASTM
Practice for Obtaining Spectrophotometric Data for ObjectColor Evaluation (E 1164).
ASTM Test Method for Color and Strength of Color Pigments with a Mechanical Muller (D 387) is used for comparing the color and strength of a pigment with a reference
standard of the same type. The test method is not to be used
with white pigments. The pigments are dispersed in a suitable
vehicle with a mechanical muller. Opaque drawdowns are
made on white paper charts that have a black band and a
surface that is impervious to paint liquids. These are then
compared either visually or instrumentally for color and
strength differences.
White Paints
ASTM Test Method for Relative Tinting Strength of White
Pigments by Reflectance Measurements (D 2745) is a procedure for determining the relative tinting strength of white
pigments by reflectance measurements made on black tints.
It is only applicable for comparing a test pigment with a
reference standard. The method is conducted by dispersing
PIGMENT DISPERSION
Mass color and tinting strength require that the pigments
be well dispersed in the binder to achieve maximum tinting
strength. Ideally, it would be desirable to break down pigment agglomerates to individual particles, i.e., to an ultimate
dispersion state. However, in actual practice this would be
difficult, if not impossible, to achieve. Therefore, pigments
under investigation for MC and TS must be processed in the
same manner and receive the same level of mechanical work.
Mechanical mullers, Fig. 1, which are instruments that have
two circular, usually ground, glass-grinding surfaces that
contain the pigment and vehicle, are used for dispersing the
two components. (A satisfactory muller is supplied by the
Hoover Color Corp., 13 Cordier St., Irvington, NJ 07111.)
Development of tinting strength is dependent on the force
applied to the glass plates, the number of revolutions used,
and the mass of pigment and of vehicle used. If muller conditions, pigment, and vehicle have not been agreed on by purchaser and seller, the mandatory dispersing conditions given
in the Annex of ASTM D 387 should be used to achieve the
maximum level of tinting strength. These conditions include:
9 Determination of the appropriate ratio of color pigment to
dispersing vehicle for the standard and test pigments.
9 Determination of appropriate masses of pigment and vehicle to use.
9 Preparation of a standard tint by application of 100 lb to
the muller plates, introducing the appropriate mass of pigment/vehicle, and mulling the paste for 100 revolutions in
two stages of 50 revolutions each. This is then repeated on
three more specimens of the standard mixture except the
mulling is carried out for 200, 300, and 400 revolutions in
stages of 50 revolutions.
9 Each of the four specimens is compared one to the other for
tinting strength, and the minimum number of revolutions
509
AUTOMATIC MULLERS
PIGMENT-DISPERSION TECHNIQUES
It should be kept in m i n d t h a t the techniques d e s c r i b e d in
this c h a p t e r p e r t a i n to p r e p a r i n g specimens for d e t e r m i n a tion of tinting strength, m a s s color, etc., and are not m e a n t
for p i g m e n t dispersion in general. The general topic of pigm e n t d i s p e r s i o n is discussed elsewhere in this m a n u a l as well
as in n u m e r o u s references [3-7]. There is a vast a m o u n t of
literature that deals with the surface t r e a t m e n t of organic
p i g m e n t s to improve ease of dispersibility, a n d interested
r e a d e r s are e n c o u r a g e d to seek such i n f o r m a t i o n in the classic w o r k of Hayes [8] as well as others [9-11 ]. Detail a b o u t the
surface t r e a t m e n t of inorganic pigments is also in the literature [12-14]. M u c h of the following i n f o r m a t i o n is a b r i d g e d
a n d modified from the c h a p t e r with the s a m e title in the
previous edition of this m a n u a l [15].
A u t o m a t i c or m e c h a n i c a l mullers have two circular glassgrinding surfaces that c o n t a i n the pigment/vehicle paste. The
grinding surfaces are usually c o n s t r u c t e d of g r o u n d glass
with one s t a t i o n a r y a n d weighted to exert a p r e s s u r e of
100 psi (440 N) a n d the o t h e r rotary with r o t a t i o n effected b y
a motor. Because r o t a t i o n is a b o u t the disk centers, paste at
the center can receive less mulling t h a n paste l o c a t e d n e a r the
edges. To c o m p e n s a t e for this effect, it has been f o u n d helpful
to s p r e a d the paste in a ring a p p r o x i m a t e l y halfway b e t w e e n
the edge a n d center. The revolutions p e r mulling cycle can be
a d j u s t e d in i n c r e m e n t s of 1 to 999. Mechanical m u l l e r advantages include very good d e v e l o p m e n t of tinting strength, possibility to rapidly mull small quantities of materials, a n d efficient processing of a large n u m b e r of samples.
The Annex of ASTM D 387, briefly d e s c r i b e d above, has a
specific way to operate an a u t o m a t i c muller w h e n determining tinting strength or m a s s color.
TABLE l--Interlaboratory pigment dispersing parameters and specific conditions obtained for
maximum tinting strength (data taken from ASTM D 387).
Parameter
100 (440)
100 (2 x 50)
1.0
1.7
Pigment Type
BON Red
100 (440)
200 (4 x 50)
0.6
1.4
Pthalocyanine Green
100 (440)
400 (8 x 50)
0.75
1.8
510
Engineering Chemistry.)
Laboratory Roller M i l l
Small three-roller mills have been found useful for grinding
small, laboratory-size batches of paint. Rolls of such mills are
a b o u t 4 in. (10.16 cm) in d i a m e t e r a n d 8 in. (20.82 cm) in
length. Batches as small as 5 g have been p r e p a r e d in such
mills.
PIGMENT CONCENTRATION
Paste viscosity has an effect on grinding efficiency, a n d it
d e t e r m i n e s the level of m a s s color a n d tinting strength that is
developed. Ayers [16] investigated i r o n oxides, a n d the results
i n d i c a t e d t h a t color developed faster as p a s t e viscosity increased. A low-viscosity paste h a d a reflectance of 26% at a
wavelength of 700 nm, w h e r e a s high-viscosity paste was
d a r k e r a n d r e d d e r with a reflectance o f 23%. There is a p o i n t
above w h i c h viscosity has no effect.
M I X I N G T I M E OF LIQUID C O L O R S
One of the p r o p e r t i e s of oil o r universal liquid colorants is
the ease with w h i c h they c a n be i n c o r p o r a t e d into white
paints. A m e t h o d for testing the speed of i n c o r p o r a t i o n has
been d e s c r i b e d by Paul a n d D i e h l m a n [19]. This m e t h o d involves use of a m e c h a n i c a l rotating bottle that contains a
white paint, the liquid colorant, a n d a g r i n d i n g media. W h e n
the test was first developed, No. 11 lead shot was used; however, t o d a y glass beads, z i r c o n i a grinding media, a n d steel
REFERENCES
[1] Zeller, R. C., "The Meaning of Tint Strength," Color Research
and Application, Vol. 3, 1978, p. 34.
[2] Vernardakis, American Ink Maker, Vol. 62, No. 2, 1984, p. 24.
[3] Varley, D. M. and Bower, H. H., Journal of the Oil and Colour
Chemists Association, Vol. 62, 1979, p. 401.
[4] Patton, T. C., Paint Flow and Pigment Dispersion, 2nd ed., WileyInterscience, New York, 1979.
[5] Carr, W., Journal of the Oil and Colour Chemists Association, Vol.
61, 1978, p. 397.
[6] Hafner, O., Journal of the Oil and Colour Chemists Association,
Vol. 57, 1974, p. 268.
[7] Parfitt, G. D., Dispersion of Powders in Liquids, 2nd ed., WileyInterscience, New York, 1973.
[8] Hays, B. G., American Ink Maker, Vol. 62, No. 6, 1984, p. 28.
[9] Hampton, J. S. and MacMillan, J. F., American Ink Maker, Vol.
63, No. 1, 1985, p. 16.
[10] Topham, A., Progress in Organic Coatings, Vol. 5, 1977, p. 237.
[11] Merkle, K. and Schafer, H. in Pigment Handbook, Vol. III, T. C.
Patton, Ed., Wiley-Interscience, New York, 1973, pp. 157-167.
[12] Linden, H., Rutzen, H., and Wegemund, B., U.S. Patent
4,167,421 (1979).
[13] Hauxwell, F., Stansfield, J. F., and Topham, A., U.S. Patent
4,042,413 (1977).
[14] Franklin, M. J. B., Goldsbrough, K., Parfitt, G. D., and Peacock,
J., Journal of Paint Technology, Vol. 42, 1970, p. 740.
[15] Mitton, P. B., "Mass Color and Tinting Strength," Chapter 1.4 in
Paint Testing Manual, STP 500, 13th ed., G. G. Sward, Ed., The
American Society for Testing and Materials, Philadelphia, PA,
1972.
[16] Ayers, J. W., "A Discussion of the Accuracy and Utility of Methods of Test for Mass Tone and Tinting Strength," Proceedings,
American Society for Testing and Materials, Vol. 34, Part II, 1934,
p. 497.
[17] Stutz, G. F. A., "Tinting Strength of White Pigments," Proceedings, American Society for Testing and Materials, Vol. 34, Part II,
1934, p. 521.
[18] Pall, D. B., "A New All-Glass Mill," Industrial and Engineering
Chemistry, Analytical Edition, Vol. 14, 1942, p. 346.
[19] Paul, M. R. and Diehlman, G., "Method and Apparatus for Determining the Interval Required to Disperse Oil Colors Throughout a Paint Medium," Proceedings, American Society for Testing
Materials, Vol. 34, Part II, 1934, p. 490.
Part 1 I:
MNLI7-EB/Jun.
1995
Adhesion
by Gordon L. Nelson 1
ORGANICCOATINGSAREAPPLIEDto a variety of substrate materials (woods, metals, plastics, ceramics) for decorative,
protective, and functional applications. In each case, it is
imperative that the coating adheres well to the substrate.
Accordingly, adhesion assessments should be an integral part
of coating development. This may seem a straightforward
task, but coating adhesion is, in fact, extremely complex and
often poorly understood. The growing use of plastics to replace metals and other "traditional" materials renders the
issue even more complex [1-2].
The objectives of this chapter are to review briefly salient
concepts of the adhesion process and to discuss currently
accepted standard test methods.
FUNDAMENTAL CONCEPTS
While the very definition of "adhesion" is of some controversy [1], adhesion may be loosely defined as the attraction
between dissimilar bodies for one another. ASTM D 907 on
Terminology of Adhesives defines adhesion as "The state in
which two surfaces are held together by interracial forces
which may consist of valence forces or interlocking action or
both." In discussing adhesion assessment, one must consider
the issue from two different aspects: basic adhesion and
practical adhesion. Basic adhesion signifies the summation of
all interracial, intermolecular forces, whereas practical adhesion is used to represent the forces or work required to
disrupt the adhering system [3]. The next section will be
devoted to theories and concepts of basic adhesion and will of
necessity be brief. The perspective will be from that of a
polymeric coating on a plastic substrate [2]. Metal and metal
oxide substrates will be discussed where appropriate. The
reader is referred to Refs 4- 7 for a more thorough discussion.
BASIC A D H E S I O N
Work of Adhesion
Bonding between polymeric coatings and substrates may
be viewed as the union of two contiguous polymer phases,
one a solid and the other a liquid which solidifies to form a
thin film. The reversible separation of the two phases may be
expressed by the work of adhesion
Wa = Y, + Y2
Y12
(1)
(2)
Fracture Theory
The area of interracial bonding between coating and substrate will, in most instances, contain voids or defects. The
result is deviation between the ideal adhesive strength and
the practical limit.
Good [10] and Williams [11] have applied the theory of
cohesive fracture to coating fracture. The concept that fracture propagates from the weakest point, a defect, is fundamental to fracture mechanics. The strength of a bond, in
terms of the energy required to induce fracture, is described
as a function of the defect size and the energy dissipated by
irreversible processes (plastic deformation, light emission,
and electric discharge). The general equation given is
f = k (EF/d) in
(3)
f = Wa + W~
513
www.astm.org
(4)
514
P A I N T A N D COATING T E S T I N G M A N U A L
~/~
~ .
(5)
9s
Wetting--Contact Theory
The wetting-contact theory states that van der Waals attractive forces alone provide sufficient coating/substrate
bond strength given perfect molecular contact, and that the
extent of contact and resulting bond strength are functions of
wetting energetics [20-28]. No one denies the importance of
wetting in adhesion, i.e., the lower the contact angles, the
more the interracial area of contact, which generally yields
improved adhesion (Fig. 2).
However, thermodynamic wetting is a necessary but not
sufficient condition for the establishment of coating film adhesion. Wetting is a kinetic phenomenon as well. Furthermore, this model does not consider the effects of weak bound~
ary layers or the effects of defects or fracture mechanics.
What is the effect of surface contamination on the contact
angle?
Diffusion Theory
Voyutskii and others [29-33] have proposed that coating
adhesion between high polymers arises from interdiffusion.
A, film
"rL
1
2
3
4
5
B, solid
DROP
", ///
r
7 LcosO
= 7S-TSL
ai = 2 (m/x) lj2
(6)
Chemical Adhesion
FIG. 1-Weak boundary layer theory. Possible zones of failure (after Good [19]).
CHAPTER 44--ADHESION
Coupling agents such as chrome complexes [41], silanes
[42], and titanates [43] have been used effectively. Organic
functionalities, including isocyanates, carboxyls, amides,
amines, hydroxyls, and epoxides [43-44], have been reacted
interfacially to enhance adhesion.
Adhesive strength has been shown to increase with functional group concentration as expressed by
f = kC~
(7)
where fis the adhesive strength, C the functional group concentration, and k and n are positive constants [45]. There,
however, appears to be an upper limit for functional group
concentration above which adhesion may tend to decrease
[46-47].
Mechanical Adhesion
In mechanical adhesion substrate roughness is thought to
provide a mechanical locking of the coating to the substrate.
However, if there is not intimate contact between the coating
and the substrate, then increased roughness should lead to a
decrease in adhesion by producing uncoated voids. In the
practical application of electroless metals on polymer substrates, etchants are used which create deep channels, increasing adhesion. Other examples are anchor coats for
PTFE, adhesion to porous anodic films on aluminum, and hot
melt polyolefin coatings on metals. Mechanical adhesion is
also important for porous substrates such as wood, cloth, and
paper. Since good adhesion can be obtained on smooth surfaces such as glass, questions can be raised about the general
validity of the mechanical adhesion mechanism. It should
also be noted that mechanical abrasive treatment of a solid
surface may also yield macroradicals and active secondary
chemical products, which if they do not come into contact
with atmospheric oxygen, may interact with components of
the coating. This has been shown for certain adhesives. Active
radicals or functionality would yield adhesion, better described as mechanico-chemical adhesion than just mechanical [7,48-49].
Electrostatic Adhesion
In the theory of electrostatic adhesion, when two dissimilar
materials are brought into contact, a charge transfer takes
place which results in the formation of an electrical double
layer, much like a capacitor. Work would then be required to
separate the two charged layers. This is thought to be particularly applicable to metal-polymer bonds. Indeed, ionizing
discharge has been shown to affect a copper to acrylic bond
but not copper on salt (NaC1) or glass. This theory would not
be applicable to two nonpolymer systems [49-50].
Acid-Base Adhesion
In the acid-base adhesion theory, it is said that the strength
of the adhesive bonds is increased significantly by acid base
interactions between coating and substrate. Appropriate
modification of surface acidity or basicity of the substrate
should increase adhesion. Modification of surface acidity or
basicity of inorganic solids can increase mechanical properties (modulus, extension to break, and toughness) of coatings
5|5
Combination o f Phenomena
The preceding theories interpret adhesion in terms of single phenomena, each of which undoubtedly plays some role
in interfacial bonding between coating and substrate. One
should be cautioned, however, against exclusive use of a single theory to explain the adhesion of a given system. A more
logical approach has been proposed by Allen [53]
(8)
Effects o f Substrates
Additional Chemistry
The adhesion of organic coatings to metals is at a high level
of development in the practical sense. The contribution of
surface energy, chemical functionality, surface irregularities,
and contaminants (oxides, adsorbed water, etc.) have been
identified.
On the other hand, coating adhesion to plastic suhstrates
has presented additional complexities. Polymer surfaces are
often more difficult to wet and bond because of low surface
energy, incompatibility, chemical inertness, or the presence
of contaminants (oils, lubricants, plasticizers, etc.), and weak
516
PRACTICAL A D H E S I O N
Given the complexities of the adhesion process, can adhesion be measured? As Mittal [3] has pointed out, the answer is
both "yes" and "no." It is reasonable to state that at the
present time no test exists which can precisely assess the
actual physical strength of an adhesive bond. But it can also
be said that it is possible to obtain an indication of relative
adhesion performance.
CHAPTER 4 4 - - A D H E S I O N
Practical a d h e s i o n test m e t h o d s are generally of two types:
Test Methods
I n practice, a b a t t e r y of tests is used to evaluate a d h e s i o n by
inducing b o n d r u p t u r e by different modes. Criteria d e e m e d
essential for a test to w a r r a n t large-scale a c c e p t a n c e are: use
of a s t r a i g h t f o r w a r d a n d u n a m b i g u o u s procedure, relevance
to its i n t e n d e d application, reproducibility, a n d quantifiability, including a meaningful rating scale for assessing
p e r f o r m a n c e . Test m e t h o d s used for coatings on metals are:
peel a d h e s i o n or "tape testing," G a r d n e r i m p a c t flexibility
testing, a n d adhesive joint testing including shear (lap joint)
a n d direct tensile (butt joint) testing. These tests do not, in
fact, strictly m e e t the criteria listed, b u t an appealing aspect
of the above tests is that in m o s t cases the equipment/instrum e n t a t i o n is readily available or can be o b t a i n e d at reasonable cost [2].
A wide diversity of test m e t h o d s has been developed over
the years. In this c h a p t e r only selected test m e t h o d s develo p e d t h r o u g h the consensus process will be discussed in
detail. The r e a d e r should recognize, however, that n u m e r o u s
test m e t h o d s have been developed w h i c h m e a s u r e aspects of
a d h e s i o n [7,58-61] and that there generally is difficulty in
relating these to basic a d h e s i o n p h e n o m e n a .
517
guish b e t w e e n h i g h e r levels of a d h e s i o n for w h i c h m o r e sop h i s t i c a t e d m e t h o d s of m e a s u r e m e n t are required. I n multicoat systems, a d h e s i o n failure m a y occur b e t w e e n coats so
that the a d h e s i o n of the coating system to the s u b s t r a t e is not
d e t e r m i n e d . In Test M e t h o d A an X-cut 1.5 in. (3.8 cm) long is
m a d e in the film (to the substrate) with a sharp cutting
device. A 1-in. (2.5-cm)-wide pressure sensitive t a p e is applied over the cut a n d firmly a d h e r e d with a pencil eraser a n d
t h e n removed, a n d a d h e s i o n is assessed qualitatively on a 0 to
5 scale.
In Test M e t h o d B, a lattice p a t t e r n with either six or eleven
cuts in each direction is m a d e in the film (to the substrate),
pressure-sensitive tape is a p p l i e d over the lattice a n d t h e n
removed, a n d a d h e s i o n is evaluated by c o m p a r i s o n with descriptions and illustrations.
F o r Test M e t h o d A, the following rating scale is used:
5A No peeling o r removal.
4A Trace peeling o r removal along incisions.
3A Jagged removal along incisions up to 1/16 in. (1.6 m m )
on either side.
2A Jagged removal along m o s t of incisions up to 1/8 in.
(3.2 m m ) on either side.
1A Removal from m o s t of the a r e a of the X u n d e r the tape.
0A Removal b e y o n d the a r e a of the X.
F o r Test M e t h o d B, 3/4 in. (1.9 cm) cross-cuts are made.
F o r coatings having a d r y film thickness up to a n d including 2.0 mils (50/xm), eleven cuts are spaced 1 m m apart.
F o r coatings having a dry film thickness b e t w e e n 2 mils (50
~xm) a n d 5 mils (125/xm), six cuts are spaced 2 m m apart.
F o r films thicker t h a n 5 mils (125 /xm), M e t h o d A is used
instead of M e t h o d B. F o r Test M e t h o d B, a d h e s i o n is r a t e d
according to the following scale (as illustrated in Fig. 5.):
5B The edges of the cuts are completely smooth; n o n e of
the squares of the lattice is detached.
4B Small flakes of the coating are d e t a c h e d at intersections; less t h a n 5% of the a r e a is affected.
3B Small flakes of the coating are d e t a c h e d along edges
a n d at intersections of cuts. The a r e a affected is 5 to
15% of the lattice.
2B The coating has flaked along the edges a n d on parts of
the squares. The a r e a affected is 15 to 35% of the
lattice.
1B The coating has flaked along the edges of cuts in large
ribbons, a n d whole squares have detached. The a r e a
affected is 35 to 65% of the lattice.
0B Flaking a n d d e t a c h m e n t worse t h a n G r a d e 1.
Repeatability within one rating unit is generally observed
for coatings on metals for b o t h methods, with r e p r o d u c i b i l i t y
of 1 to 2 units. The m e t h o d is widely used a n d is viewed as
"simple" as well as low in cost.
518
PAINT A N D COATING T E S T I N G M A N U A L
Classification
5B
None
iiilUlUllm
iIIIIIll
pllllll
Illllll
iIIIllll
i!11111
4B
FLEXIBLE
ADHE~~
~llmllullllllmlllll~j ~
//f //I///////// 9
'ADHESIVE
"/,/l~f///////////
/
RK~H~AOHERENO
- EXPERIMENTAL
3B
--
I k - . -
p.--
"r-
P'--
~'-
'
COMPRESSI
i ,
-- ~P'I
]o
o.V
FIG. 6-Peel profile [62].
2B
1B
I & d tql
l e ale I l l
I 9 r
B4A
1,6,1
It t
OB
a#l
CHAPTER 44--ADHESION
Procedural Problems
The tape test is operator intensive. By design it was made as
simple as possible to perform and requires a minimum of
specialized equipment and materials which must meet certain specifications. Therefore, the burden of accuracy and
reproducibility relies largely upon the skill of the operator
and his/her ability to perform the test in a consistent manner.
Key steps which directly reflect the importance of operator
skill include the angle and rate of tape removal and the visual
assessment of the tested sample. It is not unexpected that
different operators might obtain different results [1,2].
Visual Assessment
The final step in the test is visual assessment of coating
removed from the specimen, and this can be subjective in
nature. This assessment can vary among individuals evaluating the same specimen [65].
Performance in the tape test is based on the amount of
coating removed compared to a relative scale. But it was
found that the exposure of substrate can be due to factors
other than coating adhesion, arising from the requirement
that the coating he cut (hence the synonym "cross-hatch adhesion test"). Justification for the cutting step is reasonable;
cutting provides a free edge from which peeling can begin
without having to overcome the cohesive strength of the coating layer. This might be suitable for coatings applied to metal
substrates, but for coatings applied to plastics, the cutting
process can lead to false indications of poor adhesion. This is
due to the unique interracial zone mentioned earlier. For
coatings on soft plastics, how deep should this cut penetrate?
Is it possible to cut only to the interface?
If microscopic examination of panels is included, in several
instances it is clearly evident that coating removal results
from substrate failure at or below the interface, not from
adhesive failure between coating and substrate. At the same
time, it is also observed that cohesive failure within the coating layer is a frequent occurrence. The latter observation is
significant in that the tape test assessment criteria make no
provision for it [1,2].
519
[5,66].
It is essential that the force is applied strictly in the direct
normal to the sample and that no bending moment is active
across the test area. Deviations from symmetry in the test
arrangement, poor alignment, deviations from homogeneity
and of thickness of the adhesive (coating), and random variations in the strength of the bond between film and substrate
affect test results [5,66].
The stress at locations where the adhesive film is thinner
will be higher than the average stress and will be transmitted
to the film under test. Another factor may be peeling during
test, which is not easily identified or analyzed.
The adhesive used to bond a stud to the coating has the
potential to influence the coating film properties by penetration through the film into microcracks and possibly into the
substrate [66]. Test adhesive flexibility may also be an issue,
as well as the flexibility of the substrate, if the sample is
unrestrained.
There exist now within ASTM both laboratory and field
versions of direct tension tests for coatings. Test Method for
Measuring Adhesion of Organic Coatings to Plastic Substrates by Direct Tensile Testing, ASTM D 5179, while limited
to organic coatings on plastics, uses a restrained sample and
commonly available tension test apparatus. The second,
Method for Pull-Off Strength of Coatings Using Portable Adhesion-Testers, ASTM D 4541, defines a class of portable pulloff adhesion testers for field evaluation of coating adhesion.
ASTM D 5179 is the successor to numerous attempts to
develop a reproducible coating tension test and was approved
in 1991. It will be discussed first.
ASTM D 5179
This test covers the laboratory determination of adhesion
of organic coatings to plastic substrates by mounting and
removing an aluminum stud from the surface of a coating
and measuring the force required to break the coating/substrate bond with a tensile tester. The test method provides an
inexpensive test assembly which can be used with most tensile test machines. The method is used to compare the pull-off
strength (commonly referred to as adhesion) of coatings to
various plastic substrates, thus allowing for a quantitative
comparison of various coating/substrate combinations.
A carefully prepared aluminum stud is bonded directly to a
coated, cured panel using a cyanoacrylate adhesive. The adhesive is allowed to cure for 2 h at room temperature. Adhesive buildup is removed from around the stud. The specimen
is then subjected to test on a tensile tester equipped with an
upper coupling adapter and a restraining device (Fig. 7) to
provide for sample alignment and minimal substrate flexing.
The sample bearing the stud is installed in the restraining
device, with only the stud pertruding. The tensile machine
crosshead is lowered so the upper coupling adaptor can be
attached to the specimen.
When testing thin substrates, a piece of plastic is placed in
the restraining device behind the specimen to insure a rigid
520
Y//////~
///////~/I
- - T O P
CI
PORTION
4"
~PREPARED SAHPLE
|
UPPERCOUPLING
ADAPTOR
TOP VIEN
BOTTOHPORTION
~~SAHPLE
I
[
-
(A)
DEVIcERESTRAINING
PREPARED
SAHPLE
IN DEVICE
(B)
FIG. 7-Direct tensile restraining device. From ASTM D 5179.
(O
strengths of two orders of magnitude has been observed (Table 1) for diverse coating-plastic combinations.
A S T M D 4541
This test method defines a class of portable adhesion testers
for measuring the pufl-off strength of coatings. The method
covers a procedure and apparatus for evaluating pull-off
strength by determining either the greatest perpendicular
force (in tension) that a surface area can bear before a plug of
material is detached or whether the surface remains intact at
a prescribed force (pass/fail). Failure will occur along the
weakest plane within the system comprised of the test fixture,
adhesive, coating system, and substrate and will be exposed
by the fracture surface. The method maximizes tensile stress
as compared to the shear stress applied by other methods
such as scratch or knife adhesion, and results are not comparable. It is recognized that the pull-off strength reflects both
material and instrumental parameters and therefore provides
a relative, not absolute, measure of adhesion. The pull adhesion testers defined are portable and capable of applying a
concentric load and counter load to a single surface so that
coatings in the field can be tested even though only one side is
accessible. Measurements are limited by the strength of adhesion bonds between the loading fixture and the specimen
surface or the cohesive strength of the substrate. The pull-off
test is performed by securing a "loading fixture" (dolly or
stud) normal (perpendicular) to the surface of the coating
with an adhesive. After the adhesive is cured, the testing
apparatus is attached to the loading fixture and aligned to
apply tension normal to the test surface. The force applied to
the loading fixture is then gradually increased (in less than
100 s) and monitored until either a plug of coating material is
CHAPTER
521
44--ADHESION
Coating
Substrate
Failure
Mode
Pounds Per
Square Inch~
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Lacquer
Lacquer
Lacquer
Lacquer
Lacquer
Lacquer
Enamel
Urethane
Urethane
Urethane
Enamel
Lacquer
Enamel
Enamel
Polyester/polycarbonate
Polycarbonate
ABS
Polycarbonate
ABS
PVC
Polycarbonate
ABS
ABS
Metal
Metal
PPO/Nylon
PPO/Nylon
PPO/Nylon
C
A
C
A
C
AC
A
A
A
S
75% A
C
C
A
58
36
82
37
93
103
308
639
476
666
342
226
226
242
4624
I I
- ' ~
DETACHING
X" ASSEMBLY
C;~i~~~GGRIP
Z&,<
BASE~" ~ ~
SYSTEM -
'
' ~
l \\
'~
~ ...~....k.! ~*"
ANNULAR RING
SUBSTRATE
522
Patti
13 mm
Elcometer
Hate
20 mm
19 mm
(mean of 3 results)
Dyna
50 mm
1160
1099
1033
1678
586
674
827
888
201
185
190
297
1185
1157
1245
1686
ASTM D 2197
-Y-
'
Test ossembly A
Test ossembly B
FIG. 9-1S0 4624 test assemblies.
CHAPTER 44--ADHESION
523
For each applied load, the number of times the coating was
removed or adhered is tabulated. The load where the scrape
results change from mainly adhering to mainly removed,
ignoring the first 1/2 in. (13 mm) of the scratch if the coating
was removed, is the adhesion failure end point.
ASTM D 4146
ASTM F 692
Other ASTM standards which pertain to aspects of adhesion measurements of films and coatings include the following:
ASTM B 533
ASTM B 571
ASTM C 313
ASTM C 988
ASTM D 3281
ASTM D 3730
ASTM D 4145
ASTM F 518
Additional tests exist for electrodeposits, and bending, burnishing, and wrapping tests for coatings on wire. Tests for
adhesives have also been applied to coatings as wel]. Use of
reverse impact tests, lap and butt joint tests, and tensile shear
tests have been reported [1].
CONCLUSIONS
Basic adhesion is the summation of multiple phenomena.
Ideal adhesion is probably neither obtainable nor measurable
experimentally. Practical techniques do, however, allow sufficient assessment of relative adhesion for most purposes, if
used with care and knowledge. Workers need to understand
both basic adhesion concepts and the factors affecting practical adhesion for systems of their interest if they are to make
improvements in real world products.
REFERENCES
[1] Nelson, G. L., Gray, K. N., and Buckley, S. E., Modem Paint and
Coatings, Vol. 75, No. 10, 1985, pp. 160-172.
[2] Nelson, G. L. and Gray, K. N., "Coating Adhesion to Plastics,"
Proceedings, Waterborne and Higher-Solids Coatings Symposium, Vol. 13, New Orleans, LA, 5-7 Feb. 1986, University of
Southern Mississippi, Hattiesburg, MS, pp. 114-131.
[3] Mittal, K. L., "Adhesion Measurement: Recent Progress, Unsolved Problems, and Prospects," Adhesion Measurement of Thin
Films, Thick Films, and Bulk Coatings, ASTM STP 640, K. L.
Mittal, Ed., American Society for Testing and Materials, Philadelphia, PA, 1978, pp. 7-8.
524
[42] Plueddemann, E. P. in "Interfaces in Polymer Matrix Composites," E. P. Plueddemann, Ed., Academic Press, New York, 1974,
pp. 174-216.
[43] Monte, S. J. and Bruins, P. F., Modern Plastics, December 1964,
p. 68.
[44] Mao, T. J. and Reegen, S. L. in Adhesion and Cohesion, P. Weiss,
Ed., Elsevier, Amsterdam, 1962, pp. 209-217.
[45] Hoffichter, Jr., C. H. and McLaren, A. D., Industrial and Engineering Chemistry, Vol. 40, 1948, p. 239.
[46] McLaren, A. D. and Seller, C. J., Journal of Polymer Science, Vol.
4, 1949, p. 63.
[47] Brown, H. P. and Anderson, J. F. in Handbook of Adhesives, I.
Skeist, Ed., Van Nostrand-Reinhold, Princeton, NJ, 1962, pp.
255-257.
[48] Packham, D. E., "The Adhesion of Polymer to Metals: The Role
of Surface Topography," in Adhesion Aspects of Coatings, K. L.
Mittal, Ed., Plenum Press, New York, 1983, pp. 19-44.
[49] Mittal, K. L., Polymer Engineering and Science, Vol. 17, No. 7,
1977, pp. 467-472.
[50] Derjaguin, B. V. and Smilga, V. P. inAdhesion Fundamentals and
Practice, Maclaren and Sons, London, 1969, p. 152.
[51] Fowkes, F. M., Journal of Adhesion Science and Technology, Vol.
1, No. 1, 1987, p. 7.
[52] Massingill, J. L., Journal of Coatings Technology, Vol. 63, No.
797, 1991, pp. 47-54.
[53] Allen, K. W. in Aspects of Adhesion, Vol. 5, D. J. Alner, Ed.,
University of London Press, 1969, p. 11.
[54] Paul, S., Journal of Coatings Technology, Vol. 54, No. 692, 1982,
pp. 59-65.
[55] Croll, S. G., "Adhesion and Internal Strain in Polymeric Coatings," in Adhesion Aspects of Coatings, K. L. Mittal, Ed., Plenum
Press, New York, 1983, pp. 107-129.
[56] Sato, K., Progress in Organic Coatings, Vol. 8, 1980, pp. 143-160.
[57] Lewis, A. F. and Forrestal, L. J., "Adhesion of Coatings," in
Treatise on Coatings, Vol. 2, Part I, R. R. Myers and J. S. Long,
Eds., Marcel Dekker, New York, 1969, pp. 57-98.
[58] Gardner, H. A. and Sward, G. G., Chap. 7, Paint Testing Manual,
12th ed., Gardner Laboratory, Bethesda, MD, 1962, pp. 159-170.
[59] Corcoron, E. M., Adhesion, Chap. 5.3 in Paint Testing Manual,
ASTM STP 500, 13th ed., G. G. Sward, Ed., ASTM, Philadelphia,
PA, 1972, pp. 314-332.
[60] Mittal, K. L., Journal of Adhesion Science and Technology, Vol. 1,
No. 3, 1987, pp. 247-259, bibliography.
[61] Stoffer, J. O. and Gadodia, S. K., American Paint and Coatings
Journal, Vol. 70, No. 50, 1991, pp. 36-40, and Vol. 70, No. 51,
1991, pp. 36-51.
[62] Wu, S., Polymer Interface and Adhesion, Marcel Dekker, Inc.,
New York, 1982, p. 531.
[63] Marion E. Wolters, 3M memorandum, 1984.
[64] Product Bulletin, 3M.
[65] Proceedings, Symposium on Adhesion Aspects of Polymeric
Coatings, K. L. Mittal, Ed., The Electrochemical Society, 1981,
pp. 569-582.
[66] R. J. Jacobsson, Thin Solid Films, Vol. 34, 1976, pp. 191-199.
[67] Stichfeld, J., "Pull-Off Test, An Internationally Standardized
Method for Adhesion Testing--Assessment of Relevance of Test
Results," !n Adhesion Aspects of Polymeric Coatings, K. L. Mittal,
Ed., Plenum Press, New York, 1983, pp. 543-567.
MNL17-EB/Jun. 1995
45
Abrasion Resistance*
by Mark P. Morse 1
DEFINITIONS
M a r a b r a s i o n consists of p e r m a n e n t d e f o r m a t i o n s that
have not r u p t u r e d the surface of a coating. The resistance of a
coating to m a r r i n g is its ability to w i t h s t a n d scuffing actions
t h a t t e n d to disfigure or change the a p p e a r a n c e of its surface.
S o m e examples of potential causes of m a r r i n g of organic
coatings are: (a) sliding an object across the surface of furniture; (b) r u b b i n g of a belt buckle, button, zipper, or r o u g h
fabric on an a u t o m o b i l e finish; (c) sliding a toy across a wall
or a refrigerator door, etc.
W e a r a b r a s i o n is caused by m e c h a n i c a l action that removes m a t e r i a l from the surface of a coating. In m a n y cases,
the removal is gradual or progressive due to repetitive mechanical action.
R E L A T I O N S H I P TO O T H E R PHYSICAL
PROPERTIES
Abrasion resistance is not a unique o r isolated p r o p e r t y of a
m a t e r i a l b u t is r a t h e r related to other physical characteristics
such as hardness, cohesive a n d tensile strength, elasticity,
a n d toughness. Also, from the s t a n d p o i n t of retaining its
protective or decorative function, the thickness of a coating
can be a n i m p o r t a n t factor.
CORRELATION WITH E N D - U S E
PERFORMANCE
A b r a s i o n resistance is related to hardness, yet the relationship is not simple. A first t h o u g h t m i g h t be that the h a r d e r a
coating, the b e t t e r w o u l d be the a b r a s i o n resistance; however, this is not always true. Steel is m u c h h a r d e r t h a n rubber, for example, b u t steel "tires" on an automobile, in addi-
525
Copyright9 1995 by ASTM International
www.astm.org
526
the test method will correlate--or predict--the service performance of the material in at least a qualitative or relative
ranking respect.
When accelerated tests are being considered, even tests
that rank materials in the same sequence as actual service
tests, a quantitative correspondence with actual service is
seldom expected or obtained. Actual end-use tests, while the
most reliable in providing an indication of a material's probable long-term durability, suffer from the difficulties of ensuring equivalent usage and measurement, especially when
the comparison of different materials is attempted. Because
of such difficulties and because service tests are usually very
time consuming, a wide variety of test machines have been
developed to provide an accelerated indication of the abrasion resistance of coatings and related materials such as vinyl
flooring, linoleum, and wall coverings. In a comprehensive
review article by Harper [2], there is a list of no less than 49
different abrasion-causing machines. An investigation by the
International Study Committee for Wear Tests of Flooring
Performance [3], in which seven commercial, organic flooring materials were systematically tested on 21 abrasion machines of 17 different types, indicated that very few of these
machines were capable of providing a reliable comparison of
the abrasion resistance of widely different materials that
could be correlated with end-use performance. In addition,
the different machines did not correlate very well with each
other.
On the basis of a round robin conducted in 1956 by ASTM
with six different clear floor coatings evaluated by six different abrasion test methods [4], only two of the methods were
found to correlate with actual end-use performance and to
have the reproducibility necessary for acceptance as ASTM
standards. These were ASTM Test Method for Abrasion Resistance of Organic Coatings by Falling Abrasive (ASTM
D 968) and ASTM Test Method for Abrasion Resistance of
Organic Coatings by Air Blast Abrasive (ASTM D 658). The jet
abrader, Method 6193 of Federal Test Method Standard No.
141C, which became available after the testing, appears to
correlate well with the two cited ASTM methods and with
various types of end-use performance. In addition, the jet
abrader offers greater speed and precision of measurement
[1]. Even today, with other tests also available, these tests are
still important and widely used. However, more recent comparative testing (see COMPARISON OF WEAR ABRASION
TESTERS) indicates ASTM D 658 is superior to ASTM D 968
and that ASTM Test Method for Abrasion Resistance of Organic Coatings by the Taber Abraser (ASTM D 4060) is superior to both of these tests as regards precision and sensitivity
in differentiating between coatings.
M E C H A N I S M OF A B R A S I O N
The success of the particle impingement types of abrasion
testers in correlating with service performance is perhaps not
surprising when one considers the abrading mechanism.
Whether or not a particular type of abrasion test correlates
with end-use performance depends not only on a similarity of
abrading mechanisms in both cases, but also on the extent to
which that mechanism is maintained during the course of the
abrasion test. It is on the latter factor that many methods fail.
LOOSE F O R FALLING A B R A S I V E
METHODS
Falling Abrasive Test
This widely used abrasion test method has both ASTM and
federal counterparts. Originally developed at Gardner Laboratory [5], the method has been studied and further developed by others [6]. ASTM D 968 employs an apparatus, Fig.
1, that is simple and inexpensive compared with other more
complicated instruments, and the test results correlate reasonably welt with various types of service [4]. However, the
method is laborious and time consuming since large quantities of abrasive must be handled due to the slow rate of
abrasion, particularly when the material under test is abrasion resistant.
Over the years a variety of abrasives have been used in the
basic apparatus. These abrasives include sand, emery, and
various grades of silicon carbide (Carborundum). Sand, although having the disadvantage of a slow abrasion rate, is
readily available and has given reproducible results at low
cost. Therefore, it has been the abrasive of choice in the
standard methods. Only sand and silicon carbide are used in
CHAPTER 4 5 - - A B R A S I O N R E S I S T A N C E
527
A B R A S I V E BLAST M E T H O D S
Air Blast Abrasive (Bell Laboratory Abrasiometer)
528
CHAPTER 45--ABRASION ~ S I S T A N C E
VIBRATING
GRAVEL
HOPPER
,~.
/DOOR',,,
.
\
,n
t~ LINING
I!
E~
,,,-.--=
,cc
ssooo.,
HI
(r
529
.~
FILTER
(This m a c h i n e is available from F r a z i e r Precision Instrum e n t s Co., Inc., 925 Sweeney Dr., Hagerstown, MD 21940.)
The m a c h i n e was designed for m e a s u r i n g w e a r resistance of
textiles such as rugs a n d fabrics [15-18], b u t it offers a
potentially useful m e a n s for evaluating the w e a r a b r a s i o n of
organic coatings. It has two unique features: (a) a u n i f o r m
a b r a s i o n p a t t e r n a n d (b) i n t e r c h a n g e a b l e steel a n d Carboloy
a b r a d e n t disks with crosscut a n d rod p a t t e r n s that r e d u c e
heating a n d clogging (Fig. 7).
530
Hs
pLATE
FOR
I.IIPTINQ
CAAi~Ls
PLATE
R.s
COUN'I's
Hr
FIG. 6-FDC wear tester. Nylon fabric on rotating head is used to abrade
furniture lacquer rotating on offset
axis (courtesy of Furniture Development Council, England).
T E S T S B A S E D ON R E C T I L I N E A R M O T I O N
Straight-Line Reciprocating Machines
These machines, as shown in Fig. 9, pull a sled or boat back
and forth over the surface of a coated panel. The sled surface
can be a brush, a sponge, rubber, or sandpaper. A sled travel
of at least 10 in. (25.4 cm) is provided by the machines, and
they can provide reciprocating cycles ranging from 35 to 60
per minute.
Both dry and wet surface tests may be performed with
these machines. For dry surface tests, wear abrasion resistance is reported as: (a) number of cycles to reach a certain
visual end point, (b) degree of abrasion observed after a
specified number of cycles, and (c) number of cycles required
to abrade through the coating to the substrate.
Procedures for conducting wet adhesion (scrub resistance)
tests on interior paints are described in ASTM Test Method
for Wet Abrasion Resistance of Interior Paints (ASTM
D 4213) and in Method 6141 of Federal Test Method Standard 141C. In these test procedures, coating films are applied
to a plastic substrate and allowed to dry. A sponge surface is
mounted on the sled. Both the sled and the coating surface
are wet with a soap solution of specified composition. Wet
abrasion resistance is reported as: (a) computed rate of erosion of the wet coating film and (b) number of cycles required
to wear through the coating film to the substrate or to produce breaks in the film.
531
C O M P A R I S O N OF W E A R A B R A S I O N
TESTERS
ASTM Subcommittee D-01.23 conducted a round robin to
determine the comparative precision, sensitivity, and correlation of four wear abrasion testing procedures, The procedures were (a) air blast silicon carbide (ASTM D 658), (b)
falling sand (ASTM D 968), (c) falling silicon carbide (ASTM
D 968), and (d) Taber Abraser (ASTM D 4060). The wear
abrasion resistance of four coatings with significantly different apparent resistances to abrasion were tested with each
device. The results obtained from these tests are recorded in
ASTM Report RR D01-1037, which is available at ASTM
Headquarters.
From the results, it was concluded that the air blast silicon
carbide test and the cycles per rail Taber abraser test had
better sensitivity in differentiating coating abrasion resistances than the other test procedures. The falling sand test, air
blast silicon carbide test, and Taber abraser cycles per rail
test ranked the coatings in the same order as the expected
performance. The falling silicon carbide test reversed the
ranking of two of the coatings. The precision exhibited by the
four test procedures are as given in Table 1.
T E S T F O R MAR A B R A S I O N R E S I S T A N C E
RCA Tape Tester
This device is available from Norman Tool and Stamping
Co., 15415 Old State Rd., Evansville, IN 47711. It is being
actively used for evaluating the abrasion resistance of appliance finishes and of coatings on television set controls. It is
reported to have greater sensitivity than the Taber Abraser in
determining differences in the abrasion resistance of coatings. The machine abrades a 2 by 2-in. (5.1 by 5.1 cm) coated
panel surface by passing computer or polyester tape over the
surface. A fresh tape surface is presented for each cycle of
4%
7%
16%
10%
9%
11%
35%
45%
532
P r i n c e t o n Scratch Tester
This apparatus is similar to the balanced beam tester, but
instead of having a moveable specimen table, the beam assembly itself moves on a V-shaped track with the coated panel
remaining immobile. The stylus is held at a 90 ~ angle.
I m p i n g i n g Abrasive M e t h o d
An impinging abrasive method is described in ASTM Test
Method for Mar Resistance of Plastics (ASTM D 673) and in
Method 1093 of Federal Test Method Standard No. 406. Although this test was designed for determining the mar resistance of plastics, it has a potential for determining this property of organic coatings.
The test consists of allowing a stream of silicon carbide to
fall on the specimen and then determining the degree of
marring by gloss measurements. The apparatus consists of a
hopper that dispenses the abrasive through small openings as
it rotates at 7 rpm. Abrasive flow is about 225 g per minute.
Fingernail Test
In this test, the back of a fingernail is dragged across the
surface of a coating and the degree of marring is visually
observed. The procedure can be used as a "pass/fail" test or
for comparing the mar resistance of coatings on a relative
basis.
MISCELLANEOUS
METHODS
CHAPTER 45--ABRASION
RESISTANCE
533
REFERENCES
FIG. IO-PEI abrasion tester. Specimen in chamber on gyrating table is abraded by glass or stainless steel sphere in a
slurry of abrasive particles. (Courtesy of National Bureau of
Standards.)
MNL17-EB/Jun. 1995
46
E = 2 (1 + v,)G
DEFINITIONS
534
Copyright9 1995 by ASTM International
(1)
www.astm.org
535
i!
I
I
e
I
I
I
e
11
I
I
'
I~ S
L.. _
d
q
F
A.
E
TENSILE
=
at =
Tensile
Strain
Tensile
Stress
B.
SHEAR
Shear
Shear
as =
7 =
F
Os
----
AxB
Tensile
AxB
Modulus
O"t
E
Stress
AX
E .......
(3" t
Strain
Modulus
Gs
G
Shear
=
7
FIG. 1-Deformations of test samples: A. tensile, B. shear. The two types of deformation
have different definitions and different symbols for strain, stress, and modulus.
Tensile Storage M o d u l u s
= E'
cos8
~,,o
E0
(2)
(3)
EO
E pr
(4)
536
PAINT
AND
COATING
I
,
'
Stress
or
Strain
TESTING
MANUAL
I
i
(at)
(E)
T i m e or Angle
FIG. 2-Applied oscillating strain (~) and resulting oscillating stress (~rt) in a dynamic mechanical analysis experiment
with tensile deformation. The phase lag (6) and maximum
values of strain (Co) and stress (~rt,o) are indicated.
A check of limiting values of a is consistent with assignm e n t of elastic a n d viscous responses in Eqs 2 and 3. W h e n 8
= 0 ~ cos8 = 1.0 a n d sin8 = 0. By Eq 3, E" is zero a n d all of
the response is elastic, i.e., E ' from Eq 2. W h e n 8 = 90 ~ cos8
= 0 a n d s i n ~ -- 1.0. N o w E ' is zero b y E q 2 and all of the
response is viscous, i.e., E ' from Eq 3.
DMA relationships in Eqs 2 a n d 3 relate directly to characterization of s a m p l e s that are solid or semi-solid. Other objectives of DMA include following viscosity a n d elasticity
changes as the cure of t h e r m o s e t coatings takes place a n d
d e t e r m i n i n g the melt-flow p r o p e r t i e s of p o w d e r coatings before the onset of cross-linking. W h e n viscous response is the
m a i n interest, DMA is often carried out in shear.
The t r e a t m e n t for shear DMA is identical, b u t with selection of a p p r o p r i a t e s h e a r symbols from Fig. 1, the definitions
arc
(5)
(6)
G"
(7)
(8)
(9)
4'
Loss Tangent = - - = t a n a
4"
(10)
(11)
G 2 = G '2 + G "2
(12)
C H A P T E R 4 6 - - D Y N A M I C M E C H A N I C A L AND T E N S I L E P R O P E R T I E S
on the vertical axis versus strain (either ~ or 100 E = %
elongation) on the horizontal axis. A hypothetical example is
shown in Fig. 3 [5, 6]. The tensile modulus (E) is the slope of
the initial, linear portion of the plot (see Fig. 3). If the initial
part of the plot is not linear, several calculations for estimating E have been suggested in ASTM D 638M. Use of the
slope for E amplifies the simple definition of tensile modulus
given in Fig. 1A. Other terms used for tensile modulus include
"elastic modulus," "Young's modulus," and "stiffness."
The first point on the plot of Fig. 3 where the slope is zero is
called the "yield point." Strain at the yield point is called
"elongation at yield" (ey). Stress at the yield point is called
"yield strength" (err). Elongation is continued until the sample breaks. Strain at the break point is called "elongation at
break" (eB). Stress at the break point is called "tensile
strength" (%) as shown in Fig. 3. However, in some cases
(not shown) the stress is higher at the yield point than it is at
the break point. In such cases, ASTM standards specify that
the "tensile strength" be indicated as the higher value of stress
and be designated as "tensile strength at yield." Practice is not
uniform with regard to this latter "tensile strength" terminology.
Results of transient tests have not frequently been published for coatings. Such tests clarify viscoelastic character
quite directly. Possibly unexpected field failures of coatings
could be avoided in some cases if more attention were given
to viscoelasticity. Only the most simple form of retardation
and relaxation concepts are treated here.
In a tensile creep experiment, the sample is subjected to
constant stress, or,, and elongation is determined as a function
of time, e(t). Analysis of dependence of elongation on time
yields "retardation time," T (tau). The simplest mechanical
model that permits definition of T is the Maxwell model as
shown in Fig. 4. This model consists of a series connection of
an ideal Hookean spring of modulus, E, and a dashpot that
contains an ideal Newtonian liquid of viscosity, r/. As indicated in Fig. 4, ~-is the viscosity of the liquid in the dashpot
/llll//f
RELAXATION TIME
CREEP EXPERIMENT
1" = RETARDATION TIME
17
E
FIG. 4 - A mechanical model consisting of a spring and a
dashpot permits definition of relaxation time and retardation
time,
~(o)
q-
(13)
When stress is first applied, the spring extends instantaneously by an a m o u n t ~(0). Then retarded further elongation
takes place due to flow in the dashpot. It is evident in Eq 13
that the retarded elongation is linear with time. The value of r
can be obtained from the product (reciprocal of the slope)
(intercept) [4,5].
In a tensile stress relaxation experiment, the sample is
elongated instantaneously by an a m o u n t ~, and thereafter ~ is
held constant. Stress is determined as function of time, tr(t).
Analysis of the dependence of stress on time yields "relaxation time," r. For the Maxwell model, T values are the same
whether from creep or relaxation. For real materials, experimentation is required to determine whether or not retardation and relaxation values are equal. Results of the stress
relaxation experiment for the Maxwell model can be expressed as
or(t) = o(0)e t/T
537
(14)
OB
0u
(9
U
tO
(/)
(/~
LU
IZ
I-O~
PREPARATION
Ey
.I
EB
STRAIN
FIG. 3 - A hypothetical stress-strain curve for a ductile
film. Tensile properties are defined: tensile modulus (E),
elongation at yield (ey), elongation at break (eB), yield stress
(~ry), and tensile strength (~rB).
538
D E T E R M I N A T I O N OF D Y N A M I C
PROPERTIES
539
540
P A I N T AND COATING T E S T I N G M A N U A L
11
STORAGE MODULUS
oo
I--
bJ
-1
~
/
"8
LOSS T A N G E N T
'7
w
TENPERATURE (C)
FIG. 5 - D M A plots for a clearcoat prepared from an acrylic polyol (ACR) and an etherified
melamine formaldehyde (MF) resin, ACR/MF 70/30. The film was cured before DMA for
30 min at 120~ with 0.5% para-toluenesulfonic acid. DMA was carried out at 11 Hz. See
Table 2 for dynamic properties.
Tg, ~
TanS,
max
PW,a
A, ~
3.5
11.0
35.0
110.0
76
79
83
88
0.49
0.49
0.52
0.52
45
50
55
59
E', ( m i n ) ,
dynes/cm2
3.3
3.6
4.2
4.7
X
X
X
x
l0 s
108
108
l0 s
Temperature
of E'
(rain), ~
108
112
116
121
of Cross-Link
Density
(15)
G'
RT
E'
3RT
~ I d e a l N e t w o r k (density = 1.10g/cm 3)
v~
=3
-~C3 + 2 C4 + ~C5 + . . . . .
~fcf
21.=3
(16)
(17)
where Cf is the concentration of "f" functional reactant expressed in unusual units, i.e., moles of reactant per cubic
centimeter of final film. Difunctional reactants contribute to
v o l u m e b u t do not increase the n u m b e r of moles of chains.
Therefore, there is no C2 t e r m in Eq 17.
Ideal n e t w o r k calculations have been carried out for several types of coatings such as polyester p o l y o l / m e l a m i n e films
[17], epoxy/diamine films [19], and p o w d e r coating films
[21,22]. The ue values calculated from r e a c t a n t structures
agree r e m a r k a b l y well with e x p e r i m e n t a l Ue values from Eq
16.
Although v~ is useful for n e t w o r k characterization, m o s t
coating chemists can m o r e easily visualize a n e t w o r k b a s e d
on the value of Mc
M c = weight of s a m p l e in g r a m s that contains one
m o l e of elastically effective chains
4A 3 + 3B 4
541
(18)
p
v~
(19)
re= Vc + Up gRT
(20)
542
D E T E R M I N A T I O N OF T E N S I L E
PROPERTIES
Description of Stress-Strain Analysis (SSA)
Instrumentation for SSA is described in detail in the ASTM
test methods listed in the section of this chapter entitled
Definitions of Tensile Properties. In most cases, specific instruments are not identified, apparently to avoid commercial
implications, but it is generally known than Instron | instruments (Instron Engineering Corp.) are widely used. For organic coatings the most suitable test method is usually ASTM
D 2370. However, other tension test methods contain additional useful information. ASTM D 638M is useful for selection of metric units and units consistent with SI recommendations. ASTM D 882 has rather extensive data on statistical
treatments for plastic sheeting, but the statistical methods
could be beneficially applied to coatings films. For certain
types of coatings, such as flexible primers or coatings for
plastic substrates, rubbery behavior is expected, and ASTM D
412 provides useful information such as data treatment when
a crack moves slowly across the sample as opposed to the
more usual instantaneous failure mode. Often stress-strain
curves do not start out with constant slope as shown in Fig. 3,
but instead have an initial curvature caused by takeup of
slack. The initial curved portion is called a "toe," and toe
compensation is described in ASTM D 638M and in ASTM D
882. Some stress-strain curves have no linear (i.e., no
Hookean) region from which to calculate the slope for modulus values. In such instances the "toe corrected" origin and
another point on the curve are joined by a straight line. The
slope of the line is reported as the "secant modulus." The
elongation percentage at the second point selected is always
reported along with the value of secant modulus. Graphical
illustrations of secant modulus determinations are given in
ASTM D 638M and in ASTM D 882. Among the various test
methods, D 638M contains the most complete list of definitions and symbols.
Determination of "tensile energy to break" is described in
ASTM D 882. The area under the stress-strain curve, e.g., see
Fig. 3, is divided by sample volume to obtain this quantity,
which has also been called "work-to-break" or "toughness"
[5]. Recommended units are megajoules per cubic meter.
ASTM D 882 describes how an integrated chart paper area
(distance 2) can be converted to energy/volume by using the
ordinate setting (force/distance of chart paper), the abscissa
setting (distance of elongation/distance of chart paper), and
the sample dimensions. Now that computers are used to
control operation and to treat data for SSA [32], numerical
integration is nearly instantaneous, and tensile energy to
break is likely to be reported more often. This SSA property
may prove to be useful for correlations with paint test results.
543
~ooo
(/)
f__=
i
1o
STRAIN (%)
q)
O(~
100
STRAIN
(%)
2,ooo
03
I
500
STRAIN (%)
FIG. 6-General kinds of stress-strain curves for various
types of coatings. Scales indicate order-of-magnitude values.
544
Fief. No. 1
62.0
48.2
6
:E
34.5
5
4
20.7
6.9
~
12
16
20
24
28
PercentElongation
FIG. 7-Stress-strain curves for UV-cured cycloaliphatic
epoxide films flexibilized with oligomeric propylene oxide
triol. Strain rate is 40% per minute. See Table 3 for tensile
properties.
CHAPTER 46--DYNAMIC
545
TABLE 3--Tensile propertiesa of UV-cured cycloaliphatic epoxide films flexibilized with oligomeric propylene
oxide triol.
Film
N o. b
1
2
3
4
5
6
7
8
C~176176162
Epoxide,
Triol,
wt%
wt%
90.0
85.0
80.0
75.0
70.0
66.7
63.4
60.0
10.0
15.0
20.0
25.0
30.0
33.3
36.6
40.0
Tensile
Modulus,d
psi
3.88
3.72
3.33
2.95
2.05
1.48
0.70
0.26
x
X
x
x
10s
10s
10s
10s
105
105
10s
105
Tensile
Strength,
psi
9.5
8.9
8.4
7.0
4.3
3.7
2.5
2.0
x
X
x
X
x
x
x
10 3
10 3
10 3
10 3
103
103
103
103
Elongation,
%
6.6
6.6
7.4
8.1
16.2
24.3
54.0
88.4
CONCLUSIONS
A wide range of a u t o m a t e d a n d computer-controlled ins t r u m e n t s is available for d e t e r m i n a t i o n of d y n a m i c m e c h a n ical a n d tensile properties. Careful review of variable features
is necessary to insure suitability for property d e t e r m i n a t i o n s
o n coating samples of n o r m a l thickness. D e t e r m i n a t i o n of
basic physical properties makes it possible to integrate structure/property knowledge from m a n y polymer fields with coatings research a n d development. Free film coating data are
m u c h more useful w h e n thoughtfully interpreted in relation
to results from tests carried out with films intact o n their enduse substrates. This review includes m a n y examples that illustrate the benefits of c o m b i n i n g DMA or SSA data with
results from well controlled a n d d o c u m e n t e d tests as provided by the ASTM. The goal of m u c h of the discussion provided here is better u n d e r s t a n d i n g of hardness, flexibility,
post-formability, solvent resistance, a n d abrasion resistance.
DMA a n d SSA are often c o m p l e m e n t a r y because strains
imposed on test samples are very different. SSA provides
i n f o r m a t i o n on yield behavior a n d failure at high strains.
DMA provides low strain properties a n d reveals the viscoelastic n a t u r e of coatings very directly a n d quantitatively.
For u n p i g m e n t e d thermoset coatings, values of storage
modulus, E', in the r u b b e r y plateau can be used to calculate
cross-link density (XLD). D e t e r m i n a t i o n of XLD usually
makes it possible to confirm or deny that purposeful ref o r m u l a t i o n or changes in resin structure have had the desired effects.
REFERENCES
[1] Aklonis, J. J. and MacKnight, W. J., Chapter 2 in Introduction to
Polymer Viscoelasticity, 2nd ed., Wiley Interscience, New York,
1983.
[2] Nielsen, L. E., Mechanical Properties of Polymers and Composites, Vol. I, Marcel Dekker, New York, 1974.
[3] Murayama, T., Dynamic Mechanical Analysis of Polymeric Material, Elsevier, New York, 1978.
[4] Sperling, L. H., Chapter 1 in Sound and Vibration Damping in
Polymers, R. D. Corsaro and L. H. Sperling, Eds., ACS Symposium Series 424, American Chemical Society, Washington,
1990.
[5] Hill, L. W., "Mechanical Properties of Coatings," Federation Series on Coatings Technology, D. Brezinski and T. J. Miranda,
Eds., Federation of Societies for Coatings Technology, Philadelphia, 1987.
[6] Schurr, G. G., Section 5.5, "Tensile Strength and Elongation,"
Paint Testing Manual, 13th ed., G. G. Sward, Ed., American
Society for Testing and Materials, Philadelphia, 1972.
[7] Takano, M. and Nielsen, L. E., "The Notch Sensitivity of Polymeric Materials," Journal of Applied Polymer Science, Vol. 20,
1976, p. 2193.
[8] Wicks, Jr., Z. W., Jones, F. N., and Pappas, S. P., Organic Coatings Science and Technology, Vol. 1, Film Formation, Components and Appearance, Wiley, New York, 1992; Vol. 2,
Applications, Properties, and Performance, 1994.
[9] Hartman, B., Chapter 2 in Sound and Vibration Damping in
Polymers, R. D. Corsaro and L. H. Sperling, Eds., ACS Symposium Series 424, American Chemical Society, Washington,
1990.
[10] Manson, J. A. and Sperling, L. H., Polymer Blends and Composites, Plenum Press, New York, 1976, Chapters 3, 8, and 13.
[11] Cooper, S. L. and Estes, G. M., "Multiphase Polymers," ACS
Advances in Chemistry Series 176, American Chemical Society,
Washington, 1979.
[12] Roller, M. B., "The Glass Transition: What's the Point?," Journal
of Coatings Technology, Vol. 54, No. 691, 1982, p. 33.
[13] Hill, L. W. and Kozlowski, K., "The Relationship Between Dynamic Mechanical Measurements and Coatings Properties," Advances in Organic Coatings Science and Technology, Vol. 10,
Proceedings of the Twelfth International Conference in Organic
Coatings Science and Technology, A. V. Patsis, Ed., Technomic,
Inc., Lancaster, PA, 1986, p. 31.
[14] Provder, T., Holsworth, R. M., and Grentzer, T. H., "Dynamic
Mechanical Analyzer for Thermal Mechanical Characterization
of Organic Coatings," Chapter 4 in Polymer Characterization, C.
546
D. Craver, Ed., ACS Advances in Chemistry Series 203, American Chemical Society, Washington, 1983.
[15] Zosel, A., "Mechanical Behavior of Coating Films," Progress in
Organic Coatings, Vol. 8, 1980, p. 47.
[16] Skrovanek, D. J., "The Assessment of Cure by Dynamic Thermal
Analysis," Progress in Organic Coatings, Vol. 18, 1990, p. 89.
[17] Hill, L. W. and Kozlowski, K., "Crosslink Density of High Solids
MF-Cured Coatings," Journal of Coatings Technology, Vol. 59,
No. 751, 1987, p. 63.
[I8] Hill, L. W., "Structure/Property Relationships of Thermoset
Coatings," Journal of Coatings Technology, Vol. 64, No. 808,
1992, p. 29.
[19] Grillet, A. C., Galy, J., Gerard, J-F., and Pascault, J-P., "Mechanical and Viscoelastic Properties of Epoxy Networks Cured with
Aromatic Diamines," Polymer, Vol. 32, No. 10, 1991, p. 1885.
[20] Yeo, J. K., Sperling, L. H., and Thomas, D. A., "Rubber Elasticity
of Poly (n-butyl Acrylate) Networks Formed with Multifunctional Crosslinkers," Journal of Applied Polymer Science, Vol. 26,
1981, p. 3977.
[21] Scholtens, B. J. R., Tiemersma-Thoone, G. P. J. M., and van der
Linde, R., "Thermoviscoelastic and Thermoanalytic Characterization of Some Reactive Polyester Powder Coatings Systems,"
Verfkroniek, Vol. 62, 1989, p. 238.
[22] Higginbottom, H. P., Bowers, G. R., Grande, J. S., and Hill, L.
W., "Structure/Property Studies of MF-eured Powder Coatings,"
Progress in Organic Coatings, Vol. 20, 1992, p. 301.
[23] Oshikubo, T., Yoshida, T., and Tanaka, S., "Studies on Acrylic
Resins and Melamine Formaldehyde Resins for High Solids
Coatings," Proceedings, Tenth International Conference in Organic Coatings Science and Technology, 9-13 July 1984, Athens,
Greece, p. 317.
[24] Scanlon, J., "The Effect of Flaws on the Elastic Properties of
Vulcanizates," Journal of Polymer Science, Vol. 43, 1960, p. 501.
[25] Flory, P. J., "Molecular Theory of Rubber Elasticity," Polymer
Journal, Vol. 17, No. 1, 1985, p. 1.
[26] Flory, P. J. and Erman, B., "Theory of Elasticity of Polymer
Networks," Macromolecules, Vol. 15, 1982, p. 800.
[27] Erman, B. and Flory, P. J., "Relationships Between Stress,
Strain and Molecular Constitution of Polymer Networks. Comparison of Theory and Experiments," Macromolecules, Vol. 15,
1982, p. 806.
[28] Graessley, W. W., "The Entanglement Concept in Polymer Rheology," Advances in Polymer Science, Vol. 16, Springer-Verlag,
NY, 1974, p. 1.
MNL17-EB/Jun. 1995
DEFINITIONS
INTERPRETATION
The flexibility of a coating applied to a substrate depends
not only on its distensibility, but also on the coating thickness
and on the adhesion between coating and substrate. Good
adhesion tends to give better apparent flexibility than does
poor adhesion. The toughness of a coating is dependent on its
hardness, stiffness, resiliency, distensibility, and the existence of an energy dissipation mechanism that operates at
temperatures far below room temperature and is discernable
by dynamic mechanical measurements made over a broad
temperature or frequency range.
Generally, the bend and impact tests used to evaluate flexibility and toughness are much more severe than actual service conditions. This is because the tests are usually performed on relatively fresh, unaged coating films. Since
coating films tend to lose flexibility during use due to volatilization of free plasticizing components and chemical changes
such as degradation, cross-linking, and the like, these severe
tests that exceed normal expectations are useful in predicting
long-term serviceability [1].
BASIC P R O P E R T I E S A F F E C T I N G COATING
PERFORMANCE
Both flexibility and toughness depend on very basic properties: the viscoelastic behavior of the coating and its physical
transitions and relaxations. The following is a discussion of
these properties taken from a paper by Skrovanek and Schoff
[2].
*This chpater is an abridged and modified version of the chapter
entitled "Flexibility," written by G a r m o n d G. Schurr, found in the
previous edition of this manual.
fConsultant, 71 S. Shelburne Rd., Springfield, PA 19064.
54"/
Copyright9 1995 by ASTM International
www.astm.org
548
Humidity
W a t e r is a g o o d plasticizer for a l m o s t all p a i n t films. A
change in relative h u m i d i t y of as little as 2% can be detected
in flexibility m e a s u r e m e n t s . S o m e p a i n t films, such as those
b a s e d on latexes, i m b i b e m o i s t u r e very rapidly, whereas
others r e a c h e q u i l i b r i u m with the a t m o s p h e r e very slowly. It
is imperative that tests be c o n d u c t e d in an a t m o s p h e r e of
controlled relative h u m i d i t y a n d that the s p e c i m e n s are cond i t i o n e d in that a t m o s p h e r e for a d a y or m o r e before the tests
are p e r f o r m e d . Generally, flexibility a n d toughness tests are
c a r r i e d out at a relative h u m i d i t y of 50 _+ 5%. The 10%
tolerance is needed b e c a u s e of the difficulty in m o r e accurately controlling relative h u m i d i t y in m o s t laboratories. If
the e n v i r o n m e n t c a n n o t be controlled at this r e c o m m e n d e d
level, then the relative h u m i d i t y should be m e a s u r e d a n d
r e p o r t e d along with the m e c h a n i c a l properties.
Temperature
The flexibility a n d toughness of coatings are d e p e n d e n t on
t e m p e r a t u r e . This is p a r t i c u l a r l y true of t h e r m o p l a s t i c coatings, b u t it also is a factor for t h e r m o s e t coatings. These
Strain Rate
Strain rate is the rate at w h i c h a coating s p e c i m e n is elongated a n d is usually expressed in p e r c e n t per minute,
in./in./min o r cm/cm/min. This is the rate of extension relative
to s p e c i m e n size. That is, if a s p e c i m e n 10 c m long is elongated at rate of 1 cm/min, it is the s a m e as a s p e c i m e n 1 c m
long being elongated at a rate of O. 1 c m / m i n (1 m m / m i n ) . In
b o t h cases, the strain rate is 10% p e r minute.
Strain rate has a great influence on the flexibility a n d
toughness of a coating. In general, the effect of increasing the
strain rate is similar to decreasing the coating t e m p e r a t u r e ,
that is, as the strain rate is increased, flexibility a n d toughness decrease.
There can be critical strain rates where flexibility has s h a r p
changes w h i c h are very similar to the effects p r o d u c e d at the
glass transition t e m p e r a t u r e [7]. This m e a n s that the strain
rate used in a test m u s t be closely controlled. In s o m e tests,
such as b e n d test, this is difficult to do. This also m e a n s that
tests p e r f o r m e d at a low strain rate (cupping test) are likely to
p r o d u c e different flexibility ratings t h a n those p r o d u c e d by a
high strain rate (conical m a n d r e l test) [1, 7].
549
FIG. 1-Bending a specimen over a conical mandrel (courtesy of Gardner Laboratory) [I].
illustrated in Fig. 1. The cone is smooth steel 8 in. (203 mm)
in length with a diameter of 1/8 in. (3 mm) at one end and a
diameter of 1.5 in. (38 mm) at the other end.
When a coating is applied on a V32-in. (0.8 mm)-thick coldrolled steel panel, as specified in ASTM D 522, a bend over the
mandrel produces an elongation of 3% at the large end of the
cone and of 30% at the small end of the cone. The coated
panel is bent 135 ~ around the cone in approximately 1 s to
obtain a crack resistance rating under simulated abuse conditions. In some instances, longer bend times have been found
to be useful. For example, if the percent elongation of the
coating at the point of cracking is to be determined, the
method specifies a bend time of 15 s.
Since variations in temperature and humidity can affect
mandrel bend tests, it is imperative that the coated panels be
conditioned at a standard temperature and relative humidity
before performing the test, which is conducted under the
same conditions.
The crack resistance value of a coating is obtained by measuring the distance from the furthest end of the crack to the
small end of the mandrel. This distance is converted to cone
diameter by means of a plot given in ASTM D 522. The mandrel diameter at which cracking occurs is taken as the crack
resistance value.
If the elongation of the coating at the onset of cracking is to
be reported, a bend time of 15 s is used and the diameter at
which the onset of cracking occurred is converted to percent
elongation from a plot given in ASTM Test Methods for Mandrel Bend Test of Attached Organic Coatings (D 522).
FIG. 2-Bending a specimen over a cylindrical mandrel (courtesy of Gardner Laboratory) [ 1].
(25 mm), 3/4-in. (19 mm), 1/2-in. (12.7 mm), 3/s-in. (9.5 mm),
1/4-in. (6.4 mm), and 1/8-in. (3.2 mm) diameters. Examples of
cylindrical mandrel testers are given in Figs. 2 and 3.
The panel should be bent over a mandrel with the uncoated
side of the panel in contact with the mandrel surface. The
panel should be bent approximately 180 ~around the mandrel
at a uniform velocity in a time of i s. If cracking has not
occurred, the procedure is repeated using successively
550
TESTING
MANUAL
where t is the thickness of the coated panel a n d r is the radius
of the mandrel. Actually, observed elongations are greater
t h a n values calculated from the above expression a n d vary
with different types of metal substrates. Table 1 contains
i n f o r m a t i o n about the influence of panel thickness a n d type
metal on percent elongation of a coating.
Crack resistance of a coating is d e p e n d e n t o n its thickness,
that is, the thicker the film, the lower the crack resistance.
Values of crack resistance obtained by the m a n d r e l b e n d tests
should be corrected for film thickness w h e n c o m p a r i s o n s are
made between different coatings. ASTM D 522 contains corrections to be added to elongation values o b t a i n e d with coatings having thickness greater t h a n 1 rail (0.03 m m ) w h e n
applied to 1/8-in. (0.8-mm)-thick steel panels (Table 1).
Conical m a n d r e l b e n d test procedures similar to those
given in ASTM D 522 are found in ISO Method 6860 a n d BS
3900. Cylindrical m a n d r e l b e n d test procedures similar to
those given in ASTM D 522 are found in ISO 1519, DIN 35
152, and BS 3900 E l .
T-Bend Tests
T-bend tests are a m e a n s of evaluating the flexibility of
coated strip metal that is to be formed during a fabrication
process (Fig. 4). Multiple 180 ~ bends of the coated metal are
made, a n d the a m o u n t of cracking produced at each b e n d is
visually determined. Ratings are classified as 0T, 1T, 2T, 3T,
a n d so on. The 0T ( p r o n o u n c e d zero T) b e n d consists of
m a k i n g a 180 ~ b e n d with the p a i n t o n the outside of the b e n d
a n d pressing the b e n d flat so there is no space between the
metal surfaces. This operation is repeated successively to
produce a 1T ( p r o n o u n c e d one T), 2T, 3T, etc. b e n d s (Fig. 5).
These successive bends result in two, three, etc. thickness o f
the metal a r o u n d the first bend. It should be a p p a r e n t that the
greater the n u m b e r of thicknesses a r o u n d which the coated
metal is bent, the less severe the test. The DiAcro Brake F o r m
m a c h i n e is suitable for this test.
smaller and smaller diameter m a n d r e l s until cracking is apparent. The cracking-resistance value of a coated panel is the
m i n i m u m diameter at which cracking does not appear.
This testing procedure can be applied as a "pass~fail" test by
d e t e r m i n i n g whether cracking is produced by b e n d i n g over a
specified m a n d r e l diameter.
A table for converting m a n d r e l diameter to percent elongation is given in ASTM D 522. The relationship between diameter of a m a n d r e l and the elongation of a coating has b e e n
derived by Schuh a n d Theuerer [8] to be:
Percent Elongation = lO0(t/(2r + t))
(1)
TABLE 1--Factors affecting elongation measurements of coated panels by mandrel bend tests.
Panel Thickness
I/8
CORRECTIONSTOBE ADDEDFORTHICKNESSOFPANELSUBSTRATE
1/64in. Correction, %
1.5
2.0
3.0
4.0
5.9
1/32 in. Correction, %
3.0
4.0
5.0
7.7
11.1
1/18in. Correction, %
5.9
7.7
11.1
14.3
20.0
11.1
20.0
33.3
1/8
CORRECTIONSTOBE ADDEDFORTYPEOFMETALPANELSUBSTRATE
3/4 hard brass Correction, %
3.4
4.6
6.9
9.6
14.2
Annealed brass Correction, %
3.6
4.9
7.5
10.3
15.9
Cold-rolled steel Correction, %
3.3
4.4
6.7
9.0
13.8
29.1
33.5
28.0
3/4
1/4
Metal Type
3/4
1/4
Metal Type
3/4
1/4
1/8
1.38
1.43
1.37
551
SPECIMEN
DINGDIE
///
fl
COATEDSURFACE ~ /
2 in. MINIMUM
WIDTH
0T BEND
(.,
SCOATED 9
URFACE. /
2TBEND
3TBEND
FIG. 5-T-Bend test in which the coated specimen is bent
around itself (ASTM D 4145: Test Method for Coating Flexibility
of Prepainted Sheet).
Cupping Tests
A relatively slow rate of forming test can be conducted with
a cupping tester that pushes a punch into the unpainted side
of a coated panel until the increasing deformation produces
cracks in the coating. Test procedures are given in ISO TC 35,
BS 3900 E4, NFT 30-019, SIS 18 41 77, DIN 50 101, and DIN
50 102. There are six models of Erichsen Cupping Testers;
they provide different test conditions to simulate different
forming operations. Two of these models are shown in Figs. 6
and 7. BYK-Gardner Cupping Testers are a]so suitable for
conducting these test procedures (Fig. 8). The BYK-Gardner
devices use a spherical punch and provide a range of cupping
speeds. The maximum cupping depth is approximately
18 m m (0.7 in.). The cupping action is stopped when cracking in the coating is visually detected. The depth of cupping at
that point is indicated on a digital display and is considered to
be the flexibility rating. The cupping tester can be equipped
with a stereo microscope for observing the onset of cracking.
552
Forming Tests
553
REFERENCES
MNL17-EB/Jun. 1995
Hardness
by Paul R. Gudvin, Jr. 1
P H Y S I C A L C O N C E P T S OF H A R D N E S S
TESTING
HARDNESS IS A TERM HAVING a d i f f e r e n t m e a n i n g to d i f f e r e n t
people. It is resistance to penetration to a metallurgist, resistance to wear to a lubrication engineer, a measure of flow
stress to a design engineer, resistance to scratching to a mineralogist, and resistance to cutting to a machinist. While
these actions appear to differ greatly in character, they are all
related to the plastic flow stress of the material, i.e., Young's
Modulus, Y [1]. K. Sato wrote an overview paper on the
hardness of coating films [2] which merits mentioning and
reviewing.
Hardness is not a fundamental property of materials but a
composite one dependent on the elastic moduli, elastic limit,
the hardening produced by "working" a metal, etc. Empirical
relationships are used to determine other properties from the
easily measured hardness, but all such schemes are of doubtfill or limited validity.
Hardness testing can be a very useful tool for studying
modern materials, but it is plagued by well-known experimental difficulties. Reasons for the unusual behavior of hardness data at very low loads are explored by Monte Carlo
simulation, which will be discussed later. These simulations
bear remarkable resemblance to the results of actual hardness experiments. The limit of hardness as load or indentation depth tends to zero, which is shown to depend on experimental error rather than upon intrinsic material properties.
The large scatter of hardness data at very low loads is ensured
by the accepted definition of hardness. A new definition of
hardness is suggested which eliminates much of this scatter
and possesses a limit as indentation depth approaches zero.
Some simple calculations are used to show the utility of this
new approach to hardness testing.
Over the years, many methods and devices have been employed to measure the hardness of organic finishes. P. C.
Wheeler, chairman of a technical committee within the Dallas Paint and Varnish Production Club, as it was called then,
reported [3] the results of a survey of findings concerning
how coating hardness is measured. Following this survey, the
first meeting of what is now called ASTM Task Group
DO1.23.14, Hardness, Mar and Abrasion Resistance, was held
in June 1947. The Hardness Group of Subcommittee XVIII,
as they were called at the time, of Committee D-1 was organized in Atlantic City to provide an opportunity for expres~President, P. R. Gu6vin Associates, P.O. Box 811, Westerville, OH
43086-0811.
sion of opinions by those present concerning their understandings of concepts that were connoted by hardness as
applied to organiccoating films.
The consensus was that the subject of hardness is very
complex. Several of the characteristics of an organic film are
simultaneously judgmentally weighed in order of relative importance to obtain the usual expression of hardness judgment. The same physical characteristics of films were employed, and the weighing importance of the various
characteristics chosen is not carried out in the same manner;
choices are operator dependent and are based on experience
with results in practical use of the material.
At the time of this first meeting in 1947, the purpose of the
group was to (1) study the subject of hardness and attempt to
define some of the physical properties or attributes of an
organic coating which affect hardness, (2) limit the study to
the development of procedures for measuring the attributes
of film hardness, and (3) further evaluate limitations to
smooth films of organic coatings as they are normally applied
on a substrate. Switzer [4] conducted a survey to determine
which methods were being used by the coatings industry to
measure hardness. They found that some form of scratching
or abrasion was used 84% of the time, pendulum or damping
hardness (also referred to as entropy hardness) 56% of the
time, and indentation hardness 20% of the time. The percentages total more than 100% because some companies surveyed use more than one procedure to evaluate hardness. In
1991, ASTM Task Group D01.23.14 conducted a similar survey. The study showed pencil hardness to be the most commonly used test method with the Sward-type rocker method
the next most widely used [5]. The m o d e m trend in industries
as a whole has been towards an increasing use of indentation
methods.
Scratch Hardness
Scratch hardness is the oldest form of hardness measurement and was probably first developed by mineralogists.
Back in 1822, F. Mohs [6] evaluated comparative scratch
hardness of many materials. Assuming the liquid state to be
equivalent to "zero" hardness, he arranged solid materials
into ten hardness groups, rating them as follows: talc, 1;
gypsum, 2; calcite, 3; fluorite, 4; apatite, 5; orthoclase, 6;
quartz, 7; topaz, 8; corundum, 9; diamond, 10. As the system
was set up, any material of a given Mohs hardness number
could scratch any other material with a lower Mohs hardness,
and about 99% of all known materials have hardness ranging
from Mohs 1 to 9. However, the Mohs scale, though conve-
555
Copyright9 1995 by ASTM International
www.astm.org
556
P A I N T AND COATING T E S T I N G M A N U A L
104
w2
(1)
FIG. 1-Clemen Scratch Hardness Tester. (Courtesy of Erichsen GMBH & Co.)
CHAPTER 48--HARDNESS
~~
559
"% !. ".... ~
FIG. 2-Dantuma Scratch Tester. (Figure from previous edition of this manual.)
558
P A I N T AND COATING T E S T I N G M A N U A L
FIG. 4-Erichsen Model 318 Hardness Tester. (Courtesy of Erichsen GMBH & Co.)
ensure uniform contact. While held in this position, the instrument is drawn in a direction away from the cutter. The
nature of the mark left by the cutter, if any, is observed, and
the test may then be repeated at a different cutter loading.
CHAPTER 48--HARDNESS
559
560
Panel
No.
Knoop
Hardness
Sward
Hardness
Pencil
Brand A
Pencil
Brand B
Pencil
Brand C
Pencil
Brand D
Pencil
Brand E
1
2
3
4
5
6
7
8
9
10
3.09
4.33
2.77
2.61
5.81
9.23
11.2
21.1
17.4
25.7
11
21.0
12
13
14
39.1
34.9
...
24
28
24
22
38
50
25
58
54
54
60
40
30
40
5B
4B
5B
3B
2B
HB
HB
F
F
H
2H
3H
6H
8H
6B
6B
6B
4B
2B
F
F
H
F
H
2H
2H
5H
9H
5B
6B
5B
5B
2B
HB
HB
H
F
H
2H
3H
5H
7H
6B
6B
4B
4B
2B
HB
HB
H
H
H
4H
4H
5H
7H
4B
4B
4B
3B
3B
HB
H
2H
2H
2H
3H
4H
6H
9H
CHAPTER 48--HARDNESS
AT START OF TEST
AT END OF TRAVEL
-,; " ~ l
.~'--
J
4
INGREASING STYLUS
FORGE
--
'~:':':::!-V~,':
suP~T A2-.2~'~
'.ULL YLUS
XGURS,O..,O0 ..
\
.u ,oRT
TEST
SURFAGE
ZERO FORGE
AT STARTIN6
POSITION
561
under controlled conditions that enable quantitative evaluation of the ability of coatings to withstand repeated horizontal and vertical abrasions. There are three scratching tools: a
1-mm cutting carbide sphere, a Clemen designed scratch
cutting tool, and a VW designed scratch cutting tool; two
speeds: 35 and 1 mm/s, and two load ranges: 0 to 20 and 0 to
90 N.
The test is performed by selecting a load which is applied to
the cutter and can remain either constant in value or automatically increased at a linear rate. The weighted cutter is
brought into contact with the coated surface at a constant
speed, and it penetrates the coating when a critical force is
attained. The force required to be applied to the tool to penetrate the coating and just touch the substrate is the measure
at the scratch hardness. Testing using the automatically increased force shortens the test and quickly evaluates the
scratch resistance at the coating.
Simmons Scratch Tester--This coating hardness measuring instrument [31] is another tester of the increasing load
type and is suitable only for films on metal. When the stylus
breaks through the film, a relay stops the machine. Hardness
is reported as the weight necessary to penetrate the film.
562
FIG. 12-Sheen Scratch Tester. (Courtesy of The Paul N. Gardner Company, Inc.)
Wolff-Wilborn Scratch-Hardness Tester--This test apparatus, shown in Fig. 15, is another pencil method that belongs
to the group of scratch-hardness testing instruments that is a
CHAPTER 48--HARDNESS
563
Indentation Hardness
FIG, 15-Wolff-Wilborn Scratch Hardness Tester. (Courtesy of Erichsen GMBH & Co.)
564
d2
L = P-n--4
P -
4L
7rd2
L
Ap
(2)
(3)
(4)
w h e r e v is Poisson's ratio (lateral c o n t r a c t i o n versus longitudinal extension). In the case of viscoelastic materials, a similar relationship holds, b u t the variation with i n d e n t e r r a d i u s
a n d p e n e t r a t i o n are s o m e w h a t modified. M e r c u r i o [37] has
discussed the relationship of Tukon h a r d n e s s to modulus.
The theory of i n d e n t a t i o n h a r d n e s s tests on h o m o g e n e o u s
m a t e r i a l s has received m u c h interest in the last few decades.
D. T a b o r has b e e n w o r k i n g intensely in this area. In his recent
p a p e r [38] he said
The hardness of a solid is usually u n d e r s t o o d to m e a n its
resistance to local d e f o r m a t i o n . The simplest m e t h o d of
quantifying it is to press a h a r d i n d e n t e r of specific geometry into the body, divide the load by the a r e a of the
i n d e n t i o n formed, a n d express the a n s w e r in units of
k i l o g r a m s p e r square millimeters o r pascals (1 kg m m -2
10 7 Pa) . . . .
F o r elastic solids such as rubber, the
i n d e n t a t i o n p r e s s u r e is a direct m e a s u r e of the elastic
p r o p e r t i e s of the material.
A n o t h e r example of this type study is that of Lebouvier et al.
[39].
W. W. W a l k e r [40] evaluated the K n o o p h a r d n e s s of three
organic coatings using a Model LR Tukon M i c r o h a r d n e s s
Tester in a c c o r d a n c e with ASTM Test Methods for Indentation H a r d n e s s of Organic Coatings (D 1474) except he calib r a t e d the i n s t r u m e n t at 100 g l o a d a n d ran the tests at 200 g
load. In addition, he tested the pencil hardness of the s a m e
coatings in a c c o r d a n c e with ASTM Test M e t h o d D 3363.
C o m p a r a t i v e d a t a are shown in Table 2.
W. W. W a l k e r c o n c l u d e d that a useful correlation existed
between the 200-g K n o o p i n d e n t a t i o n h a r d n e s s a n d pencil
TABLE 2--Comparison of pencil and Knoop hardness of selected
coatings.
Paint
Epoxy powder
Polyurethane
Solvent Epoxy
Metal Panel
Pencil
Lead No.
Lead
Hardness,
KI-IN
5H
51.5
3H
45.3
H
31.7
. . . . . .
Paint
Hardness,
KHN
Difference
30.2
22.7
8.9
195 _+ 1
21.3
22.6
22.8
...
HARDNESS
hardness of thick paint films but that further work needs to be
done.
Krautkrgmer Branson conducted a similar test using their
MicroDur Portable Hardness Tester fitted with a Vickers indenter. The preliminary results, shown in Fig. 18, represent
an evaluation of eight organic coatings. The results are promising. However, additional work is needed.
To achieve this, two separate head assemblies were required. Basically the rheometer consists of a specimen stage
or platform, indenter-LVDT transducer head assembly,
weights, transducer amplifier indicator, and a 10-in. (25.4
cm) strip chart recorder. In normal use, the specimen or test
panel is clamped on the platform, and the instrument is
zeroed in with the indent or tip just touching the specimen.
This is done by using the knurled rings on the heads and the
platform ring (the rings on the sensitive head have 80 threads
per inch or 80 threads/25.4 mm) to obtain a coarse adjustment follow by a fine adjustment on the transducer amplifierindicator. A load (weight) is applied to the weight tray (by
means of an overhead pulley), and the depth of indentation is
recorded as a function of time. After a specified period of
time, the load is removed and the recovery is recorded.
Hardness
800
700
'
600
L-. . . . . . . . . . . . ~
....
500
......................................................................................................................................................
400
.........................................................................................................................................................................................
300
.........................................................................................................................................................................
200
I
2H
I
2H
L
2H
I
H
565
J
H
,
H
i
H
Pencil Hardness
FIG. 18-Comparison of Vickers hardness versus pencil hardness.
i
H
566
(5)
1rD (D - X/-D
~ - d2
2
The r e l a t i o n s h i p b e t w e e n the h a r d n e s s H a n d the d i a m e t e r of
the d e p r e s s i o n d has b e e n w o r k e d out on a form for a given
size steel ball whose d i a m e t e r is D.
CHAPTER 4 8 - - H A R D N E S S
the apparatus and went further than Gardner et al. [46] in the
interpretation and meaning of the curves. Included in the
data were curves showing how an alkyd finish changed properties as a function of temperature and accelerated weathering.
R
o
C.,SEL--H
567
J
;
30 ~ BEVEL-'--
EO
._t
FIG. 2 2 - C D I C H a r d n e s s P e n e t r o m e t e r .
Ap
ICp
(6)
where
L = load in kilograms applied to the indenter,
Ap -- projected area of indention in m m 2,
l = measured length of the long diagonal of the indentation in ram, and
Cp = indentor constant relating l t o Ap, usually 7.028
10-10.
Most writers refer to I and Ap as the unrecovered length and
area, but as we shall see later, this is not true. Elastic recovery
of the indentation impression takes place the instant the
indentor is removed, and substantial viscoelastic recovery
takes place before a measurement can be made.
The real difference between the P fund and Knoop methods
is that with the Pfund, the hardness measurement is made
when the indenter is under load, while with the Knoop the
measurement is made of the indentation impression remaining after both the load and indenter have been removed. This
remaining Knoop impression is smaller than the original
made while under the loaded indentor because all of the
elastic and substantially all of the viscoelastic (creep) recovery occur in the indentation impression once the load is
568
quite coincidentally, the numerical results can be quite similar. This similarity in numerical results (PHN ~ KHN) with
organic coatings probably could never have been achieved
deliberately. How fortunate for the paint industry that the
equivalence exists.
Of the two test methods, the Modified Pfund and the Tukon
gage with the Knoop indenter, the former is a dynamic hard-
CHAPTER 48--HARDNESS
~
RATIOOF
DIAGONALS
ness test and the latter is a static hardness test. Those in the
automotive industry know how difficult it can be to obtain
repeatable Knoop hardness numbers on metallic finishes.
Secondly, with some types of finishes, the ends of the long
diagonal of the Knoop impression recover, yielding rounded
ends. In others, the organic finish sometimes recovers in such
a manner as to partially close the indent near the ends of the
long diagonal. However, the main reason for this preference
is that the Pfund measures the indent under load. That is
when the coating is resisting the indentation.
Pfund Hardness Tester--After numerous, unsuccessful attempts to grade the hardness of varnishes by means of the
scratch test in which graded pencils, crystals, etc. were used,
A. H. P fund, an associate professor of physics from Johns
Hopkins University, Baltimore, MD, modified the Brinell Indention Test [50]. In this method the measurements are made
on the organic coating while the loaded indentor is in contact
with the coating. At first a 1/16-in.-diameter steel ball was
forced under load into the varnish, and the diameter of the
resultant circular impression was measured under the microscope. This was soon changed to a quartz cylinder terminating in a hemisphere 1/4-in. (6 ram) in diameter. The results are
expressed as the load on the indentor, in grams, necessary to
achieve a specified diameter of indent. The device, shown in
--[
E.EO
Y=)I +Y2
.
)'2 =
569
S
.
i-e
st)
YU= f ( ~ l
TIME
LOAD
LOAD
APPLIED
REMOVED
FIG. 26-Creep and creep recovery curves of viscoelastic material.
-t/k1
570
PAINT
AND
COATING
TESTING
MANUAL
C)
,L
M2
Ai
V, /
L
L
1.27
- - - - - A
'rrd 2
d2
(7)
4
FIG. 28-BTL designed modified Pfund Hardness Gage.
TABLE 3--Pfund hardness.
Thickness,
rail
Hardness at
Three Divisions
0.7
1.3
3.0
730
380
47
0.6
1.I
3.5
435
130
<5
0.5
188
35
Coating"
1.0
1.8
0.6
1.1
3.1
<5
875
720
370
where
L = l o a d in k i l o g r a m s (1 kg) a p p l i e d to the indenter,
A = p l a n a r or p r o j e c t e d a r e a of i n d e n t i o n in square millimeters, a n d
d = d i a m e t e r of the i n d e n t a t i o n in millimeters.
Therefore, the PHN is the load, in kilograms, divided by the
p l a n a r o r projected a r e a of indentation.
The p l a n a r or p r o j e c t e d area of i n d e n t deserves s o m e explan a t i o n a n d was covered in detail in the introduction. Figure
30 illustrates w h a t is m e a n t by this for the case of a spherical
i n d e n t o r where the h a r d n e s s m e a s u r e m e n t is m a d e while the
h e m i s p h e r e is u n d e r l o a d a n d in contact with the coating.
Initially the h a r d n e s s o r PHN was r e p o r t e d as 10d. The reason for changing it to the l o a d divided b y the p l a n a r a r e a of
i n d e n t a t i o n was to m a k e the r e p o r t e d PHN results have the
s a m e units of m e a s u r e m e n t as the K n o o p h a r d n e s s n u m b e r
HARDNESS
571
where the cone had an included angle of 120~ and the tangential spherical tip of 0.40 mm in diameter.
Wilson|
| Hardness TesterS--Vincent E. Lysaght of
Wilson Mechanical Instrument Co. took the work of the late
Frederick Knoop and applied the technique to the testing of
nonmetallic materials ranging from plastics to diamonds [48]
using their Tukon Hardness Tester.
The Wilson|
| Microhardness Tester offers a variety
of possibilities as a tool in research and development, materials testing, and quality control program. Some coating manufacturers use the Sward Hardness Tester to get approximate
hardness values but rely on this tester to qualify a coating. It
can be fitted with either a Vickers or a Knoop indenter. A
comparison of these two indenters is shown in Fig. 31. A
Knoop indenter is typically used to measure the hardness of
coatings, whereas the Vickers indenter is used for hardness
testing of harder materials such as metals.
This instrument, with the precision of x-y stage, makes it
possible to locate indentions with great accuracy. The instrument has undergone many refinements such as having a
computer controlled X-Y Auto Traversing Stage System and a
software program for running statistical process analyses.
One of their latest instruments is shown in Fig. 32.
/
R
S P H E R I C A L INDENTER
A= 7 r r 2
D= DIAMETER OF INDENT
Wallace Microhardness Tester H-76--The Wallace Microindention Tester [55], like the Wilson|
| Hardness
Tester, can also employ a Vickers diamond pyramid indentor
and uses a capacitive form of measurement to determine the
depth of indention under load. Figure 33 shows the Wallace
tester. This instrument measures the depth of penetration of
an indentor into a material under a known load, the depth of
penetration being a function of that indicated on a dial gage.
Basically, the instrument consists of an indentor, supported by leaf springs, attached to a parallel plate capacitor
which forms one half of a capacitance balance circuit. When
no load is applied, the indentor "floats" in a "null" position,
electronically balanced by the second half of the capacitance
balance circuit. This "null point" (i.e., the point of electrical
balance) is indicated by a zero reading on the center zero
meter located in the base of the instrument.
The test panel is supported on a table that is raised or
lowered by means of an accurately made wedge. The dial
micrometer gage follows and indicates the lateral movement
of the wedge which is, in turn, converted to vertical movement of the table. Primary loads of usually less than 1 g and
secondary loads between 1 and 300 g are placed on the weight
platform, which, in turn, is attached to the indenter.
In operation, the instrument is first set to a zero position,
and a test panel is placed on the specimen table or stage. The
panel is raised to the indenter. The primary load is applied to
the indentor, and the system is once again zeroed. The secondary load is applied for the predetermined time during which
the panel is raised to maintain the indenter in its zeroed
position. At the end of the predetermined time, the reading on
the gage is taken and the corresponding depth of indentation
is obtained by dividing the gage reading by the wedge ratio
(20 to 1 or 40 to 1). The Wallace Microhardness Tester was
5Available from Wilson Instruments, 6 Emma Street, Bingham,
NY 13905.
6Available from H. W. Wallace & Co., Ltd., St. James Road,
Croydon, England and Testing Machines, Inc., 400 Bayview Avenue,
Amityville, N.Y. 11701.
572
FIG. 31-Comparison between a Knoop and Vickers Indenter. (Courtesy Wilson Instruments, Inc.)
FIG. 32-Wilson|
son Instruments, Inc.)
used in a cooperative investigation by the M a n c h e s t e r Section of the Oil and Colour Chemists' Association [56] a n d is
c o m m e r c i a l l y available. According to Fink-Jensen [57], it is
possible to o b t a i n an accuracy of 0.3 to 0.5/xm or a b o u t 0.01
to 0.02 mil.
CHAPTER 4 8 - - H A R D N E S S
573
BE -
G -
AV
(8)
F/A
,X//l
F/A
(9)
(10)
(11)
E
3 (1 - 2v)
(12)
B -
This simple, basic method was adopted by the Federal Government (Federal Test Method Standard No. 141, Method
6211, Print Test). However, in 1980, the federal government
canceled this test method in favor of an ASTM test method (D
2091: Test Method for Print Resistance of Lacquers). Another
ASTM test method is Test Method D 1640: Test Methods for
Drying, Curing, or Film Formation of Organic Coatings at
Room Temperature. Print resistance may be evaluated by the
load required to make an impression within a given time, the
time required under a given load, or by comparing the imprint under identical loads and duration of test. The temperature may also be varied. This test is sometimes used as a
drying time test.
is employed for coating hardness testing in France and Europe. The specific apparatus employed in these methods is
different, but, in principle, the tests are the same. These tests
are described below.
The pendulum hardness tests are closely related to the
Sward Rocker Hardness Test. The hardness pendulum rests
on the test surface and pivots on two hardened steel balls. The
time required for the pendulum to decay from some initial
amplitude to some final amplitude is a measure of the hardness of the coating film.
The theory of the pendulum or rocker hardness testing was
derived by Persoz [59]. Pierce et al. [60] made a detailed
experimental investigation of the Sward Rocker Hardness
Test. The observed mechanics of the Sward Rocker were
found to be in complete agreement with the Persoz analysis.
The Sward hardness of a coating was found to be influenced
by temperature, humidity, film thickness, substrate hardness,
and air pressure. Coefficient of rolling friction values were
recovered from the values of Sward hardness and the physical parameters of the rocker. The coefficients of rolling friction are related to the shear modulus and loss tangent of the
coating. The analysis shows that if the physical parameters of
different rockers or hardness pendulums are known, it is
possible to relate the hardness values obtained on different
instruments.
Pendulum or damping is the least understood hardness test
method. A pendulum supported on the specimen by a ball or
cylinder was applied to hardness testing by Le Rolland [61]
and can be used to measure strain hardenability. Similarly,
the Herbert Pendulum Tester [62] employed the strainhardenability principle to measure hardness. The Herbert
Pendulum Tester consists of a 4-kg arched casting which is
supported on the horizontal plane surface of the specimen by
a 1-mm-diameter ball. The ball can be either hard steel or
574
Persoz Pendulum--Persoz designed the p e n d u l u m h a r d ness tester [59] shown in Fig. 35. It is m a n u f a c t u r e d in Germ a n y by Erichsen GMBH & Co. It was a result of Persoz's
m a t h e m a t i c a l analysis a n d e x p e r i m e n t a l studies. It is w r i t t e n
up in the ISO R e c o m m e n d a t i o n 1522 as follows:
The p e n d u l u m rests on two stainless steel balls, 8 _+
0.005 m m diameter, of h a r d n e s s HRC 59 _+ 1, 50 -+ 1 m m
apart. A c o u n t e r p o i s e is not provided. The p e r i o d of oscillation should be 1 -+ 0.001 s on a polished plate glass
panel a n d the t i m e for d a m p i n g from a 12 ~ d i s p l a c e m e n t
to a 4 ~ d i s p l a c e m e n t on the s a m e s u b s t r a t e s h o u l d be at
least 420 s. The total weight of the p e n d u l u m s h o u l d be
500 _+ 0.1 g, a n d its center of gravity at rest s h o u l d be 60
_+ 0.1 m m b e l o w the p l a n e of the fulcrum, the p o i n t e r tip
being 400 + 0.2 m m b e l o w the plane of the fulcrum.
The Persoz p e n d u l u m is p r o n e to skidding on surfaces
having a low coefficient of friction. However, c o m p a r e d to the
K6nig p e n d u l u m , the Persoz p e n d u l u m is p a r t i c u l a r l y useful
with relatively soft organic coatings. This is a result of longer
d a m p i n g time of the Persoz p e n d u l u m (about two times t h a t
of the K6nig), w h i c h m a k e s it m o r e sensitive to small differences b e t w e e n soft organic finishes where the d a m p i n g times
are relatively short. The Persoz p e n d u l u m h a s b e e n s t a n d a r d ized: United States, ASTM D 4366; France, NTF 30 016.
A c o m p a r i s o n of similarities a n d differences b e t w e e n the
K6nig a n d the Persoz p e n d u l u m h a r d n e s s i n s t r u m e n t s is
shown in Table 4. BYK-Gardner, Inc. d i s t r i b u t e d a g r a p h
w h i c h c o m p a r e s K6nig h a r d n e s s values with Persoz h a r d n e s s
values. This g r a p h is shown in Fig. 36. The source of the d a t a
is r e p u t e d to be from Volkswagen Co.
HARDNESS
575
Weight
Ball diameter
Deflection:
Start
End
Period of oscillation (1 oscillation)
Damping time on glass
K6nig
Persoz
200 +_ 0.2 g
5 mm/0.2 in.
500 +_ 0.1 g
8 ram/0.3 in.
6~
3~
1.4 s
250 _+ 10 s
12~
4~
1s
420 +_ 10 s
400T 380360340320300,.>
280-
260-
2401
220
2oo1
~
18o1
16o
14o.
120i0080-
604020-
;0
I
50
70
I
90
I
iiO
I
I
i
130
150
170
./
.o-
~-
576
tb
2Tr
(% + ~) ~fMga__
- -- log--.
2Try (0, + ~)
V I
(13)
where
a = distance of center of gravity from instantaneous center,
0 -- angle between the vertical and the plane containing
the instantaneous center of rotation and the mass
center,
00 = initial amplitude of the rocker, and
e~ = amplitude of the rocker after N rocks.
Mathematical analysis of pendulums, balls, and rockers,
have been made by B. Persoz [59], Baker et al. [70], D. G.
Flom [71], and P. E. Pierce et al. [60]. Persoz developed the
relatively heavy (500-g) pendulum shown in Fig. 35. Baker et
al. found that heavy rockers with a high moment of inertia
appeared to give the best results. Flom investigated the relation of rolling friction to the dynamic shear modulus for
polymers and emphasized the importance of elastic hysteresis losses in rolling friction (not to mention the viscous damping effect). They demonstrated that, for the case of a rigid
sphere rolling on a viscoelastic surface, the following relationship existed
p~ = Ktan8 (W/Ga2) 1/3
where
~, -- coefficient of roiling friction,
tan8 = dynamic loss tangent,
G = shear modulus,
(14)
CHAPTER
48--HARDNESS
577
Value of a (cm)
Moment of inertia I about
center of gravity (cm.g 2)
Period, T (s)
Mass, M (g)
Radius, r (cm)
Value of 0o
Value of 0,,
0.896
2085
0.400
1616
1.175
1829
1.093
114.2
5.075
44~
27~
2.10
87.4
5.075
42~
27~
0.95
105.4
5.075
43~
27~
(18)
(19)
a = sphere radius,
W = load, a n d
g = a constant.
For the Sward rocker, a a n d W are c o n s t a n t a n d Eq 14
becomes
tx = K ' G
l/3tan~
(15)
(16)
E = KtN3/t 3
where
E
Kt
N
t
(17)
=
=
=
=
elastic modulus,
c o n s t a n t for varying thickness,
Sward rocker hardness n u m b e r , a n d
film thickness.
(20)
K t = 39t TM
(21)
E = 39N 3t0"54
(22)
hence
showing, as was stated earlier, that the Sward rocker hardness is related to, or is a m e a s u r e of, the m o d u l u s (stiffness) of
a material as a f u n c t i o n of its thickness. However, this is true
only within certain l i m i t a t i o n s - - t h e film m u s t be thick
e n o u g h a n d the substrate hard enough so that only the film
properties are being measured.
578
P A I N T A N D COATING T E S T I N G M A N U A L
150
100
50
/
i
2
i
10
20
30
40
50
60
70
80
S w a r d H a r d n e s s in s e c o n d s
FIG. 41-Comparison of K6nig hardness values with Sward
Rocker hardness values.
320
280
240
200
[73:75].
R = hJho = exp ( - wtanS)
(23)
160
120
80
40
10
20
3o
40
50
60
7o
S w a r d H a r d n e s s in s e c o n d s
FIG. 42-Comparison of Persoz hardness values with Sward
Rocker hardness values.
CHAPTER 48--HARDNESS
of a penetrometer and a brass block containing a heating
element enclosed in a glass dome that can be subjected to a
vacuum. The brass block can be heated from 0 to 300~ at
rates of up to 30~ per minute. The specimen block can be
cooled very quickly by sucking a stream of cold CO2 gas
through a side arm straight upon the specimen disk. The
polymer film to be tested is mounted on the brass block,
which has a circular perforation through which the ball hits
the specimen disk. The mounted specimen is placed inside
the glass dome, which can be evacuated or filled with an inert
gas. The test ball (1/8 in. steel ball bearing) is released electromagnetically from the top of the dome. The rebound height is
measured against an illuminated scale at the back of the
dome. The rate of testing (i.e., the interval between successive
ball rebounds) may be adjusted from 3 to I0 s per test. A
similar apparatus was used by Jenckel and Klein [79] investigation of the relationship between ball rebound energy absorption and temperature in polymers.
P H Y S I C A L C O N C E P T S OF M A R
RESISTANCE TESTING
The mar resistance of an organic coating is its ability to
withstand scratching, scuffing, and/or denting actions, which
tend to disfigure or mar (change) the surface appearance of
the coating. Mar resistance, as defined above, is a resistance
of the surface of the coating to permanent deformation, as a
consequence of the application of dynamic mechanical
forces. In this sense it is distinguished from print resistance,
pressure mottling, and block resistance, in which the applied
mechanical forces are static. Some examples of potential
marring of organic coatings are: sliding an ash tray or other
object across a desk or other item of furniture, rubbing one's
belt buckle, zipper, or buttons along the organic coating on
an automobile as it is being washed, a child sliding a toy or
other object along a wall, refrigerator door, etc., and a woman
dragging a wash basket full of wet clothes off the top of a
washer or dryer.
When we refer to the scratching associated with marring,
we are really referring to relatively fine surface scratches.
This distinguishes the type of scratch encountered in mar
testing from that encountered when attempting to evaluate
hardness or adhesion by means of various types of scratch
tests. There are, in general, three different ways in which
materials are scratched when being tested for mar resistance:
579
580
P A I N T A N D COATING T E S T I N G M A N U A L
TABLE
Sample/
Collaborator
No. 1 Zero
No. 2 Medium
No. 3 Hi resis
No. 4 Urethane
Orange lacquer
No. 188
tering. A m a r or b r e a k d o w n point is distinguished from depressions in the coating by holding the m a r r e d specimen
nearly at eye level in flat lighting, so that no highlight reflections are visible. The least weight required to make a line that
shows a distinct light scattering or whitish reflection in the
depression made by the needle is the m a r resistance value of
the organic finish. Care m u s t be taken to avoid reflections
from the wall of depressions in the finish which are not cut
through.
Years ago w h e n telephone sets were made of metal, it was
found that the baked black enamel used on the metal base of
the desk type telephone would get through the n u m e r o u s assembly operations in a n u n m a r r e d condition if the value of
m a r resistance was 200 g or better. Materials having m a r
resistance levels of less t h a n 200 g would not necessarily
suffer damage to a degree sufficient to expose the base metal,
but were rejected in m a n y cases on the basis of unsatisfactory
appearance.
ASTM Task Group D01.23.14 Hardness, Abrasion a n d Mar
Resistance r a n a p r e l i m i n a r y r o u n d - r o b i n test seeking a candidate apparatus a r o u n d which they could write a test
method. The results of the r o u n d - r o b i n tests are shown in
Table 6.
As a result of their findings, they wrote D 5178: Test Method
for Mar Resistance of Organic Coatings [53] using the equipm e n t R. Phair originally designed for adhesion testing. Several operators have expressed a lack of interest in this test
method as the end p o i n t is difficult to recognize. Also a m a r k
judged to be a m a r m a y disappear overnight.
Princeton Scratch Tester--This apparatus is somewhat similar to the balanced b e a m tester, b u t instead of having a
movable specimen table, the b e a m assembly itself moves on a
V-shaped track, the specimen r e m a i n i n g immobile. Also, the
needle is held at a n angle of 90 ~ to the surface of t h e specimen.
Hoffman Scratch Tester--This device, described in the section on hardness in this m a n u a l , has also been used to
determine m a r resistance. However, its use as a m a r tester
has never gained wide acceptance. The scratches obtained
are usually quite large a n d often go down to the substrate.
Rondeau Scratch Tester--The same criteria that apply to
the H o f f m a n scratch tester just m e n t i o n e d also apply to the
R o n d e a u Scratch Tester.
6--ASTM Task Group D01.23.14 on hardness, abrasion and mar resistance. Results of round-robin tests on mar.
1
F/H
H/2H
H/2H
H/2H
H/2H
HB/H
Hardness (Pencil)
2
3
F
F
F
F
F
HB
F
H
2H
2H
2H
2H
4
H
H
2H
2H
H
B
Eraser
(Rubs)
1
4
4
5
5
4
5
3
F
H
2H
HB
Slight
Slight
~Cointest (nickel)scratched the film but did not mar (metal marking) the surface.
bGrams, weight.
Coin
(Mar)
Erichsen
(Swing)
P
P
P
P
"Fair
aFair
P
P
P
P
P
P
58
67
62
68
90
47
Scrape
Adhesion
(Balanced
Beam)b
2
3
6
10
>10.5
10.5
10.0
10.5
4
8
12
10
12
10
RCA Tape
Abrader
4
9 cycles
7 cycles
15 cycles
14 cycles
55 cycles
10 cycles
CHAPTER 48--HARDNESS
581
Scuffing Methods
gloss, p e r c e n t = 10011 - I2
11
(24)
where
I1 = photoelectric cell r e a d i n g at the specular angle (45~
and
I2 = photoelectric cell r e a d i n g at the 60 ~ angle (15 ~ off
specular).
The percentage gloss of the a b r a d e d or m a r r e d spots is
plotted against the respective a m o u n t s of abrasive used to
o b t a i n a characteristic curve for each different material.
Since such curves for different m a t e r i a l s are often f o u n d to
change slope irregularly, they m a y cross each other, a n d the
rating of a series of different m a t e r i a l s using a given a m o u n t
of abrasive m a y not b e representative of their relation at
o t h e r a m o u n t s of abrasive. One w a y to arrive at an overall
p e r f o r m a n c e is to average the percentage of gloss at the
various a m o u n t s of abrasive or the area u n d e r each curve.
In 1988, C o m m i t t e e D-20 stated in the Precision a n d Bias
section of Test M e t h o d D 673: "a m e a n i n g f u l p r e c i s i o n statem e n t c a n n o t be developed at this t i m e b e c a u s e of the small
n u m b e r of l a b o r a t o r i e s presently k n o w n to be using this test
method."
582
Miscellaneous Methods
Belt Buckle Test--At least as late as 1969, one of the m a j o r
automotive companies used a belt buckle as one m e t h o d of
evaluating the m a r resistance of the organic coatings on their
automobiles. However, the exact method is not k n o w n to this
writer.
Coefficient-of-Friction Mar Test--One of the leading m a n u facturers of m a r resistance additives for organic coatings
uses a sort of coefficient-of-friction test to evaluate m a r resistance. This test consists of w r a p p i n g a 500-g weight i n cheesecloth, placing the weight at one end of a test panel a n d slowly
l i k i n g the weighted end of the panel. The angle at which the
weight slips off is taken as a n indication of the coefficient of
friction. The lower the angle, the better the m a r resistance.
Coin Mar Test--A leading m a n u f a c t u r e r of organic coating
resins uses a nickel (five-cent piece) to evaluate the m a r resistance of p i g m e n t e d organic coatings. The m a n n e r or method
that is used makes it a streaking or m a r k i n g type of m a r test.
The test consists of dragging a nickel over a pigmented coating a n d seeing how m u c h metal is transferred to the coating,
as manifested by the size a n d color of the streak.
Fingernail Mar Test--Another leading m a n u f a c t u r e r of m a r
resistance additives for organic coatings uses a fingernail to
evaluate m a r resistance. To make a test the back of a fingernail is dragged along the surface of the coating. If the coating
is marked, it is considered to be marred. This is also a streaking or m a r k i n g type of m a r test. Others have used the edge of
a fingernail in a similar m a n n e r .
FIG. 43-Scar-Resistance Tester. (Courtesy of Erichsen
GMBH & Co.)
ance result is the spring force at which the surface just shows
a mark.
FDC Fine Scratch Test--The F u r n i t u r e Development Council, L o n d o n (FDC) designed a test in 1957 to determine the
resistance of newly formed nitrocellulose lacquer films to
damage w h e n scratched, b u t it m a y be used o n any type of
coating. It consists of d e t e r m i n i n g the loss of gloss of the
organic coating when it is r u b b e d with a wool blanket.
A r u b b i n g head with a n area 3/4 in. in diameter, u n d e r a load
of 4 lb, is rotated on the specimen at 10 r p m for 2 m i n (20
rotations). The head is covered with No. 778, No. 3 Super
White Blanketing from James K e n y o n & Son, Ltd., made
from 52/6S Good Quality English Wool, plain weave, 26 picks
per inch, 32 ends per inch, 171/2 ounces per square yard,
scoured, and milled finish. Blanketing produces more
scratches t h a n most other c o m m o n materials a n d is also
more reproducible. A disk of blanketing m a y be used twice,
once o n each side.
Tests are made on films applied to two black glass plates.
Five tests are m a d e o n each plate. A 45 ~ gloss meter is standardized at 100 on a n unscratched portion of the film, a n d the
gloss of each scratched area is measured. For a difference in
gloss to be considered significant, the difference in gloss between the m a r r e d a n d u n m a r r e d area m u s t be greater than:
1. 1.7 for gloss of between 88 a n d 100, a n d
2 . 2 . 7 for gloss below 88.
REFERENCES
[1] Shaw, M. C., "The Science of Hardness Testing and Its Research
Applications," Vol. 1, The Fundamental Basis of the Hardness
Test, American Society for Metals, Metals Park, OH, 1972.
[2] Sato, K., "The Hardness of Coating Films," Progress in Organic
Coatings, Vol. 8, 1980, pp. 1-18.
[3] Wheeler, P. C., "A Survey of Methods Used in the Federation of
Paint and Varnish Production Clubs for the Testing of Paints
and Varnishes," Official Digest, Federation of Paint and Varnish
Production Clubs, Vol. 18, No. 263, December 1946, pp. 653657.
[4] Switzer, M. H., "The Concept of Organic Coating Hardness,"
ASTM Bulletin, Vol. 156, January 1949, pp. 67-71.
[5] Unpublished study by ASTM Task Group D01.23.14: "Hardness,
Mar and Abrasion Resistance."
[6] Mohs, F., Grundriss der Mineralogie, Dresden, Germany, 1822.
[7] Starkie, D., "The Hardness and Scratch Resistance of Plastics,"
Journal, Society of Glass Technology, Vol. 26, June 1942, pp. 130144.
[8] Bierbaum, C. H., Capp, J. A., and Diederichs, H., "Testing Hardness of Bearings and Journals," Iron Age, Vol. 106, 1920, pp.
1727-1730.
[9] Bierbaum, C. H., "A Study of Bearing Metals," Chemical Metallurgical Engineering, Vol. 28, 1923, pp. 304-308.
[10] Bierbaum, C. H., "Microcharacter Hardness Tester Avoids Core
Effect," Iron Age, VoL 126, No. 17, 23 Oct. 1930, p. 1143.
[11] Bierbaum, C. H., "Hardness Determined by Microcut," Metal
Progress, Vol. 18, No. 5, November 1930, pp. 42-44.
[12] Barber, R. J., "A Precise Measurement of Surface Hardness of
Lacquers," American Paint Journal, Vol. 17, No. 44, 1933, pp.
7-8.
CHAPTER 48--HARNESS
[13] Kline, G. M. and Axilrod, B. W., "Transparent Plastics for Aircraft," Journal of Research, National Bureau of Standards, Vol.
19, RP 1031, 1937, pp. 367-400.
583
[39] Lebouvier, D., Gilormini, P., and Felder, E., "A Kinematic Model
for Plastic Indentation of a Bilayer," Thin Solid Films, Vol. 172,
1989, pp. 227-239.
[40] Walker, W. W., "Knoop Microhardness Testing of Paint Films,"
Microindentation Techniques in Materials Science and Engineering, ASTM STP 889, P. J. Blau and B. R. Lawn, Eds., American
Society for Testing and Materials, Philadelphia, 1986, pp. 286289.
[41] Brinell, J. A., Congres International Method d'Essai, Paris, 1900.
[42] Erichsen Technical Information Leaflet 263E, Group 14.
[43] CDIC Paint and Varnish Production Club, "The Effect of Aluminum Stearate on Embrittlement of Highly Pigmented Oil
Films," Official Digest, Federation of Paint and Varnish Clubs,
Vol. 20, No. 286, 1948, pp. 826-831.
[44] Weiler, W. W., "Dynamic Loading: A New Microhardness Test
Method," Journal of Testing and Evaluation, Vol. 18, No. 4, July
1990, pp. 229-239.
[45] Monk, C. J. H. and Wright, T. A., "A Pneumatic Micro-Indentation Apparatus for Measuring the Hardness of Paint Coatings,"
Journal, Oil and Color Chemists Association, Vol. 48, 1965, pp.
520-528.
[46] Gardiner, K. W., Jordan, T. F., and Adams, F. W., "A Vicat Type
Penetration Tester for Evaluating Hardness and Elastic Recovery of Polymeric Materials," ASTM Bulletin, Vol. 246, May 1960,
pp. 38-40.
[47] Knoop, Frederick, Peters, Chauncey G., and Emerson, Walter
B., "A Sensitive Pyramidal-Diamond Tool for Indentation Measurements," Journal of Research, National Bureau of Standards,
Vol. 23, July 1939, pp. 39-61.
[48] Lysaght, V. E., "The Knoop Indentor as Applied to Testing
Nonmetallic Materials Ranging from Plastics to Diamonds,"
ASTM Bulletin, American Society for Testing and Materials, No.
138, January 1946, pp. 39-44.
[49] Gusman, S., "Test Methods for Evaluation of Organic Coatings,"
[50] Pfund, A. H., "Tests for Hardness, Gloss, Color and Leveling of
Varnishes," Proceedings, American Society for Testing and Materials, Vol. 25, 1925, pp. 392-397.
[51] Schuh, A. E. and Theuerer, H. C., "Physical Evaluation of Finishes," Industrial and Engineering Chemistry, Analytical Edition,
Vol. 6, 1934, pp. 91-97.
584
[77] Raphael, T. and Armeniades, C. D., "Significance and Interpretation of the Thermophysical Profiles' Obtained by the ADL
Rebound Tester," American Chemical Society, Organic Coatings
and Plastics Chemistry Division, Preprints, Vol. 23, No. 2, 1963,
pp. 273-280.
[78] Gordon, M. and Grieveson, B. M., "Rebound of Relaxation
Sprectra and Principle of Constant Isoelastic Curing Rates,"
Journal of Polymer Science, Vol. 29, 1958, pp. 9-35.
[79] Klein, E. and Jenckel, E., "Dependence of the Modulus of Elasticity of High Polymers on the Temperature," Z. Naturforsch.,
Vol. 7a, 1952, pp. 800-807.
[80] Phair, R. J., "Scratch Adhesion and Mar Testing of Organic
Finishes," Bell Laboratories Record, Vol. 23, August 1945, pp.
284-286.
[81] ASTM Annual Book of Standards, Vol. 08.01.
[82] Boor, L., "Mar Resistance of Plastics," Modern Plastics, Vol. 20,
September 1942, pp. 79-83.
[83] Barnett, F. R. and Prosen, S. P., "Validity of Mechanical Tests for
Glass Reinforced Plastics," Materials Protection, Vol. 3, June
1964, pp. 32-40.
[84] Starkie, D., "The Hardness and Scratch Resistance of Plastics-A New Method of Test," Journal, Society of Glass Technology,
Vol. 26, 1942, pp. 130-144.
[85] Sward, G. G., "Improved Abrasion Apparatus," Scientific Section
Circular, National Paint, Varnish, and Lacquer Association, No.
581, June 1939.
[86] Sherr, A. E. and Martin, F. G., "Mar Resistance as Measured by
the Taber Abraser," American Chemical Society, Organic Coatings and Plastics Chemistry Division, Preprints, Vol. 24, No. 2,
1964, pp. 174-179.
[87] Erichsen Technical Information Leaflet 435E, Group 14.
MNL17-EB/Jun. 1995
O R I G I N S OF S T R E S S IN ORGANIC
COATINGS
Stresses originate in organic coatings as a result of their
a d h e s i o n to the substrate. G o o d a d h e s i o n is, on the one hand,
i n d i s p e n s a b l e for a d e q u a t e s u b s t r a t e protection, b u t on the
other h a n d prevents the n o r m a l m o v e m e n t of a coating.
The three m a i n causes w h i c h provoke stress in an organic
coating are [11]:
1. Film formation.
2. Variation in t e m p e r a t u r e .
3. Variation in relative h u m i d i t y (RH).
The stresses i n d u c e d by film formation, v a r i a t i o n in temperature, a n d variation in RH are known, respectively, as
internal, thermal, a n d hygroscopic. The latter two stresses are
also referred to as h y g r o t h e r m a l (sur).
It is i m p o r t a n t to realize that, due to the coating a d h e s i o n
to its substrate, stress exerts its action m a i n l y in a plane
parallel to the substrate [6, I2,13]. Therefore, one can write
s -
E9
1--u
(1)
where
S = stress,
E = elastic modulus,
~Head of Department, Coatings Research Institute (CoRI), Ave. P.
Holoffe, B-1342 Limelette, Belgium.
9 = strain, a n d
v = Poisson's ratio.
Stresses are especially d a m a g i n g at edges [14] w h e r e they
c a n n o t cancel each o t h e r o r in the m i d d l e of the plate if
defects or heterogeneities are present.
Film F o r m a t i o n
During film f o r m a t i o n a n d regardless of the m e c h a n i s m
involved (evaporation of solvent, coalescence, c h e m i c a l reaction, o r their c o m b i n a t i o n ) , in almost all cases the coating
tends to contract. If this c o n t r a c t i o n is p r e v e n t e d by coating
a d h e s i o n to its substrate a n d / o r the m o b i l i t y of m a c r o m o l e c ular segments is hindered, a tensile stress will develop in the
coating.
I n the literature a certain confusion reigns a b o u t the
d e n o m i n a t i o n of the stress arising during film formation.
F o r example, for solvent-based coatings a n a u t h o r m a y use
these terms: cure stresses, solvent removal stresses, residual
stresses, shrinkage stresses, internal stresses. F o r simplification, I suggest referring to the stress arising d u r i n g film form a t i o n as internal stress (St).
If a liquid p a i n t is a p p l i e d on a substrate [8] a n d the develo p m e n t of stress is m e a s u r e d as a function of time, a n u m b e r
of stages can be observed (Fig. 1).
In Stage 0, the coating is still liquid a n d is m o b i l e e n o u g h to
p e r m i t volume contraction, a n d consequently no stress develops,
I n Stage 1, the film starts to form, the volume c o n t r a c t i o n is
restricted a n d stress develops.
In Stage 2, a n u m b e r of processes can occur. Depending on
the coating composition, the evolution of stress can include
various c o m b i n a t i o n s of increasing, decreasing, a n d stationa r y stress levels. If no d a m a g e occurs to the film (cracks,
microfissures, loss of adhesion), a decrease in stress results
from r e l a x a t i o n processes w h i c h occur from the m o m e n t the
stress develops b u t only b e c o m e evident at this stage. It also
follows that the m e a s u r e d stress values are a result of two
opposite processes, one tending to develop stresses in the
coating (in this case due to the v o l u m e shrinkage) a n d the
other tending to decrease t h e m (due to stress relaxation).
E x a m p l e s of stress d e v e l o p m e n t as a function of t i m e for
latex coatings [15] above a n d below the CPVC are shown in
Fig. 2.
It is i m p o r t a n t to a d d that stress starts to develop in a
coating w h e n its Tg is at least equal to the e x p e r i m e n t a l
t e m p e r a t u r e [6]. F o r solvent-based coatings (Fig. 3), this is
585
Copyright9 1995 by ASTM International
www.astm.org
586
TESTING
MANUAL
S
2
Variation of Temperature
__0___/
When coated substrates are exposed to variations in temperature, dimensional changes are induced. If the thermal
expansion coefficients of the coating (a~) and the suhstrate
(as~) are different, which is usually the case, a thermal stress
(S r ) will develop in the coating [2, 7,11,19,20].
Since the thermal strain, er is given by
TIME
er ~ (aFt _ asr) AT
3Vs
- -
AV
(2)
3Vs
where
Vs = volume of coating at solidification, and
V t = volume of coating at time t after solidification.
One can write [18] that
sF =
E
1-v
1 dV
3V s
a.
(3)
(4)
E
I
--
(~ - ~)c/r
(5)
Determination of Tg
A schematic description of the stress dependence on temperature [18] is represented in Fig. 4.
Such a dependence indicates the possibility of determining
the Tg of a coating from the stress measurement. This is due
to the fact that E, ars, and v (see Eqs 1 and 5) also show a
profound change at Tg.
Below temperature a the coating is in the glassy region, and
above temperature b the coating is in the rubbery region.
The linear dependence of S on temperature in the glassy
region greatly facilitates the measurement of Tg. This linearity is due to the fact that in this region 17,, a r, and u are
practically independent of temperature.
Three examples of the stress dependence on temperature
and Tg determination by thermal stress measurements [18]
are shown in Fig. 5.
When the stress magnitude in the rubbery region is small
(e.g., elastomers, coatings with a low degree of cross-linking),
c.
b.
e.
I >,,
TIME
FIG. 2-Schematic description of stress (S) dependence on time for latex coatings
[15]: (a) and (b) PVC < CPVC; (c) and (d) PVC > CPVC; (e) PVC < CPVC in the
presence of a poor coalescent; (f) PVC > CPVC in the presence of a poor coalescent.
CHAPTER
49--STRESS
PHENOMENA
IN ORGANIC
COATINGS
587
vs
E,. = 3veRTr
(6)
Sr 2Er r
(7)
and
giving
ve .
Er
Sr
. . .
3R T~ 6R Trr
(8)
where R, S,, Er, and Tr are, respectively, the gas constant, the
stress, the elastic modulus, and the temperature at the beginning of the rubbery region. If Sr is measured and e~ is known
or determined from separate measurements (e.g., by
thermomechanical analysis, TMA), ve can be calculated.
Others have used the evaluation of Tg by stress measurements to investigate the effect of a pretreatment on certain
pigments [24], the state of cure of baking enamels [21], and
the modification of epoxy coatings [19a,25].
TIME
FIG. 3-Schematic representation of the dependence of V s / V E and stress (S) on time [16].
V s = volume of solvent present in the film; Vr =
volume of the dry film.
[',
I
(9)
fRH2
JRHI
E
I
(a~ - aH)dRH
(10)
-- V
INTERDEPENDENCE
T~-%-T
FIG. 4-Schematic re ~resentation of dependences of S, E, ~ r and v on temperature
(D US].
the Tg can be determined with fair accuracy just by carrying
out a few measurements in the glassy region and then extrapolating the straight line to S T = O.
For coatings with a significant stress in the rubbery region
(e.g., highly cross-linked thermosets), the measurement of
stress in this region might provide a way to approximately
determine the cross-link density, Ve [21].
OF STRESSES
(11)
588
PAINT
AND
COATING
TESTING
MANUAL
10" S
'"~
6 1'0 2b 3'o 4'o 5'o 6'0 -fo T
" ~
SH
10-
(12)
86
4
"gQ~
I
(13)
(14)
100
FIG. 6-Stress (S, MPa) dependence on
relative humidity (RH, %) for a polyester
powder coating (1); an epoxy (2); a polyurethane (3); and a latex coating (4) [27].
589
HeO
(I)
TINE
0
I
I
I
t
I
I
FIG. 7-Schematic description of the stress (S) dependence on time at two experimental conditions (water and 50% RH). X = the initial stress [28].
4-%
3'
0
2'
~_
1:
0-
--2'
27d
H20
(1)
76d
50
(X)
TIIE (d)
0
20
40
60
80
100
FIG. 8-Epoxy coating. Stress (S, MPa) dependence on time (d, day) at two experimental
conditions (water and 50% RH); ~ = initial stress [28].
STRESS
MEASUREMENT
590
strate deflection, its measurement should be made at a distance higher than 80 m m from the clamping point [8].
Variation (2) is m u c h simpler to analyze and can be designed
to eliminate the effect of weight loss on the coated substrate
deflection by choosing the right distance between the two
knife edges [43].
Each variation has its advantages, but if correctly used they
should give identical results. For example (1) is more suited
to evaluating stress in water [28] and (2) to determine the
effect of temperature [2,11].
Among the techniques used to measure the deflection of
coated substrates, one can mention: capacitive transducers
[42,43], laser [44], travelling microscope [4, 8,26], automatic
micrometer [11].
A commercial apparatus, the CoRI stressmeter (Fig. 11), is
based on Variation (2) and the mathematical analysis described in Ref 43. This apparatus is almost completely automatic and enables one to measure the stress from about - 5
to 100~ under a variety of RH's.
A n u m b e r of mathematical equations are proposed in the
literature to calculate the stress, but in the author's opinion
those proposed by Corcoran [40] are the closest to the real
situation (e.g., considers the fact the stress develops in two
directions)
S =
S --
dEst3
dE(t + c)
+ 312c(t + c)(1 - Vs) 12(1 - v)
4d'Est3
+ 4d'E(t + c)
3Fc(t + c)(1 - Vs)
12(1 - v)
(15)
(16)
where
d = deflection of the substrate (Fig. 9),
d' = deflection in the middle of substrate (Fig. 10),
E s = elastic modulus of the substrate,
=
=
=
=
p/3
Es
(17)
4d't3b
where
P = weight placed in the middle of the substrate,
b
width of the substrate, and
d', l, t = as in Eq 16.
=
Pigmentation
It has been shown that pigmentation, both the pigment
volume concentration (PVC) and the type of filler (i.e., pigments and extenders), affects the development of internal
stress [7,41,45-50]. To illustrate this, examples are presented
in Figs. 12 to 17.
Figures 12 and 13 show, respectively, the stress dependence on time for a thermoplastic binder in solution and a
latex, filled with a titanium dioxide (TiO2). Some PVCs are
above the CPVC, and some are below the CPVC.
The different stages occurring during the film formation,
discussed previously, can be recognized. In Stage 1 stress
increases relatively rapidly. For latex coatings, this stage corresponds to the transition phase of the evaporation kinetics
when the greatest part of the coalescence occurs. In Stage 2
(which corresponds to Phase 2 of evaporation kinetics), depending on the PVC and the type of filler, the stress can
decrease or first decrease and then increase. For PVC <
CPVC, this decrease is mostly due to the relaxation process,
but for PVC > CPVC is mostly due to relief processes such as
filler/binder dislocations and/or formation of microfissures.
t3: S
so
"IJ
I
....o..---o
z ~ r'"
l&_
I ~ ~,s5
I
591
1
3
5
7
5
25
105
5
FIG. 1 2 - S t r e s s (S, MPa) as a function of time [hour (h) and day (d)] for a polyisobutyl
methacrylate filled with Ti02. The numbers in the figure indicate the different PVCs (%) investigated [48]. CPVC = 51%.
592
1.1t S
0"91
0.7
0.1]~
I"
HOUR
I
I
I
I
l
l
I
I
I
I
I
1
3
5
7
1
5
FIG. 1 3 - S t r e s s (S, MPa) as a function of time for a
TiO~) [50]: 45% (O); 5 0 % ([]); 55% (X); 60(A). C P V C
n~Smx
(18)
I
'
l
I
l
I
I
I
I
I
I
l
l
I
r
9
13
17
21
25
29
33
latex (vinyl acetate/vinyl versatate copolymer filled with
= 52%.
~s]SB
XI
II
t3
It
9
PVC
t0
20
30
40
50
60
70
FIG. 1 4 - M a x i m u m internal stress (Sm, MPa)
as a function of PVC (%) for a solvent-based
thermoplastic binder filled with a TiO2 (X), a red
iron oxide (O), a yellow iron oxide (A), and a
talc (G) [48].
Sm
593
7Sm
5 ./
,',
3,2-
3-
2.4--
1.6-
.?.-
28-
OA-
(9 [49].
where
nl, n2, n~ = volume fraction of different fillers present in the mixtures, and
The presence of solvents in a coating can affect the magnitude and especially the rate of development of internal stress.
This is illustrated in Fig. 19.
For thermoplastic binders in solution, the slower the evaporation of a solvent from a coating, the slower the development of internal stress and vice versa. One should note that
the coating cast from fast-evaporating solvents (Curve 1, Fig.
19) produces slightly higher stress values than those cast
from more slowly evaporating ones (Curves 3 and 4, Fig. 19).
The results obtained were explained by using Eq I, the
principle of plasticizing effectiveness of solvents and the
stress relaxation favored by the presence in the coating of the
slower evaporating solvent [16].
For coatings containing a mixture of solvents (Fig. 20),
both the development rate and the stress magnitude are
mainly determined by the presence in the film of the less
volatile solvent(s).
The situation may be different if the film formation is a
result of solvent evaporation and cross-linking processes
(e.g., epoxy and polyurethane coatings). Under such circumstances the coating containing faster evaporating solvents
can develop smaller stress values [58]. For such coatings, the
volume of solvent present in the film after most of the crosslinking has occurred (Eq 2) and which determines the magnitude of eF will increase the slower the solvent evaporates. If
the stress relaxation process is negligible, it follows that for
594
3,6"
Sm
3.2-
Binder
2.8
I
I
2.4-
I
I
I I
I II
2.
1.6
Il
I I
1.20.8
0.4
10
30
50
70
To understand the role of the binder, the essential component of an organic coating on stress development, one can
consider once again the general Eq 1 (see also Eqs 3, 5, and
10) and/or the Tg of a coating with respect to the experimental temperature.
Equation 1 indicates that the stress is directly affected by
the magnitude of E, e, and u of the binder. The smaller the
values of E, e, and v, the smaller the magnitude of stress.
With respect to the Tg, it should be remembered that the
binders having their Tg below or close to the film formation
temperature (T) develop a negligible internal stress, while
those having their Tg > T develop an important one. This is
due to the fact that at T > Tg~ the mobility of the binder
molecular segments is high and the stress arising during film
formation can partially or totally relax. Moreover, it can be
shown that for a thermoplastic binder in solution having a Tg
> T, the lower the Tg of the binder, the less will be the solvent
in the film after its formation (see Eqs 2 and 3) and therefore
the smaller the internal strain and stress in the dry coating
[16].
In brief, any change occurring in the molecular structure of
a binder (e.g., crosslinking, crystallinity, molecular weight,
steric hindrance) might induce a change in E, E, v, and Tg and
thus affect stress development.
(19)
(20)
FIG. 18-Determination of the CPVC by comparing the curvature of painted plastic substrates [57].
4-5
1
2-
1TIME
'
2'0
'
,~
'
~o
'
do
'
16o
'
do
'
'
'
FIG. 19-Stress (S, MPa) as a function of time (day) in a thermoplastic varnish cast
from methyl ethyl ketone and ethyl acetate (1); toluene (2); xylene (3); methyl isobutyl
ketone and isobutyl acetate (4--), at 52% RH and 21~ [.16"].
3.2-
2.4~ e
1.60.8-
O~
~o ~ ~
A0 A
~o
TIN(
J 2'o ' ~
' 6'0'
~o
' ~o'
1~o'
!~o'
1~o'
~o'26o
FIG. 20-Stress (S, MPa) as a function of time (day) for a thermoplastic varnish
595
596
PAINT
AND
COATING
TESTING
MANUAL
2.o-_S
1.6-
1.2-
0.8-
71+'~
1.4
1.
0.6
1
3
5
7
10
FIG. 22-Stress (S, MPa) as a function of time (h, hour; d, day) for a styrene acrylic
latex paint containing Texanol (9 Dalpad A (X); Dalpad A + propylene glycol (0)
[501.
Since stress develops in most organic coatings, the product
c S e should also be considered in adhesion tests performed in
(21)
F
b
- ~- "1, - cSE
where
o- =
K =
3' =
F =
b =
(22)
out applying any external force. This is due to the fact that at
a particular film thickness a spontaneous detachment should
occur [61]. Unfortunately, this method can only be used for
badly adherent coatings. For all other coatings, extremely
high film thicknesses, difficult to apply and cure, would be
necessary.
If the adhesion forces exceed the cohesive strength of a
coating and the stress developed is high, damage will preferentially occur in the coating (cracking, fissuring) rather than
at the coating/substrate interface. The verification of this
principle can be realized by determining the stress and the
ultimate properties of a coating. Since most of organic coatings are viscoelastic, it is essential that these properties be
evaluated under the conditions (strain rate, temperature, RH)
corresponding to the stress development in the coating. The
presence of stress concentrations (e.g., existence of heterogeneities) in the coating and of a fatigue process are factors decreasing the overall stress at which the coating will
crack.
sis
16s.
RH = 5%
597
4
9 Initial
9 168h
9 552 h
x 1008 h
12
60 ~ 5% RH
2~
8
-I
4
-2
-3
21 ~ 90% RH
-4
,
0
20
40
60
80
FIG, 23-Stress (S, MPa) as a function of temperature (T, ~ for a primer/clearcoat system
after different periods of weathering [9].
400
800
1200
tauv
Screen
FIG, 25-Stress ($, MPa) as a function of
time of weathering (tour, hour) for a primer/
ciearcoat system at two climatic conditions
12
[g].
T=21 ~
~. Initial
9
W E A T H E R I N G AND S T R E S S
DEVELOPMENT
168h
9 552 h
x 1008 h
-4
I
20
40
60
80
'l
I O0
RH
FIG. 24-Stress (S, MPa) as a function of RH
(%) for a primer/clearcoat system after different
periods of weathering [9].
In most cases when organic coatings are exposed to weathering (accelerated or natural), they undergo chemical and
physical modifications which are expressed in the change of
Tg, E, a, v, and cross-link density. Under such circumstances
and according to Eqs 1, 3, 5, and 10, one can also expect to see
changes in stress development.
Confirmation of this and the role played by stress in the
coating deterioration is given in Ref 9.
In this study a clearcoat/basecoat system exposed in a QUV
apparatus to alternating dry and wet cycles cracked after
about 1000 h.
By measuring the stress as a function of temperature and
RH, it has been shown that weathering provoked: (1) an
increase of Tg, which in turn induced higher tensile stresses
(Fig. 23), and (2) an increase of coating sensitivity to moisture, which induced higher compressive stresses (Fig. 24).
The representation of the stress as a function of time of
weathering for two experimental conditions similar to those
present in the accelerating apparatus (Fig. 25) indicates that
every time the experimental conditions changed (every 4 h)
the coating ~was exposed to an increasing stress.
The processes thought to lead to fissuring of the clearcoat
are described in Fig. 26.
Briefly, the chemical degradations induced by UV, water,
and oxygen, which decrease the coating cohesion, combined
598
Chemical
Weathering
Degradation
Physical Effects
Light/Oxygen/Water
- Breaking of bonds
Formation of new
crosslinks
Clearcoat
Embdttlement
+
Stress development
[
Cracking
=-_.---
w i t h t h e fatigue p r o c e s s at steadily i n c r e a s i n g h y g r o t h e r m a l
stress levels are t h e c a u s e s of t h e c o a t i n g d e g r a d a t i o n .
REFERENCES
[I] K6ning, W., Proceedings, VIth FATIPEC Congress, Wiesbaden,
Germany, 1962, p. 424.
[2] Dannenberg, H., Society of Plastic Engineering Journal, Vol. 21,
1965, p. 669.
[3] Prosser, J. L., Modern Paint and Coatings, July I977, p. 47.
[4] Saarnak, A., Nilsson, E., and Kornum, L. O., Journal of the Oil
and Colour Chemists" Association, Vo]. 59, 1976, p. 427.
[5] Hamburg, H. R. and Morgans, W. M., Hess's Paint Film Defects:
Their Causes and Cure, 3rd ed., Chapman and Hall, London,
1979.
[6] Croll, S. G., Journal of Applied Polymer Science, Vol. 23, 1979, p.
847.
[7] Sato, K., Progress in Organic Coatings, Vol. 8, No. 2, 1980, p. 143.
[8] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Technology, Vol. 53, No. 677, 1981, p. 39.
[9] Oosterbroek, M., Lammers, R. J., van der Ven, L. G. T., and
Perera, D. Y., Journal of Coatings Technology, Vol. 63, No. 797,
1991, p. 55.
[10] Kamarchik, P., Jr. and Jurezak, E. A., Proceedings of Radtech,
Edinburgh, Scotland, Great Britain, 1991.
[11] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Technology, Vol. 59, No. 748, 1987, p. 55.
[12] Crackin, F. L. and Bersch, C. F., Society of Plastic Engineers
Journal, Vol. 15, 1959, p. 791.
[13] Bierwagen, G. P., Journal of Coatings Technology, Vol. 51, No.
658, 1979, p. 117.
[14] Bauer, C. L., Farris, R. J., and Vratsanos, M. S., Journal of Coatings Technology, Vol. 60, No. 760, 1988, p. 51.
[15] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Technology, Vol. 56, No. 716, 1984, p. 111.
[16] Perera, D.Y. and Vanden Eynde, D., Journal of Coatings
Technology, Vol. 55, No. 699, 1983, p. 37.
[17] Hansen, Ch. M., Industrial and Engineering Chemistry Research,
Vol. 9, 1970, p. 282.
[18] Perera, D. Y., Proceedings, XVlth International Conference in
Organic Coatings Science and Technology, Athens, Greece,
1990, p. 309.
[19] Shimbo, M., Ochi, M., and Arai, K., Journal of Coatings Technology: (a) Vol. 56, No. 713, 1984, p. 45, and (b) Vol. 57, No. 728,
1985, p. 93.
599
[43] Croll, S. G., Journal of the Oil and Colour Chemists' Association,
MNL17-EB/Jun. 1995
Slip Resistance
by Paul R. Gudvin, Jr. 1
Definitions
The following are useful, specific definitions that have b e e n
developed by ASTM C o m m i t t e e D-21 on Polishes a n d f o u n d
in ASTM Test M e t h o d for Static Coefficient of F r i c t i o n of
Polish-Coated F l o o r Surfaces as M e a s u r e d by the J a m e s Machine (D 2047) [12].
Coefficient of Friction--The ratio of the h o r i z o n t a l
c o m p o n e n t of force r e q u i r e d to overcome friction, to the
vertical c o m p o n e n t of the object weight or n o r m a l force
a p p l i e d t h r o u g h the object, which tends to cause the
friction.
Dynamic Coefficient of Friction--The ratio of the horizontal c o m p o n e n t of force required to cause a b o d y to
slide at a relatively constant velocity to the vertical comp o n e n t of the weight of the object or force a p p l i e d to it.
The relatively constant velocity used to cause the b o d y to
slide over the surface is to be not less t h a n 0.125 ft/s n o r
m o r e t h a n 0.5 ft/s (38 to 152 mm/s). The vertical c o m p o nent shall result in a contact pressure of not less t h a n
1 psi (6.9 kPa) n o r m o r e t h a n 13 psi (90 kPa) applied
u n i f o r m l y over the area in m u t u a l contact.
Friction--The resistance developed b e t w e e n the physical contacting surface of two bodies when there is movem e n t or t e n d e n c y for m o v e m e n t of one b o d y relative to
a n o t h e r parallel to the plane of contact.
Slip Resistance--That p r o p e r t y of a floor surface that is
designed to prevent slipping. A surface having a static
coefficient of friction of 0.5 o r greater as m e a s u r e d in
a c c o r d a n c e with ASTM D 2047 is considered to be a slipresistant surface.
Static Coefficient of Friction--The ratio of the horizontal c o m p o n e n t of force a p p l i e d to a b o d y that just overcomes the friction or resistance to slipping to the vertical
c o m p o n e n t of the weight of the object or force a p p l i e d to
it. The vertical c o m p o n e n t shall result in a contact pressure of not less t h a n 1 psi (6.9 kPa) n o r m o r e t h a n 13 psi
(90 kPa) applied u n i f o r m l y over the area in m u t u a l contact.
ASTM ACTIVITY
M a n y studies of COF m e a s u r e m e n t by various ASTM committees o c c u r r e d over the p a s t 20 years. F o r the most part,
these studies have been divided into specific c o m m i t t e e s with
a task group of C o m m i t t e e F-13 on Safety a n d Traction for
F o o t w e a r u n d e r t a k i n g the task to i m p r o v e c o m m u n i c a t i o n s
between the various groups studying COF a n d thus prevent
d u p l i c a t i o n of effort.
Task G r o u p D01.23.15 on Slip Resistance is involved with
m e a s u r e m e n t of p a i n t and coatings COF. The group has developed a test m e t h o d that describes a slip-angle test a p p a r a tus a n d a horizontal-pull slip m e t e r that functions u n d e r wet
a n d d r y conditions a n d t h a t can be used to m e a s u r e b o t h
static a n d d y n a m i c COF.
Other areas of activity dealing with the COF include cer a m i c s [5], plastics [6], polishes [7], skid resistance [8], a n d
footwear [9]. A study b y the Consumers' Union [10] i n d i c a t e d
a need for good m e a s u r e m e n t of slipperiness. Evidence in
1976 i n d i c a t e d that available i n s t r u m e n t a t i o n was inadequate a n d that results o b t a i n e d with it d i d not correlate with
practical observations. The N a t i o n a l Institute of Occupa~Consultant, P. R. GuOvin Associates, P.O. Box 811, Westerville,
OH 43086-0811.
In a general sense, slipperiness can be defined as the tendency or liability to cause s o m e t h i n g to slide s u d d e n l y or
involuntarily. In m a n y cases, an organic p o l y m e r surface (i.e.,
a coating) is involved. In terms of the flooring m a r k e t area,
for which these definitions were written, the flooring surface
600
Copyright9 1995 by ASTM International
www.astm.org
CHAPTER
C O N C E P T OF T H E C O E F F I C I E N T OF
FRICTION
Slip is a w o r d that has m a n y m e a n i n g s [13,14]. In certain
areas of the coating industry, slip is c o n s i d e r e d to be the
ability of an object to move in a relatively free or
u n e n c u m b e r e d b u t controlled m a n n e r w h e n one sheet of
metal passes over a n o t h e r sheet as in a coating-line feeding
operation, w h e n it moves along a conveyor system in coating,
printing, fabrication, or p a c k a g i n g operations, and the like.
The coating m u s t have p r o p e r "slip" or "lubricity" to allow the
coated object to pass t h r o u g h the coating system to a further
fabrication or p a c k a g i n g section of the line. In fact, slip is
very i m p o r t a n t to fabrication operations w h e r e i n the c o a t e d
object is in contact with a tooling system as in fabrication of
bottle caps, or with other m e t a l surfaces in b e n d i n g operations, etc. Yet, o t h e r coatings such as floor coatings are designed to decrease this ability to move easily u n d e r an applied
force. In either case, the frictional resistance b e t w e e n objects
is being modified a n d controlled with such control being att a i n e d b y the inherent p r o p e r t i e s of the m a t e r i a l s used for the
coating or use of additives in the coating. It is i m p o r t a n t to
u n d e r s t a n d that at times low friction is desired a n d that at
other times r e a s o n a b l y high friction is desired.
Friction is the p r o p e r t y t h a t d e t e r m i n e s the degree of slip
or resistance to slip t h a t exists. Both static a n d d y n a m i c o r
kinetic friction are i m p o r t a n t p r o p e r t i e s of coatings. Static
friction is the a m o u n t of friction b e t w e e n two surfaces at the
precise instant w h e n one c o m m e n c e s to move over the other.
D y n a m i c friction is the friction b e t w e e n two surfaces w h e n
they are moving p a s t one a n o t h e r w i t h o u t interruption. The
coefficient of static friction is usually equal to or greater t h a n
t h a t of d y n a m i c friction [15]. The coefficient of friction, ix, is a
m e a s u r e of slip with a high coefficient of friction denoting
p o o r slip a n d a low coefficient of friction denoting g o o d slip
[16]. This p a r a m e t e r is the ratio of the force F (frictional
force) r e q u i r e d to move one surface over a n o t h e r surface to
the total force W pressing the two surfaces together
ix = F/W
A c u r r e n t theory of the m e c h a n i s m of dry friction describes
the force of friction arising from the s h e a r strength of m i n u t e
interaction areas or areas of true c o n t a c t b e t w e e n the contacting surfaces. These i n t e r a c t i o n areas are d i s t r i b u t e d in a
m o r e or less r a n d o m m a n n e r over the total a p p a r e n t contact
area. This can be expressed b y the following relation for the
friction force
F = s.A
50--SLIP
RESISTANCE
601
t h a t actually c a r r y the n o r m a l l o a d W b e t w e e n the two surfaces, the following relation also exists
W = p,~.A
F r i c t i o n is the universal force b e t w e e n surfaces t h a t opposes sliding motion. W h e n surfaces of bodies are in contact,
the interactive force at the surface m a y have c o m p o n e n t s
b o t h p e r p e n d i c u l a r a n d tangential to the surface. The perpendicular c o m p o n e n t is called the " n o r m a l force," a n d the tangential force is called the "friction force." W h e n there is
relative sliding b e t w e e n the bodies, the frictional force always
acts in the opposite direction of this motion.
Most dry surfaces behave a p p r o x i m a t e l y a n d within limits
according to Coulomb's frictional law. C o u l o m b f o u n d that
just before motion, the friction b e t w e e n two surfaces is
slightly greater t h a n w h e n the surfaces are in steady m o t i o n
relative to each other, that the frictional force is p r o p o r t i o n a l
to the n o r m a l force pressing the surfaces together, and t h a t
this force is i n d e p e n d e n t of both the contact a r e a and, except
at the start, the speed of relative m o t i o n of the bodies. The
constant ratio of the tangential force to the n o r m a l force is
k n o w n as the "coefficient of friction" (COF) a n d d e p e n d s on
the n a t u r e of the two surfaces. To initiate sliding against
friction, it is necessary to a p p l y a tangential force at least as
great as the COF a n d the n o r m a l force before the onset of
m o t i o n take place. The a p p l i e d tangential force is resisted by
the equal a n d opposite force of static friction, a n d the force
r e q u i r e d to overcome static friction is usually greater t h a n
the force n e e d e d to sustain u n i f o r m sliding motion.
D E T E R M I N A T I O N OF T H E C O E F F I C I E N T
OF FRICTION
Three types of i n s t r u m e n t s are used to m e a s u r e the COF,
a n d these are illustrated in Fig. 1 [17]. These are drag-type
meters that are b a s e d on fx = F/W, p e n d u l u m - t y p e m e t e r s
that m e a s u r e the energy loss of the p e n d u l u m as an indirect
i n d i c a t i o n of the d y n a m i c friction, a n d articulated-strut devices that are b a s e d on the direct a n d f u n d a m e n t a l principle
of the resolution of forces that take place w h e n an object
slides d o w n an incline as described below. The angle at which
a flat or plane surface m u s t be inclined for a solid object to
slide with a steady speed d o w n the incline is the "angle of
friction." The tangent of this angle is the COF b e t w e e n the
solid block of m a t e r i a l a n d the inclined plane
/x = tan4~
The principle involved in this equation is used in the slipangle a p p a r a t u s d e s c r i b e d in ASTM Test Methods for Measuring Static F r i c t i o n of Coatings Surfaces (D 4518) [18]. The
state of the art of slip-resistance studies t h r o u g h 1975 has
b e e n s u m m a r i z e d by B r u n g r a b e r [19].
602
l:Ol~lM*=ilal
FLOORSURFACE
b. ARTICULATED STRUT
DEVICE
' ~ S I T I O N AT
INITIAL
POSITION
FLOORSURFACE / i
C. PENDULUM
DEVICE
\\
i
FLOORSURFACE
FIG. 1-Schematics of different friction measurement devices (courtesy of the National Institute of Standards and Technology).
S E N S O R MATERIALS
It is obvious that two surfaces are required for COF measurements of any surface, and the sensor material, or surface
against which the specified compound is tested, should be
defined and specified. It is essential to obtaining meaningful,
reproducible results that the sensor material be selected
to represent use conditions and be well defined. Properties
such as uniformity (surface character including flatness,
roughness, chemical composition, resilience, and shear modulus), permanence in that chemical and physical characteristics should not change with time, and availability in a usable
form that does not require excessive preparation should all be
considered when selecting a sensor. Both sensor material and
test material should be reported when the coefficient of friction is given.
The sensor material may be composed of the same compound as the test compound or different. In most ASTM
studies of flooring, leather is used as the primary sensor
material. It is commonly used in the manufacture of shoes,
and, probably more important, it has the lowest COF of any
shoe-sole material. Although the rationale for its selection is
not well documented, leather conforming to Federal Specification KK-L-165C is specified as the sensor material. Where a
nonleather sensor material is to be used, rubber conforming
to ASTM Test Method for Rubber Property--Abrasion Resistance (NBS Abrader) (D 1630) [20] is used. Neoprene has
been used in certain round-robin studies. In other instances,
three leathers with three levels of oil content, two Kraton |
thermoplastic elastomers, and l 5 different rubbers were used
to generate statistical data [21] for ASTM Test Method for
LUBRICANTS
In those instances w h e r e slip is to be i n c r e a s e d (friction
decreased), a variety of slip agents or lubricants are available.
These include m i c r o n i z e d polyethylene p o w d e r s a n d silicones. See Table 1 for m o r e slip agents. M a n y slip agents also
function as a b r a s i o n - r e s i s t a n c e a n d m a r - r e d u c t i o n agents. In
certain instances, they can be u s e d as a n t i b l o c k agents. Lubricants are often used in the plastics processing industry where
they function as melt viscosity reducers, flow agents to improve flow onto metal surfaces, and, at times, costabilizers.
Factors t h a t s h o u l d be c o n s i d e r e d in selecting a l u b r i c a n t
include melting point, polarity, a n d solubility. Of course, the
l u b r i c a n t should not interfere with a d h e s i o n or any crosslinking m e c h a n i s m that is used. C o m m o n l u b r i c a n t families
as well as selected specific lubricants are listed in Table 1.
Polyethylene a n d polytetrafluoroethylene are available in a
p o w d e r o r m i c r o n i z e d form in a variety of particle sizes [23],
a n d silicones are available as f o r m u l a t e d p r o d u c t s designed
for use in the coating i n d u s t r y [24,25]. The m i c r o n i z e d polymers are i n c o m p a t i b l e a n d act as a filler that rises to the
coating surface where they function as tiny "ball bearings"
that decrease friction a n d often i m p r o v e a b r a s i o n a n d m a r
resistance.
TABLE 1--Lubricants.
Esters
Wax esters
Fatty alcohol esters
Fatty esters
Glycerol esters
Fatty Acid Amides
Alkanolamides
Monoamides
Bisamides
Metallic Compounds
Aluminum stearate
Barium stearate
Calcium stearate
Molybdenum sulfide
Zinc stearate
friction.
603
Dry
Static COF
Wet Oily
Dry
Sliding COF
Wet Oily
0.75
0.85
0.75
0.85
-..
-..
0.50
0.50
0.50
0.50
--.
.--
1.00
1.00
0.90
0.85
0.70
1.00
0,80
0.85
0.80
0.85
0.40
0.70
604
P A I N T A N D COATING T E S T I N G M A N U A L
TABLE 3--Devices for measuring the coefficient of friction.
Device
Dynamometer Pull Meter
Manufacturer
Comment
Reference
DRAG-TYPEFRICTIONMEASURINGDEVICES
Chatillion Inc.
Tests are being discontinued by
ASTM C21.06
[27]
[27]
Instrumentors, Inc.,
Cleveland, OH;
available from IMASS,
Accord, MA
Portable device
Universal Slip-Resistance
Tester
DYNAMICPENDULUM-TYPESKIDRESISTANCETESTER
Road Research
ASTM E 303 utilizes this device
Laboratory,
Crowthorne,
Berkshire, England
[7]
[29-32]
[28]
Frazier Precision
Instrument Co.,
Hagerstown, MD
[33-34]
Ceramic Research,
Penkhall Stake-onTrout, England
[35-38]
Ergodyne Slip-Resistance
Tester
ARTICULATEDSTRUTTESTERS
William English Ltd.,
Small and lightweight in nature
Alva, FL
James Machine
[12,39]
Slip-Test Inc.,
Lewisburg, PA
[5,32,40-41]
Few slip-resistance standards exist in m o s t industries, including the coating industry, even though there are m a n y
painted surfaces in pedestrian walkways. The United States
Navy has two specifications--MIL-D-23003A Military Specification-Deck Covering Co m p o u n d , Nonslip, Rollable and
CHAPTER 50--SLIP ~ S I S T A N C E
MIL-D-24483A Military Specification-Deck Covering, SprayOn, N o n s l i p - - t h a t specify COF values. Both specifications
use h o r i z o n t a l slip testers.
The C a n a d i a n G o v e r n m e n t Specification B o a r d a d o p t e d
two s t a n d a r d s for deck coatings based on the above U.S. Navy
specifications. One involves nonslip epoxy coatings, I-GP192, and the o t h e r nonslip involves p o l y u r e t h a n e coatings, 1GP-200. The COF specifications for these materials are given
in Table 2. This i n f o r m a t i o n points out s o m e i m p o r t a n t aspects of slip resistance m e a s u r e m e n t s . First, value differences in slipperiness of various shoe-sole m a t e r i a l s u n d e r
different conditions are used. Second, it points out the importance of specifying the n a t u r e of the shoe-sole material. Overall, leather has lower COFs t h a n rubber.
TEST D E V I C E S F O R M E A S U R I N G T H E COF
As m e n t i o n e d earlier, there are three types of devices used
to m e a s u r e the COF, n a m e l y drag, p e n d u l u m , and articulated
strut-based devices, The drag-type meters can be subdivided
into two classes: (1) horizontal-pull slip meters that are portable, inexpensive, a n d u s e d directly on a floor or o t h e r surface
u n d e r test a n d (2) b e n c h - t o p slip meters that are used p r i m a r ily in the laboratory. Both of the devices in these subclasses
are s o m e t i m e s referred to as "fish scale-type testers." The
devices are simple, m o t o r i z e d p o w e r units with force-measuring devices such as d y n a m o m e t e r s . One such device, developed at an i n s u r a n c e c o m p a n y [42], has been used by an
ASTM s u b c o m m i t t e e in a r o u n d - r o b i n study [21] to evaluate
w a l k w a y slipperiness [43]. Use of such devices has b e e n valid a t e d in a n o t h e r study [44]. General results from s o m e ASTM
m e m b e r s indicates that p e n d u l u m - t y p e devices are not applicable for further c o n s i d e r a t i o n in the m e a s u r e m e n t of the
COF.
P e n d u l u m - t y p e COF devices [12, 33-34] consist of a p e n d u l u m that is faced with a certain shoe-sole or heel material.
The p e n d u l u m can be adjusted to sweep a p a t h across a
flooring surface so that the contact pressure between the
facing a n d the floor follows a p r e d e t e r m i n e d , t i m e - d e p e n d e n t
pattern. The p e n d u l u m ' s resultant loss of energy is p u r p o r t e d
to be a m e a s u r e of the d y n a m i c friction.
Articulated-strut meters [12,39-41] involve a p p l i c a t i o n of a
known, constant vertical force to a shoe that is faced with a
p a r t i c u l a r sole o r heel m a t e r i a l along with a p p l i c a t i o n of an
increasing lateral (forward) force until slip occurs. The ratio
of the lateral force at slip to the k n o w n vertical force is the
static COF. The vertical force is a p p l i e d to the top so t h a t the
article tested is only subjected to a vertical load. As the test
progresses, the articulated strut is slowly inclined so the test
article continues to be u n d e r a constant vertical l o a d a n d in
a d d i t i o n u n d e r an increasing h o r i z o n t a l or tangential l o a d
until slip occurs. The tangent of the angle that the articulated
strut m a k e s with respect to the vertical at the instant of slip is
taken to be the ratio of the horizontal a n d vertical c o m p o nents of the force a p p l i e d to the show a n d thus is the COF.
Devices of the three types are s u m m a r i z e d in Table 3.
605
REFERENCES
[1] Guevin, P. R., "Review of Skid and Slip Resistance Standards
Relatable to Coatings," Journal of Coatings Technology, Vol. 50,
No. 643, August 1978, pp. 33-38.
[2] Federal Register, Vol. 24, (Tuesday, 17 March 1955), pp. 15131524.
[3] Federal Register, Vol. 55, No. 69 (Tuesday, 10 April 1990), pp.
13360-13441.
[4] Federal Register, Vol. 56, No. 14 (Tuesday, 22 Jan. 1991), pp.
2296-2395.
[5] Ceramic Engineering and Science Proceedings, Vol. 13, Nos. 1-2,
1992, pp. 1-91.
[6] ASTM Research Report D20-1131, 9 Sept. 1986.
[7] Annual Book of ASTM Standards, Vol. 15.04 (1984, 1985, 1986).
[8] "Walkway Surfaces: Measurement of Slip Resistance," Walkway
Surfaces: Measurement of Slip Resistance, ASTM STP 649, C.
Anderson and J. Senne, Eds., ASTM, Philadelphia, 1978.
[9] "Slips, Stumbles, and Falls: Pedestrian Footwear and Surfaces,"
Slips, Stumbles, and Falls: Pedestrian Footwear and Surfaces,
ASTM STP 1103, B. E. Gray, Ed., ASTM, Philadelphia, 1990.
[10] Consumer Reports, Vol. 42, No. 7, July 1976, pp. 417-419.
[11] Stanevich, R., "Correlation of Subjective Slipperiness Judgments with Quantitative COF Measurements for Structural
Steel," CDC Contract No. 200-86-2929, NIOSH, Morgantown,
WV, 31 Oct. 1987.
[12] Book of ASTM Standards, Vol. 15.04.
[13] Paint~Coatings Dictionary, S. LeSota, Ed., Federation of Societies for Coatings Technology, Philadelphia, 1978.
[14] Additives for Plastics, Vol. 1, R.B. Seymour, Ed., Academic
Press, New York, 1978.
[15] Cramp, A. P. and Masters, L.W., "Preliminary Study of the
Slipperiness of Flooring," National Bureau of Standards, NBSIR
74-613 (July 1974).
[16] Burwell, J. T. and Rabinowicz, E., "The Nature of the Coefficient
of Friction," Journal of Applied Physics, Vol. 24, 1953, pp.
136-139.
[17] Adler, S. C. and Pierman, B. C., "A History of Walkway SlipResistance Research at the National Bureau of Standards," NBS
Special Publication 565, National Bureau of Standards, Washington, DC, December 1979.
[18] Annual Book of ASTM Standards, Vol. 06.01.
[19] Brungraber, R. J., "An Overview of Floor Slip-Resistance Research With Annotated Bibliography," Report NBSTN 895, National Bureau of Standards, Washington, DC, January 1976.
[20] Annual Book of ASTM Standards, Vol. 09.01.
[21] ASTM Research Report F13-I001, 27 July 1979.
[22] Annual Book of ASTM Standards, Vol. 15.07.
[23] "Innovation in Powder Technology," Technical Data Brochure,
Shamrock Chemicals Corporation, Newark, NJ.
[24] "Byk-Mallinckrodt Paint-Additives," Technical Data Notebook,
Byk-Mallinckrodt USA, Inc., Wallingford, CT.
[25] "Dow Coming | Additives," Technical Data Brochure 24-391
E-93, Dow Coming Corporation, Midland, MI.
[26] Annual Book of ASTM Standards, Vol. 15.02.
[27] Annual Book of ASTM Standards, Vol. 08.02.
[28] Annual Book of ASTM Standards, Vol. 04.03.
[29] English, W., "Horizontal Pull Slipmeter," U.S. Patent 4,895,015
(1990).
[30] English, W., "Improved Tribometry on Walking Surfaces," Slips,
Stumbles, and Falls: Pedestrian Footwear and Surfaces, ASTM
STP 1103, B. E. Gray, Ed., ASTM, Philadelphia, 1990, pp. 73-81.
[31] English, W., "Improved Static Coefficient of Traction Meter,"
Ceramic Engineering & Science Proceedings, Vol. 13, Nos. 1-2,
1992, pp. 22-28.
[32] Kohr, R. L., "A Comparative Analysis of the Slipperiness of
Floor Cleaning Chemicals Using Three Slip Meters," Ceramic
606
14-21.
[33] Sigler, P. A., Geib, M. N., and Boone, T. H., "Measurement of
Slipperiness of Walkway Surfaces," Research Report, 1897, National Bureau of Standards, Washington, DC, Journal of Research, Vol. 40, 1948, pp. 339-346.
[34] Jablonsky, R. D., "Standardization of Test Methods for Measurement of Floor Slipperiness," Walking Surfaces: Measurement
of Slip Resistance, ASTM STP 649, C. Anderson and J. Senne,
Eds., ASTM, Philadelphia, 1978.
[35] Harrison, R. and Malkin, F., "A Small Mobile Apparatus for
Measuring the Coefficient of Friction of Floors," Journal of Physics D: Applied Physics, Vol. 13, 1980, pp. L77-L79.
[36] Brough, R., Malkin, F., and Harrison, R., "Measurement of the
Coefficient of Friction of Floors," Journal of Physics D: Applied
Physics, Vol. 12, 1979, pp. 517-528.
[37] Proctor, T. D. and Coleman, V., "Slipping, Tripping and Falling
Accidents in Great Britain--Present and Future," Journal of Occupational Accidents, Vol. 9, 1988, pp. 269-285.
[38] Andres, R. O. and Chaffin, D. B., "Ergonomic Analysis of SlipResistance Measurement Devices," Ergonomics, Vol. 28, No. 7,
1985, pp. 1065-1080.
[39] James, S. V., "What is a Safe Floor Finish?" Soap and Sanitary
Chemicals, Vol. 20, October 1944, pp. 111-115.
[40] Brungraber, R. J., "Portable Tester for Measuring the Static
Coefficient of Friction between a Floor Surface or the Like and a
Shoe Sole or Heel Material or the Like," U.S. Patent 3,975,940
(1976).
[41] Brungraber, R. J., "Portable Tester for Measuring Slip Resistance," U.S. Patent 4,759,209 (1988).
[42] Irvine, C.H., "A New Slipmeter for Evaluating Walkway
Slipperiness," Materials Research & Standards, Vol. 7, No. 12,
December 1967, pp. 535-542.
[43] Irvine, C. H., "Evaluation of Some Factors Affecting Measurement of Slip Resistance of Shoe Sole Materials on Floor Surfaces," Journal of Testing and Materials, Vol. 4, No. 2, March
1976, pp. 133-138.
[44] Irvine, C. H., "Evaluation of the Effect of Contact-Time When
Measuring Floor Slip Resistance," Journal of Testing and Evaluation, Vol. 14, No. 1, January 1986, p. 19-22.
MNL17-EB/Jun. 1995
51
enjoys
significant economic leverage, and, as evidence, one may cite
the widespread use of coatings, films, and inhibitors for metals and semiconductors in many service environments. All
engineering metals used in modern technological societies
are unstable with respect to corrosion, and the result is a loss
of properties. Natural oxide films provide protection against
continued attack for some metals, and alloying extends the
life of other metals by developing highly stable passive films.
Where metals may not be protected by oxide films, other
modification methods have been developed to reduce corrosive attack. In reality, the improvement of corrosion resistance of metals by modification of the surface has been practiced since the invention of metal tools. Some of the earliest
techniques to prevent corrosion involved coating with
greases or natural oils. More modern methods were developed in the 19th and 20th centuries and include multiple
coatings, zinc galvanizing, electroplating of other pure metals, and vacuum physical vapor deposition of mostly pure
metal coatings by electron beam and sputtering techniques.
The metal coatings are better barriers than organic films because of the lower permeability of the former to moisture,
oxygen, and ions. Inhibitors or conversion coatings and
primers for paints are cheaper than metal coatings and are
used widely by paint manufacturers even though they remain
highly proprietary in nature.
The use of organic coatings to protect metal surfaces is
practiced widely. Much of the use is for atmospheric exposure of motor vehicles as well as for structural units such as
bridges and buildings. The successful implementation of existing technologies has greatly reduced the effects of corrosion of automobiles, for example, in the past decade in response to consumer demand. Despite many recent advances,
coating technologists and scientists acknowledge that much
is unknown and that new processes and understanding are
the keys for further progress [1]. Defects in the metal substrate and in the overlayers are among the primary concerns
because they are the source of localized corrosion phenomena. Defects may occur on length scales from atomic-level
lattice vacancies to arrays of defects at grain boundaries (for
crystalline materials) or to random pores or cracks (for example, in noncrystalline films). Avoiding such defects by proper
quality control is a major concern in coatings science and
technology.
THE PREVENTION OF CORROSION BY SURFACE PROCESSING
Aa=ECproducts
The summation signs are used as a general notation to indicate that all reactants and products are included in the calculation. From the nature of the free energy function, this calculation applies to initial (reactants) and final (product) states
and is independent of intervening states. The reaction may be
investigated under controlled reversible conditions such as in
an electrochemical cell or under irreversible conditions such
as in corrosion, and the same total free energy change (AG)
will be appropriate. A quite general predictive capability may
be applied to specific corrosion reactions since all the available thermodynamic data may be used for corrosion calculations directly. This enables the position of final equilibrium of
the corrosion system to be established. The thermodynamic
calculations have the limitation that no information concerning the rate of the reaction is provided, only what the final
state will be for the process.
The value of AG for reactions of elements to form a compound, all in their standard states at a particular temperature, is the standard free energy of formation of the compound, AG~r. Here, the subscript T denotes the temperature.
Description of the detailed calculations are beyond the scope
of this discussion, but several excellent textbooks are available [2,3].
The most extensive tabulations of thermochemical data for
chemical compounds in their standard state at 25~ are in a
series of National Bureau of Standards publications [4].
These are NBS Technical Notes 270-3, 270-4, and 270-5,
which supersede the older NBS Circular 500 for the elements
they cover. These tabulations also update the older data of
609
Copyright9 1995 by ASTMInternational
EC
reactants
www.astm.org
610
PAINT A N D COATING T E S T I N G M A N U A L
EIo=anodic
E
cathodic
A T M O S P H E R I C C O R R O S I O N OF M E T A L S
Most atmospheric corrosion tests have been conducted in
environments such as indoor atmosphere, outdoor atmosphere, and laboratory tests under simulated conditions. Indoor corrosion studies have been performed for the electronics, computer, and communication industries for the
development of more durable materials with desirable structural, magnetic, and electrical properties. On the other hand,
outdoor studies aimed at understanding corrosion behavior
are highly dependent on atmospheric weather factors, especially in marine and urban areas. The latter studies have been
performed in the automobile, marine, and aircraft industries.
Laboratory tests attempt to use accelerated methods under
611
simulated atmosphere or aqueous conditions. Electrochemical methods have been used extensively in such tests to analyze and monitor the corrosion behavior of metals.
Several weather factors are known to influence outdoor
corrosion [10-13]. Precipitation, ambient and dew-point
temperatures, atmospheric pollutants, wind direction and
wind velocity, and solar radiation can be considered as
weather factors in outdoor and/or urban corrosion tests.
Among these factors, moisture or relative humidity, temperature, and pollutants such as sulfur dioxide and chlorides are
the most important variables.
Relative humidity is known to be the most important factor
in determining the atmospheric corrosion rate. It has been
reported that rapid acceleration of corrosion occurs beyond a
certain value of relative humidity, defined as the critical humidity [14-15]. The period in which the relative humidity
exceeds the critical humidity is called the time-of-wetness,
and this factor is quite significant in determining atmospheric corrosion rate of metals [16]. In addition, in the presence of a pollutant such as sulfur dioxide, the critical humidity at which corrosion is enhanced to a significant extent will
decrease with increasing pollutant concentration [17-I8].
It has been reported that comparatively large aggregates of
water are present on oxyhydroxide surfaces at humidities
below 40% [19]. Even on clean metal surfaces obtained under
ultrahigh vacuum or reducing conditions, significant quantities of water are adsorbed on air-formed films when exposed
to the environments containing only oxygen and water vapor
for more than a microsecond [13]. As a result, monolayers of
adsorbed water may provide the medium for electrochemical
microcells that may drive a heterogeneous corrosion process.
Water may also exist in the form of complex mixtures with
oxides, hydroxides, and mixed oxyhydroxides [19-20].
The corrosion rate of metals is accelerated by the presence
of air pollutants such as sulfur dioxide, nitrite, nitrate, hydrogen sulfide, chloride, and some kinds of salts [10,15]. These
species may derive from gas-borne particles or from reactions at the surface. Reaction with adsorbed water monolayers yield electrolyte films that facilitate further corrosion
processes. Among these pollutants, sulfur dioxide, chlorine
gases, sulfur gases, and ozone are important species that
promote corrosion in the presence of water.
The corrosion-accelerating effect of sulfur dioxide with humidity has been reported by many investigators [I0,13,15].
Vernon [15] suggested that sulfur dioxide may change the pH
in electrolyte films present on metal surfaces and enhance the
corrosion rate. Rice et al. [13] also suggested that sulfur dioxide is readily soluble in water to form sulfurous acid; these
local acidic regions accelerate oxide formation, and the corrosion rate is also enhanced by other electrochemical effects.
It has been reported that wetting of the metal surface is
promoted in the presence of ammonia, and the water droplets
contain higher concentrations of sulfates than for the same
concentration of sulfur dioxide with no ammonia [10,22].
The effect of chlorine gas or chloride on atmospheric corrosion has been reported [10,13]. In aqueous electrochemical
corrosion studies, the chloride ions usually enhance pitting
corrosion of many metals and also degrade the oxide surfaces. Rice et al. [13] reported that chlorine gases reduce the
surface pH and yield hygroscopic corrosion products that
influence the amount of adsorbed water. A direct relationship
612
[25-27].
Electrochemical methods have been developed to take advantage of the electrochemical basis for atmospheric corrosion [28-29]. Corrosion currents can be monitored electrochemically, and the instantaneous value of current can be
detected. One way to monitor atmospheric corrosion with an
electrochemical method is to design a cell that will work
under thin electrolyte layers (less than 500 ~xm) with consideration of the effects of corrosion products and dilute pollutants [30].
Electrochemical methods for monitoring atmospheric corrosion have been well reviewed by Mansfeld [30-31]. Most of
the studies have been aimed at macroscopic measurement of
time-of-wetness that is associated with electrochemical corrosion [10,12,16,17]. Galvanic cells with electrodes of different metals have been commonly used [16, 32]. Sereda [10] has
developed galvanic cells of platinum-iron and platinum-zinc
couples to determine the time-of-wetness. Time-of-wetness
was arbitrarily defined as the interval during which the external potential exceeded 0.2 V. This figure was the period during which the relative humidity was greater than 85% [12,16].
Tomashov [33] has used sandwich-type galvanic cells of ironcopper, iron-zinc, iron-aluminum, and copper-aluminum.
They concluded that the method was suitable for fast determination of the corrosivity of the atmosphere and that the
direct measurement of corrosion rate for testing metals was
possible.
Several investigators [17,34-36] have used galvanic cells
consisting of steel-copper and electrolytic cells consisting of
individual metals (steel, zinc, or copper) to which an external
potential was applied. They concluded that the cell current
gave qualitative agreement with the weight-loss data. Recently, extensive studies have been performed by Mansfeld
and his coworkers [30-31,37-39]. They used galvanic cells
and electrolytic cells which consisted of two electrodes and
three electrodes. Galvanic cells such as copper-steel, copperzinc, steel-zinc, steel-aluminum, and aluminum-zinc couples
C O R R O S I O N OF T H I N METAL FILMS A N D
MICROSTRUCTURES
Corrosion of a metal occurs by the same fundamental
reactions whether it is used in a large structure like an automobile, a bridge, or a heat exchanger, or in a small structure
characteristic of magnetic, optical, or microelectronic devices, or under a protective layer [49]. The uniqueness of each
application is tied up in the definition of the environment to
which the metal is exposed or which develops with time, as
well as the definition of a characteristic size of the corroding
material. Since the time to failure of a material (i.e., its lifetime) is normally inversely proportional to the corrosion rate
and directly proportional to the thickness of the corroding
CHAPTER 5 I - - P R E V E N T I O N OF METAL C O R R O S I O N
material (its characteristic size), small dimensions are more
susceptible to corrosion failure and loss of properties. For
example (see Fig. 1), a 50-nm cobalt magnetic film may be
corroded completely in about 38 h at a corrosion rate of
1 /~A/cm2. The desired lifetime is about five years, so a protective film (e.g., diamond-like carbon) must be used to moderate the rate of attack. The protective layer must be thin to
read or write to the cobalt film with the magnetic head, and
defects in the protective layer will lead to localized corrosion
attac. Wear and friction are mechanical processes that result
from the relative movement of the disk and head. The head is
designed to fly very close to the disk to take advantage of the
magnetic properties [50], but it comes to rest on the disk
surface when the system is idle. Humidity and other factors
affect wear and friction, and layers or films may be added to
lubricate the magnetic film. Of more interest here, however,
are the chemical effects that cause corrosion. Accelerated
tests have been used to determine disk reliability [51], tests
that measure the affects of wear, friction, atmospheric contaminants, humidity, oxygen diffusion, and galvanic corrosion. Also described by Antler and Dunbar et al. [51] is the
comparison between field test experience and laboratorysimulated corrosion test results. Earlier results on microelectronics failures are reviewed by Schnable et al. [52],
Comizzoli et al. [53], Wood [54], and Stojadinovic et al. [55].
Whatever the mode, the result is a loss of information at the
site of degradation and the loss of properties. Better preparation and processing, or better design, may reduce flaws and
defects that cause mechanical failure, but they may not re-
IMULTIPLELAYERSANDWICHARRAYS
5oo ~,
DL- CARBON
~I'
COBALTALLOY
500 ,~
Ni P
J PARALLELLINES- SPOTS
Fq
FI
CVD - SiO 2
F
AI
TYPICAL DIMENSIONS
TYPICAL DIMENSIONS
50 nm (500~,) THICKNESS
1 grn
EXAMPLE:
FIG. 1-Thin film materials for magnetic, optical, metal conductor lines and microelect~onic contacts make them highly
susceptible to have small dimensions are highly susceptible to
corrosion.
613
614
where they join, and more remote areas of each are relatively
unaffected by the galvanic coupling. It has recently been
found that the active perimeter measure of the interactions is
more relevant than the area ratio, and the former may be
used to correlate the behavior of several geometries [61-63].
The nonuniform current distribution is also obtained if
the cathodic surrounding plane is highly resistive but
electroactive. For example, resistive sputtered carbon films
would cause the cathodic galvanic current to flow only to
areas at the periphery of holes and defects [65], and the total
area would not be important in determining the galvanic
current. However, smaller holes would increase the galvanic
current at a constant area ratio because the active perimeter
would increase.
In summary, investigations in bulk solution provide a basis
on which to begin to analyze atmospheric corrosion behavior. As the electrolyte phase decreases in thickness, ohmic
and diffusion effects become more dominant and galvanic
OR
615
616
SUMMARY
The a t m o s p h e r i c c o r r o s i o n of metals is one of the m o s t
i m p o r t a n t single p r o b l e m s facing c o r r o s i o n science a n d technology. F r o m small n a n o s t r u c t u r e s to large buildings a n d
bridges, coating techniques are being developed to m o d e r a t e
the rate of d e g r a d a t i o n with s o m e success. The use of lowcost coatings continues to increase as the coatings are m a d e
m o r e i m p e r m e a b l e a n d m o r e a d h e r e n t to the p r o t e c t e d substrate. Higher-cost films applied b y high-energy m e t h o d s are
finding wider use in critical a p p l i c a t i o n s w h e r e conventional
coatings are inadequate. In all systems w h e r e p r o t e c t i o n is
necessary, the early detection of c o r r o s i o n is desirable in
o r d e r to p l a n r e p l a c e m e n t a n d m a i n t e n a n c e m e a s u r e s a n d to
avoid c a t a s t r o p h i c failures. Detection of the presence of corr o s i o n can be a c c o m p l i s h e d in two ways: detection of the
agent that causes c o r r o s i o n or detection of the results of the
c o r r o s i o n process either on the m a t e r i a l of interest or on a
s p e c i m e n of the material. Sensors a n d m o n i t o r s are receiving
greater attention in accelerated life testing of materials, a n d
eventually they will be developed m o r e widely for o p e r a t i n g
systems or in p o r t a b l e m o n i t o r i n g systems. The savings to
i n d u s t r y a n d the public at large w o u l d be in the billions of
dollars if the onset of failure processes could be detected
p r i o r to their c u l m i n a t i o n in a c a t a s t r o p h i c event [79].
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[1] Funke, W., Leidheiser, H., Jr., Dickie, R. A., Dinger, H., Fischer,
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Ruf, J., Scantlebury, J. S., Vogoda, M., and Sykes, J. M., "Unsolved Problems of Corrosion Protection by Organic Coatings: A
Discussion," Journal of Coatings Technology, Vol. 58, 1986, p. 79.
[2] Guggenheim, E. A., Thermodynamics, North-Holland, Amsterdam, 1959.
[3] Lewis, G. N. and Randall, M., Thermodynamics, revised by K. S.
Pitzer and L. Brewer, McGraw-Hill, New York, 1961.
[4] NBS Technical Notes 2710-3, 270-4, 270-5, U.S. Government
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[5] Latimer, W. M., Oxidation Potentials, Prentice-Hall, Englewood
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[6] JANAF Thermochemical Tables, NSRDS-NBS 37, U.S. Government Printing Office, Washington, DC, 1968-1971.
[7] Smyrl, W. H., "Electrochemistry and Corrosion on Homogeneous and Heterogeneous Metal Surfaces," Comprehensive Treatise on Electrochemistry, Vol. 4, Bockris, Conway, Yeager, and
White, Eds., Plenum Press, New York, 1981.
[8] Newman, J. and Tiedeman, W., "Flow Through Porous Electrodes," Advances in Electrochemistry and Electrochemical Engineering, Vol. 11, H. Gerischer and C. W. Tobias, Eds., Wiley
Interscience, New York, 1978, p. 353.
[9] Newman, J., "Mass Transport and Potential Distributions in the
Geometries of Localized Corrosion," Localized Corrosion, R.
Staehle, Ed., NACE, Houston, 1974.
[10] Sereda, P. J., "Weather Factors Affecting Corrosion of Metals,"
Corrosion in Natural Environments, ASTM STP 558, ASTM, Philadelphia, 1974, p. 7.
[11] Perez, F.C., "Atmospheric Corrosion of Steel in a Humid
Climate-Influence of Pollution, Humidity, Temperature, Solar
Radiation and Rainfall," Corrosion, Vol. 40, 1984, p. 170.
C H A P T E R 5 1 - - P R E V E N T I O N OF M E T A L C O R R O S I O N
[12] Guttman, H., "Effects of Atmospheric Factors on the Corrosion
of Rolled Zinc," Metal Corrosion in the Atmosphere, ASTM STP
435, 1968, p. 223.
[13] Rice, D. W., Cappell, R. J., Phipps, P. B. P., and Peterson, P.,
"Indoor Atmospheric Corrosion of Copper, Silver, Nickel, Cobalt, and Iron," Atmospheric Corrosion, W. H. Ailor, Ed., John
Wiley & Sons, New York, 1982, p. 651.
[14] Freitag, W. O., "Testing for Indoor Corrosion," Atmospheric Corrosion, W. H. Ailor, Ed., John Wiley and Sons, New York, 1982.
[15] Vernon, W. H. J., "A Laboratory Study of the Atmospheric Corrosion of Metals. Part 1. The Corrosion of Copper, with Particular Reference to the Influence of Sulfur Dioxide in Air of Various
Relative Humidities," Transactions of the Faraday Society, Vol.
27, 1931, p. 255.
[16] Chawla, S. K., Anguish, T., and Payer, J. E., "Microsensors for
Corrosion Control," Materials Performance, May 1980, p. 68.
[17] Kucera, V. and Mattson, E., "Electrochemical Technique for
Determination of the Instantaneous Rate of Atmospheric Corrosion," Corrosion in Natural Environments, ASTM STP 558, 1974,
p. 239.
[18] Phipps, P. B. P. and Rice, D. W., "The Role of Water in Atmospheric Corrosion," Corrosion Chemistry, Vol. 235, G. Brubaker
and P. B. P. Phipps, Eds., ACS Symposium Series 89, 1979.
[19] Rice, D. W., Phipps, P. B. P., and Tremoureux, R., "Atmospheric
Corrosion of Cobalt," Journal of the Electrochemical Society, Vol.
126, 1979, p. 1459.
[20] Klier, K., Shen, J. H., and Zettlemoyer, A., "Water on Silica and
Silicate Surface. Partially Hydrophobic Silicas," Journal of Physical Chemistry, Vol. 77, 1973, p. 1458.
[21] Smyrl, W. H. and Newman, J., "Current and Potential Distributions in Plating Corrosion Systems," Journal of the Electrochemical Society, Vol. 123, 1976, p. 1423.
[22] Scott, W. D. and Hobbs, P. V., "The Formation of Sulfate in
Water Droplets," Journal of the Atmospheric Sciences, Vol. 24,
1967, p. 54.
[23] Smyrl, W. H. and Lien, M., "The Electrochemical OCM (Quartz
Crystal Microbalance) Method," New Methods and Experimental
Approaches in Electrochemistry, T. Osaka et al., Eds., Kodansha,
Tokyo, 1993.
[24] Smyrl, W. H. and Naoi, K., "Corrosion Studies with the Quartz
Crystal Microbalance," Perspectives on Corrosion, G. Prentice
and W. H. Smyrl, Eds., AIChE Symposium Series 278, Vol. 6,
1990.
[25] Burns, R.M. and Campbell, W.E., "Electrical Resistance
Method of Measuring Corrosion of Lead by Acid Vapors," Transactions of the Electrochemical Society, Vol. 55, 1929, p. 271.
[26] Sereda, P. J., "Atmospheric Factors Affecting the Corrosion of
Steel," Industrial and Engineering Chemistry, Vol. 52, 1960, p.
157.
[27] Enrico, F., Riccio, V., and Martini, B., "An Electrical Resistance
Method for Measuring Rates of Corrosion of Electrodeposited
Metals in Laboratory Tests," Transactions of the Institute of
Metal Finishing, Vol. 41, 1964, p. 74.
[28] Evans, U. R., "Mechanism of Atmospheric Rusting," Corrosion
Science, Vol. 12, 1972, p. 227.
[29] White, H. S., "Corrosion Principles in Microelectronics," Electronic Packaging and Corrosion in Microelectronics, M. E. Nicholson, Ed., ASM International, Metals Park, OH, 1987.
[30] Mansfeld, F., "Electrochemical Methods for Atmospheric Corrosion Studies," Atmospheric Corrosion, Vol. 139, W. H. Ailor, Ed.,
John Wiley & Sons, New York, 1982.
[31] Mansfeld, F., "Evaluation of Electrochemical Techniques for
Monitoring of Atmospheric Corrosion Phenomena," Electrochemical Corrosion Testing, ASTM STP 727, 1981, p. 215.
617
618
[52] Schnable, G. L., Comizzoli, R. B., White, L. K., and Kern, W., "A
Survey of Corrosion Failure Mechanisms in Microelectronic
Devices," RCA Review, Vol. 40, 1979, p. 416.
[53] Comizzoli, R. B., White, L. K., Kern, W., and Schnable, G. L.,
Report RADC-TR-80-236, July 1980, Final Technical Report,
Contract F30602-78-C-0276, 1 Sept. 1978 to 31 Aug. 1979, Rome
Air Development Center (RBRP), Griffiss AFB, NY.
[54] Wood, J., "Reliability and Degradation of Silicon Devices and
Integrated Circuits," Reliability and Degradation: Semiconductor
Devices and Circuits, M. J. Howes and D. V. Morgan, Eds., John
Wiley, New York, 1981.
[55] Stojadinovic, N. D. and Ristic, S. D., "Failure Physics of Integrated Circuits and Relationship to Reliability," Physica Status
Solidi, Vol. A75, 1983, p. 11.
[56] Howard, J. K., "Thin Films for Magnetic Recording Technology:
A Review," Journal of Vacuum Science and Technology, Vol. A4,
1986, p. 1.
[57] Jansen, F., Machonkin, M., Kaplan, S., and Hark, S., "The Effects of Hydrogeneration on the Properties of Ion Beam Sputter
Deposited Amorphous Carbon," Journal of Vacuum Science and
Technology, Vol. A3, 1985, p. 605.
[58] Nyaiesh, A. R., Kirby, R.E., King, R. K., and Garwin, E. L.,
"New Radio Frequency Technique for Deposition of Hard Carbon Films," Journal of Vacuum Science and Technology, Vol. A3,
1985, p. 610.
[59] Koeppe, P. W., Kapoor, V. J., Mirtich, H. J., Banks, B. A., and
Bulino, D.A., "Summary Abstract: Characterization of IonBeam Deposited Diamond-like Carbon Coating on Semiconductors," Journal of Vacuum Science and Technology, Vol. A3, 1985,
p. 2327.
[60] Savvides, N. and Window, B., "Diamond-like Amorphous Carbon Films Prepared by Magnetron Sputtering of Graphite,"
Journal of Vacuum Science and Technology, Vol. A3, 1985, p.
2386.
[61] Morris, R. G. and Smyrl, W. H., "Galvanic Interactions on Random Heterogeneous Surfaces," Journal of the Electrochemical
Society, Vol. 136, 1989, p. 3237.
[62] Morris, R. G. and Smyrl, W. H., "Current and Potential Distributions in Thin Electrolyte Layer Galvanic Cells," Journal of the
Electrochemical Society, Vol. 136, 1989, p. 3229.
[63] Morris, R. B. and Smyrl, W. H., "Electrode Processes on Heterogeneous Surfaces. I. Galvanic Interactions on Regular Geometry," American Institute of Chemical Engineers Journal, Vol. 34,
1988, p. 723.
[64] Winterfeld, P. H., Ph.D. thesis, University of Minnesota (1980).
[65] Kassimati, A. and Smyrl, W. H., "Galvanic Corrosion of Sandwich Structures," Journal of the Electrochemical Society, Vol.
136, 1989, p. 2158.
[66] Smyrl, W. H., Halley, J. W., Hubler, G., Hurd, A., MacDonald,
D., Snyder, D., and Williams, J., "Corrosion Protection," Critical
Reviews in Surface Chemistry, Vol. 3, 1993, p. 271.
[67] McCafferty, E., Natishan, P. M., and Hubler, G. K., "Surface
Modification of Aluminum by High Energy Ion Beams," Interface, Vol. 2, No. 3, 1993, p. 45.
[68] Leidheiser, H., Jr. and Granata, R. D., "Ion Transport Through
Protective Polymeric Coatings Exposed to an Aqueous Phase,"
[70] Armstrong, R. D., Handyside, T. M., and Johnson, B. W., "Factors Determining Ionic Currents in PVC Protective Coatings,"
[72] Mastronardi, P., Carfagna, C., and Nicolais, L., "The Effect of
the Transport Properties of Epoxy Based Coatings on Metallic
Substrate Corrosion,"Journal of Materials Science, Vol. 18, 1983,
p. 197.
[73] Yamamoto, T., Okai, T., Oda, M., and Okumura, Y., "A Novel
Anti-Corrosive Pigment Containing Vanadate/Phosphate," Ad-
vances in Corrosion
D.
MNL17-EB/Jun. 1995
Natural Weathering
by Lon S. Hicks I and Michael J. Crewdson 2
NATURALWEATHERINGDESCRIBESTHE PROCESSof exposing materials to the effects of the outdoor environment. Deterioration caused by the atmosphere occurs to all materials placed
in an outdoor environment. Natural weathering tests are an
extremely important part of the process of determining the
aging characteristics of a material. Weathering tests are used
to improve the durability of exposed materials.
All materials exposed to the elements deteriorate; the rate
and extent of deterioration is dependent upon the material
and the severity of the exposure conditions. Weathering tests
provide the means to improve the resistance of a material to
those factors.
Paint is currently the single most important material tested
for its weathering-resistance properties. Paint is used as a
decorative item, but equally as important, paint is used as a
protective layer. Painted products are found in many varied
environments with equally varied effects upon exposed surfaces. Weathering tests offer an initial view of the expected
performance of the paint to the environment.
Natural weathering tests are not, however, simply a case of
setting specimens out in the sun and watching what happens;
a meaningful test involves a more thorough understanding. A
number of important factors must be carefully considered
when planning and conducting a weathering test: the cause
and effect relationship between the weather and the material,
the subtle differences in exposure techniques, and the reporting and inspection methods employed. To achieve the most
reliable test result, these fundamentals must be appreciated.
HISTORICAL
The origins of natural weathering testing of paints goes
back as far as early caveman drawings in the Ice Age. We do
not know if these cave dwellers painted on the outside walls,
for if they did, the elements would have long since eroded
away the evidence. Inside, where conditions are less severe,
the paintings have survived tens of thousands of years.
The modern paint era was the catalyst for current weathering tests. Consumer awareness of deterioration propelled the
search for more durable products. At the same time, paint
manufacturing companies became cognizant of the fact that
durable products sell better; thus they have increased their
efforts to improve paint durability. At this time, the only
~Vice president and technical director, respectively, Sub-Tropical
Testing Service, 8290 S.W. 120th St., Miami, FL 33156.
2General manager/technical director, Q-Lab, 13131 SW 122nd
Ave., Miami, FL 33186.
F A C T O R S OF I N F L U E N C E
in
1.
2.
3.
4.
5.
619
Copyright9 1995 by ASTMInternational
www.astm.org
620
Paint will degrade w h e n exposed to the elements in the atmosphere due to the action of these influencing factors, w h i c h
cause the basic structure to b r e a k down. These factors interact synergistically to p r o d u c e the d e t e r i o r a t i o n of the material we see as a w e a t h e r i n g effect.
The relative p r o p o r t i o n of each of these factors is i m p o r tant in d e t e r m i n i n g h o w the overall d e g r a d a t i o n process will
occur. W h e n the factors of influence are changed, so is the
Sunlight
The effect of exposure to sunlight is the fundamental cause
of the weathering deterioration of most materials. The primary component of paint weathering is photodegradation.
Range
Wavelengths, nm
UVC
UVB
UVA
Range
Wavelength,
nm
UVC
UV UVB
UVA
<280
280-320
320-400
Visible
400-800
Infrared
Total
800-3000
280-3000
Irradiance,
W m 2
SUNLIGHT SPECTRUM
TOTAL HEMISPHERICAL
1.8
1.6
1.4
1.2
0.8
0.6
0.4
0.2
0
Y
i
300
I l l l l l
400
621
500
600
I l l
700
WAVELENGTH nm
FIG. 3-Solar power distribution, Miami, Florida (solar noon, 26 ~ tilt).
8OO
Percent
0
5
63
6.1
580
51.8
472
1120
42.1
100.0
622
1.4
1.2
Radiant Exposure
SOLAR SPECTRUM
WAVELENGTH RANGE PERCENT
300-400 (6.1%)
800-3000 (42.1%)
400-800 (51.8%)
SUNLIGHT SPECTRUM
TOTAL ULTRAVIOLET
0.8
0.6
z_
0.4
0.2
0
..........
300 310 320 330 340 350 360 370 380 390 400
WAVELENGTH nm
FIG. 5-Ultraviolet spectral power distribution (solar noon, 26 ~
tilt).
SOLAR SPECTRUM
WAVELENGTH RANGE P E R C E N T
10090
IZ
LU
O
rr
w
o_
Seasonal Variations
80
70
60
50
40
30
20
10
0
VISIBLE
UVC
CHAPTER 5 2 - - N A T U R A L W E A T H E R I N G
623
WAVELENGTH ENERGY
RELATIVE ENERGY PER PHOTON
Z
600
If
z
I
UII
v
>-
500 i
400
300 ~
20O
LU
IIlII
100
0
2O0
300
400
500
600
700
800
W A V E L E N G T H nm
I
FIG. 7-Energy per photon at each wavelength in sunlight.
--B-E = hNaC/r]
SOLAR ENERGY
DALLY INTENSITY
1200
1000
04
E
800
>..
I.co
z
uJ
Iz
600
400
200
0
10
11
12
T I M E O F DAY
TOTAL
TUV
(xlO)[
FIG. 8-Daily intensity levels of sunlight, Miami, Florida: Total and ultraviolet, 26~
tilt angle. (TUV is shown by the lower line.)
Temperature
The temperature of a material on exposure is a primary
factor whose influence must be understood in order to relate
624
,u. I
NOV.-MAR.
SOUTH
IL
ANGLE AT
S O L A R NOON
FIG. 9-Angle subtended by sunlight on exposed panel,
the cause and effect relationship of weathering. For most
materials, the moderate high temperatures found in service
do not cause deterioration per se. However, when the temperature rises in conjunction with solar radiation, the rate and
type of deterioration can vary greatly.
In a normal first-order chemical reaction, raising the temperature of the environment by 10~ leads to a doubling of
the speed of that forward reaction. However, because material degradation is not a simple one-step chemical reaction,
weathering deterioration does not proceed twice as fast when
the temperature is raised by 10~ There is a definite indica-
600
400
300
200
J/,N F~S M/,R ACR UkY JdN J6L AU'GSEPT OCT NOV D~;C
MONTHS
I'-'~'- 45 DEGREES
5 DEGREES
26 DEGREES
I
J
D
Month
45~
Solar Radiation, MJ m 2,
Angleof Exposure
5~
26~
VA~
January
Florida
Arizona
556.79
612.50
420.48
425.49
514.34
556.79
February
Florida
Arizona
587,50
607.94
483.37
476.40
618.09
587.50
601.51
631.54
569.90
601.35
661.61
661.61
545.76
724.23
573.12
784.77
623.35
573.35
468.30
735.51
600.77
897.85
577.21
600.77
441.17
648.94
589.38
856.13
529.25
589.38
434.21
649.66
566.95
830.43
531.66
566.95
475.86
684.23
572.30
774.86
557.65
572.30
475.00
658.02
502.78
647.56
526.62
526.62
March
Florida
Arizona
April
Florida
Arizona
June
Florida
Arizona
July
Florida
Arizona
August
Florida
Arizona
September
Florida
Arizona
545.50
712.30
500.14
596.29
561.06
545.60
522.87
669.54
425.90
471.38
509.88
522.87
524.10
601.06
394.72
400.22
492.33
524.10
6178.55
7935.44
6199.76
7762.70
6703.02
6827.51
November
Florida
Arizona
December
Florida
Arizona
Total
Florida
Arizona
Moisture
Water is a p r i m a r y factor affecting the deterioration of
exposed materials. I n c o n j u n c t i o n with solar radiation a n d
high temperatures, the moisture content in a n d s u r r o u n d i n g
a n exposed sample is very i m p o r t a n t in d e t e r m i n i n g the
weathering response of that material [8]. The presence of
water falls into two categories:
1. Gaseous.
2. Aqueous.
NOTE:VA = variableangle,
Rainfall
October
Florida
Arizona
Relative Humidity
May
Florida
Arizona
625
626
TEMPERATURE
MIAMI 1990
'~
I,
~
~
uJ
._1
0
or)
~^k,J
.,,~,,,J,
'
'~1
A A, .i
vy
v[ ~....
I!
,o t
mluu
imUUl
[~BLACK
imi
PANEL(C)
AMBIENT(C)
FIG. l 1-Daily maximum black panel versus ambient temperature. (Lower line
equals ambient temperature.)
RADIANT
ENERGY
AND
TEMPERATURE
MIAMI 1990
80
70
-~
C~
50
u~
4O
20
1
SOLARENERGYMJ / m,'[
FIG. 12-Daily maximum black box temperature versus daily solar radiant energy.
(Upper line equals black box temperature,)
Condensation
Condensation arises when the sample temperature drops
below the dew point temperature of the surrounding air. This
causes water vapor in the air to condense on the material. The
physical and chemical responses of the material caused by
condensation have a far greater effect on the material than
rainfall. The condensation effect can also be apparent at
much deeper levels within the material. Condensation moisture has high levels of dissolved oxygen, which accentuates
photodegradation by taking part in the chemical reaction.
The total amount of time a sample is wet is an extremely
important factor in the determination of the degree and rate
of degradation. Prolonged exposure to surface condensation
will allow the absorption or permeation of a relatively high
level of water and oxygen, and as the day progresses a strong
pressure will be exerted by the atmosphere for water desorption. The longer the intervals of wetting and drying, the
CHAPTER 5 2 - - N A T U R A L W E A T H E R I N G
MOISTURE EQUILIBRIUM
+
MATERIAL V E R S U S ATMOSPHERE
"z
/k J/' Ix,//
1.1,1
>
V V'v" v
._1
iii
,
, ,
, ,
, ,
4
5
6
TIME SCALE (DAYS)
I "-~'= MATERIAL
, ,
, i
ATMOSPHERE l
Pollution
Atmospheric pollution is a significant, but lesser part of the
overall weathering effect. Industrial emissions consisting of
compounds that mix with water to form acid rain cause
chemical reactions to occur on exposed materials. The severe
long-term effect of pollution on even durable materials can be
seen by the effect on ancient monuments and statues, which
have withstood centuries of exposure only to succumb in
recent years to atmospheric contaminants. Short-term exposure to pollution can be just as severe if the material is
susceptible.
Pollution is a powerful influence on paint durability, but its
effect is difficult to control and monitor. Analysis of the
atmosphere will reveal the constituents of the pollution, and
comparison to exposure in a clean pollution-free atmosphere
627
Biodeterioration
The phenomenon of material degradation due to attack by
biological organisms can take many forms. The most common form of biodeterioration of specimens exposed outdoors
in Florida is mildew. The organisms that constitute mildew
are fungi, which are individually microscopic but can be seen
with the unaided eye when grouped in colonies or having
threaded structures called hypha. The spores of the fungi
attach to the surface of the material, using the constituent
chemicals at the surface as a food source. All fungi are characterized by their inability to synthesize their own foods from
carbon dioxide and water. They must therefore utilize an
external supply of carbohydrate as their energy source. The
exact chemical nature of that source will vary for each fungal
species, but the more opportunistic species can use the paint
directly.
As the mildew grows, surface conditions are altered. Breakdown products are formed that can act as a food source for a
second fungal species, which will find the surface of the paint
a favorable place to live. This succession of different organisms constitutes the microecology of the painted material's
surface [12]. The complicated natural order that occurs in
mildew attack on exposed products makes it very difficult to
ascertain which species is causing the most damage.
Real-time exposure testing outdoors in conditions favorable to growth is the only way to truly test the mildewresistance properties of any product. Single culture testing of
mildewcides and mildewstats are useful as a preliminary test
o n l y .
628
MOISTURE LEVELS
MIAMI 1990
_ _ .
.0
<
w
.J
60
50
G0
,,
.,
'v'
40
30
20
10
0
JAN FEB MAR APR MAY JUN JUL AUG SEPT OCT NOV DEC
MONTHS
RELATIVE HUMIDITY %
shaded, damp location without the natural mildewstatic effect of solar UV radiation. A vertical south position is also
used to study mildew growth as part of the total deterioration
mechanism. Exposure under a roof overhang is commonly
used (Fig. 15), and a tropical forest exposure is the most
rigorous example of natural exposure conditions.
Mildew organisms thrive in the damp conditions found in
subtropical-type climates, and growth is greatest during the
summer months when rainfall and ambient relative humidities are at their highest level and temperatures are 20 to 30~
Growth is slowed when average daily humidity drops significantly below 70%; however, during the winter, steady growth
will still occur on northern exposures and in tropical forests,
where moisture levels are higher and temperatures are in the
optimum range.
Algae as a biodeterioration factor is different from mildew.
Algae is a green plant and able to synthesize food from sunlight, carbon dioxide, and water. Its attachment to paint surfaces is not an actively attacking one as' is the case with
mildew. The paint film is merely supplying a substrate for the
algae. By its presence on the surface, however, algae affects
the microclimate and resulting deterioration may occur.
CLIMATOLOGY
Natural weather exposure testing of paints and coatings is
conducted at many different sites, each with its own distinct
set of influencing factors. It is the combination of the weathering factors that causes the deterioration particular to that
location.
As indicated earlier, paint exposure testing facilities are
located in many areas, but the subtropical area of Florida is
regarded by the United States and by much of the rest of the
world as the primary benchmark testing climate. This is be-
Subtropical
The subtropical climate of southern Florida is recognized
worldwide as the primary benchmark testing location. It is
the climate to which all other locations are inevitably compared. It is no accident that this area is as important as it is,
for it is the only true subtropical region within the United
States. Due to the historical considerations discussed earlier,
Florida is accepted worldwide as the standard in natural
weathering. The great majority of materials will fail faster in
Florida than anywhere else because the climate contains all
of the major influencing parameters except pollution and in
relatively high amounts (Fig. 16). The factors act together
synergistically, each one increasing the effect of the other.
The high temperatures and humidity complement the photodegradation from solar radiation. The sun's energy is more
potent as there is a greater relative proportion of UV to total
energy. The time of total wetness is close to 50% of the total
time, thereby ensuring a constant cycle of wetting and drying.
Desert
The desert of the Southwest United States (especially the
Phoenix area) has also come to be regarded as a primary
weathering testing site. Exposure conditions in the desert are
very different than in Florida. The desert is widely used because the climate consists of clear skies and prolonged un-
CHAPTER 5 2 - - N A T U R A L WEATHERING
629
Marine
Marine Atmosphere--Exposure to a marine atmosphere
FIG. 15-Vertical exposure under roof.
Extreme Cold
At the opposite end of the exposure scale from the desert is
exposure testing in extreme cold weather. Low temperatures
are accompanied typically by lower sunlight. International
Falls, Minnesota is used as an exposure site for cold weather
testing because this area frequently records the lowest temperature in the continental United States (Fig. 18). Cold
weather exposure is used to test for specific failure types: cold
cracking and freeze thaw deterioration. As the temperature
passes through the freeze threshold, any water on the surface
or in the bulk of the material forms into ice crystals. As the
water freezes, its volume increases by approximately 10%,
which is enough to create a substantial physical force on the
paint film. This is the one environmental factor that cannot
630
MIAMI, FLORIDA
CLIMATE RANGE
100
90
80
70
60
50
40
30
~=
-" ~
20
~
+8.7
~.
-- - ~ - - - t = - ~ . ~ _ . . . ~ _
10
0
-"='-Avg Temp
(c)
Rainfall (in)
PHOENIX, ARIZONA
CLIMATE RANGE
100
90
80
70
60
50
40
30
+22.2
20
i0
0]
illl
J N F B MAR APR
I - = = - A v g Temp (C)
Rainfall (in)
will become susceptible. When the factors interact, the overall influence is a complicated matrix that is constantly changing.
Degradation is the result of the material's response to its
environment. When the environment changes, so do the
changes that occur in the material. This does not always
manifest as a slower or faster response, but also perhaps as a
different one. Generally, however, it is practical to consider
Florida as the most severe climate because it has all the
influencing parameters in high abundance all year round.
631
31
70
60
50
40
30
20
10
0
-10
-20
NbV
O C
Rainfall (in) ,I
LOUISVILLE, KENTUCKY
CLIMATE RANGE
100
90
80
+35
70
60
50
40
30
20
10
0
-I-
JAN FEB M,~R APR MAY JUN JUL AUG SEPT OCT NOV DEC
MONTHS
; Percent Sun ~
Rainfall (in)
which is sensitive in the range of 300 to 3000 nm. The ultraviolet is measured using a sensor that is sensitive in the range of
300 to 400 nm. The widely used Eppley Total UV Radiometer
(TUVR) (Fig. 22) has a sensing range of 295 to 385 nm. These
"total" sensors collect incoming radiation from all angles,
having a 180 ~ sensitive diffusion cover. This is termed hemispherical radiation. Total radiation measurements include
both the direct beam from the sun and the diffuse energy
from the atmosphere [15]. Direct beam radiation, excluding
the diffuse sky, is measured with a pyrheliometer such as the
632
,~..
97.co
9 6,3,$
/ /
/
4.'
Equipment Used
Total hemispherical
Total ultraviolet
Normal incidence
Solar Energy
Pyranometer (hemispherical) PSP
UV Radiometer (hemispherical) TUVR
Pyrheliometer (6 ~ solid angle) NIP
Ambient
Black panel
White panel
Sample temperature
Temperature
Thermometer
Black panel sensor RTD probe
White panel sensor RTD probe
Thermocouple attached to panel
Rainfall amount
Rainfall duration
Total wet time
Relative humidity
Wet bulb temperature
Wind speed
Salt aerosols
Sea water temperature
Air quality
Moisture
Rain gage
Heated wetness sensor (impedance)
TOW sensor (impedance)
Psychrometer or hygrograph
Thermometer (in wick)
Miscellaneous
Anemometer and wind vane
Wet candle
Floating thermometer
EPA measurements
633
634
ture of the sensor above the d e w p o i n t will also prevent cond e n s a t i o n from forming.
In a d d i t i o n to the specialized i n s t r u m e n t s detailed above,
m a n y m o r e recognizable p a r a m e t e r s m u s t be m e a s u r e d . Ambient t e m p e r a t u r e a n d relative h u m i d i t y can yield general
i n f o r m a t i o n c o n c e r n i n g the climate at the test site a n d the
c o n d i t i o n of the a t m o s p h e r e s u r r o u n d i n g the exposed specimen. These m e a s u r e m e n t s are m a d e following W o r l d Meteorological O r g a n i z a t i o n (WMO) practices with m e r c u r y therm o m e t e r s , psychrometers, o r - - m o r e c o m m o n l y - - r e c o r d i n g
h y g r o t h e r m o g r a p h s in a W M O shelter (Fig. 25). W i n d speed
is a factor in the cooling of p a i n t panels a n d is m e a s u r e d with
an a n e m o m e t e r . A r a i n gage (Fig. 26) collects rainfall to determ i n e the a m o u n t of precipitation. The rate of rainfall can be
important; 25 m m in 30 m i n can be quite different from the
effect of 5 m m in 2 h.
M1 of these d a t a can be collected a n d displayed in such a
m a n n e r as to c h a r a c t e r i z e a w e a t h e r i n g climate. If the influencing p a r a m e t e r s are c o m p a r e d , it is possible to convey the
severity of the w e a t h e r with respect to the exposed m a t e r i a l s
(Fig. 27).
EXPOSURE TYPES
Exposure Frames
CHAPTER 5 2 - - N A T U R A L W E A T H E R I N G
635
50
40
LU
,_J
30
r
20
10
0
2 3 4 5 6 7 8 9 10 11 12 13 14 1516171819202122
232425262728 293031
DAYS
I --I-- BLACK PANEL (C) -'t-SOLAR RADIATIONl ~
636
posited on the sample, the a m o u n t of time the sample remains wet from rainfall or dew, and the t e m p e r a t u r e of the
sample (Table 4). To generate meaningful test results, it is
i m p o r t a n t to expose specimens at an angle similar to end use.
The basic angles of exposure that are used m o s t c o m m o n l y
are as follows:
Maximum
White
Black
45
50
48
52
55
60
70
67
73
76
(32)
Minimum
White
Black
20
19
20
19
17
18
17
18
17
15
(20)
CHAPTER 5 2 - - N A T U R A L WEATHERING
637
FIG. 3 1 - P a n e l s on e x p o s u r e at 5 ~.
Orientation
638
P A I N T A N D COATING T E S T I N G M A N U A L
Tilt Angle
Latitude
Latitude
Latitude
Latitude
angle
angle - 20 ~
angle
angle + 20 ~
NOTE: Latitude angle = tilt angle equal to the latitude at the exposure
location.
o t h e r factor of influence was c o n c e n t r a t e d so heavily in a
different direction that it took p r e c e d e n c e over the solar
influence. This m a y be the case w h e r e m a r i n e a t m o s p h e r e
exposures are used a n d the s a m p l e faces the shoreline r a t h e r
t h a n south.
The m a j o r exception to the south exposures is found with
the testing of p a i n t s for residential use. Paint applied to
w o o d e n sidings is extremely susceptible to the effect of
m i l d e w attack, especially on the s h a d e d side of the house,
w h i c h is p r e d o m i n a t e l y m o r e conducive to fungus growth. A
vertical (90 ~) n o r t h exposure is c o m m o n for p a i n t e d w o o d e n
sidings. However, at times, equal m i l d e w g r o w t h on replicate
specimens has been observed by the a u t h o r on vertical (90 ~
south exposures.
Mounting
There are several different m e t h o d s for m o u n t i n g specim e n s onto a test frame. The type of backing chosen d e p e n d s
m o r e or less on the m a t e r i a l being tested a n d the end use
application. Generally, since m o s t paints are applied to a
wood, a l u m i n u m , or steel substrate, m o u n t i n g of specimens
is done on an o p e n - b a c k e d rack. However, if a s o m e w h a t
accelerated test is necessary or a s p e c i m e n m u s t be tested to a
p a r t i c u l a r standard, then m o u n t i n g specimens in a black box
m i g h t be necessary. A different m o u n t i n g technique w o u l d
apply to residential siding material. In this case, m o u n t i n g
against a w o o d e n backing w o u l d m o r e closely simulate end
use conditions.
A n o t h e r i m p o r t a n t criterion that can have an effect on the
o u t c o m e of an exposure test is the location a n d s u r r o u n d i n g
obstructions in the i m m e d i a t e a r e a of the test site. In accordance with ASTM Practice for A t m o s p h e r i c E n v i r o n m e n t a l
E x p o s u r e Testing of N o n m e t a l l i c Materials (G 7), the test
r a c k is to be p l a c e d in a l o c a t i o n so that no s h a d o w from a
n e i g h b o r i n g o b s t r u c t i o n shall fall on a n y s p e c i m e n w h e n the
sun's angle of elevation is greater t h a n 20 ~. Also according to
ASTM G 7, the a r e a b e n e a t h a n d in the vicinity of the weathering racks should be c h a r a c t e r i z e d by low reflectance a n d by
g r o u n d cover typical of that climatological area. In desert
areas this will be gravel, w h e r e a s in m o s t t e m p e r a t e areas the
g r o u n d cover will be low-cut grass.
Black Box
The first p a r a m e t e r n o r m a l l y modified w h e n there is a need
for acceleration is the test for s p e c i m e n t e m p e r a t u r e b e c a u s e
it is the easiest to control. There will be an increase in the rate
of the f o r w a r d d e g r a d a t i o n r e a c t i o n as the t h e r m a l l o a d is
increased.
The simplest w a y to increase the t e m p e r a t u r e is to p o s i t i o n
the s p e c i m e n on a solid backing of d a r k color with a high
insulation factor (R). This m e t h o d is widely used for residential sidings, roofing materials, a n d others. A c o m p a r i s o n of
the t e m p e r a t u r e s of black a n d white panels on various exposure frames on one s u m m e r day in F l o r i d a is shown in Table
4.
The black box exposure is used to test a u t o m o t i v e finishes,
a n d its specific p u r p o s e is to increase the t e m p e r a t u r e of the
test panels to the s a m e as the nearly h o r i z o n t a l surfaces of a
car. This test m e t h o d is d e s c r i b e d in ASTM Practice for Conducting Accelerated O u t d o o r E x p o s u r e Tests of Coatings
(D 4141). C o m m i t t e e DO 1.27 on Accelerated Testing of Paints
has c o n d u c t e d several studies r e g a r d i n g the black box [17],
w h i c h was originally developed by General Motors. The box
is m a d e of a l u m i n u m , p a i n t e d black, with the p a i n t panels
forming the top surface. The black box exposure also serves
to lower the panel t e m p e r a t u r e overnight b e l o w that of the
s u r r o u n d i n g air, creating a longer c o n d e n s a t i o n period.
The conditions as they affect the p a i n t panels are a good
s i m u l a t i o n of the actual end use condition, so this test m a y be
considered by s o m e n o t as an accelerated test b u t as one that
is realistic of the end use for that climate. If the definition of
an accelerated o u t d o o r test is one w h e r e the influencing
conditions are altered over the o p e n - b a c k e d direct weathering test, the Black Box Test is indeed a n accelerated test.
A further acceleration is i n t r o d u c e d using the H e a t e d Black
Box Test. This is a black box i n c o r p o r a t i n g heating elements
inside the air space. The air t e m p e r a t u r e inside the box is
m a i n t a i n e d at an artificially high level even w h e n there is no
incident solar energy.
CHAPTER 5 2 - - N A T U R A L W E A T H E R I N G
Salt Spray
In Florida, corrosion tests are accentuated by spraying with
salt water in the Scab Test. This uses the natural effects of the
weather to break down the coating, then increases the corrosion at a scribe mark.
The paint panels are exposed to direct weathering at either
45 or 5~ and are sprayed at regular intervals (normally twice
weekly) with a 5% sodium chloride solution (Fig. 33). The
spray is scheduled for times when the paint panel will be dry,
thus maximizing the absorption effect.
This test has proven to be an excellent method for determining the corrosion resistance of automotive coatings. The
advantage is that the results are very similar to the results of
actual car corrosion determined from field studies. The simultaneous effect of sunlight and saltwater produces an overall deterioration effect rather than a single failure mode as is
usually given by salt fog tests such as ASTM Test Method of
Salt Spray (Fog) Testing (B 117).
Spray Rack
The stresses due to moisture vapor content into and out of
the specimen are important for the overall breakdown of
most materials. Moisture vapor acts as a catalyst in the photochemical breakdown process. In Arizona's desert environment with high temperature and solar radiation, exposure
tests are accelerated using the spray rack, which wets the
specimens on a regular basis during the day and overnight.
The result produces an effect similar to Florida exposure,
plus a slight speedup in the deterioration rate. This rate of
increase has been seen as ranging from one to two times the
rate for direct weathering in Florida.
The exposure is conducted as a solid-backed direct weathering, with the specimens sprayed daily on a regular basis
during the night and/or day with distilled or deionized water.
639
The day-time spray is normally of very short duration, intended as a harsh thermal and moisture shock to the paint
surface. The nighttime spray cycles are of longer duration,
intended to soak the paint thoroughly in a simulation of the
overnight condensation effect. This occurs naturally very
rarely in the desert of Arizona.
Both of these accelerated outdoor tests recognize the importance that wetness plays in deterioration. One important
note here is that the timing of the water application is vital to
produce the correct type of failure.
640
Reporting Scales
W h e n evaluating the ability of a coating to w i t h s t a n d
w e a t h e r i n g effects, the changes over a p e r i o d of t i m e m u s t be
charted. To do this with consistency, r e p o r t i n g scales are
e m p l o y e d to r e c o r d the a m o u n t of change. In m a n y instances
it is not practical for the p e r s o n m o s t interested in the durability of a coating to see h o w a p a r t i c u l a r coating p e r f o r m s
over a p e r i o d of time. This is quite often the case as s p e c i m e n s
are exposed in a different c o u n t r y or region of the United
States in o r d e r to achieve answers in a s h o r t e r p e r i o d of time.
This m a k e s it necessary to leave the inspection process up to
a n o t h e r individual. A p r o b l e m is the fact that no two people
perceive a degree of change in exactly the s a m e way. In o r d e r
to m i n i m i z e this p r o b l e m , certain p r o c e d u r e s are followed so
that all interested parties will "'see" the defect(s) the same
way. This is done by using generally accepted e x a m i n a t i o n
p r o c e d u r e s a n d the use of p h o t o g r a p h i c reference standards.
The A m e r i c a n Society for Testing a n d Materials (ASTM),
the F e d e r a t i o n of Societies for Coatings Technology (FSCT),
a n d the I n t e r n a t i o n a l S t a n d a r d s Organization (ISO) each
have e x a m i n a t i o n p r o c e d u r e s similar in quantitative descriptions. The m a i n difference lies in the quantitative a n d qualitative n u m b e r i n g scales used. FSCT uses a scale from 10 to 0,
with 10 being "perfect" o r "absent of failures." ISO uses a
scale from 0 to 10, with 0 representing a n " u n c h a n g e d " condition. I n d e p e n d e n t test labs in the United States use the
ASTM/FSCT scale in their ratings unless i n s t r u c t e d otherwise
by their client. It should be n o t e d that "perfect" is not a
p r e f e r r e d term, a n d the testing labs will use the t e r m "as
received."
Failure Modes
Evaluating a n d recording type a n d degree of failure m o d e s
in a p a r t i c u l a r coating is not a difficult task if visual inspections are p e r f o r m e d properly. Although m o s t ratings are subjective in t e r m s of degree of failure, an experienced a n d wellt r a i n e d i n s p e c t o r consistent in his or h e r ratings is able to
p o r t r a y a good image of any d e g r a d a t i o n present. In o r d e r to
do this, all relevant s t a n d a r d s including the FSCT pictorial
s t a n d a r d s m u s t be used w h e n applicable. Table 6 lists the
m o r e c o m m o n l y u s e d evaluation s t a n d a r d s for p a i n t failure
ASTM Method
ASTM D 1729
ASTM D 4214
ASTM D 4214, TNO
ASTM D 3274
ASTM D 660
ASTM D 661
ASTM D 772
ASTM D 714
ASTM D 610
ASTM D 1654
ASTM D 662
ASTM D 2244
ASTM D 523
ASTM E 413
Nondestructive
Nondestructive testing is a i m e d at inspection w i t h o u t the
d i s t u r b a n c e of the integrity of the specimen. This will, by the
above definition, include mostly all the visual evaluations a n d
all the i n s t r u m e n t a l l y assisted optical m e a s u r e m e n t s . True
nondestructive testing, however, is a i m e d at investigating defects that c a n n o t be seen easily with the eyes or surface
s c a n n i n g equipment.
Nondestructive tests aim to d e t e r m i n e physical changes in
the structure of a m a t e r i a l that c a n n o t be d e t e r m i n e d visually. It is particularly useful in seeing changes at the molecular level, in the b u l k p a r t of the material, or in underlying
layers.
Many of the c o m m o n physical tests e m p l o y e d to assist in
evaluating the effect of w e a t h e r i n g are in fact "destructive,"
The p a i n t s a m p l e is d i s t u r b e d during the m e a s u r e m e n t process, as in testing a d h e s i o n or chalking. W h e n a destructive
test is used, several disadvantages are evident: the s p e c i m e n
c a n n o t continue exposure b e c a u s e the place w h e r e the test
was c o n d u c t e d will affect the continuity, a n d a p e r m a n e n t
r e c o r d of the c o n d i t i o n at that time is lost. These p r o b l e m s
can be overcome by using a large n u m b e r of replicates so t h a t
there will be enough virgin m a t e r i a l for testing.
W h e n the s a m e s a m p l e can be studied t h r o u g h o u t the test,
it m a y be easier to get a m u c h clearer picture of the sequence
of events of the p r o g r e s s i o n of failure m e c h a n i s m . This is
especially true at the earliest sign of changes in the material.
If it is possible to d e t e r m i n e the changes that o c c u r at the
m o l e c u l a r level during the initial stages of d e t e r i o r a t i o n a n d
follow the p r o g r e s s i o n t h r o u g h to failure, it is possible to
develop m o d e l s which will assist in p r e d i c t i n g long-term durability from s h o r t - t e r m testing.
The range of m e t h o d s i n c l u d e d in nondestructive testing is
varied, a n d Table 7 lists those which have b e e n d e m o n s t r a t e d
to have an a p p l i c a t i o n in weathering.
642
ASTMMethod
Electromagnetic
Strain gage
Infrared thermography
Electron microscopy
X-ray radiography
Ultrasonic holography
Video imaging systems
ASTM D 1186
...~
...a
...a
...a
...a
...~
ASTMMethod
Impact
Elasticity
Elongation
Bend
Hardness
Adhesion
Abrasion
Mar
Chip resistance
ASTM D 2704
ASTM D 522
ASTM D 522
ASTM D 3363
ASTM D 3359
ASTM D 4060
ASTM D 3170
Mechanical Properties
There is a m a j o r distinction that m u s t be made between
surface appearance changes in a material a n d intrinsic physical properties. Changes can occur on the surface without
affecting the bulk of the material.
A m a j o r portion of a complete weathering p r o g r a m is the
m e a s u r e m e n t of the physical changes produced during exposure. A result of UV degradation a n d associated failure modes
can have a direct impact on the relationship between stress
a n d strain of a coating and the elastic a n d inelastic reaction
w h e n force is applied. To have a better u n d e r s t a n d i n g of the
true performance of a weathered specimen, it is necessary to
perform tests to determine certain mechanical properties.
Table 8 lists the more c o m m o n l y performed m e c h a n i c a l tests
o n weathered p a i n t panels. A more complete description of
their relevance is given in other chapters of this m a n u a l .
REFERENCES
[1] Luckiesh, M., Artificial Sunlight, D. Van Nostrand Co., Inc., New
York, 1930.
[2] Searle, N.D., "Weathering," Encyclopedia of Polymer Science
and Engineering, Wiley, New York, 1989.
[3] Mathew, W. R., "Predicting the Effects of Weathering on Color,"
Plastics Engineering, May 1986.
[4] Bennett, I., "Monthly Maps of Mean Daily Insolance for the
United States," Solar Energy, Vol. IX, No. 3, July-September
1965.
[5] Juriaanse, A. and Zahradnik, B., "Natural Weathering of Polypropylene: Counteracting the Influence of Season and Exposure
Orientation," Proceedings, ANTEC, 1986.
[6] Auld, W. E., natural weathering engineering drawings, personal
copy, 1961.
[7] Fischer, R.M., Murray, W. P., and Ketola, W. D., "Thermal
Variability in Outdoor Exposure Tests," Progress in Organic
Chemistry, Fall, 1990.
[8] Kreese, P., "Influence of Inert Pigments on the Anti-Corrosive
Properties of Paint Films," Polymers Paint and Colour Journal,
1978.
[9] Lindberg, B., "Moisture and Painted Wood," Journal of the Oil
and Colour Chemists Association, June 1986.
[10] Evans, U. R., The Corrosion and Oxidation of Metals: Scientific
Principles and Practical Application, Arnold Publishing, London,
1960.
[11] Crewdson, M. J., "Corrosion Test Methods: A Further Review,"
National Coil Coaters Association Proceedings, April 1986.
[12] O'Neill, T.B., "Succession and Interrelationships of Microorganisms on Painted Surfaces," Journal of Paint and Coatings
Technology, Vol. 58, No. 734, 1986.
[13] Likens, G. E., "Acid Precipitation," Chemical and Engineering
News, November 1976.
[14] Crewdson, M.J., "The Present Status of Weathering in the
United States," Proceedings, Suga International Weathering
Symposium, October 1988.
[15] Zerlaut, G. A., "Solar Radiation Measurements: Calibration and
Standardization Efforts," Advances in Solar Energy, American
Solar Energy Society, 1982, pp. 43-66.
[16] Sereda et al., "Measurement of the Time of Wetness by Moisture
Sensors and their Calibration," Atmospheric Corrosion of Metals,
ASTM STP 767, 1982.
[17] Morse, M. P. in Permanence of Organic Materials, ASTM STP
781, ASTM, Philadelphia, 1982.
MNLI7-EB/Jun.
Accelerated Weatherin9
1995
53
by Valerie D. Sherbondy I
643
Copyright9 1995 by ASTMInternational
www.astm.org
644
and the UV-C region is 200 to 280 nm. Although the UV-C is
the most damaging region, these wavelengths are filtered out
by the atmosphere. Therefore, if light sources produced output in this region, they would cause abnormal degradation
and their use should be avoided when performing accelerated
weathering unless there is a possibility of UV-C exposure.
Both the UV-A and the UV-B regions cause degradation of
coatings. The energy of the shorter wavelengths present in the
UV-B region, - 9 1 to 102 kcal/mol (3.8 to 4.3 J/tool), cause
more severe and rapid degradation of coatings than the wavelengths in the UV-A region. In the UV-B region, the energy
levels are high enough to break carbon-nitrogen, carbon-carbon, nitrogen-hydrogen, carbon-oxygen, and carbon-hydrogen bonds in the polymeric portion of the coating. In the
UV-A region, the longer wavelengths do not have sufficient
energy, - 7 1 to 91 kcal/mol (3.0 to 3.8 J/tool), to break certain
bonds, namely carbon-hydrogen. Thus, it is apparent that
UV-A radiation differs from UV-B radiation in both wavelength and severity of damage.
The breaking of chemical bonds first leads to a degradation
of the coating surface layers and is manifested by chalking,
fading, and loss of gloss. Once the outer layers of polymer are
lost, pigments are exposed. Without the protective polymeric
binder, the pigments can fade and erode, causing a change in
color and/or appearance.
Light has been simulated in accelerated weathering devices
by mercury arcs, open and enclosed carbon arcs, fluorescent
lamps, and reflection of collected sunlight. However, as the
results produced by accelerated testing were compared to the
results obtained from natural weathering, the light sources
were modified to attempt to achieve similar results. Depending on the exact coating type and the service environment,
several different specifications have been developed that indicate which light source should be used. Most of these test
specifications require the use of open or "sunshine" carbon
arcs, xenon arcs, and fluorescent lamps. These light sources
were chosen since they were found to more closely simulate
the degrading ultraviolet light range of sunlight or to rapidly
produce dramatic changes in the coating.
E L E M E N T S OF W E A T H E R I N G
There are many component factors that contribute to the
weathering of a coating. The general components are light,
moisture, heat, and oxygen, which are always present in various amounts. This section concentrates on these general
components and on how they are simulated and intensified.
L i g h t [4]
The Electromagnetic
Spectrum
Ultraviolet
Schuman
I
0
I
100
t
I
200
.=
Ultraviolet
Infrared
,3
I
300
LI_
Visible
I
500
400
Wavelength--Nanometers
FIG. 1-The
electromagnetic
6
i
600
(nm)
spectrum.
n-
I
700
I
800
I
900
I
1000
645
Carbon
1.80 -
1.20-
o
Z
<
.80 - -
rr
tr
.40 - -
0.00
300
375
450
525
600
675
750
W A V E L E N G T H - nanometres
Xenon Arc
The a d o p t i o n of the xenon arc l a m p for accelerated weathering devices was the next i m p r o v e m e n t in artificial weathering equipment. The xenon l a m p consists of a b u r n e r tube a n d
a light filter system. There are two types of xenon arc lamps.
One type of xenon arc l a m p is cooled by w a t e r circulated
t h r o u g h the l a m p housing. The cooling w a t e r also filters out
the long-wavelength infrared light. The o t h e r type of xenon
l a m p is air cooled. Both l a m p types p r o d u c e a s p e c t r u m
closer to sunlight w h e n filtered a n d set at the correct irr a d i a n c e setting. There are several filters a n d c o m b i n a t i o n s of
filters that can be used. The three c o m m o n filter c o m b i n a tions used for artificial w e a t h e r i n g of p a i n t are quartz/borosilicate, borosilicate/borosilicate, a n d quartz/quartz. The first
c o m b i n a t i o n allows the UV region to extend d o w n to 270 n m
(Fig. 4). The borosilicate/borosilicate c o m b i n a t i o n has a cutoff at 280 nm, w h i c h makes the s p e c t r u m closer to t h a t of
2.00
X e n o n .35 / 340 n
Enclosed C a r b o n
1.80 - -
1.80 --
%
=
1.20
'~ 1 . 2 0 -
--
o
z
<
.80-
.40--
~
<
~
<
0.00
I
300
375
450
525
600
675
750
WAVELENGTH - nanometres
.80 -,
.40 o.0o
300
375
450
525
600
675
750
WAVELENGTH - nanometres
646
1.2
1.0
E
r-
0.8
0.6
0
t-
~5
I--
0.4
09
0.0
260
280
The most recent development in light sources is the fluorescent UV lamp. These lamps were not developed to simulate
the entire spectral range of natural sunlight. Rather, they
simulate only the damaging UV region found in sunlight.
Currently there are three types of fluorescent UV bulbs. The
FS-40 and UVB-313 produce light with a m a x i m u m output at
313 n m (Fig. 5)9 The UVB-313 has a higher intensity and thus
a greater weathering acceleration rate than the FS-40, The
UVB-313 also has a higher, more stable output than the
FS-40. Both of these lamps have outputs down to 275 nm,
which is below the cutoff of natural sunlight. The third type
of fluorescent lamp is the UVA-340 lamp that produces a
spectrum very similar to that of natural sunlight (Fig. 6). The
spectrum is made up of wavelengths in the UV-A region with
a small a m o u n t of the UV-B region wavelengths. The cutoff
matches that of natural sunlight. Although the results produced by the UVA-340 lamp are closer to that of sunlight, the
UVB lamp is the most widely used fluorescent light source
1.2
1.0
0.8
UVB-313 ~ j
0.6
0
t-
0.4
"0
t~
--
0.2
0.0
260
J
.-<,.
280
300
320
340
360
380
400
Wavelength (nm)
~-
300
320
340
360
380
400
Wavelength (nrn)
UV-B Lamps Compared to Summer Sunlight
U V B - 3 1 3 a n d FS-40
FIG. 5-UV-B lamps versus summer sunlight, Used with permission of the Q-panel Co.
Lamp Stability
Once a light source has been selected, it is assumed that
several tests run over a period of months or years can be used
to evaluate the relative performance of the paints 9 However,
this assumption is not always true. The xenon-arc source is
currently the only device that always is sold with the irradiance measurement as an operating parameter and not
just as an option. Even with this control, the output of the
light source m a y vary depending on the care and maintenance of the device9 The devices should be cleaned and
changed as r e c o m m e n d e d to ensure the most reproducible
and even spectral distribution and irradiance. The newer devices have the option of monitoring and adjusting the light
output for all of the different light sources. In the future,
these settings m a y become a required part of the report for
the testing results.
There are several monitoring instruments available to measure the light output including pyranometers, radiometers,
spectroradiometer, and light-sensitive materials 9 However,
each of these devices m a y be used to measure different characteristics of light9 Two different-colored light sources could
produce the same response if a pyranometer is used to measure the light. These devices measure the a m o u n t of radiant
power regardless of the spectral distribution. Even when filtered to restrict the wavelength of light being measured, it
was found that the response was not sufficiently sensitive for
the UV range.
Radiometers have been modified with filters to select areas
of the spectral distribution 9 These are classified as wide band,
broad band, or narrow band. The wide-band instruments
CHAPTER 53--ACCELERATED W E A T H E R I N G
measure the light output over a range of several hundred
nanometers. Broad-band instruments function over a range
of 20 to 100 nm, while narrow-band instruments measure
less than 20 nm. The most commercially successful radiometer measured the total ultraviolet light using a wide-band UV
filter. However, when these devices were used to measure
natural sunlight in comparison to the light sources, it was
found that sensitivity to shorter wavelength UV was less than
its peak sensitivity to visible light, which could be affected by
temperature changes.
The currently used radiometer, developed for exterior
monitoring, has a narrow band filter and a thermoelectrically
cooled detector. This is suited for long-term use and is easily
operated in the field by relatively inexperienced personnel.
For internal use and for the most accurate measurements,
spectroradiometers are available. These would not withstand
external use and normally require operation by skilled personnel.
In contrast to actual light measurements, there are industries, other than the paint industry, that rely on the use of
light-sensitive reference materials. The reference material is
placed on the cabinet at the same time as the test samples and
monitored, usually for color changes, to evaluate the effectiveness of the light source. These materials must be inherently unstable to achieve the desired result. This instability
should be considered when choosing a reference material.
The reaction of some materials may vary widely, and the
sensitivity is often a result of the total environment, so all of
the other factors of exposure must remain constant. One of
the major problems with using this technique in the paint
industry is the short life of these materials relative to the
more durable paint systems.
Even with all of the variability of light sources, proper care
of the instrument can yield consistent results between laboratories. Most of these instruments have been run for many
years with less monitoring and fewer quality-control procedures than are in use today, and the data have been acceptable over many years. This is due to the fact that most companies understand that the test results can only be used relative
to other test results and to that end often include several
competitive materials in the test protocol.
Moisture
Another important characteristic of weathering is moisture. Moisture is commonly overlooked as a significant factor
of paint degradation because it is a common belief that structures are only wet when it rains, when they are splashed, and
when they are immersed in fluids. Actual time-of-wetness
studies have shown that samples placed outside in several
different locations in the United States and Canada were wet
approximately 30% of the time [7]. This averages to approximately 8 h per day. The water in a natural environment is
caused by dew or condensation, rain, or melting snow or ice.
The water may be absorbed or pass through the coating. If the
liquid passes through and interacts or reacts with a watersoluble material, an osmotic cell may be formed. If it passes
through the coating and reacts with the substrate, for example wood, the interracial bond between coating and substrate
may be destroyed or weakened.
647
Temperature
The third factor of weathering is heat or temperature. The
degradation of coatings occurs more rapidly at elevated temperatures, and temperature variation can lead to expansion
and contraction stresses in the coating. These stresses may be
magnified by the expansion and contraction of the substrate
itself, which can lead to cracking, peeling, checking, or loss of
adhesion. Temperature can also accelerate the effects of
other weathering factors such as light and moisture. In accelerated weathering, cyclic testing at only slightly elevated temperatures can produce accelerated results. The temperature
chosen for testing should be within the expected temperature
range of the service environment. Drastic increases in temperature are not necessary to produce noticeable effects and
in fact should be avoided. Testing at excessive temperatures
can either cause premature or unreasonable failures or even
enhanced performance that would not be realized under actual use conditions. High temperatures may cause the coating to bake or cure excessively and cause it to become brittle
with decreased impact resistance, or it may become more
resistant to the environment than would occur if it were only
air dried under ambient conditions. To prevent these occurrences, temperatures near those of actual or expected exposure should be used. The temperature should be monitored so
the data have meaning relative to other test results.
Oxygen
Changing the degree of oxygen exposure of specimens by
introduction of ozone or pure oxygen is possible with a few
testing devices, but this modification technique is not commonly practiced. Oxygen exposure is usually inadvertently
changed in artificial weathering devices. The condensation,
fog, immersion, or water spray used to create moisture can
introduce oxygen to the test environment and the surface of
the panels. Even in natural weathering, oxidation of a coating
surface usually occurs in the presence of moisture.
648
Other Factors
Although light, heat, moisture, a n d oxygen play i m p o r t a n t
roles in the d e t e r i o r a t i o n process, it should be r e c o g n i z e d
t h a t there are o t h e r factors that affect coating stability.
W e a t h e r resistance is d e p e n d e n t on the curing or drying
process, the s u b s t r a t e being painted, a n d a p p l i c a t i o n methods. These conditions c a n n o t be fully s i m u l a t e d u n d e r controlled l a b o r a t o r y conditions since, as with n a t u r a l weathering, these conditions are s e l d o m the same.
In actual service, most coatings experience e n v i r o n m e n t a l
factors that often continually change, are not reproducible, or
are unforeseeable at the t i m e of application. E x a m p l e s are
acid r a i n or o t h e r transient e n v i r o n m e n t a l pollutants. Chemical exposure, p a r t i c u l a r l y in the vicinity of chemical plants or
o t h e r heavy industrial environments, can also c o n t r i b u t e to
degradation. Testing for c h e m i c a l resistance is discussed
elsewhere in the manual.
FIG. 7-Xenon arc weathering device used with permission of A.E.D. Co.
Fluorescent UV/Condensation
With fluorescent UV bulb devices as described in ASTM
Practice for Operating Light- and Water-Exposure Apparatus
(Fluorescent UV-Condensation Type) for Exposure of Nonmetallic Materials (G 53), specimens are cycled between exposure to UV light and condensation in a heated environment
(Fig. 8).
The light source for the QUV [8] and UV-CON [9] is composed of eight fluorescent lamps that produce light in the
ultraviolet range. The light source may be any of the UV
fluorescent bulbs produced. The particular bulb used will
determine the nature and speed of results acquired. The
649
exterior of the specimen rack is exposed to room temperature, and the ifiside is exposed to heat and humidity produced
by the lights and a heated water bath. The condensation is
caused by the temperature differential that exists between the
front and back of the mounted specimens. The exposure can
be varied by changing the temperature, the length of the lighL
and/or the condensation segments of the cycle. A few models
are also available with a spray option. The spray option can
be used to simulate thermal shock or erosion by water.
The samples are mounted in brackets, which form the
cabinet wall. The panels are stationary and set at an angle so
condensate can run off the test surface and be replaced by
fresh condensate in a continuous manner. Vents along the
bottom of the chamber permit an exchange of ambient air
and water vapor to prevent oxygen depletion of the condensate. The specimens are placed approximately 50 m m from
the lamps. Both the lamps and the panels should be manually
rotated at specified intervals to ensure even UV exposure. To
maintain consistent irradiance, the fluorescent lamps are
UV Light-Cyclic Immersion
A proposed ASTM method entitled "Standard Practice for
Conducting Cyclic Immersion/Atmospheric Exposure Tests"
is currently being developed. Its intended use is for the cyclic
testing of specimens, either manually or automatically,
through an atmospheric environment and an immersion environment. The atmospheric environment may consist of
light, heat, air, and/or chemical gases or fumes. The immersion portion of the cycle varies and is dependent on the construction material used to make the individual devices. In
addition, the liquid may be heated, cooled, oxygenated,
and/or filtered.
Cyclic exposure alternates wetting and drying of the samples in combination with UV light. The immersion portion of
the cycle allows permeation of the test liquid into the coating.
This imbibing of the test liquid may cause swelling of certain
coatings and substrates that would not occur during a salt fog
or condensation cycle. During the drying cycle, reverse permeation or evaporation may occur, causing the coating to
shrink and cause cyclic stressing/straining of the system.
Reactions during the immersion portion of the cycle are
influenced by the permeability of the coating and require
time to initiate. The rate of water/chemical degradation is
increased by increased temperature. However, long, hot exposures may cause abnormal degradation. The atmospheric
exposure after immersion may cause concentration of salts
and chemicals on the surface, further increasing the rate of
degradation. Care should be taken to select exposure media
that approximate those expected during intended service.
651
Fresnel Reflector
There are three methods for accelerating natural weather
exposure: black box, heated black box, and fresnel reflector.
These are described in ASTM Practice for Conducting Accelerated Outdoor Exposure Tests of Coatings (D 4141). The
652
EMMA,
EMMAQUA,
or
Ultrafast Weathering
In contrast to all of the above methods, this technique of
ultrafast w e a t h e r i n g does n o t wait for visual changes to occur
on the surface. At the present time, this m e t h o d is still being
evaluated to d e t e r m i n e if there is any correlation b e t w e e n the
i n f o r m a t i o n g a t h e r e d using electron spin r e s o n a n c e (ESR)
s p e c t r o s c o p y to m o n i t o r radical f o r m a t i o n a n d n a t u r a l
w e a t h e r i n g results [2]. The t h e o r y b e h i n d ultrafast weathering is b a s e d on the a s s u m p t i o n that the radicals w h i c h form
within the first several hours of the test will reveal the relative
stability of the coating. F o r this testing, the process of radical
f o r m a t i o n is i n d u c e d by ultraviolet r a d i a t i o n greater t h a n
t h a t of sunlight. The light is filtered to remove u n w a n t e d
s h o r t e r wavelengths a n d also focused on the s a m p l e using a
cooled mirror. The s a m p l e is placed b e t w e e n the poles of a
m a g n e t in the microwave r e s o n a t o r of the spectrometer. The
radical f o r m a t i o n is plotted as a function of light-exposure
time. E a c h p a i n t will p r o d u c e a characteristic curve. If a
correlation is f o u n d to exist, the curves of different paints are
then to be c o m p a r e d to d e t e r m i n e w h i c h exhibits the best UV
light stability. This testing could be c o m p l e t e d over several
hours instead of days, months, or years.
o~
]
1000
600
400
SPECTRAL REFLECTANCE
OF MIRRORS
90 LU~
O
85 Z
LL
kU
"~
E
c9 200
~,
34 ~ S GLOBAL
AIR MASS 1.35
100
-~
m"
zO
-<
a
~
__
>
D
rr
UV IRRADIANCE
AT TARG ET
rr
<
/~
.J
IJJ
O_
u)
60
40
DIRECT BEAM
AIR MASS 1.35
20
10
5
4
2
300
320
340
360
380
400
W A V E L E N G T H , nm
REFERENCES
[1] Kampf, G., Sommer, K., and Zirngiebel, E., "Studies in Accelerated Weathering. Part I. Determination of the Activation Spectrum of Photodegradation in Polymers," Progress in Organic
Coatings, Vol. 19, 1991, pp. 69-67.
[2] Sommer, A., Zirngieble, E., Kahl, L., and Schonfelder, M.,
"Studies in Accelerated Weathering. Part II. Ultrafast Weathering--A New Method for Evaluating the Weather Resistance of
Polymers," Progress in Organic Coatings, Vol. 19, 1991, pp.
79-87.
[3] Fischer, R.M., Ketola, W.D., and Morrey, W.P., "Inherent
Variability in Accelerated Weathering Devices," Progress in Organic Coatings, Vol. 19, 1991, pp. 165-179.
[4] Brennan, P. J. and Fedor, C., "Sunlight, UV and Accelerated
Weathering," SPEAutomotive RETEC, 1987, Technical Bulletin
L-822, The Q-Panel Company, 2600 First Street, Cleveland, OH
44145.
[5] Grossman, G., "Correlation of Weathering," Journal Coatings
Technology, Vol. 49, No. 633, 1977, pp. 78-82.
[6] Fischer, R., "Accelerated Test with Fluorescent UV-Condensation," SAE Technical Paper, No. 84/1022, 1984.
[7] Grossman, D. M., "Know Your Enemy: The Weather," Journal
Vinyl Technology, Vol. 3, No. 1, 1981, pp. 12-19 (also available as
a reprint from the Q-Panel Company).
[8] ASTM has found suitable devices available from Atlas Electric
Devices Co., 4114 Ravenswood Ave., Chicago, IL 60613 and
from Quartzlampen GmbH, 6450 Hanau/Main, Germany (domestic distributor is Batson Machinery, Inc., P.O. Box 3978,
Greenville, SC 28608).
653
[16] ASTM has found suitable devices available from the Q-Panel
Co., 26200 First Street, Cleveland, OH 44145.
[17] ASTM has found suitable devices available from Suga Test instruments Co., Ltd., 4-14 Shinjuku 5-chome, Shinjuku, Tokyo,
160, Japan.
[18] ASTM has found suitable devices available and used by DSET
Laboratories, Inc., Box 1850 Black Canyon Stage 1, Phoenix, AZ
85029 and at Sub-Tropical Testing Service, 8290 S.W. 120th
Street, P.O. Box 560876, Miami, FL 33156.
BIBLIOGRAPHY
Hamburg, H. R. and Morgans, W. M., Hess's Paint Film Defects and
Their Causes and Cure, 3d ed., Capman and Hall, London, 1979.
Reich, L. and Stivala, S., Elements of Polymer Degradation, McGrawHill, New York, 1971.
Slusser, J., Kinmonth, R., and Leber, R., Atlas Sun Spots, Vol. 18,
Issue 39, 1988.
MNL17-EB/Jun. 1995
Biological Deterioration of
Paint Films
by David L. Campbell 1
D E S C R I P T I O N OF T H E P R O B L E M
Water-borne liquid paints can experience viscosity loss, putrefaction, gas formation, color change, and pH drift as a
result of the degradation of some or all of the organic constituents [1]. This deterioration can be caused by bacteria or
fungi-releasing enzymes in the paint or by enzymes which
have been introduced into the paint through contaminated
raw materials or equipment. Viscosity loss in water-borne
paints can also be caused by the presence of oxidants/reductants in raw materials [2,3].
Micro- and macroorganisms can destroy both the decorative and protective properties of paint films. Algal and fungal
growth can cause discoloration of water- and solvent-borne
paint films and ultimately destroy their integrity (Figs. 1 and
2). The susceptibility of paint films to attack by microorganisms is determined in part by the chemical nature of the
nonvolatile binder, the choice of pigmentation, and the pigment volume concentration. To a much greater degree, however, the susceptibility or resistance of a paint film to biological attack is determined by the presence and concentration of
antimicrobial agents.
M I C R O O R G A N I S M S ASSOCIATED WITH
PAINT
Microorganisms associated with paint and paint films have
been well established. These organisms include bacteria,
fungi, and terrestrial algae.
The bacteria genera Pseudornonas, Aerobacter, Enterobacter, Flavobacterium, and Bacillus are frequently isolated from
spoiled paints [4,5]. Of these, the Bacillus are unique in that,
under conditions of stress such as heat, cold, or dehydration,
some are able to form spores which are resistant to high
temperatures and dry environments and more resistant to
bactericides. Opperman and Goll [6, 7] found anaerobic bacteria in contaminated water-borne paints and raw materials.
The aerobic culture methods commonly used would not detect the presence of these bacteria, which are capable of
utilizing organic paint components as nutrients.
Fungi are present on the surface of paint films in two
forms. They may be present as thread-like structures technically referred to as mycelia or as clusters of spherical, usually
black-colored, spores. These two different appearances of
IProject manager, Technical Center, Rust-Oleum Corporation,
8105 Fergusson Drive, P.O. Box 70, Pleasant Prairie, W153158-0769.
654
Copyright9 1995 by ASTMInternational
www.astm.org
655
Numerous fungi are found on and within paint films, although a few predominate. Goll and Coffey [8] were the first
to observe and report the wide-spread growth of
Aureobasidium pullulans. In isolation studies of oil and alkyd
paint films at six wide-spread geographical locations,
Rothwell [9] confirmed the predominance of Aureobasidium
puUulans but noted the close resemblance of, and predominance in certain geographical areas of Cladosporium species
(sp.). Other fungi frequently isolated include Ahernaria
dianthicola and Phoma pigmentivora. The same studies indi-
656
D E T E R M I N I N G T H E P R E S E N C E OF
FUNGAL OR ALGAL G R O W T H ON PAINT
FILMS
When doubt exists as to whether the defacement is due to
algae, fungi, or dirt, the surface can be examined using magnification of 10 to 100 to distinguish among fungal, algal,
or dirt disfigurement as described in the ASTM Test Method
for Evaluating Degree of Surface Disfigurement of Paint
Films by Microbial (Fungal or Algal) Growth or Soil and Dirt
ANTIMICROBIAL A G E N T S
Chemical agents used to control or prevent the deteriorating effect of microorganisms are referred to as microbistats if
they do not kill microorganisms but prevent their reproduc-
C H A P T E R 5 4 - - D E T E R I O R A T I O N OF P A I N T F I L M S
tion and as microbicides if they kill microorganisms. Most of
the microbistats and microbicides used in paint films effectively control fungi, algae, and bacteria by interfering with
their metabolic functions.
Table 1 lists more frequently employed antimicrobial
agents used in paints as bactericides, algicides, or fungicides
as r e c o m m e n d e d by the manufacturers.
Microorganism
ATCCNumber
ASTM D 2574
Method 627 la
Nuodex
Hutchinson
Pseudomonas aeruginosa
Aspergillusoryzae
Aureobasidium pullulans
Aspergillus
flavus
AspergiUus niger
PeniciUium funiculosum
Aureobasidium pullulans
Aspergillus niger
Penicillium citrinum
10145
10196
9348
9643
9642
9644
9348
9642
9849
ASTM D 3273
DETERMINING MICROBIOLOGICAL
R E S I S T A N C E OF P A I N T S
The microbial resistance of paints and paint films is an
important characteristic of such paints, and considerable attention has been given to developing laboratory and field tests
that will predict the resistance of paints to biodeterioration.
Some of the tests require the use of pure culture microorganisms. Those employed are listed in Table 2 and m a y be obtained from: American Type Cultures Collection, 12301
Parklawn Drive, Rockville, Maryland 20852. Many tests
FUNGICIDES
diiodomethyl-p-tolylsulfone
barium rnetaborate
2 -n-octyl-4-isothiazolin-3 -one
potassium dimethyldithiocarbamate
methylene bis(thiocyanate)
2-(thiocyanomethylthio) benzothiazole
2-(4-thiazolyl)benzimidazole
N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide
zinc dimethyldithiocarbamate
zinc 2-mercaptobenzothiazole
3-iodo-2-propynyl butyl carbamate
tetrachloroisophthalonitrile
N-(trichloromethylthio)phthalimide
tributyltin benzoate
tribntyl tin salicylate
tributyltin oxide
zinc oxide
BACTERICIDES
tributyltin oxide
tributyltin benzoate
barium metaborate
potassium dimethyldithiocarbamate
p-chloro-m-cresol
alkylamine hydrochlorides
6-acetoxy-2,4-dimethyl- 1,3-dioxane
tetrahydro-3,5 -dimethyl-2H- 1,3,5,-thiadiazine-2-thione
2 (hydroxymethyl)amino ethanol
1,2-dibromo-2,4,-dicyanobutane
1-(3-chloroallyl)-3,5,7-triaza- 1-azoniaadamantane chloride
hexahydro- 1,3,5-triethyl-5-triazine
2-(hydroxymethyl)amino-2-methyl-1-propanol
4-(2-nitrobutyl)morpholine
3,4,4-trimethyloxazolidine
4,4-dimethyloxazolidine
5-chloro-2-methyl-4-isothiazolin-3-one
2-methyl-4-isothiazolin-3-one
1,2-benzisothiazolin-3 -one
1,3-bis(hydroxymethyl)-5,5 -dimethylhydantoin
hydroxymethyl-5,5-dimethylhydantoin
657
658
Ingredient
NaNO3
NH4NO3
NH4SO4
KCI
MgSO4. .
7H20
KH2PO4
K2HPO4
Agar
Glucose
Sucrose
Malt
extract
Tryptone
Beef extract
H20 to
make
-..
. .
. .
...
Federal
Test
Method
6271
.
.
.
3.0
.
. .
0.25
0.5
Malt
Agar~
.
.
.
g
g
. . . . . .
.-.
1.0 g
15.0 g
15.0 g
1.0 g
. .
-..
30.0 g
. . . . . .
5.0 g
3.0 g
1000 mL
.
.
.
.
1000 mL
.
.
.
.
Hutchinson
...
...
.
.
.
.
.
.
.
.
. .
1.5 g
Zabel
.
.
...
1.47 g
...
0.5 g
0.5 g
0.5 g
. . .
...
1.0 g
15.0 g
15.0 g
. . . . .
. . . . . . . . .
30.0 g
. . . . .
.
.
.
.
1000 mL
.
.
.
.
.
.
.
.
.
.
1000 mL
10.0
0.5
15.0
10.0
g
g
g
g
.
.
1000 mL
aPrepared Tryptone-GlucoseExtract Agar and Malt Agar may be obtained from Difco Laboratories, Inc.,
Detroit, Michigan,and Baltimore BiologicalLaboratories, Inc., Baltimore, Maryland.
organism, a n d observing growth during a prescribed incub a t i o n period.
Nuodex Method
I n order to improve the accuracy of the mildew test as
required by the exterior p a i n t Federal Specification TT-P-19,
Nuodex laboratories modified the test as follows: Aureobasidium pullulans replaced Aspergillus oryzae because it is
the fungus most frequently isolated from exterior house
paints. Malt-extract agar replaced the sucrose-mineral salts
agar because, in it, A. puUulans exhibits growth forms typically observed o n exterior paints rather t h a n yeast-like forms
that it exhibits w h e n grown o n the sucrose-mineral salts agar.
Hutchinson Method
The H u t c h i n s o n Method [14] is similar to the Federal
Method 6271, b u t employs glass string rather t h a n filter paper
as the p a i n t substrate, a liquid broth culture m e d i a containing no c a r b o n source a n d a mixed s u s p e n s i o n of AspergiUus
niger, AspergiUus flavus, a n d PeniciUium funiculosum.
Zabel Test
The Zabel Test [15] was developed to overcome the difficulty in achieving the growth of Auseobasidium pullulans in
the ASTM environmental chamber. The procedure involves
five major steps: (1) the preparation and treatment of partially painted wood specimens; (2) the preparation of stain
chambers; (3) sterilization of the specimens and assembly in
the stain chambers; (4) inoculation of the painted wood and
incubation; and (5) disfigurement evaluation.
Stain Chambers
The stain chambers are screw cap 16-oz French square
bottles. These are vertically positioned, and 20 g of vermiculite are added.
The agar medium is prepared according to the formula
shown in Table 3. A micronutrient solution is prepared as
follows: Fe(NO3)3.gH20, 723.5 rag; ZnSO4.7H20, 439.8 mg;
and MnSO4.4H20, 203.0 mg; dissolved in 600 mL of double
distilled water, cleared of precipitate with H2SO4 (CP grade),
and made to a final volume of I L. The micronutrient solution
is added to the nutrient media in amounts of 2 mL per liter.
The micronutrient-enriched nutrient media is then poured
into the vermiculite-containing stain chambers (100 mL per
chamber). A small square of filter paper is placed on the
surface to minimize vermiculite displacement during the
pouring, then removed.
Disfigurement Evaluation
Blue stain development in the wood and fungus growth on
the paint are observed and recorded weekly.
Insect-Resistant Paints
While insects do not pose a deteriorative threat to paints or
paint films, their attachment to paints following application
and prior to the hardening of the paint film presents a serious
decorative problem in many geographical areas. Thus, insectresistant paints are requested continuously, and tests measuring this property are needed. The best-known test for measuring insect resistance of paints is that devised by Westgate
660
P A I N T AND COATING T E S T I N G M A N U A L
REFERENCES
[1] Howard, P.H., Saxema, J., and Durkin, P. R., "Review and
Evaluation of Available Techniques for Determining Persistance
and Routes of Degradation of Chemical Substances in the Environment," EPA Report No. 560/5-75-006, 1975, p. 474.
[2] Winters, H. and Goll, M., "Nonenzymatic Oxidative Degradation
of Hydroxyethyl Cellulose Thickened Latex Paints," Journal of
Coatings Technology, Vol. 48, No. 622, November 1976, pp.
80-85.
[3] Winters, H., "Viscosity Loss in Cellulosic Ether-Thickened Latex
Paints Caused by Oxidant/Reductant Impurities," Journal of
Coatings Technology, Vol. 52, No. 664, May 1980, pp. 71-76.
[4] Winters, H., "Synthesis of Extracellular Cellulases in Aqueous
Emulsion Coatings by Pseudomonads," Journal of Paint Technology, Vol. 44, No. 575, December 1972, pp. 39-46.
[5] Buono, F., Stewart, W. J., and Freifeld, M., "Evaluation of Latex
Paint Preservatives," Journal of Paint Technology, Vol. 45, No.
577, February 1973, pp. 43-53.
[6] Opperman, R. A. and GoU, M., "Presence and Effects of Anaerobic Bacteria in Water-Based Paint. I," Journal of Coatings Technology, Vol. 56, No. 712, May 1984, pp. 51-54.
[7] Opperman, R. A., "Presence and Effects of Anaerobic Bacteria
in Water-Based Paints. II," Journal of Coatings Technology, Vol,
57, No. 730, November 1985, pp. 33-38.
661
[8] Goll, M. and Coffey, G., "Mildew on Painted Surfaces," Paint, Oil
and Chemical Review, POCRA, Vol. 111, No. 14, 1948.
[9] Rothwell, F. M., "Microbiology of Paint Films, IL Isolation and
Identification of Microflora on Exterior Oil Paints," Official Digest, Federation of Paint and Varnish Production Clubs, ODFPA,
Vol. 30, 1958, p. 368.
[10] Drescher, R. F., "Microbiology of Paint Films, IV. Isolation and
Identification of Microflora on Exterior Emulsion Paints," American Paint Journal, APJOA, Vol. 42, No. 38, 1958, pp. 80-102.
[11] Krumperman, P. H., "Microbiology of Paint Films, V. Microorganisms Found on the Interior Paint Films of Food Processing
Plants," American Paint Journal, APJOA, Vol. 42, No. 38, 1958, p.
72.
[12] Skinner, C. E., "The Role of Algae in the Deterioration of Decorative and Marine Paints," Paint Research Association, Teddington, Middlesex, England.
[13] Drisko, R. W. and Crilly, J. B., "Control of Algae Growth on
Paints at Tropical Locations," Journal of Paint Technology, Vol.
46, No. 595, August 1974, pp. 48-55.
[14] Hutchinson, W. G., "The Use of Glass String as a Carbon-Free
Substrate for the Rapid Evaluation of Fungus Resistant Paints,"
Report 5687, Office of Scientific Research and Development, 31
Oct. 1945.
[15] Zabel, R.A. and Homer, W. E., "An Accelerated Laboratory
Procedure for Growing Aureobasidium pullulans on Fresh Latex
Paint Films," Journal of Coatings Technology, Vol. 53, No. 675,
April 1981, pp. 33-37.
[16] Westgate, M.W. and Bolton, A. N,, Jr., "Testing Insecticidal
Paints," Scientific Section Circular, National Paint, Varnish and
Lacquer Association, No. 715, 1946.
MNLI7-EB/Jun.
1995
Chemical Resistance
by Alan H. Brandau 1
STAINING
Staining tests provide a thorough method of determining
the ability of a coating to resist staining from household
chemicals, chemical reagents, and other materials c o m m o n
in today's environment. The tests generally expose the coating surface to a spot of the reagent on the coating surface or
by immersion of a coated test panel in the reagent for a
specified period with timed check points.
662
Copyright9 1995 by ASTM International
www.astm.org
CHAPTER 5 5 - - C H E M I C A L R E S I S T A N C E
663
SOLVENT/FUEL RESISTANCE
ASTM D 2792, Test Method for Solvent and Fuel Resistance of Traffic Paint, relates a method of evaluating the resistance of a coating to solvent and fuel that causes blistering,
wrinkling, loss of adhesion, and loss of hardness. The coating
is applied to tin panels and air dried for 90 h. Half the panel is
immersed in the test liquid, and the vessel is covered for a
period of 4 to 18 h as may be specified by the customer. The
panels are then removed and examined for defects. The panels are allowed to dry for another 24 h and reexamined for
film defects and softening as compared to the unimmersed
portion of the control panel.
If subtle differences between coatings are important such
as comparative research and development efforts, then the
panels can be examined more often without drying at intervals such as 1, 2, 4, 6, 24, and 48 h.
664
_ _~__;_~_: IZ ~ - - ~ -
3-' 2
=t~J
->~,
t
t
5"
"~[
Fl
--.Iii/ ) ~ i
Wood
~,
Cork
Stopper
I/4"Dowel
Pins
I by 6" Test
Tube
I-Liter ChemicallyResistont Gloss
Beaker
300 ml of Na OH
Solution to this Level
&
l
FIG. 4-Distensibility test for solvent resistance.
(Courtesy of F. M. Ball.) A = specimen clamp; B =
tensile specimen strip; C = alligator clip and weight; D
= one inch distance marking.
solvent is poured over the film, and the length of time required to puncture the film is noted. This test would be considered a crude screening test. More precise data can be
derived from the distensibility test where a tensile strength
strip (see ASTM D 2370.8) is clamped with either a tensile
tester jaw or an alligator clip on the upper end, and the
bottom end is clamped with an alligator clip with a 12-g
weight and immersed in a clear beaker containing the solvent
reagent (Fig. 4). The beaker is immediately marked with the
initial length, and the time required to elongate the strip one
inch is recorded.
provides a quick relative test without having to wait for exposure results. The MEK resistance of some two-component
ethyl silicate zinc-rich primers has been shown to correlate
well with the cure of the primer as determined by diffuse
reflectance infrared spectroscopy.2
ACID R E S I S T A N C E
Acid resistance is determined by exposing a coated panel to
freshly prepared mortar as well as a hydrochloric acid solution and is fully described in ASTM D 3260, Test Method for
Resistance to Acid and Mortar of Factory-Applied Clear Coatings on Extruded Aluminum Products. The acid resistance
test is performed by first sealing the edges of a specially
coated panel with a paraffin and beeswax mixture and then
FIG. 6 - Q
panel is
scored with an "x" to expose bare substrate.
II]
~=::1
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+o
1
-
li-
+-"
665
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;'
",'~,
2O
)..+t 12A
ao
+16
ALKALI A N D D E T E R G E N T R E S I S T A N C E
ASTM D 1308, Test Method for Effect of Household Chemicals on Clear and Pigmented Organic Finishes, is also recommended for evaluating alkali and detergent resistance. It is a
simple common sense technique that can be used for many
materials or chemicals that can stain or discolor a coating.
The choice of testing materials should be related to the coatings end use. As previously mentioned, ASTM D 1308 describes techniques for either immersing the coated substrate
in the reagent, putting a small amount of the material on the
666
WATER A N D M O I S T U R E R E S I S T A N C E
There are a n u m b e r of types of chambers such as moisture
chambers, salt fog cabinets, and other accelerated weathering equipment that tests coating moisture resistance as well
as other resistance criteria. This type c h a m b e r is useful for
spot checking accelerated long-term environmental durability. But to be practical, all that is needed to test moisture or
water resistance is to partially immerse a coated sample in a
glass beaker containing water. The water is maintained at
100~ (37.7~ for an extended period of time, and the panels
are periodically checked for discoloration, whitening, or blistering of the film. The test results are compared to a specification or a standard sample run concurrently. The procedure
for this test is ASTM D 870, Standard Practice for Testing
Water Resistance of Coatings Using Water Immersion.
REFERENCES
SALT FOG T E S T
Salt fog resistance is important for marine, automobile,
and aircraft coatings and any other exterior coating exposed
to salt spray by being near the ocean or exposed to salted road
conditions. The severe corrosion caused by salt is well
known. The test requires a salt fog cabinet and coated panels.
The coating is scored to the bare substrate with a X shape
(Fig. 6). The edges are sealed with a weather-proof tape, and
the panel is placed in the cabinet for a specified period of
[1] Lambourne, R., Ed., "Paint and Surface Coatings: Theory and
Practice," John Wiley and Sons, New York, 1987, pp. 664-671.
[2] Nowacki, L. J., "Protective Linings for Steel Shipping Containers," Corrosion, CORRA, Vol. 14, 1958, p. 100.
[3] Hough, R. W., Chairman, "The Bratt Conductivity Cell for Measuring Chemical Resistance," Official Digest, Federation of Paint
and Varnish Production Clubs, ODFPA, Vol. 31, 1959, p. 1460.
[4] Gearhart, W. M. and Ball, F. M., "Half-Second Cellulose AcetateButyrate: IV," Official Digest, Federation of Societies for Coatings
Technology, Vol. 31, 1959, p. 1460.
MNL17-EB/Jun. 1995
HEAT RESISTANCE
degradation including rust formation, blistering, loss of adhesion, dulling, and ~chalking.
tures, the initial effect is usually softening, followed by hardening, embrittlement, and degradation. The rate of response
and the extent of degradation depend on coating composition, temperature, and length of exposure. There is a distinction in the terminology used to define the resistance of coatings to such changes. Below 400~ (200~
the property is
called "thermal resistance," while above that temperature the
property is identified as "heat resistance." Both thermal and
heat resistance relate not to occasional heating, but to resistance to change from exposure to a constant heat influence
over months or years. Special organic coatings can be formulated to provide thermal resistance, such as those designed to protect steel surfaces exposed to elevated temperature during service life. The upper temperature limit for most
organic coatings is in the range of 400~ (200~ In general,
inorganic coatings exhibit better heat resistance than organic
coatings. A special group of products are thermal protection
coatings, including ablative coatings to protect space vehicles
during atmospheric re-entry and intumescent coatings that
protect wood or other cellulosic surfaces exposed to fire.
Evaluation of heat resistance is carried out on coated specimens exposed to selected temperatures representative of service conditions and later subjected to other exposure conditions to determine susceptibility to loss of protective function.
ASTM M e t h o d D 1211
Another test method involving temperature exposure is
ASTM Test Method for Temperature-Change Resistance of
Clear Nitrocellulose Lacquer Films Applied to Wood (D
1211). A common failure of clear films applied to wood is
cracking or checking that may occur over a period of time,
either with the grain or at an angle to the grain. This "cold
check" test is designed to accelerate the occurrence of checks
or cracks by cycling at the temperatures of exposure. In this
procedure, which constitutes a single cycle, lacquer-coated
wood panels are first subjected to a temperature of 120 5~
(48.9 + 2.8~ for 1 h, followed by exposure at - 5 - 2~
( - 21 l~ for 1 h, and then a return to room temperature
for 30 min. The number of cycles used is a decision by the
testing agency.
FLAME RETARDANCE
Terminology
The technical terminology relating to flame retardance
must be understood. The general concept concerned is
burning characteristics. (With one exception [1], these standard definitions are found in ASTM Terminology of Fire
Standards (E 176). Several interrelated terms are:
9 fire performance test--A procedure that measures the response of a material, product, or assembly to heat or flame
under controlled conditions. A fire performance test allows
the quantitative description of one or more fire performance characteristics for the specific fire and other parameters of the test.
9 fire resistance--The property of a material or an assemblage
to withstand fire or to provide protection from it.
9 fire retardancy--In paint, this is the ability of a paint to
retard the spread of flame over a coated suhstrate, usually
at the sacrifice of the paint film.
9 fire-retardant coating--A fluid-applied surface covering on a
combustible material that delays ignition and combustion
of the material when the coating is exposed to fire.
o flame resistance--The ability to withstand flame impingement or give protection from it.
9 flame-retardant coating--A fluid-applied surface covering
on a combustible material which delays ignition and re-
ASTM M e t h o d D 2 4 8 5
Typical of this kind of testing is ASTM Test Methods for
Evaluating Coatings for High-Temperature Service (D 2485).
This method provides an accelerated means of determining
performance when coatings are exposed to high temperatures. In Method A, for interior service coatings, coated steel
panels are heated for 24 h in a muffle furnace at a selected
temperature. One panel is plunged immediately into water
for thermal shock, while another is cooled and then subjected
to a bend test. In Method B, for exterior service coatings,
coated steel panels are heated in a muffle furnace at increasing steps of temperature from 400 to 800~ (205 to 425~
One panel is subjected to salt spray for 24 h, while another is
exposed outdoors for twelve months. When test exposures are
completedelhe panels are examined and evaluated for film
~Deceased, formerly of Harleysville, PA.
667
Copyright9 1995 by ASTMInternational
www.astm.org
668
P A I N T A N D COATING T E S T I N G M A N U A L
A S T M Method D 2863
ASTM Test Method for Measuring the Minimum Oxygen
Concentration to Support Candle-like Combustion of Plastics
(Oxygen Index) (D 2863) is a small-scale method that measures the minimum concentration of oxygen in a flowing mixture of oxygen and nitrogen that will just support flaming
combustion. Figure 2 shows the typical equipment layout.
Film or thin-sheet test specimens are nominally 2.0 in (52
T H E R M O C O U P L E LEADS T3AND T,
(THERMOCOUPLE T= PLACED AT
I t~P.ATI~hl r T 1=r IMITIAI
THERMOCOUPL
(204ram DOWN)
TERMINALS FOR 5(
NICHROME WIRE
~ES
~,L
ER
HIGH TE
INSULA1
l CYLINDER
YLINDER
:~COVER
SPACING AND SU
(3) FOR INNER C~t
METAL RING
Inch-Pound Equivalents
mm
in,
76
3
102
4
152
6
FIG. 1 - C r o s s
254
10
section of furnace assembly.
273
10-V4
6.4 cm 2
1 in.2
1.29
No, 16 Awg
METAL SHROU
A~
GLASS COLUMN
SECTION A - A
OPTIONAL DEVICE FOR
RESTRICTING COLUMN
OPENING (SEE NOTE 3)
E NOTE 5)
1.
2.
3.
4.
5.
BurningSpecimen
Clampwith Rod Support
Igniter
Wire Screen
Ring Stand
6.
7.
8.
9.
10,
11.
12.
13.
14.
15.
PressureGage
PrecisionPressureRegulator
Filter
NeedleValve
Rotameter
669
670
mm) wide and 5.5 in. (140 mm) long. The minimum oxygen
concentration is measured under equilibrium conditions of
candle-like burning. The equilibrium is established by the
relation between the heat generated from the combustion of
the specimen and the heat lost to the surroundings as measured by one or the other of two arbitrary criteria, namely, a
time of burning or a length of specimen burned. This point is
approached from both sides of the critical oxygen concentration to establish the oxygen index.
While this method is useful for comparing resistance to
combustion of organic materials, correlation with burning
characteristics under actual use conditions is not implied.
Precision: In a testing program in which 18 laboratories
checked the same five materials, the standard deviation was
0.4 for materials with an oxygen index below 21% and 0.7 to
1.4 for materials with an oxygen index above 21%. Table 1
contains results from another test series. Bias: There are no
recognized standards on which to base an estimate of bias.
A S T M Method D 1360
ASTM Test Method for Fire Retardancy of Paints (Cabinet
Method) D 1360 is a small-scale test method. This procedure
measures the relative fire-retardant properties of coatings by
determining the weight loss and char index of coated wood
panels exposed to flaming ethyl alcohol. It is useful for comparing the burning behavior of coating materials under specified conditions; however, the test results do not always correlate with large-scale spread-of-flame tests, such as ASTM Test
Method for Surface Burning Characteristics of Building Materials (E 84). D 1360 is a measure of combustibility, through
weight loss, rather than a measure of flame-spread index
value. The precision of this method is yet to be determined.
Laboratory-To-Laboratory
Standard Deviation
B
C
D
0.5 to 1,1
0.4 to 1.5
0.5 to 1.4
Within Laboratory
Standard Deviation
Below 0,2
0.1 to 0.3 (est.)
Below 0.6
The method is useful in laboratory comparison of intumescent paint formulations, but large-scale testing by
Method E 84 is desirable for correlation with real fire conditions. Precision: Table 2 indicates the repeatability of this
method. The standard deviation shown relates to the maximum difference that would be expected between duplicate
specimens. The degree of repeatability is dependent on the
level of flame-spread ratings.
A S T M Method E 162
ASTM Test Method for Surface Flammability of Materials
Using a Radiant Heat Energy Source (E 162) is a small-scale
procedure, intended for research and development purposes,
for measuring the surface spread of flame under exposure to
a radiant heat source. Figure 4 shows details of the test equipment. The specimen, which is representative of the material
or assembly being evaluated, has dimensions of 6 by 18 in.
(150 by 460 mm) by the sheet thickness. It is placed at a
downward angle of 30~ from the vertical, facing a gas-fired
porous refractory heat-radiating surface, 12 by 18 in. (300 by
460 mm), operating at 1238~ (670~
The rate at which
flames travel along the surface depends on the physical and
thermal properties of the specimen. The orientation of the
specimen is such that ignition is forced near its upper edge
and the flame front progresses downward. The time of arrival
of the flame front at each of 3-in. (76-mm) marks on the
specimen holder is recorded, and observations are made for
flashing, dripping, and any other behavior characteristics
that appear to be of interest. The maximum temperature rise
as indicated by thermocouples in the stack is recorded. The
test is completed when the flame front has progressed to the
15-in. (380-mm) mark or after an exposure of 15 rain, whichever occurs first, provided the maximum temperature of the
stack thermocouples is reached.
A flame-spread index, I~, is calculated as the product of the
flame-spread factor, Fs, and the heat evolution factor, Q. F~ is
calculated from a plot of
I s = FsQ
with vertical distance as a function of flame-arrival time at
each horizontal mark. The Q factor is calculated from the
equation Q ~ CT//3, where C is an arbitrary constant, T is the
observed maximum stack-thermocouple temperature difference between the temperature-time curve for the specimen
and that for a similar curve of a calibration specimen, and/3 is
the mean stack thermocouple rise for unit heat input of a
calibration burner. The flame-spread indices determined by
this method may be compared with those determined in
ASTM Method E 84, although correlation is not necessarily
obtained. A precision and bias statement for this method is
being developed by ASTM Committee E-5 on Fire Standards.
A S T M Method E 84
ASTM Test Method for Surface Burning Characteristics of
Building Materials (E 84) is also called the 25-ft (7.6-m)
tunnel test, or the Steiner tunnel test, or the NFPA 255 test. A
large-scale test, E 84 is applicable to exposed finishes on
ceilings or walls. The test is conducted with the material in a
horizontal position with the exposed surface facing downward. The purpose of the test is to determine the relative
671
Item
A
B
C
D
Base Plate
Framework
Side and Front Panels
Side Glass
Burner
Gas Control Valve
(not shown)
Gage, Gas (not shown)
Item No
Item
F
G
H
I
Glare Shield
ignition Transformer
Spark Switch
Ceramic Insulator
J
K
Spark Wire
Thermocouple
1Ae OD Nichrome
Megopak Type J, totally shielded
M,,,e,"'- M-
\liil~r,,.
/"1
-"d
- k - 2 1/4
Description
Description
K J"lJ,,ft" 3.
TO 115 V.
SECTION A ~ A
A,-.
73;,8 II v
TO 3 oz./in 2
FRONT VIEW
in.
%e
3/a2
l/a
1/4
i/=
1
11/z
21/4
2z/4
101/2
SIDE VIEW
METRIC EQUIVALENTS
mm
in.
1.6
3
2.4
4
3.2
7
6.4
7`%
12.7
10
25.4
101/2
38
18-%
57
22
70
24
FIG. 3 - F l a m e
tunnel.
mm
76
102
178
187
254
267
480
560
610
Type J concl
IT
It ";'1
=J
REAR VIEW
672
Flame-Spread Ratings
StandardDeviation
Coefficientof Variation
0 to 25
25 to 75
75 to 135
0 to 135
1.2
3.1
3.65
2.85
9.6
6.2
3.5
4.6
|I
k..--~9 -~--j_
Location of Thermo-
45" E
.....
4 ......
.....
-t .......
~ -
13 by 19in. Radiant
Panel 12by 18in.fl
Radiating Surface
~--~
Reducing
,--/
;tar
~4b
Traverse R o d s ~ ( 2 ) ~
2.8;n. Water
~ ~
)e Topped
For Gas
from
afar
an(
2 by2
Steel $
rte Valve
Filter f
Rodi
F .........
Metric Equivalents
in.
mm
in.
0.040
1/2
1.0
12.7
16.0
22.2
44
51
64
71
102
111
121
6
9v2
18
19a/8
3/4 by 3/,
1'/2 by 1'/,
12 by 18
13 by 19
2 by 2 by 1/8
0.050 by 201/4 by 36
rye
7/a
13/,
2
21/2
2.8
4
43/s
43/,
mm
152
241
457
492
19.2 by 19.2
38 by 32
305 by 457
330 by 483
51 by51 by3.2
13 by 514 by 914
DRAFT
FIRE END
G~I I r.F'
CONN-E-CTION~'~
'A' 82
~- "l~"
INTAJ~JE S H U ~ R
,'I- . . . .
OPENINC
~RAIR
's' 82
"
II'A'~
REMOVABLE
EOUIDISTANTLY
ANALYSI S --------~
TOP LID
SPACED WINDOWS
(OPTIONAL)
'
-r-% . . . .
~, ~ :~ ~.
' ~
~ .
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-- 0
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F~ERSU R E ~ N T S
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IGNITING FIRE
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SECTION
INSULATED
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PIPE
DAMPER
+_ 1 / 2 "
SECTION A-A
SECTION C-C
Sl Uldts
Inch-Pound Units
12 1/2 in.
173/4 I/4 in.
54 5 in.
25 ft
305 ~'12.7 mm
451 6.3 mm
1371 127 turn
7.62 m
REMOVABLE
~LIQUID SEAL
TOP L I D
"~
CFJ'gENTBOARD
2" HINERALCOMPOSITIONINSULA
DOUBLEP
OBSERVATION
WINDOWs
OUTSIDE P
" BY 4 1 / 2 ~ BY
i~
OPTION: CASTABLE ~ /
REFRACTORY OR FIRE
8RICK
Inch-Pound Units
1 .
Ifl.
2 in.
1 9
4 _+ ~m.
I
1.
,n.
12 + ~ in.
7~ _+~,
TElCP. 2 6 0 0 ~
SECTION B-B
Sl Units
6.3 mm
51 mm
102
191 13 mm
305 + 13 mm
Inch-Pound Units
20 in.
9 by 41/2 by 21/2 in.
1200"F
2600~
Sl Units
508 mm
230 by 115 by 65 mm
649~
1427~
FIG. 5 - ( t o p ) T e s t f u r n a c e , s h o w i n g s o m e critical d i m e n s i o n s ( n o t a c o n s t r u c t i o n d r a w i n g ) ; ( b o t t o m ) t e s t
f u r n a c e s h o w i n g s o m e critical d i m e n s i o n s ( S e c t i o n " B - B " is n o t a c o n s t r u c t i o n d r a w i n g ) .
673
674
TESTING
MANUAL
affles
~ d p p o r t Rod
in.I
of o t h e r laborawith large-scale
to this chapter.
Test Methods E
Method D 3894
Method E 603
Average,
in.
l.*ra
VRb
lrc
IR d
34
27
5
21
13
32
14
59
37
91
vR b
lrc
ll~d
Historical M e t h o d s
The heat a n d fire test m e t h o d s d e s c r i b e d are those m o s t
used t o d a y in c h a r a c t e r i z i n g coatings. Historically, a variety
of o t h e r bench-scale screening tests have b e e n used, b u t they
are no longer in vogue as they do not relate to actual service
Coatings
These special-purpose coatings are i n t e n d e d to protect substrates from d a m a g e by fire exposure. I n t u m e s c e n t coatings
are designed for cellulosic substrates, as fire-retardant coatings for structural steel substrates, a n d as ablative coatings
for the exterior of re-entry space vehicles. See the reference
section for m o r e specific references.
I n t u m e s c e n t coatings a p p l i e d to w o o d panels are tested for
flame-spread index by ASTM E 84. Evaluation of fire-retard a n t coatings for the p r o t e c t i o n of structural steel is cond u c t e d a c c o r d i n g to ASTM E 119.
24 O0
~J
"1200
IIIIBJ
!BHH
~=z60G
(0
//
- Boo
-600
E BO0
-400
400
200
675
00
Time~, h
FIG. 7-Time-temperature relationship used
for test control.
676
REFERENCES
[1] McGuire, J. H., "The Spread of Fire in Corridors," Fire Technology, Vol. 4, No. 2, May 1968, pp. 103-108.
[2] Plunkett, J. D., "NASA Contributions to the Technology of Inorganic Coatings," NASA SP-5014, 1964.
[3] Van Heuckeroth, A. W., "Fire Retardance and Heat Resistance,"
Chap. 6.3, Paint Testing Manual, 13th ed., American Society for
Testing and Materials, Philadelphia,1972, pp. 355-365.
[4] Babrauskas, V. and Williamson, R. B., "Historical Basis of Fire
Resistance Testing," Fire Technology, Vol. 14, Nos. 3 and 4, 1978,
pp. 184-198, 304-316.
[5] Magee, R. S. and McAlevy, R. F., III, "The Mechanism of Flame
Spread," Journal of Fire and Flammability, Vol. 2, 1971, pp. 271297.
[6] Shorter, G. W., Ed., Fire Test Performance, ASTM STP 464, p.
1070.
[7] Williamson, R. B. and Baron, F. M., "A Corner Test to Simulate
Residential Fires," Journal of Fire and Flammability, Vol. 4, April
1973, pp. 91-105.
MNL17-EB/Jun. 1995
Water-Resistance Testing of
Coatings
by Wayne Ellis*
hand, is evaluated on free films.) W a t e r resistance m a y be
evaluated as p a r t of o t h e r test regimes, such as exposure
testing, w a t e r repellency, corrosion, c h e m i c a l resistance, saltfog resistance, a n d cycling tests such as humidity-cycling a n d
light-and-water-exposure testing.
E F F E C T S O N C O A T I N G S OF E X P O S U R E TO
WATER AND WATER VAPOR
The a d h e s i o n of coatings to substrates is strongly influenced b y the a b s o r p t i o n of w a t e r a n d b y the p e r m e a b i l i t y of
the coating to w a t e r vapor. The m e c h a n i s m of this influence
proceeds as follows: 1
1. A b s o r p t i o n of w a t e r molecules in the coating film.
2. Inclusion of w a t e r in the interface b e t w e e n film a n d substrate.
3. Blister formation.
4. Corrosion/erosion of the substrate.
5. Flaking o r peeling of the film.
Spot tests a n d i m m e r s i o n tests of coatings a p p l i e d to substrates t r a d i t i o n a l l y have b e e n used as "quick a n d dirty" techniques to c o m p a r e specimens. Criteria for evaluation include
softening, blistering, solvation, color change, loss of adhesion, a n d rusting o r o t h e r d e t e r i o r a t i o n of the substrate.
These observations should lead to further a n d m o r e c o m p r e hensive testing related to i n t e n d e d conditions of p r o d u c t use.
Such testing m a y include exposure to controlled condensation, 100% relative humidity, or w a t e r fog to evaluate moisture blistering resistance. Even m o r e intensive testing m a y
involve w a s h a b i l i t y a n d scrub resistance.
SPECIMEN PREPARATION
IMMERSION TESTING
ASTM Practice for Testing W a t e r Resistance of Coatings
Using W a t e r I m m e r s i o n (D 870) describes basic principles
aD 609, Practice for Preparation of Cold-Rolled Steel Panels for
Testing Paint, Varnish, Conversion Coatings, and Related Coating
Products.
4D 1734, Method of Making and Preparing Concrete and Masonry
Panels for Testing Paint Finishes.
5D 1730, Practices for Preparation of Aluminum and AluminumAlloy Surfaces for Painting,
6D 823, Test Methods for Producing Films of Uniform Thickness of
Paint, Varnish, and Related Products on Test Panels.
677
Copyright9 1995 by ASTM International
www.astm.org
678
~:~12 " ~
ings by the partial or complete immersion of coated specimens in distilled or demineralized water at ambient or elevated temperatures. Coated specimens are partly or wholly
immersed in water in a container that is resistant to corrosion. The exposure conditions are varied by selecting the
temperature of the water and the duration of the test.
Failure may be caused by a number of factors, including a
deficiency in the coating itself, contamination of the substrate, or inadequate surface preparation. Any effects such as
color change, blistering, loss of adhesion, softening, or embrittlement are observed and reported. These test results
typically are a pass or fail determination, but the degree of
failure also may be measured.
WATER FOG T E S T I N G
ASTM Practice for Testing Water Resistance of Coatings
Using Water Fog Apparatus (D 1735) covers the basic principles and operating procedures for testing water resistance of
coatings in an apparatus similar to that used for salt spray
testing. 7 The apparatus required consists of a fog chamber
7ASTM B 117, Test Method of Salt Spray (Fog) Testing.
100% RELATIVE H U M I D I T Y T E S T I N G
Practice for Testing Water Resistance of Coatings in 100%
Relative Humidity (D 2247) covers the basic principles and
operating procedures for testing water resistance of coatings
by exposing coated specimens in an atmosphere maintained
at 100% relative humidity so that condensation forms on the
679
I
I
Ii
io,'~
IS
sJ
I
I
k
I
I
I
/11
I
0---Angle of lid, 90 to 125 ~
l--Hinged top, hydraulically operated, or counterbalanced
2--Water seal
3---Constant-level water tank unheated with overflow outlet and equalizer connection
C--Heater water tank for supplying heat and humidity to cabinet
5--Immersion heater
6--Watertemperature limit control
7--Thermostatic controller for room temperature. Pdmaw limit control for immersion heater (5)
8--Wator line
9--Insulation if necessary (see A1.3)
I 0--Temperature recorder (optional)
11 --Drain
FIG. 2 - H u m i d i t y cabinet (Fig. A1.1 of A S T M D 2247),
CONDENSATION
TESTING
680
BIBLIOGRAPHY
Lieff, M. and Trechsel, H. R., Eds,, Moisture Migration in Buildings,
ASTM STP 779, 1982.
Schwartz, T. A., Ed., Water in Exterior Building Walls: Problems and
Solutions, ASTM STP 1107, 1991.
Trechsel, H. R. and Bomberg, M., Eds., Water Vapor Transmission
Through Building Walls and Systems: Mechanisms and Measurement, ASTM STP 1039, 1989.
MNL17-EB/Jun. 1995
ORGANICCOATINGSARE PRIMARILYapplied to aircraft for environmental protection and appearance. Reference 1 condudes, "The rate controlling parameter for the corrosion of
aircraft alloys, excluding the mechanical damage factor, is
the degradation time of the protective coating system." This
dearly indicates the importance of the coating system's durability and its ability to control corrosion and erosion. Relative
to appearance, commercial aircraft benefit from the aesthetic
characteristics of the coating system, while military aircraft
rely on camouflage properties to minimize enemy detection
and tracking during mission operations.
To meet operational requirements, aircraft coating systems
traditionally consist of a primer and a topcoat. Primers inhibit corrosion of the substrate and enhance adhesion of
subsequent topcoats, while topcoats are applied for appearance and to enhance overall durability of the coating system.
Self-priming topcoats, which perform as both primer and
topcoat in a single coating, have recently been introduced
[2,3]. In addition, specialty coatings are strategically applied
to perform various functions such as protection against rain
erosion, chafing, immersion in fuel, and high temperature.
References 4 through 6 provide more detail on the formulation and properties of aircraft coatings.
A number of factors affect the performance of aircraft coatings, including the substrate material, the aircraft's operational environment, and flight conditions. Aircraft structures
and skins are manufactured from numerous metallic alloys
and polymeric composites with a variety of pre-paint treatments, thus complicating the adhesion and corrosion inhibition characteristics of the coating system. Environmental
conditions also can vary dramatically (arctic, tropical, mafine, industrial, desert, etc.). Skin temperatures during flight
can range from - 5 4 to 177~ ( - 6 5 to 350~ while ground
conditions may be relatively benign or highly corrosive. Aircraft type and mission also play important roles in coating
system performance. A commuter aircraft that hops from
island to island in the tropics sees frequent pressurization
and depressurization along with high temperature, humidity,
and salt water. In contrast, a military tactical aircraft may fly
far fewer hours but will experience extreme structural loads
during flight conditions. These flight conditions place environmental and mechanical stresses on the aircraft coating
~Lead Applications Chemist, Air Products and Chemicals, 7201
Hamilton Blvd.. Allentown, PA 18195-1501.
2Chemical Engineers, Materials Engineer, and Materials Engineering Technician, respectively, Naval Air Warfare Center, Aircraft Division, Warminster, PA 18974-0591.
system. Therefore, selection of appropriate test and evaluation procedures is an essential component for determining
acceptable coatings for aircraft application.
VISCOSITY
The viscosity of aircraft coating components, component
mixtures, and raw materials is valuable to the formulator,
manufacturer, and applicator for assessment of rheological
characteristics. These characteristics affect paint application
properties such as atomization, leveling, sagging, and
brushability.
683
Copyright9 1995 by ASTM International
www.astm.org
684
DENSITY
Wet coating density measurements provide a check on the
theoretical density value and on the uniformity of the manufactured product. Determination of density by any convenient or suitable method in this Manual is acceptable; however, a weight-per-gallon cup is normally used due to the ease
of use of this instrument.
F I N E N E S S OF G R I N D A N D COARSE
PARTICLES
Fineness of grind and presence of coarse particles are determined to assess the quality and uniformity of the pigment
dispersion and coating finish. In order to produce a high gloss
coating of good appearance, a paint should be free of coarse
particles. However, the extremely low gloss requirements of
some aircraft camouflage paints require relatively large particle sizes. Fineness of grind is determined by ASTM Test
Method for Fineness of Dispersion of Pigment-Vehicle Systems (D 1210), commonly referred to as the Hegman scale.
The coarse particle content is determined by the weight retained on a 325-mesh sieve as specified in ASTM Test Methods for Coarse Particles in Pigments, Pastes, and Paints
(D 185).
S O L I D S A N D VOLATILE C O N C E N T R A T I O N /
CONTENT
General
Several analysis techniques are used to determine the total
solids, pigment concentration, and volatile concentration of
aircraft coatings. This information can be used as a check on
the coating composition when compared to the theoretical
value as determined from the formulation. It can also be used
to determine the quality of an as-received product and its
potential surface coverage per volume of paint. In addition,
restrictions on the volatile organic compounds (VOC) content
of coatings increase the importance of determining the volatile concentration, and methods to determine this value are
continuously being developed and refined. The following
methods are currently used to determine these compositional
properties for aircraft coatings.
Pigment Concentration
Three methods are available to determine the pigment
weight concentration within a coating: ASTM Test Method
for Determination of Pigment Content of Solvent-Type Paints
by High Speed Centrifuging (D 2698); ASTM Practice
for Separation of Vehicle from Solvent-Reducible Paints
(D 2372); and Federal Standard 141 Method 4021, Pigment
Content (Ordinary Centrifuge). These methods use the fact
that pigment particles, generally being more dense than the
vehicle, will settle under centrifugal force. One distinction
between these methods is the variation in rinsing solvent(s)
used to separate the polymer from the pigment. Although
each method utilizes a different solvent blend, it is common
to deviate from the specified method by using solvents which
are appropriate for the specific paint under analysis. All three
methods result in a quantitative determination of pigment
weight concentration in the paint; however, the latter two
methods lend themselves to chemical analysis of the pigment
sample after this determination.
Volatile Concentration
ASTM D 2369 is a standard experimental method to determine the total volatile content of a coating. In contrast, ASTM
Practice for Volatile Organic Compound (VOC) Content of
Paints and Related Coatings (D 3960), offers a method of
calculating the VOC using the nonvolatile content, the water
content (if any), and the density of the coating. These latter
values are predetermined using referenced ASTM methods,
and they are subsequently used in the calculations to determine VOC of the paint. It should be noted that in solventborne coatings the VOC is the volatile content; however,
water-borne coatings obviously have a nonorganic volatile
component which must he taken into account when performing these calculations. The VOC is typically recorded in units
of grams of organic volatiles per liter of paint with pounds per
gallon used as an alternate.
Chemical Analysis
A variety of methods are used to analyze the chemical composition of aircraft coatings and their components. The specific technique which is selected is determined by the material being analyzed and the level of quantitative or qualitative
data required. Some of the more common techniques to
analyze polymer and solvent systems are gas chromatography, infrared and ultraviolet spectroscopy, and nuclear magnetic resonance (NMR). Atomic absorption and X-ray spectroscopy are common techniques for determining the
chemistry of inorganic pigments. Table 1 provides some of
the common ASTM methods used to analyze aircraft coatings.
Water
Lead, Cadmium, and
Cobalt
Chromium
ASTMMethod
D 2804: Test Method for Purity of
Methyl Ethyl Ketone by Gas
Chromatography
D 3432: Test Method for Unreacted
Toluene Diisocyanates in
Urethane Prepolymers and
Coating Solutions by Gas
Chromatography
D 4017: Test Method for Water in
Paints and Paint Material by Karl
Fischer Method
D 3335: Test Method for Low
Concentrations of Lead,
Cadmium, and Cobalt in Paint by
Atomic Absorption Spectroscopy
D 3718: Test Method for Low
Concentrations of Chromium in
Paint by Atomic Absorption
Spectroscopy
Because of growing concerns over potentially toxic materials, restrictions are being placed on the lead and chromium
content of many aircraft paints. These restrictions are in
direct conflict with corrosion control requirements since
chromate salts, such as strontium chromate, barium chromate, and zinc chromate, have been shown to be excellent
corrosion inhibitors for many metals. Therefore, many specifications require analysis for these pigments to ensure either
their presence or their absence. Specific methods to determine lead and chromate content are listed in Table 1.
S T O R A G E STABILITY
685
Accelerated Conditions
To speed the evaluation of a coating's behavior under storage conditions, methods have been devised to accelerate this
behavior by subjecting the coating to extreme conditions.
One common example is specified in FTMS 141 method
3019.1, Storage Stability at Thermal Extremes, which subjects the coating to 49~ (120~ or - 12~ (10~ for 168 h,
depending on the type of storage suspected. Methods involving cyclic exposure to high and low temperatures have also
been used. With the development of high-performance waterborne coatings for aerospace applications, one major concern is the freeze-thaw stability of these coatings. ASTM Test
Method for Freeze-Thaw Resistance of Water-Borne Paints
(D 2243) is used to evaluate coating consistency and performance after 17 h at - 18~ (0~
Another technique for predicting storage stability of coatings is by evaluating the settling properties of pigments under
accelerated conditions. Aircraft coating specifications rarely
contain this type of evaluation; however, centrifugation is
often used as a research tool to evaluate the tendency of
various pigments to settle and compact in specific vehicles.
The centrifugal force and the duration are selected on a case
by case basis to ascertain differences between systems.
General
The effects of long-term storage on aircraft coating performance are a major concern. Long durations of time and
extreme temperatures can have drastic effects on the chemical and physical nature of paints, causing them to have different properties than when they were originally manufactured.
Since many aircraft manufacturing, rework, and maintenance activities have paint storage facilities which have only
moderate environmental controls, determining the effects of
these conditions is necessary. Of primary importance are
chemical stability and pigment dispersion. These properties
are assessed in the laboratory following long-term and accelerated storage conditions.
FLASH POINT
General
The flash point of a coating is the minimum fluid temperature at which the solvent vapors are ignited by a spark or
flame. It can be predicted roughly as the weighted average of
the individual flash points for each of the solvents in a coating
formulation. The closed-cup technique is generally preferred
since container breakage during shipment and storage often
leads to flammable vapors being trapped in a confined space.
Naturally, these flash points tend to be lower than the corresponding open-cup values.
Long-Term Evaluation
Methods typically used for determination of stability of
aircraft coatings are specified in ASTM Test Method for Package Stability of Paint (D 1849), and Federal Test Method
Standard (FTMS) 141 method 3022.1, Storage Stability
(Filled Container). In these methods, the packaged coating is
allowed to sit undisturbed at ambient conditions for an appropriate period of time. (One year is typical for aircraft
coatings.) At that time, the coating is reevaluated to compare
its physical and optical properties with those originally found
for the as-manufactured material. Other methods may be
Pensky-Martens
The Pensky-Martens test is a closed-cup method that can be
conducted on an admixed coating or on one of the separate
components in the liquid (uncured) state. The material may
be refrigerated to bring it to a temperature below the expected flash point. It is then placed in a closed metal cup, heated
slowly while stirring, and periodically exposed to a pilot flame
through a shutter mechanism. A thermometer immersed in
the fluid measures the coating temperature. The flash point is
the minimum temperature at which the solvent vapors ignite,
686
The Setaflash test uses an enclosed apparatus with automatic controls to determine the flash point. It is easier to
operate than the Pensky-Martens tester and utilizes an electric heater for efficient heat transfer and greater accuracy.
ASTM Test Methods for Flash Point of Liquids by SetaflashClosed-Cup Apparatus (D 3278), Method B describes the test
procedure.
Tag
Set-to-Touch
POT LIFE
Tack-Free
Setaflash
Dry-to-Recoat
This stage of drying is considered to be the most important
for painting of aircraft because it is one of the major factors
controlling the production rate. Dry-to-recoat is the time at
which a second coat, or specified overcoat (such as, topcoat),
can be applied without developing irregularities in the coating system, such as lifting, blistering, or loss of adhesion. If
overcoated prior to the recoat time, these defects can be
caused by a number of factors, one of which is the trapping of
solvent in the original coat.
Dry-Hard
The most common technique is to squeeze or pinch the
coated surface with the thumb and forefinger with maximum
pressure. The dry-hard time is when this procedure can be
performed without leaving a permanent mark on the coating
surface. This drying stage is also important in production
painting of aircraft since painting is usually the last stage of
maintenance and the aircraft can be flown after the coating is
dry-hard.
FILM THICKNESS
DRYING TIME
ASTM Test Method for Drying, Curing, or Film Formation
of Organic Coatings at Room Temperature (D 1640) defines
687
OPTICAL PROPERTIES
General
The appearance of an applied coating is determined by a
number of optical properties (color, gloss, opacity, etc.). In
the commercial aerospace industry, where public opinion is a
consideration, these optical properties can strongly affect the
initial impression of the aircraft and are considered to be
important with respect to customer recognition. The optical
properties of coating systems for military aircraft affect the
detectability of these aircraft and thus effect their survivability in potentially threatening scenarios. In both the
commercial and military sectors, optical properties are specified with strict tolerances and are closely monitored with
instrumentation as well as with the naked eye.
Color
The colors used on commercial aircraft tend to be strong
and vibrant for recognition and attraction. The colors of military aircraft coatings are empirically selected in order to
achieve either theater-specific (desert, forest, arctic, etc.) or
multi-theater (world-wide) camouflage paint scheme requirements. In either case, paint color is considered to be impor-
688
ADHESION
General
For aircraft coatings to provide maximum protection
against degradation, they must firmly adhere to their substrate. Because of the complex nature of adhesion, various
techniques have been devised to determine the adhesive characteristics of coatings. Since a coating's adhesion to its substrate can be significantly affected by environmental conditions, these tests are often performed after exposure to
accelerated conditions such as immersion in water at elevated temperature. Common adhesion tests used to evaluate
aircraft coatings are tape and scrape tests. Other techniques,
such as mechanical peel, tensile, and shear tests, are used less
frequently.
Tape Tests
Adhesion tape tests are described in ASTM Test Methods
for Measuring Adhesion by Tape Test (D 3359). These are the
easiest and most versatile of the adhesion tests because they
can be conducted in both laboratory and field environments.
Tape tests are performed by cutting through the applied coating, into the substrate. A variety of scribe patterns can be
used. One common pattern (described in the "A" method of
D 3359), which is used to evaluate aircraft coatings, is two
scribes forming an "X." An alternative pattern (described in
the "B" method of D 3359), is formed by scribing eleven parallel lines through the coating, followed by a second set of
eleven lines which are perpendicular to the first set. These
689
FLEXIBILITY
General
Flexibility is an important property for aerospace coatings,
particularly at low temperatures ( - 51~ which is common
for aircraft cruising at high altitudes. Cracking of coatings at
skin joints and around fastener heads can lead to corrosion of
exposed areas. Corrosion inhibiting epoxy primers used on
aircraft tend to be brittle and exhibit poor flexibility, whereas
the urethane topcoats are generally more flexible, especially
at low temperatures. Sealant materials and elastomeric
primers occasionally are used to improve the overall flexibility of the paint system.
Mandrel Bend
The flexibility of high-performance coatings is commonly
characterized by the mandrel bend test method outlined in
ASTM Test Methods for Mandrel Bend Test of Attached Organic Coatings (D 522). This test is normally conducted at
low temperatures such as - 51~ and is performed by bending a painted specimen 180~ around mandrels of various
diameters with the coating aligned away from the mandrel.
After allowing the specimen to return to room temperature,
the coating is examined for cracking along the bend. The
smallest (most severe) mandrel diameter which the coating
can withstand without cracking is recorded. One standard
military specification requirement for this test on low gloss
coatings is a 2-in. mandrel bend while more flexible coatings
can withstand mandrel bends of 88 to 88 in. at low temperatures without cracking.
WEAR RESISTANCE
General
Impact Tests
The most universal test for measuring impact flexibility of
aerospace coatings is Method 6226 (G.E. Impact) of Federal
Test Method Standard 14 lB. The test apparatus consists of a
solid steel cylinder weighing 1.69 kg (3.7 lb) which has spherical knobs protruding from the end. These knobs are designed
such that the coating system is subjected to elongations of
0.5, 1, 2, 5, 10, 20, 40, and 60%. The impact is accomplished
by allowing the steel cylinder to fall freely from a height of
1.05 m (42 in.) through a hollow cylinder guide, striking the
reverse uncoated side of the specimen. The imprints formed
from the knobs are examined, and the impact elongation is
recorded as the highest deformation without cracking of the
coating. A standard requirement for this test on aircraft top
coats is 20% elongation.
Another commonly used test is the Gardner impact test
specified in ASTM Test Method for Resistance of Organic
Coatings to the Effects of Rapid Deformation (Impact)
(D 2794). This test is performed in a similar fashion to the
G.E. impact test described above; however, the weighted
cylinder has a rounded end and is dropped from various
Aircraft coating systems can experience wear due to a number of causes and mechanisms. The most obvious of these is
abrasion at leading edges of wings, antennas, and radomes
caused by impingement of rain, sleet, dirt, and other debris.
Since these leading edges are critical to flight dynamics, special wear-resistant coatings are often applied to these areas to
protect the underlying substrate from damage. Another form
of wear can be caused from the movement of adjacent parts
such as flaps and stabilizers. In addition, internal parts such
as bearings may be coated to prevent excessive wear. Since all
of these types of wear cause different mechanisms of coating
degradation, a number of varying tests are performed to
simulate in-service conditions. For example, coatings which
protect against rain erosion do not usually protect well
against erosion from sand. Specifications for aircraft coatings (other than those for rain erosion) typically do not contain wear tests; however, development and selection of new
aerospace coatings often require that characterization of
wear properties be performed. Therefore, careful evaluation
of wear mechanisms and selection of suitable evaluation
methods is essential for these types of coatings.
690
Rain Erosion
Shore Hardness
Arco Microknife
Although the microknife test was originally designed to
evaluate adhesive strength of coatings, it has been used to
determine hardness. This can be performed by placing a specified weight on the diamond stylus and determining the number of scratch cycles required to cut through the coating. It
can also be performed by determining the weight needed to
get through the coating with a specified number of cycles.
Mar Resistance
Air Blast
Techniques that are used to evaluate erosion from sand,
dirt, and other foreign debris typically involve an air blast to
impinge particles on to the coating surface. A common
method is ASTM Test Method for Abrasion Resistance of
Organic Coatings by Air Blast Abrasive (D 658). This method
uses 75-/~m silicon carbide particles flowing at a rate of 45
g/rain with an air supply pressure of 13 kPa. The method is
often modified to evaluate effects of other particles and air
pressures. The results can be reported as the weight of debris
necessary to abrade a unit film thickness or as the weight loss
of coating per weight of abrasive used.
Taber Abraser
ASTM Test Method for Abrasion Resistance of Organic
Coatings by the Taber Abraser (D 4060) is a frequently used
test throughout the coatings industry because it is well defined and relatively easy to perform. As such, it is often used
for aircraft coatings to assess their wear characteristics. Care
must be taken in interpreting Taber abraser results since
reproducibility of data from lab to lab is not consistent.
CORROSION INHIBITION
Salt Spray
Corrosion resistance is an important property for aerospace coatings, and numerous tests have been developed to
evaluate the corrosion preventive properties of coatings,
ranging from simple exposure studies to sophisticated electrochemical analysis.
Salt spray tests are commonly used as accelerated corrosion resistance tests for coatings. The two primary methods
used for aircraft coating systems are the 5% NaC1 neutral salt
spray test covered by ASTM Test Method of Salt Spray (Fog)
Testing (B 117) and the acidified SO2/salt spray test covered
by ASTM Practice for Modified Salt Spray (Fog) Testing
(G 85). Specimens coated with an aircraft finishing system
are usually scribed with an "X" through the coating into the
substrate and then exposed for various times (usually 1000 to
3000 h for ASTM B 117 and 48 to 1000 h for ASTM G 85).
Exposure periods for coatings vary for different substrate
materials and can be selected either as a specified duration or
as the point where significant differences in finishing system
performance are observed. After exposure, the panels are
inspected for corrosion in the scribe area and blistering or
uplifting of the coating across the specimen. Subsequently,
the coatings can be carefully removed from the surface without disturbing the underlying substrate by using a chemical
stripper, and the specimen surface can be examined for evidence of corrosion.
Standard aircraft epoxy primer/polyurethane topcoat systems perform well on aluminum substrates in the neutral
test, normally exhibiting no significant corrosion products in
the scribe or any blistering of the coating after 1000 h. These
Immersion Studies
691
cial adhesion. References 12 and 13 provide detailed descriptions of EIS and its application for analyzing organic coating/
metal substrate systems. EIS measurements can be made
using equipment like EG&G Princeton Applied Research
Corp. (PARC) Model M388 Impedance System. Test cells
consist of a glass o-ring joint clamped onto a coated metal
specimen [12]. Electrolytes used for specimen exposure can
range from distilled water to neutral or low pH salt solutions.
For an EIS experiment, the test cell described above is filled
with the selected electrolyte solution. A reference electrode
(such as, Calomel) and a counter electrode (such as, platinum
or graphite) are immersed in the cell with the metal substrate
serving as the working electrode. The EIS cell is allowed to
reach equilibrium as indicated by its open circuit potential or
steady-state rest potential. Small excitation amplitudes, usually in the 5 to 10-mV range, are introduced to the system, and
the response signal is measured. These data can be correlated
to an electrical circuit consisting of resistors and capacitors.
The information from this electrical circuit is a model depicting the electrochemical reactions occurring in the coatingsubstrate system. Because of the detailed quantitative information that is obtained from EIS analysis, it's use as a tool to
research high-performance aircraft coatings is growing. In
many cases, attempts are made to correlate EIS data with
results from other corrosion studies such as salt spray. This
approach provides a detailed assessment of coating integrity,
durability, and corrosion inhibition.
Filiform Corrosion
Outdoor Exposure
Outdoor exposure tests are normally conducted over periods of one year or more. In an effort to produce timely
results, these tests are not frequently performed on aircraft
coatings. However, one common specification for an aerospace topcoat, MIL-C-83286, does require a one year exposure of coated panels on an outdoor test rack in Florida. It is
specified that the panels must be at a 45 ~ angle and facing
south. After this exposure period, the coating is evaluated for
changes in color, gloss, and flexibility.
The U.S. Navy has instituted a program to evaluate the
exterior durability of coatings in its operational environment
by placing exposure racks on aircraft carriers and other ships.
Results of these exposures have resulted in identification of
successful aircraft coatings. Details of this effort are provided
in Ref 14.
Accelerated Weathering
Electrochemical Analysis
Reference 11 provides a thorough review of electrochemical methods used to evaluate the performance of corrosion
protective coatings. Of these methods, electrochemical impedance spectroscopy (EIS) is one of the most promising
techniques because it provides both qualitative and quantitative information about the corrosion resistance properties of
the coatings and the substrates to which they are applied. In
addition, EIS can give insight on the nature of their interfa-
692
Humidity
Since high temperature and humidity can cause coating
disbondment and substrate corrosion, extreme humidity exposure is often performed on aircraft coatings to evaluate
their resistance to such environments. Again, exposure parameters vary and must be clearly specified for reproducibility and interpretation of results. ASTM Practice for Testing
Water Resistance of Coatings in 100% Relative Humidity
(D 2247) is usually followed. The chamber conditions are
49~ (120~ and 100% relative humidity with constant condensation on the coated panels. A typical exposure period can
range from 30 to 90 days.
variable. Following exposure, the specimen is usually evaluated for degradation of the coating (discoloration, softening,
blistering, etc.) and substrate (corrosion).
Water Resistance
Resistance to water is usually performed by total immersion. The severity of the exposure can range from 24 h at
ambient temperatures to seven days at 65~ (150~
Since
water can play a significant role in coating disbondment [15],
adhesion tests are frequently performed immediately upon
removal of the coated specimen from water immersion.
Another technique is to measure the water absorption (uptake) of a coating as a function of immersion time. This is
performed by simply weighing the coated panel (or free film)
as a function of immersion time. Water up-take values for
high-performance aircraft coatings can range up to 20%.
A third technique to characterize the effects of water on a
coating is to determine its water vapor transmission rate
(WVTR). WVTR is a measure of the rate at which water will
permeate through a coating. ASTM Test Method for Water
Vapor Transmission of Organic Coating Films (D 1653) describes two methods to determine WVTR. In Method "A," a
free film of the coating is sealed to the open mouth of a cup
containing distilled water. In Method "B," the free film is
sealed to a cup containing desiccant. These fixtures are exposed to controlled environments (temperature and humidity), and they are weighed periodically to determine the rate
of water vapor diffusion through the coating. Aircraft coatings must exhibit low WVTRs to maintain their adhesion and
corrosion inhibition.
FLUID RESISTANCE
HEAT RESISTANCE
Aircraft coatings are frequently subjected to aggressive operational and environmental fluids. Several examples are hydraulic fluids, engine oils, fuel, deicing solutions, and
cleaners. In order to assess the resistance of aircraft coatings
to these fluids, a number of exposure tests are performed. The
exposure can range from a simple wiping action to long-term
immersion. The temperature of the exposure is also a critical
C H A P T E R 5 8 - - A E R O S P A C E AND A I R C R A F T C O A T I N G S
Temperature
12l~ (250~
66~ (150~
21~ (70~
2 l~ (70~
1.0).
Thermal Fatigue
Thermal fatigue refers to the resistance of a coating to
stresses induced by rapid temperature changes. Often called
thermal shock, this simulates the effect of take-off from hot
(and sometimes humid) ground temperatures to the cold atmosphere at high altitudes and then back again. The MIL-C81945B intumescent coating used on weapons must withstand 60~ (140~
95% relative humidity for 24 h followed
by -40~ (-40~
for 24 h. The coating is then cycled between the two chambers for 28 days. Cracks extending deep
into the coating indicate failure in this test. Method 503.1 of
MIL-STD-810 provides further guidance.
693
CLEANABILITY
Low-gloss aircraft coatings, such as those used in camouflage schemes on military aircraft, become dirtier and are
more difficult to clean and restore than high-gloss coatings.
This is primarily due to the increased surface roughness of
low-gloss coatings, which entraps carbonaceous and oily
soils as discussed in References 17 and 18.
The cleanability or the ease at which dirt and soil can be
removed from a coating surface can be quantified by consistently soiling a coating and using a standard cleaner and
cleaning motion in attempts to remove this soil. Measuring
the color difference of the coating prior to soiling and subsequent to cleaning provides an indication of the coatings
cleanability. The following is a detailed procedure for the
evaluation of the cleanability of aircraft coatings. The soil in
this procedure was generated using a hydraulic fluid. This
soil is representative of that found on operational aircraft.
Other soils can be derived from greases and lubricating oils.
Thermal C o n d u c t i v i t y
APPARATUS REQUIRED
STRIPPABILITY
Aircraft are periodically returned to depot maintenance
facilities for inspection and overhaul. At this time, the aircraft's exterior coating system is removed by chemical and/or
mechanical means. In order to insure that this procedure can
P R E P A R A T I O N OF SOIL
1. Place 50 g of carbon black (such as Raven 1040 manufactured by Columbian Chemical Company) in 500 g of hydraulic fluid meeting military specification MIL-C-83282.
2. Homogenize the carbon black and hydraulic fluid mixture
using a high shear mixer for 15 min. Prior to application of
the soil to the specimen, thoroughly stir or shake the mixture to obtain a thorough dispersion.
P R E P A R A T I O N OF T E S T P A N E L S
1. To the c h r o m a t e conversion coated a l u m i n u m s p e c i m e n s
described, a p p l y a suitable p r i m e r for the desired topcoat.
One such m a t e r i a l is epoxy p r i m e r c o n f o r m i n g to MIL-P23377 Type I or II to a thickness of 15.2 to 2 2 . 9 / z m (0.6 to
0.9 rail). Allow to dry for 1 h at a m b i e n t conditions. Apply
the desired t o p c o a t to the i n t e n d e d thickness. Allow the
coating to cure u n d e r the a p p r o p r i a t e conditions.
2. After allowing the desired cure t i m e a n d conditions, use a
bristle acid b r u s h to coat the p a i n t e d surface of a test panel
with the soil d e s c r i b e d in the "Preparation of Soil" section.
Remove excess soil by covering the test panel surface with
tissue a n d exerting p r e s s u r e b y rolling the tissue with the
roller. R e p e a t this blotting three times using fresh tissue
each time. B r u s h the soiled surface ten times in one direction only, parallel to the long d i m e n s i o n of the test panel,
using the bog bristle brush. Bake the test p a n e l at 105~
(221~ for 60 min.
3. Measure the L, a, a n d b tristimulus values on a suitable
c o l o r i m e t e r a n d r e c o r d the values as Li, ai, a n d b i, respectively.
CLEANING P R O C E D U R E
1. Dilute the control cleaner b y one p a r t cleaner with nine
parts distilled w a t e r (by volume).
2. Clean the test p a n e l w i t h i n 4 h using the w e a r tester as
follows. Cut the sponge with a n y texture "ribs" r u n n i n g
p e r p e n d i c u l a r to the cleaning stroke. W h e n the dry sponge
is a t t a c h e d to the cleaning h e a d on the w e a r tester, the
c o m b i n e d weight shall be between 1350 a n d 1400 g. Place
the soiled test panel in the t e m p l a t e at an angle 45 ~ to the
cleaning stroke. S a t u r a t e the sponge a n d cover the test
panel with the diluted cleaner. After 55 to 65 s, clean the
test panel using 5 cycles (10 strokes) of the w e a r tester,
then i m m e d i a t e l y t u r n the test panel 90 ~ in the t e m p l a t e
REFERENCES
[1] Miller, R. N., Predictive Corrosion Modeling Phase I/Task II Summary Report, Air Force Wright Aeronautical Laboratories Report
AFWAL-TR-87-4069, Wright-Patterson Air Force Base, OH, August 1987.
[2] Hegedus, C. R., Eng, A. T., and Hirst, D. J., Program Summary:
Unicoat Development, Laboratory Characterization, and Field
Evaluation, Naval Air Development Center, Warminster, PA,
March 1990.
[3] Hegedus, C. R., A Combination Primer/Topcoat for Aluminum,
Society of Manufacturing Engineers, Finishing '87 Conference
Paper FC87-625, September 1987.
[4] Chattopadhyay, A. K. and Zentner, M. R., Aerospace and Aircraft Coatings, Federation of Societies for Coatings Technology,
Philadelphia, PA, May 1990.
[5] Lewin, J. B., "Aircraft Finishes," Treatise on Coatings Volume 4,
Formulation Part/, R. R. Meyers and S. J. Long, Eds., Marcel
Dekker, 1975, pp. 1-84.
[6] Hegedus, C. R., Pulley, D. F., Spadafora, S. J., Eng, A. T., and
Hirst, D. J., "A Review of Organic Coating Technology for U.S.
Naval Aircraft," Journal of Coatings Technology, Vol. 61, No. 778,
1989, p. 31.
[7] Nicodemus, F. E., Richmond, J. C., Hisia, J. J., Ginsberg, I. W.,
and Limperis, T., Geometrical Considerations and Nomenclature
for Reflectance, National Institute for Science and Technology,
Washington, DC, NBS Monograph 160, October 1977.
[8] Wanhill, R. J. H., DeLuccia, J. J., and Russo, M. T., The Fatigue
in Aircraft Corrosion Testing (FACT) Programme, North Atlantic Treaty Organization (NATO), Advisory Group for Aerospace
Research and Development (AGARD), Report No. 713, p. 68,
February 1989.
[9] Stander, A. O., Summary Report of Rain-Erosion Phenomena,
Naval Air Engineering Center, Report No. NAEC-AML-2547,
Philadelphia, PA, December 1966.
[10] Military Standard MIL-STD-810, Environmental Test Methods
and Engineering Guidelines.
[11] Leidheiser, H. Jr., "Electrochemical Methods for Appraising
Corrosion Protective Coatings," Journal of Coatings Technology,
Vol. 63, No. 802, 1991, p. 20.
[12] Princeton Applied Research Corp., Electrochemical Instruments Group, Application Note: AC-2, Evaluation of Organic
Coatings by Electrochemical Impedance Measurements, Princeton, N J, not dated.
[13] Scully, J.R., Electrochemical Impedance Spectroscopy for
Evaluation of Coating Deterioration and Underfilm Corrosion-A State-of-the-Art Review, Report No. DTNSRDC/SME-86/006,
David W. Taylor Naval Ship Research and Development Center,
Annapolis, MD, September 1986.
[14] Agarwala, V. S., "Corrosion Monitoring of Shipboard Environments," Degradation of Metals in the Atmosphere, STP 965, S. W.
CHAPTER 58--AEROSPACE
Dean and T. S. Lee, Eds., American Society for Testing and
Materials, Philadelphia, PA, 1986, pp. 354-365.
[15] Spadafora, S. J., "Synergistic Soiling, Cleaning and Weathering
Effects on Aircraft Polyurethane Topcoats," Journal of the Oil
and Color Chemists' Association, Vol. 71, No. 9, 1988, p. 276.
[16] Fish, R., "Soil Retention of Aircraft Topcoats," NASA Ames Research Center, Technical Brief 70-10450, Moffett Field, CA, May
1970.
695
[17] Hegedus, C. R. and Hirst, D. J., Metal Finishing, Vol. 86, No. 7,
1988, p. 39.
[18] Hirst, D. J. and Hegedus, C. R., "Water Disbondment Characterization of Polymer Coating/Metal Substrate Systems," Metal Finishing, Vol. 87, No. 1, 1989, p. 37.
MNL17-EB/Jun. 1995
59
Architectural Coatings
by Harry E. Ashton ~
INTRODUCTION
Scope
The intended uses and generic gloss range for conventional
types of architectural coatings are as follows:
696
Copyright9 1995 by ASTMInternational
www.astm.org
Substrate Conditions
The condition of the surface is important in determining
the type of coating and surface preparation that might be
697
Exterior Coatings
The durability and appearance of these coatings can be
affected by short- and long-term environmental conditions.
Surface dampness during application and drying can adversely affect the adhesion of solvent-borne coatings but not
of water-borne coatings. However, low temperatures during
the drying stage can prevent water-dispersed (latex) coatings
from forming cohesive films. Of course, no water-borne coating can be applied at temperatures below the freezing point of
water. A sunny service environment can be expected to encourage chalking and other forms of film deterioration. In
contrast, a shady location, such as on the north side of a
structure or nearby trees and shrubs, can protect the film
from sunlight but it can promote mildew growth. Orientation
of the coating toward sun or shade varies on different parts of
a building, e.g., fascia boards and porches.
Interior Coatings
The porosity, smoothness, and color of the surfaces are
important factors for both new and repaint jobs. On new
construction, low temperatures must be avoided when applying water-borne finishes, and painting is preferably done at
normal room temperature. If drying temperatures are too
low, long drying times are needed and this can result in
significant dust and dirt accumulation on the film. If drying
temperatures are too high, the film will dry too rapidly and
side-by-side application areas may appear different because
they did not flow into each other. High relative humidity is
also to be avoided when applying both solvent- and waterborne coatings. Primer coats should be allowed adequate
time to dry before applying the next coat.
General
It should be recognized that proper surface preparation
and correct application techniques are as important as the
inherent properties of a coating in contributing to adequate
performance. This is especially true for high-performance
coatings. After selecting the best material for a given service,
it is essential that the manufacturer's instructions be followed.
698
S E L E C T I O N OF T E S T S
Service Location
Because coatings on different surfaces, e.g., ceiling, floor,
wall, and in different service environments, e.g., exterior or
interior, are subjected to a variety of conditions, specialized
coatings have been developed. The test methods discussed in
this chapter cover practically all of the properties of architectural coatings. Not all of the tests are needed with any one
coating type or location. Coatings intended for exterior use
only or for both exterior and interior uses require certain
properties not relevant to those intended for interior use only.
Property selection and methods of testing for these properties
must be governed by experience and the requirements in each
individual case and, preferably, by agreement between purchaser and seller.
V a l u e Judgments
The purchaser should first determine the properties required of a coating and then select only the test methods
appropriate for those properties. After test selection the purchaser should decide which properties are most important
and establish specification requirements accordingly. Since
coating properties frequently tend to oppose each other, such
as low sheen versus good cleansability or good sag resistance
versus good leveling, some properties may need to be less
emphasized if others are to be accentuated. This balance of
properties must be considered when selecting the tests and
establishing the requirements. No attempt is made herein or
in the ASTM standard guides listed above to indicate relative
importance of the various tests. Also, the referenced standards do not recommend specific test values because properties considered very important by one purchaser may be less
so to another.
P R O P E R T I E S OF LIQUID COATINGS
Coarse Particles
To form uniform films with good appearance, liquid coatings must be free of coarse particles and foreign matter. In
general the glossier the film, the more detrimental such particles are to appearance. These particles are far larger than
those determined in the fineness of dispersion method described below. They normally occur as a defect in the production process that permits introduction of clumps of dry pigment or foreign matter such as pieces of shipping bags and
the like. The content of objectionable material is determined
with ASTM Test Methods for Coarse Particles in Pigments,
Pastes, and Paints (D 185) by straining the diluted coating
through a 325-mesh (45-/~m) screen and weighing the
amount retained. A typical maximum requirement is 0.5% by
weight. Objects such as pigment lumps, polymer seeds, etc.
with a generally spherical shape are retained on such a
screen. Linear objects like fiber strings can flow through this
screen and may require other removal methods, such as centrifuging. Screens are inexpensive and readily available, and
results obtained with them are easy to comprehend. Devices
such as centrifuges are more expensive and more time consuming than screens, but they often yield more accurate
results than the latter.
Density
Fineness o f Dispersion
699
Odor
D i l u t i o n Stability
Flash Point
Penetration (Absorption)
This term refers to the tendency of the nonvolatile vehicle
or binder in a coating to penetrate and be absorbed by porous
surfaces. Good resistance to absorption (hold-out) is desirable with interior primers and undercoats because it enables
them to seal such surfaces, thus promoting uniformity in
both gloss and color of subsequent finish coats. Conversely, a
700
Color Compatibility
A colorant sometimes fails to disperse completely and yield
the desired color in a white or tint base owing to poor compatibility that can be related to the colorant (color development), the base (color acceptance), or both. If colorants are
not adequately compatible with bases, lighter or nonuniform
shades are produced. Although the problem is generally related to poor dispersability of the colorant, especially those
designed for use with both solvent- and water-reducible coatings, the white pigment in the base may not have been adequately dispersed or may have subsequently flocculated. In
that case, if the shear applied to disperse the colorant also
disperses the white pigment, the color will be lighter and less
colorful (i.e., less saturated) than expected. When both the
colorant and the white are poorly dispersed, the color change
due to shear stress will be some combination of the two
effects.
Poor color compatibility can be a problem both in the
production and use of organic coatings. In the factory it
causes a loss of monetary value and unpredictable tinting
results. In application it results in nonuniform color of the
final film due to the variation in shear forces with different
modes of application. This is commonly evaluated by applying the coating with an applicator blade and subjecting a
small area of the drawdown to high shear by finger rubbing
the partially dried film. Since rubbing simulates the high
shear involved with some application methods, a variation
between the unrubbed and rubbed areas indicates that the
product will probably exhibit the same defect in the field. The
color difference can be measured photometrically to obtain
numerical values that are more useful than visual evaluations
for establishing limits for control work. Unfortunately, the
finger-rub method has been found to have poor repeatability
Coating Rheology
This term refers to the viscometric characteristics of liquid
coatings. Simple liquids that maintain a constant viscosity at
varying shear conditions are said to be Newtonian. Most
architectural coatings are non-Newtonian in character and
have a higher viscosity at low shear rates than at high shear
rates and vice versa. Systems of this type require the application of a minimum force to flow and when this force, the
"yield value," is exceeded, the phenomenon is called plastic
flow. Paints that exhibit plastic flow are called Bingham liquids.
In the coating industry, thixotropy is a favorable form of
non-Newtonian flow in which a liquid decreases in viscosity
when subjected to a shearing force and then recovers when
undisturbed for some time. It is possible for a material to
exhibit both plastic flow and thixotropy. These flow characteristics are directly related to practical application properties. High viscosity at low shear rates results in poor leveling
and good sag resistance. Low viscosity at moderate shear
rates leads to good leveling but poor sag resistance. High
viscosity at high shear rates, such as occur during brush
application, results in brush drag or poor brushability. Consequently, a balance between the different properties must be
sought.
The different instrumental test methods used for coatings
are described below. Empirical methods for evaluating various application characteristics are described in a later section. The topics of rheology, viscometry, and related characteristics are dealt with on a theoretical, mathematical basis
elsewhere in the manual.
Sag Resistance
Some coatings sag and form curtains before the film sets.
Resistance to this type of flow is an important property, particularly for semigloss and gloss finishes, because of the resultam unsightly film appearance. Sag resistance is determined
in accordance with ASTM Test Methods for Sag Resistance of
Paints Using a Multinotch Applicator (D 4400). In this test, a
presheared coating is applied to a test chart with a drawdown
applicator that contains a number of different-sized notches
to form stripes of the coating. The chart is then hung vertically with the drawdown stripes in a horizontal position. The
coating chart is allowed to dry and then examined for sagging
characteristics.
Leveling Properties
Leveling is an important property when smooth, uniform
surfaces are to be produced because it affects hiding and
appearance. Brush marks and imperfections are much more
conspicuous in semigloss and gloss finishes than they are in
low-gloss materials. ASTM Test Method for Leveling of Paints
by Drawdown Method (D 4062) is the most recently developed method for evaluating this property. In it, a series of
ridges is produced by applying the film using a serrated rod.
After drying, the ridges are compared under a strong oblique
light to a numbered series of plastic levelness standards. The
results have been shown to correlate well with brush applications.
Package Stability
Since paints normally are not used immediately after manufacture, they must remain stable in the can for some reasonable time. At normal temperatures most architectural
coatings can be stored for over a year with little change in
properties. However, exposure in uninsulated warehouses or
during shipping to high temperatures in summer or, for
water-dispersed coatings, to low temperatures in winter may
cause unacceptable changes in the products. Another unsatisfactory condition that may occur during storage is excessive
settling.
APPLICATION PROPERTIES
Application or working properties of a coating are generally compared to a standard or described by requirements in
the product specification. Working properties are determined
in accordance with Method 4541 of FTMS 141.
Brush Application
Brushed films should be smooth and free of seeds and
when applied to vertical surfaces they should show no sagging, color streaking, or excessive brush marks. Brush drag
should not be excessive, although some degree of drag may be
desirable for adequate film thickness application. Wall finishes are tested on vertical surfaces and floor coatings on
horizontal surfaces, although evaluation of the latter on vertical surfaces may be necessary to determine performance on
stair risers, railings, posts, etc. Brushing properties are determined in accordance with Method 2141 of FTMS 141. Even
though the test is subjective, someone experienced in the art
can produce quite consistent results, particularly in the evaluation of drag qualities.
Brush Drag
As the brush drag (resistance encountered when applying a
coating by brush) increases, any natural tendency of the
painter to spread the material too far is reduced. All other
factors being constant, increased brush drag results in
greater film thickness with consequent improvements in hiding and film durability. Conversely, increasing brush drag too
much can cause difficulties in easily and uniformly spreading
the coating. This can lead to excessive sagging, prolonged
drying time and, in highly pigmented materials, possibly
"mud-cracking" due to excessive thickness. The determination of the relative brush drag of a series of coatings applied
by brush by the same operator is described in ASTM Test
Roller Application
Both wall and floor coatings are frequently applied by
roller. This type of application tends to produce some stipple
pattern. The evaluation of a material's characteristics when
applied by roller is covered by Method 2112 of FTMS 141.
Since foaming often occurs when water-borne coatings are
roller applied, the amount of foam produced and the number
of craters that remain after the bubbles have broken should
be determined during the test.
Roller Spatter--Some coatings spatter more than others
when applied by roller. The degree to which a material spatters when roller applied can be determined by the density of
the spatter. In ASTM Test Method for Measurement of Paint
Spatter Resistance to Roller Application (D 4707) a specially
designed notched spool is rolled through a film of the test
material that has been applied to a plastic panel. Any spatter
generated falls on a catch paper and after drying is rated
against photographic standards. This procedure eliminates
the influence of the roller cover, thus determining the spattering characteristics of the material alone.
Spray Application
Architectural coatings are some times applied by spray.
Both air and airless spray are used on commercial work.
Spray application properties are determined in accordance
with Method 2131 of FTMS 141. Manual application is very
subjective and should be performed only by an individual
skilled in the art of using spray equipment.
Color
The appearance of color is greatly influenced by several
factors. A color next to a yellow wall looks different than the
same color next to a blue wall. The visual appearance of a
colored object illuminated by incandescent light, fluorescent
light, and natural light differs because the spectral composition of the different incident light sources varies. Gloss also
affects color appearance. The same color in a low-gloss finish
usually appears to differ when in a high-gloss coating even
though instrumentally the colors may be identical. A more
theoretical discussion of optical characteristics of coatings
appears elsewhere in the manual.
Touch-Up Uniformity
After a paint has dried, areas where less material was applied sometimes become noticeable. If the paint has suitable
touch-up properties, additional material can be applied to
these areas only, instead of refinishing the complete object-wall, side of building, etc. The color, gloss, and leveling of the
touched-up areas and the previously coated area should be
uniform. Differences in these properties are often caused by
short wet-edge time, poor leveling on recoat, and pigment
orientation or flotation during and after application. Touchup properties are determined in accordance with ASTM Test
Method for Evaluation of Gloss or Sheen Uniformity
(D 3928).
Directional Reflectance
This property is a measure of the appearance of lightness of
a coating. It is usually assigned a value in specifications for
white and pastel shades with a typical range of 76 to 86% for
white finishes. In ASTM Test Method for Color and Color
Difference Measurement by Tristimulis (Filter) Colorimetry
(E 1347), the directions of illumination and viewing are specified so the effect of gloss on the reflectance determination is
eliminated.
Gloss
Gloss is a measure of the capability of a coating surface to
reflect light in a mirror-like (specular) manner, i.e., light
strikes the surface and is reflected at the equal but opposite
angle. In ASTM Test Method for Specular Gloss (D 523), the
numerical gloss units are the ratio of light reflected by a
specimen to that reflected by the standard black glass that is
assigned a gloss value of 100. The gloss of some coatings
Gloss, 60 ~
Semigloss enamels are particularly sensitive to poor
enamel hold-out of primers and undercoats. Low or uneven
gloss readings are indicative of this defect. Oil and alkyd
house paints typically have values of 30 to 70 while trim
enamels have values of 70 to 90 for 60 ~ gloss. Floor enamels
generally have a high (90 + ) gloss reading when first applied,
but this decreases with time and traffic. Interior semigloss
enamels after drying 48 h are usually in the range of 40 to 70,
but measurements taken shortly after drying should be repeated after one week because the gloss can decrease significantly in the first few days of drying.
Sheen, 85 ~ Gloss
Although low-gloss paints with good uniformity of appearance at low viewing angles often have little sheen and those
with good cleansability usually have moderate sheen, this is
not always the case so that sheen should not be used as a
measure of other paint properties. ASTM D 523 is useful for
characterizing the low-angle appearance of low-gloss coatings when the 85 ~geometry is employed. Most flat wall paints
have a sheen of about 1 to 10 whereas velvets or eggshells
range from 15 to 35.
Hiding Power
An in-depth discussion of this appearance property can be
found elsewhere in the manual, so this section only briefly
reviews the commonly used test methods. ASTM Test Method
for Hiding Power of Paints by Reflectometry (D 2805) is precise and gives an absolute rather than a comparative result.
The coating is applied with a blade-type applicator to minimize the effects of flow and leveling. Film thickness is precisely measured and film opacity is instrumentally determined. ASTM Test Method for Relative Hiding Power of
Paints by Visual Evaluation of Brushouts (D 344) is a more
practical test in which paint is applied with a brush on a
checkerboard chart, wet-film thickness is approximately controlled by spreading rate, and hiding power is visually evaluated by comparison with a standard paint. However, results
are affected by the flow and leveling of the paint. ASTM Test
Method for Hiding Power of Architectural Paints Applied by
Roller (D 5150) is designed to simulate application with the
common tools. Although other tools may be used, the method
describes use of a roller to coat a 6-ft2 (0.56-m 2) chart printed
with a series of gray stripes. The test is intended to demon-
703
P R O P E R T I E S OF T H E D R Y F I L M
Interior and Exterior Coatings
Abrasion Resistance
This characteristic is a measure of the ability of a dried film
to withstand wear from foot traffic and marring from objects
rolled or pulled across the surface. Dry abrasion resistance is
determined in accordance with ASTM Test Method for Abrasion Resistance of Organic Coatings by Air Blast Abrasive
(D 658), ASTM Test Method for Abrasion Resistance of Organic Coatings by Falling Abrasive (D 968), and ASTM Test
Method for Abrasion Resistance of Organic Coatings by the
Taber Abraser (D 4060). In these methods, dry abrasive is
applied to a coated panel using a jet blast (D 658) or the force
of gravity (D 968) when the abrasives are free flowing. In the
case of the Taber test, a weighted wheel that has abrasive
embedded in a resilient rubber matrix is used. Because of the
poor reproducibility of abrasion methods, testing should be
restricted to only one laboratory when numerical abrasion
resistance values are to be used. Interlaboratory agreement is
improved significantly when rankings are used in place of
numerical values.
Adhesion
The ability of a film to resist removal from a substrate is
certainly an important coating property. It is evaluated by
many different procedures, almost all of which are not completely satisfactory because the removal force is not applied
at the coating-substrate interface but at the coating surface.
Consequently, when the adhesive bond between coating and
substrate is greater than the cohesive strength of the coating,
failure occurs within the film, so that adhesion, per se, is not
measured. When muhicoat systems are involved, the failure
can also be between coats. Nevertheless, the tests are used to
estimate whether the adhesion is adequate for the intended
service.
The test most commonly used with coatings is ASTM Test
Methods for Measuring Adhesion by Tape Test (D 3359). In
it, a simple procedure for use in the field comprises cutting an
X in the film, applying pressure-sensitive tape over the cut,
removing the tape, and qualitatively assessing adhesion on a
zero to five scale. The more quantitative procedure involves
making a six- or eleven-cut lattice in the film. After applying
and removing the tape, coating removal is evaluated by comparison with a scale that is related to the estimated area of
removal. If a tool that makes all cuts in one direction is
available, the test can be made in the field. However, when
individual cuts are made using a metal cutting guide, the test
is practical only for laboratory use. Since the cuts~ must be
made through the coating to the substrate, the latter must be
sufficiently hard to resist the cutting tool. Consequently, the
test is not applicable on soft substrates such as wood, plastic,
or wallboard [3].
Another laboratory method that requires a relatively hard
substrate is ASTM Test Method for Adhesion of Organic
Coatings by Scrape Adhesion (D 2197). In this method,
704
Wet Adhesion
It is essential that a finish tightly adhere to a given substrate
or primer under the wet conditions of washing or scrubbing.
The wet adhesion procedure described in Method 6301 of
FTMS 141 is essentially an earlier version of Method A of
ASTM D 3359. In it, two parallel cuts are made 1 in. (25 mm)
apart instead of the X-cut. Then masking tape, which changes
markedly in adhesiveness with time, is pressed against the
coating surface with a roller instead of semitransparent tape
being rubbed with a pencil eraser. In this method, the water
immersion prior to testing is described in detail instead of
being referred to in a Note.
Flexibility
Elongation is a measure of a coating's flexibility. Most
semigloss and full gloss coatings can be bent over a i/s-in.
(3.2-mm) mandrel without affecting the film. However, interior flat and eggshell water-borne finishes usually pass at
1/4 in. (6.4 mm), while solvent-borne coatings of the same
category may pass only a 1A-in. (12.7-mm) bend. Flexibility of
interior coatings is usually evaluated using one of the mandrel procedures in ASTM Test Methods for Mandrel Bend
Test of Attached Organic Coatings (D 522). However, measuring elongation directly with a tensile testing machine as
described in ASTM Test Method for Tensile Properties of
Organic Coatings (D 2370) is a much more discriminating
way of estimating the flexibility retention of exterior coatings
[4].
Resistance to Household Chemicals
An important property of some finishes is their ability to
resist discoloration, spotting, softening, blistering, or removal when subjected to household chemicals or strong
cleaners. In ASTM Test Method for Effect of Household
Chemicals on Clear and Pigmented Organic Finishes
(D 1308), the resistance may be evaluated with household
items ranging from cold water, to detergent solutions, to
Interior Finishes
Block Resistance
This is an important property for interior semigloss and
gloss finishes since it governs the resistance of dried coating
surfaces to sticking together when stacked or placed in contact with each other. An interior finish often comes in contact
with itself, especially on doors, windows, and drawers where
it sometimes adheres to itself. Such blocking is dependent on
the hardness of the coating and the applied pressure, temperature, humidity, and time while the surfaces are in contact.
ASTM Test Method for Blocking Resistance of Architectural
Paints (D 4946) covers an accelerated blocking-resistance
procedure especially developed for this type coating.
Print Resistance
The ability of a coating to resist printing is important because its appearance is adversely affected if the surface texture is modified by contact with another surface, particularly
one with a pattern. Interior gloss and semigloss systems applied to window sills and other horizontal surfaces are often
loaded with flower pots and similar objects that tend to leave
a permanent impression from the applied pressure. The tendency for a film to "print" is often a function of the hardness
of the coating and the applied pressure, humidity, and time
while the surfaces are in contact. In ASTM Test Method for
Print Resistance of Architectural Paints (D 2064), the resistance is evaluated by placing a piece of four-ply cheesecloth on
a coated glass slide, and a 500-g weight on a rubber stopper
are added to create pressure. The test is accelerated by
placing the assembly in an oven at 140~ (60~ for an hour.
After cooling, the film is subjectively rated for the degree of
imprinting.
Film Porosity
The more porous a coating, the worse are its cleansability
and enamel holdout. In ASTM Test Method for Porosity of
Paint Films (D 3258), a special, colored penetrating medium
is applied to the coating and the change in reflectance indicates the degree of porosity.
Washability
This p a r a m e t e r is also referred to as "resistance to scrubbing" or "resistance to wet abrasion." ASTM Test M e t h o d for
Scrub Resistance of I n t e r i o r Latex Flat Wall Paints (D 2486)
was developed for interior latex flat wall p a i n t s b u t can be
a p p l i e d to coatings of a l m o s t any type, In the test, the coating
is applied to a b l a c k plastic panel that, during s c r u b b i n g with
a nylon b r u s h a n d abrasive cleaning agent, is raised b y a
n a r r o w shim to c o n c e n t r a t e the test area. The n u m b e r of
b a c k - a n d - f o r t h strokes (cycles) r e q u i r e d to remove the film
over the shim is d e t e r m i n e d . I n t e r i o r latex low-gloss finishes
can vary in scrub resistance from less t h a n 100 to m o r e t h a n
1000 cycles.
ASTM Test M e t h o d for W e t A b r a s i o n Resistance of I n t e r i o r
Paints (D 4213) is similar except that a sponge is used in
place of the bristle b r u s h a n d the shim is not used. In the
original method, the loss p e r 100 cycles to erode the film
a l m o s t to exposure of the b l a c k substrate was calculated on
the basis of either weight or volume. In the c u r r e n t m e t h o d
weight was eliminated, even t h o u g h it is easier to determine,
b e c a u s e volume characteristics, such as p i g m e n t v o l u m e content, usually have a m o r e direct relation to p e r f o r m a n c e ,
w h i c h in this case is scrub resistance or washability.
Cleansability
The older of the m e t h o d s for this type m e a s u r e m e n t , ASTM
D 3450, is s i m i l a r to the w e t - a b r a s i o n method, ASTM D 4213,
except a sponge is used with either the n o n a b r a s i v e o r abrasive cleaning agent to r e m o v e a c a r b o n black-oil stain. The
ability to r e m o v e the stain is expressed as the ratio (in relative
percent) of the reflectance of the cleaned a r e a to that of the
a r e a before a p p l i c a t i o n of the stain. In ASTM Test M e t h o d for
Practical W a s h a b i l i t y [sic] of Organic Coatings (D 4828), num e r o u s staining a n d soiling agents found in service, a n d commercial abrasive or n o n a b r a s i v e cleansers, as well as the
s t a n d a r d i z e d cleaning agents, can be used. In the revised edition, the film m a y be cleansed m a n u a l l y o r mechanically, b u t
only the latter is suitable for i n t e r l a b o r a t o r y testing.
Exterior Coatings
Adhesion to Chalky Surfaces
Latex p a i n t s generally have little ability to p e n e t r a t e powdery substrates. Consequently, a d h e s i o n to previous coatings
that have chalked is p o o r unless the latex p a i n t has been
modified to p e n e t r a t e a n d b i n d the chalk layer to the old
coating. However, certain latexes do exist that are designed to
705
a d h e r e well to chalky surfaces a n d thus do not require modification. At the t i m e of writing, there are no ASTM test methods for a d h e s i o n to chalky surfaces, although w o r k t o w a r d
d e v e l o p m e n t of such a test is proceeding. The i n d u s t r y generally uses a pressure-sensitive tape to test for this property.
The t a p e is pressed firmly onto the dried latex film (fresh films
do n o t a d h e r e as well as aged, d r i e d films) a n d t h e n r e m o v e d
r a p i d l y b y pulling b a c k on itself. M e t h o d 6301 of FSTM 141
describes a similar m e t h o d b u t it includes w a t e r exposure.
Dirt Pickup
Low-gloss exterior latex paints generally have good resistance to dirt pickup, b u t gloss or semigloss latex paints m a y be
m o r e subject to this type of disfigurement. Exterior exposure,
p a r t i c u l a r l y u n d e r a n overhang (soffit), should indicate in a
relatively short time (about one year) a paint's t e n d e n c y to
collect dirt w h e n evaluated in a c c o r d a n c e with ASTM Test
M e t h o d for Quantifying Dirt Collection on Coated Exterior
Panels (D 3719).
F u m e Resistance
S o m e p a i n t s u n d e r g o a change in a p p e a r a n c e , usually
color, w h e n subjected to air containing certain sulfur compounds, notably h y d r o g e n sulfide a n d sulfur dioxide. This
type of a t m o s p h e r e m a y be present n e a r industrial o r o t h e r
p o l l u t e d areas a n d can cause a p a i n t to yellow or d a r k e n in as
little t i m e as overnight. At the t i m e of writing, no ASTM or
federal test m e t h o d s are available for evaluating this color
change, but one p r o c e d u r e used by the i n d u s t r y is as follows:
Apply a sufficient n u m b e r of coats of the p a i n t to two glass
plates to hide completely the glass surface a n d allow to d r y
for 6 h. Then expose one plate in a moist a t m o s p h e r e of
h y d r o g e n sulfide for 18 h. C o m p a r e the color of the exposed
film with that of the unexposed one. The color difference
should not exceed that w h i c h exists b e t w e e n two plates
coated with a p a i n t m a d e with t i t a n i u m dioxide pigment,
lead-free zinc oxide, r a w o r refined linseed oil, and sufficient
cobalt a d d e d for drying purposes, and similarly treated.
REFERENCES
[1] Paint~Coatings Dictionary, Stanley LeSota, ed., Federation of Societies for Coating Technology, Blue Bell, PA 19422, 1978.
[2] Brezinski, J.J., Manual on Determination of Volatile Organic
MNL17-EB/Jun. 1995
60
Artists' Paints
by Benjamin Gavett 1
through experience and education, must be aware of the particular limitations inherent with each type of paint. When
new applications are explored, as is often the case with art, it
becomes necessary to select and perform tests which will
provide confidence that the finished artwork will have the
desired physical integrity.
The tests described in this section have been found to be
useful to quantitatively and qualitatively describe various
characteristics of artists' paints. Acceptability of quality is
determined between buyer and seller. In practice, it is largely
dependent upon what is considered characteristic of the particular paint type. Many of these test methods are ASTM
standards that the reader should consult for further details. It
is important to note that there are ASTM standard specifications for several types of artists' paints, including acrylic
emulsion, watercolor, oil, resin-oil, and alkyd. These represent the current consensus, between producers, consumers,
and other interested parties, of minimally acceptable performance characteristics and other criteria. Most of the following test methods were not developed for artist paints in
particular. Due to the wide spectrum of types of artists' paints
and potential uses, this listing does not include all test methods that may be relevant. Those included are of varying importance and applicability. They are in alphabetical order,
grouped loosely into several categories: Shelf Stability, Working Properties, Film Properties, and Safety and Compliance.
Shelf Stability
It is common for art materials to languish for years on store
shelves prior to being purchased. Once purchased, a container is typically opened and closed many times during a life
cycle which may take months or years. Stability is evaluated
to help ensure endurance of the product through foreseeable
conditions of storage and use.
Appearance
The appearance of the undisturbed paint in the container
creates an impression of quality, regardless of the ease of
restoring it to a homogenous condition. Evaluations for appearance in the retail container are most accurate when
based on true conditions of storage and use. However, this is
not practical when developing new products. Potential failure
may be more quickly realized by placing samples in a laboratory oven at moderately elevated temperature. As the difference between normal and test temperature increases, accuracy in predicting potential problems may decrease because
higher temperatures may exaggerate changes. In a study of
www.astm.org
Color Change
Sometimes the color of a paint film produced from a container of paint changes during storage, for example, as can
happen when a pigment is not compatible with the pH of the
formulation. This may be determined by preparing a fresh
batch of the paint to be tested and immediately preparing a
drawdown from it. Subsequent drawdowns at the same thickness may be periodically prepared from the same batch after
the paint has aged in the container. The subsequent
drawdowns are compared against the original. The results
obtained from this test may be accelerated by using a laboratory oven.
Consistency
During storage and use, it is desirable that the paints maintain their intended texture and body. Evaluations are based
on visual observation and workability with typical application tools. Items to note include mealiness, tackiness, elongation, and break, as well as other body characteristics. Conclusions may be drawn by comparing batches of the same
formula, made at different times, which have been stored and
otherwise treated similarly. It is useful to evaluate both full
and partially empty containers.
Flocculation
To determine if the pigment is fully dispersed or has remained dispersed over time, a tint of the color is prepared
with a compatible white. A drawdown is made and the excess
paint is recovered and set aside until the drawdown is dry.
Next, a small amount of the original wet mixture is placed on
top of the dried paint film. This paint is then rubbed under
pressure in a circular motion (a gloved thumb is suitable) in
an effort to cause further dispersion of the pigment. If it has
become more fully dispersed, the rubbed paint will appear as
a stronger tint against the original drawdown.
Freeze-Thaw Stability
Shipping and storage often expose artists' paints to extreme
temperature fluctuations. Water-based paints can be quickly
ruined if not formulated for protection from freezing. ASTM
Specification for Artists' Acrylic Emulsion Paints (D 5098), in
Section 6.10 of the ASTM Book of Standards, describes the
procedure used for testing acrylic paints. The same procedure is used for watercolors. To meet the requirements of the
standard, the paints must pass five freeze-thaw cycles while
retaining proper consistency.
Package Integrity
The expected life and use of the package containing the
paints should be considered when designing appropriate
tests. Consider, for example, how the container will be shipped or how many times a tube will be flexed. Potential interactions between the paint and packaging should also be eval-
Seeding
Paint ingredient incompatibilities may result in the formation of agglomerates. This can be readily observed by preparing drawdowns of the paint, as described in ASTM Practice for Preparing Drawdowns of Artists' Paste Paint (D 4941)
and examining the dried paint film. ASTM Test Methods for
Coarse Particles in Pigments, Pastes, and Paints (D 185) may
also be used.
Settling
In low-viscosity formulations, it is common for pigments to
exhibit some settling. Ideally this would not happen, but if it
does, it is important that the pigments are easily remixed.
Settling that occurs over time may be evaluated according to
ASTM Test Method for Evaluating Degree of Settling of Paint
(D 869).
Spoilage~Putrefaction
It is necessary to protect against microbial contamination
from raw materials and packaging or that may be introduced
during manufacturing. Also, since artists' paints are typically
opened, used, and reclosed many times, it is important that
they be formulated to resist microbial growth from contamination occurring subsequent to purchase by the consumer.
ANSI Z356.5, American National Standard for Art and Craft
Materials-Paints and Inks, Section 4.2, describes a test
method for evaluating the effectiveness of preservatives used
in paint formulations. Paints to be tested are inoculated with
pieces of bread which have been covered with a sugar solution and allowed to mold. After two weeks, the paints are
inspected for decomposition.
Viscosity Changes
Paint stability is quickly and quantitatively evaluated by
monitoring viscosity. Viscometer type and method have not
been standardized for artists' paints. If needed, a method may
be agreed upon between buyer and seller. For most purposes,
it is sufficient to ensure consistency of test conditions and
equipment when doing periodic rechecks. Accelerated aging
with the use of a laboratory oven is usually predictable of
real-time viscosity stability of water-based paints.
Working Properties
Many attributes of importance to the consumer of artists'
paints are difficult to measure and report with repeatability.
This subjectivity is often coupled with varying preferences
among users. An ideal paint for one artist may be lacking in
certain qualities for the next. It is not as important to standardize these characteristics as it is to determine them and
transfer this knowledge to the buyer.
Brushing Characteristics
Paints are brushed out on standard substrates by experienced technicians and rated as being smooth, sticky, tacky, or
fluid, as described in Section 6.6 of Commercial Standard
708
(CS98) for Artists' Oil Paints [2]. This was the original quality
standard for artists' paints and was the base from which the
subsequent ASTM artists' paint quality standards were developed. It is also common to describe artists' paints for their
tendency to flow and level or hold brush strokes and peaks.
Color Variation
If constancy of color is desired, it may be determined by
placing samples next to each other on a test card and drawing
them down together using a thin film applicator. Comparisons of masstone, undertone, and tint are useful. For quantification and reporting, spectrophotometric measurements
and C.I.E. L*a*b* color difference may be obtained according
to the practices described in ASTM Test Method for Calculation of Color Differences from Instrumentally Measured
Color Coordinates (D 2244).
Drying Time
ASTM D 5098, for acrylics, and ASTM Specification for
Artists' Oil, Resin-Oil, and Alkyd Paints (D 4302), specify drying time requirements. Dust-free drying time of these and
other types of paints are determined by following the procedures described in ASTM Test Methods for Drying, Curing, or
Film Formation of Organic Coatings at Room Temperature
(D 1640).
Viscosity
Artists' paints are available in a wide range of viscosities,
from pourable ink-like to heavy impasto. Oil paints are typically expected to maintain definition of the brush stroke,
provide sharp peaks, and retain their shape as they emerge
from the tube. Water-based vehicles are highly manipulative,
and the desired viscosity is dependent on the intentions of the
user and manufacturer. Viscosity, thixotropy, and dilatancy
may be determined with the equipment and techniques described in ASTM Test Methods for Rheological Properties of
Non-Newtonian Materials by Rotational (Brookfield) Viscometer (D 2196).
Film Properties
Fineness of Dispersion
Adhesion
Finely dispersed pigments are important for smooth brushing, realizing tinting strength potential, and maximizing encapsulation of pigment within the binder. ASTM Test Method
for Fineness of Dispersion of Pigment-Vehicle Systems
(D 1210) may be followed to measure this characteristic.
Intercoat and substrate bonding of artists' paints are extremely important. They become especially critical to evaluate when determining surface preparation techniques for
new or unusual substrates or when considering multi-media
applications. There are many types of adhesion testing apparatuses, but a useful and inexpensive test involves cutting the
paint films and attempting to lift them with pressure-sensitive tape. This is described in ASTM Test Methods for Measuring Adhesion by Tape Test (D 3359).
Odor
Evaluation of odor may be important in determining potential consumer acceptance of artists' paints. The different
vehicles have characteristic odors and what is objectionable
to some may not be to others. Formula variations may be
rated, based on the acceptability of their odor, by a panel of
intended users.
Bleeding
Tinting Strength
Block Resistance
Opacity
Chemical Resistance
Resistance to the various liquids which a painting may be
expected to come into contact with is an important characteristic. These include varnish vehicles, solvents used in varnish
removal, and cleaning solutions that may be used on the
paint film. Chemicals to be tested with a particular paint vary
depending on the type of paint and what is expected of it. A
procedure for designing appropriate tests may be based upon
the Spot and Immersion Tests described in ASTM Test
Method for Effect of Household Chemicals on Clear and
Pigmented Organic Finishes (D 1308).
Flexibility
Paints applied to flexible supports, such as stretched cotton
or linen canvas, may be susceptible to potentially destructive
forces. The different types of artists' paints vary in the degree
they will flex without failure. Although there are no established standards, they have different thresholds of expectation and, therefore, acceptability.
During storage or shipping, paintings are often rolled up.
ASTM Test Methods for Mandrel Bend Test of Attached Organic Coatings (D 522) describes equipment and methods for
determining and rating flexibility. Relevancy is increased by
testing the coatings over the intended substrate and primer.
Combined with the use of accelerated aging techniques, the
mandrel test will help predict natural embritflement of the
paint film.
Paintings must also endure expansion and contraction of
the fabric due to changes in environmental humidity and
temperature. Sometimes these conditions become extreme,
as when a painting is shipped during freezing weather. Failure will occur more quickly if the individual components of
the painting have greater relative differences in their moduli
of elasticity. Use of a temperature and humidity-controlled
environmental chamber programmed to expose paintings to
repeated cycles of extreme conditions will accelerate the failure that might be observed over time under normal conditions.
Another force of concern is mechanical impact against the
film that may occur during handling. For example, when a
painting is mounted on an open-back stretcher, fingers may
inadvertently press into it as it is being carried. The risk of
damage increases as temperature decreases and the glass
transition temperature is approached. The rate at which external forces are applied also influences susceptibility to damage.
Lightfastness
ASTM Test Methods for Lightfastness of Pigments Used in
Artists' Paints (D 4303) describes three methods used to determine resistance to fading of acrylic, watercolor, alkyd, and
resin-oil artists' paints. Included are conditions of exterior
exposure under glass, artificial daylight fluorescent lamps,
and xenon-arc apparatus. Prior to exposure, samples to be
tested are tinted with white until they reach 35 to 45% reflectance at their wavelength of maximum absorption, between
420 and 620 nm. With each method, exposure is continued
until specimens have been exposed to a total radiant dose of
1260 MJ/m 2. To meet the ASTM standard specifications for
use in artists' paints, the pigments must be tested under at
least two of the three methods and exhibit a mean color
change of less than eight color difference units (CIE 1976
L*a*b* color difference equation). These test methods are
designed to predict performance of artists' paints displayed in
typical household or museum environments. Results may not
be indicative of performance if the intended use is more
rigorous, such as in exterior mural applications.
The most recently developed ASTM practices for determining the lightfastness of artists' materials uses a method of
exposing samples indoors to sunlight filtered through window glass while simultaneously exposing a series of eight ISO
Blue Wool Reference materials to control the duration of
exposure. One half of each specimen and control is shielded
from exposure during the test. This test takes longer to run,
but it is relatively inexpensive. It is intended for artists' materials which are not specifically covered by other ASTM standard test methods. For details, see ASTM Standard Practice
for the Visual Determination of the Lightfastness of Art Materials by the User (D 5398) and ASTM Standard Practice for
the Visual Determination of the Lightfastness of Art Materials
by Art Technologists (D 5383).
Yellowing
While traditional paint vehicles may be expected to yellow
to some degree, this may be considered a serious flaw if encountered in the newer generation of synthetic media. To
determine the relative potential for yellowing of a vehicle, a
standard titanium dioxide white pigment may be formulated
into the test vehicle and into one of known stability. They are
then exposed to the accelerated methods described in ASTM
D 4303 and amount of yellowing determined with ASTM
Practice for Visual Evaluation of Color Differences of Opaque
Materials (D 1729) or Test Method D 2244. It is also useful to
subject films of the unpigmented vehicles to the same tests.
Gloss
Some manufacturers of artists' paints will add inert flatting
agents to control the gloss values of the various colors so that
they are similar within a line. Others will allow a color's gloss
to be dictated by the characteristics of the colorant, i.e., tolerable load and particle size. Gloss values for artists' paints
have not been standardized. It is a matter of preference and
manufacturing philosophy. When required, gloss may be
specified between the buyer and seller, with measuring parameters identified.
Flash Point
Solvent-based paints may require flash point determination for label warnings and to determine applicability of
shipping regulations. The prescribed test method can vary
depending on the authority. ASTM Test Methods for Flash
Point of Liquids by Setaflash-Closed-Cup Apparatus (D 3278)
is usually applicable.
710
P A I N T A N D COATING T E S T I N G M A N U A L
Toxicological Evaluation
The Federal Hazardous Substances Act (FHSA) requires all
art materials to be evaluated by a board-certified toxicologist
for potential to cause acute and chronic health effects. This
law was incorporated into the FHSA with the Labeling of
Hazardous Art Materials Act (LHAMA), the basis of which is
ASTM Practice for Labeling Art Materials for Chronic Health
Hazards (D 4236). A wide assortment of test methods provide
the information required for the toxicological assessment.
These are not specified by the Standard Practice or LHAMA,
but include all which are embodied in the field of toxicology
as well as compositional analysis of the paints and their
constituents. For example, test procedures described in EN71-3:1988, Safety of Toys, are used to determine solubility of
metals present in paint, under conditions intended to simulate 4 h in the human alimentary tract. In vitro techniques are
also used for determining potential eye and skin irritation.
The toxicologist determines any testing that may be required
to supplement the information that exists for the raw materials in a product. Appropriate precautionary label information
is then assigned. The toxicologist must supply the criteria
used in making these determinations to the Consumer Product Safety Commission, the enforcement agency of the Federal Hazardous Substances Act.
REFERENCES
[1] Yates, T. P., Boyer, M., Braunshausen, R., Drucker, T. R., Greenwald, J., Marek, E. F., Foote, F., Olholt, G., Stromberg, D., and
Scimecca, F. S., "Oven vs Shelf Stability of Latex Paints," Journal
of Coatings Technology, Vol. 59, No. 745, February 1987.
[2] Mayer, R., The Artist's Handbook of Materials and Techniques, 4th
ed., 1981, The Viking Press, New York, pp. 651-665.
BIBLIOGRAPHY
The following books provide additional reading on the subjects of artists' materials, their uses, history, and characteristics. These books also contain extensive reference sections.
Feller, R., Ed., Artists" Pigments, Vol. 1, 1986, Cambridge University
Press, Cambridge, England.
Gottsegen, M., The Painter's Handbook, 1993, Watson-Guptill Publications, New York.
Mayer, R., The Artist's Handbook of Materials and Techniques, 1981,
The Viking Press, New York.
MNL17-EB/Jun. 1995
61
by Rose A. Ryntz I
Electrodeposited Primer
Anodic electrodeposition was first i n t r o d u c e d in the 1960s
a n d was subsequently r e p l a c e d b y the cathodic process in the
1970s. A p p r o x i m a t e l y 75% of all cars m a n u f a c t u r e d in the
w o r l d are p r i m e d using this process.
Following p r e t r e a t m e n t , metal parts are i m m e r s e d in the
electrocoat dip tank. The p a i n t itself is 75 to 95% water. Upon
a p p l i c a t i o n of an electrical potential, i.e., voltage, a p a i n t film
possessing 85 to 100% solids is d e p o s i t e d u p o n the parts.
Once deposited, the p a i n t film acts as a resistor, increasing
the resistivity as the film thickness increases. This accounts
for the fact that as one a r e a of a p a r t is coated, uncoated, or
relatively less coated, areas d r a w increased current, resulting
in a very u n i f o r m coating regardless of the substrate s h a p e o r
complexity.
The electrocoat technology, often consisting of an a m i n o
extended epoxy resin cross-linked with a blocked isocyanate,
provides c o r r o s i o n p r o t e c t i o n over cold-rolled steel for u p to
400 to 500 h in a salt fog cabinet. N o r m a l film builds of the
d r i e d electrocoat film range from 0.8 to 1.5 mils. The elect r o c o a t technology is referred to as n o r m a l build, low build,
www.astm.org
712
Conductive Primer
Conductive Primer
Weatherable, conductive p r i m e r s can be utilized over flexible or rigid substrates to provide a p a r t w h i c h can be electrically grounded. The r e q u i r e m e n t s for conductivity are m u c h
the s a m e as those d e s c r i b e d above for n o n w e a t h e r a b l e conductive p r i m e r s with conductive p i g m e n t s utilized to provide
resistance.
W e a t h e r a b l e conductive p r i m e r s are often utilized in rubstrip areas, i.e., the black strip on a b u m p e r or fascia, to
provide a two-tone a p p e a r a n c e . Accent colors are applied
a d j a c e n t to the conductive p r i m e r to provide aesthetically
pleasing parts.
W e a t h e r a b i l i t y r e q u i r e m e n t s are m u c h the s a m e as those
d e s c r i b e d later for m o n o c o a t technology. The c h e m i s t r y utilized to achieve the w e a t h e r a b l e n a t u r e of the p r i m e r is the
s a m e as that d e s c r i b e d above for w e a t h e r a b l e primers.
Nonconductive Primer
A n o n c o n d u c t i v e p r i m e r is not c a p a b l e of holding an electrical potential a n d is utilized to provide a "Class A" surface. A
"Class A" surface is a surface which, w h e n topcoated, will
provide the s a m e a p p e a r a n c e characteristics (gloss a n d distinctness of image) as a t o p c o a t e d m e t a l part. The nonconductive p r i m e r can be utilized over metal or plastic parts to
provide filling characteristics to p o r o u s o r m a r r e d surfaces.
The c h e m i s t r y of a nonconductive, n o n w e a t h e r a b l e p r i m e r
is often the s a m e as that e m p l o y e d in the conductive primer.
F i l m thicknesses range from 0.8 to 1.2 mils. Very often, the
n o n c o n d u c t i v e p r i m e r is utilized over only rigid substrates,
i.e., m e t a l a n d rigid plastics. The p r i m e r can be "color keyed"
to the t o p c o a t color (i.e., red if a r e d t o p c o a t is to be applied)
so that a b e r r a t i o n s in the t o p c o a t (i.e., chips, scratches) will
not be as noticeable.
Primer (Weatherable)
Primer~Surfacer
W e a t h e r a b l e p r i m e r s are utilized to provide a UV d u r a b l e
finish over mostly flexible plastics. The p r i m e r is often color
c o o r d i n a t e d to the t o p c o a t color to provide an aesthetically
pleasing accent color. One could also refer to w e a t h e r a b l e
p r i m e r s as m o n o c o a t topcoats.
Primers in this class are m o s t l y flexible acrylic or polyesterb a s e d resins cross-linked with m e l a m i n e (one-component) o r
an aliphatic isocyanate (two-component). They m u s t m e e t
the s a m e flexibility r e q u i r e m e n t s as t o p c o a t s at 1.2 to 1.5
Topcoats
Interior Topcoat
An interior t o p c o a t is utilized to provide a protective a n d
decorative surface suitable for use on interior parts m a d e of
steel, a l u m i n u m , zinc-based die castings, plastics, pulp preform m o l d e d board, or o t h e r substrates. The t o p c o a t often
provides a p a r t i c u l a r feel, i.e., "soft leather feel," o r a desired
gloss, i.e., less t h a n 6/60 ~ gloss meter, to stop blinding reflections.
The c h e m i s t r y of the interior t o p c o a t varies d e p e n d i n g on
the curing process utilized, i.e., air-dry, low-temperature, or
h i g h - t e m p e r a t u r e cure. Acrylic a n d u r e t h a n e technology have
been the m a j o r chemistries utilized. On h a r d - t o - c o a t substrates, a p r i m e r is often utilized to gain adhesion.
W e a t h e r a b i l i t y a n d "fogging" are two i m p o r t a n t test specifications to which the t o p c o a t m u s t abide. "Fogging," described later, refers to the m i g r a t i o n of plasticizers in the
coated substrate. This is of p a r t i c u l a r concern on i n s t r u m e n t
panels a n d d a s h b o a r d s since embrittleness of the substrate
and/or w i n d s h i e l d c o n t a m i n a t i o n will occur.
Exterior Topcoats
Monocoat--A m o n o c o a t technology, as the n a m e implies,
is a final single coat w h i c h provides color, gloss, DOI (distinctness of image), a n d durability. It is a p p l i e d to a total d r y
film thickness of b e t w e e n 1.5 a n d 2.5 mils d e p e n d i n g u p o n
color a n d hiding requirements. It should be satisfactory for
use over specified primers, sealers, or o t h e r enamels, as in
r e p a i r or two-toning operations. Paints specified u n d e r this
s t a n d a r d can contain acrylic resin, u r e t h a n e resin, alkyd
resin, etc. as the m a i n b i n d e r w h i c h is subsequently crosslinked with a m e l a m i n e resin [referred to as a o n e - c o m p o n e n t
(1K) paint] or an isocyanate resin [referred to as a two-comp o n e n t (2K) paint]. Necessary p i g m e n t s a n d additives are
b l e n d e d a n d included to achieve final color match. Paints
shall not contain toxic substances such as chrome, c a d m i u m ,
etc. u n d e r the Toyota specification.
The c h e m i s t r y of the m o n o c o a t is modified as n e e d e d to
reflect its use over flexible or rigid substrates. The corres p o n d i n g cure r e q u i r e m e n t s are m a t c h e d with the s u b s t r a t e
713
Gray:
L*
65.61
a*
- 1.55
b*
9.84
(utilizing 10~ Standard Observer and Illuminant D65).
PFUND Crytometer Hiding Power--The hiding power in
Chrysler Material Standard MS-PP 1-1 covering paint requirements and performance over plastics is determined with a
Pfund crytometer, utilizing the 0.09-ram (0.0035-in.) wedge
(unless otherwise specified). The hiding power is specified in
the material standard covering the individual coating.
Odor
The material's odor is reviewed in reference to current production materials. Any significant differences must be evaluated in laboratory and production trials. Odor testing is performed at an approved laboratory.
Flammability
Although not a requirement for the supplier, a flash point
of below 27~ necessitates the user to classify paint as a
potential fire hazard. Plant security must assure that proper
fire precautions are provided.
Smoke Characteristics--General Motors requires that a
material's tendency to smoke during processing be reviewed
in comparison to current production materials. Any significant differences must be evaluated in laboratory and production trials.
Material Requirements
Solvent Emissions
ASTM Test Method for Hiding Power of Paints by Reflectometry (D 2805) covers the determination, without reference to a material paint standard, of the hiding power of
paints with Y tristimulus values greater than about 15%. It
uses the Kubelka-Munk equations to calculate the hiding
power from reflectance results obtained by broad-band filter
reflectometry. It is utilized by General Motors for all automotive exterior topcoat materials.
All topcoat materials must meet specific plant solvent emissions restrictions at spray viscosities which yield acceptable
applied appearance. Chrysler specifies that the material shall
comply with all the requirements of the Clean Air Act ( u s e
1857, as amended) and any applicable federal, state, or local
statute pertaining to the establishment and maintenance of
the National Ambient Air Quality Standards as administered
by the Environmental Protection Agency (EPA) or any authorized state or local governmental unit. The material shall
comply with all of the requirements of the Water Pollution
Control Act (PL 92-500, as amended) and shall be formulated
to eliminate, as far as possible, constituents that would be
classified as hazardous under the Resource Conservation and
Recovery Act (40CFR 260-265, as amended). The material
shall contain no benzene, chlorinated, or other toxic compounds.
Percent Solids by Weight--The weight solids of a material
are determined according to ASTM Test Methods for Volatile
Content of Coatings (D 2369B).
Percent Solids by Volume--The volume solids of a material
is determined according to ASTM Test Method for Volume
Nonvolatile Matter in Clear or Pigmented Coatings (D 2697).
REQUIREMENTS
L*
a*
b*
25.74
-0.13
-0.11
714
C 70_+4
D 62 _+ 3
E 50+_3
H 10+_3
J 6 max
Viscosity
1. Newtonian Viscosity
For Newtonian materials, the viscosity is measured according to ASTM Test Method for Viscosity by Dip-Type Viscosity
Cups (D 4212) with a dip-tank viscosity cup.
2. Non-Newtonian Viscosity
For non-Newtonian materials, the viscosity is determined
according to ASTM Test Method for Rheological Properties
of Non-Newtonian Materials by Rotational (Brookfield) Viscometer (D 2196) with a rotational (Brookfield) viscometer.
3. Viscosity Stability
The stability of a material to settling or change in viscosity
is usually conducted at package viscosity (as shipped). Tests
are run after standing for 90 days at room temperature and as
a function of accelerated heat aging (oven stability). The material after aging must be free of settling which cannot be
dispersed by normal agitation and must not increase in viscosity by a percentage of its original viscosity.
Throwpower
The throwpower, in reference to cationic electrodeposition
coatings, is the degree to which an electrodeposited film coats
interior or recessed areas. Specific requirements are dependent upon voltage, resin type, and auxiliary electrode type
and will vary by production plant.
pH
The pH of waterborne materials shall be determined according to ASTM Test Method for pH of Aqueous Solutions
with the Glass Electrode (E 70) and for electrocoat baths
according to ASTM Test Method for Measurement of Apparent pH of Electrocoat Baths (D 4584).
Resistivity~Conductivity
The resistivity of a material shall be determined according
to ASTM Test Methods for Electrical Conductivity and Resistivity of Water (D 1125).
Performance Requirements
Color
The material shall match the appropriate master color
standard after all the baking cycles for the particular color.
Gloss
The gloss of an interior coating is measured on a Hunter
specular glossmeter at 60~ and shall be specified by means of
a letter suffix to the color number assigned by styling as
follows:
A 92min
F 35 _+ 3
B 80_+4
G 20_+3
The material shall be subjected to a DORIGON (distinctness of reflected image goniometer) and shall he within specified materials standard values.
Appearance
The topcoat shall be smooth and uniform, free of sags,
craters, pinholes, seediness, abnormal roughness, or excessive metallic mottling. It shall have reasonable tolerance for
ordinary cleaning and exhibit excellent polishing characteristics.
Film Thickness
A material's film thickness shall be determined according
to ASTM Test Method for Nondestructive Measurement of
Dry Film Thickness of Nonmagnetic Coatings Applied to a
Ferrous Base (D 1186).
Hardness
The material shall have sufficient hardness to resist
marring through normal handling.
Micro Hardness--The microhardness of materials applied
over rigid substrates shall be determined on a TUKON hardness tester according to ASTM Test Methods for Indentation
Hardness of Organic Coatings (D 1474A).
Taber Wear Resistance--There shall be no material removal
greater than the approved reference panels when tested according to ASTM Test Method for Abrasion Resistance of
Organic Coatings by the Taber Abraser (D 4060-81).
Adequacy o f Cure
Upon subjection to solvent exposure by (methyl ethyl ketone or xylene) double rubs with a cloth, there shall be no
transfer of the material's color nor dulling or softening of a
clearcoat.
Adhesion
Initial Adhesion--The film shall adhere tightly and not
flake, crack, or powder from the substrate. When scribed with
a crosscut (X-scribe) or crosshatch, the coating should maintain a minimum of 99% adhesion after taping the area.
Moisture Resistance--After exposure to 100% relative humidity [ASTM Practice for Testing Water Resistance of Coatings in 100% Relative Humidity (D 2247)], the coating should
maintain 99% adhesion when tested as above.
Gravelometer
The chip resistance of a coating is determined according to
SAE J400 and ASTM Test Method for Chip Resistance of
Coatings (D 3170). The chipping shall not exceed a predetermined ranking.
Fluid Resistance
When subjected to the specified fluids by the methods and
times specified in the applicable standards, the coating shall
show no loss of adhesion, blistering, softening, swelling, or
discoloration:
9 xylene
9 synthetic gasoline
9 synthetic gasohol
9 naphtha
9 recommended cure check solvent
9 tap water
9 acid rain mixture
Immersion Test--The material shall show no loss of adhesion, blistering, softening, swelling, or discoloration when
subjected to immersion testing in the specified fluids according to ASTM Test Method for Effect of Household Chemicals
on Clear and Pigmented Organic Finishes (D 1308).
Corrosion Resistance
There shall be no blistering or more than 3-ram rust
creepage or loss of adhesion from a line scribed through to
bare steel when exposed to salt spray resistance according to
ASTM Test Method of Salt Spray (Fog) Testing (B 117) conditions for a specified time interval.
Permeability
For porous plastic substrates, i.e., SMC (sheet molding
compound), certain manufacturers are requiring that coating
materials be tested to solvent penetration resistance standards. General Motors, in particular, has developed a "fluorescent dye microscopy" test to limit the amount of solvent
permeation into SMC from conductive primers.
Crock Resistance
The material shall not transfer any color onto a cloth when
exposed to the dry crock method set out in the SAE J861
method.
Flexibility
Coatings intended for use on flexible or semirigid substrates shall exhibit no cracking or induced substrate failure
when subjected to bending over mandrels of various diameters at predetermined temperatures.
Water Resistance
The material shall not blister, dull, wrinkle, or peel when
subjected to controlled condensation according to ASTM
Practice for Testing the Water Resistance of Coatings Using
Controlled Condensation (D 4585) m e t h o d a n d X-scribed.
Weatherability
Test panels for Florida durability (facing 5~ south from
horizontal) and accelerated weathering durability are prepared in accordance with manufacturer's recommendations
for film thickness and bake. The coating shall meet customer
goals for useful life as measured by gloss retention and general appearance guidelines (color, adhesion, etc.).
QUV Exposure--Accelerated exposure is run according to
SAE J2020 or ASTM Practice for Operating Light- and WaterExposure Apparatus (Fluorescent UV-Condensation Type)
for Exposure of Nonmetallic Minerals (G-53) methods depen-
Process Requirements
Basic property feasibility must be established as part of
material qualification with each automotive manufacturer.
Boundary conditions for key process control parameters
must be established as to their effects on film build, appearance, and durability.
Viscosity
Viscosity versus temperature charts at various shear rates
must be furnished.
Color Feasibility
A statistically designed experiment matrix must be run on a
minimum of colors per standard procedure.
Transfer Efficiency
Initial comparisons will be made with current approved
materials under controlled laboratory conditions to establish
relative transfer efficiency.
Bake Latitude
A chart depicting acceptable, unacceptable, and marginal
conditions for cure based on appearance, durability, and
glass bonding (if applicable) characteristics of the coating
must be furnished.
716
Circulation Stability
The supplier must establish that coating performance will
not be degraded under typical, normal production use. Flow
velocity required to maintain suspension or redisperse settled
pigment must be provided prior to loading a circulation system.
Crater Resistance
Compatibility with plant-specific materials must be verified
with all materials. Typical materials with which the coating
must be compatible include sealers, primers, underbody
deadeners, plastic substrates, competitive coatings, etc.
The sensitivity of a coating to crater from common in-plant
contaminants (i.e., equipment oils, personal hand lotions,
etc.) must also be established.
BIBLIOGRAPHY
ASTM, Annual Book of ASTM Standards, Section 6 Paints, Related
Coatings, and Aromatics, vol. 6.01, 1990.
Chrysler Motors Corporation Engineering Standard, Material Standards MS-PP14-1, MS-PPI-1, MS-PD48-1.
Ford Motor Company Engineering Material Specifications ESBM33J100-A, ESB-M6J106-C, ESB-M2J218-A1, ESB-M2J218-A2,
ESB-M33J3-A1, ESB-M33J3-A2, ESB-M33J3-A3, ESB-M2J222-A.
General Motors Corporation Engineering Standards GM4349M,
GM4365M, GM4367M.
Toyota Motor Corporation Engineering Standard TS H3111G.
MNL17-EB/Jun. 1995
62
Can Coatings
by Martin B. Price 1
THE CONTAINERINDUSTRY IS A MAJOR USER of p a i n t s a n d coatings. The r e p o r t e d n u m b e r of cans u s e d in the United States
p e r y e a r is a b o u t 130 billion. The m a j o r i t y of these are coated
individually, m o s t with different coatings on each side. These
coatings provide c o r r o s i o n resistance, c o m p l i a n c e with strict
food safety and taste requirements, a n d p r e s e n t attractive
long lasting identification characteristics to each container.
The processes r e q u i r e d for the efficient a n d e c o n o m i c a l l y
acceptable m a n u f a c t u r e of two- a n d three-piece cans a n d can
ends involve c o m p l e x engineering. Unique coatings characteristics are r e q u i r e d to c o n f o r m with these complex m e c h a n ical systems. A m a j o r i t y of the tests currently in use to ensure
t h a t all the r e q u i r e m e n t s are m e t are discussed. A brief description of the processes for can p r o d u c t i o n is included.
D E S C R I P T I O N OF T H E CAN I N D U S T R Y
1991
Beer Cans
Aluminum
Steel
Total
Soft Drink Cans
Aluminum
Steel
Total
All Beverage Cans
Aluminum
Steel
Total
% Change
38 428
400
38 828
38 751
400
39 151
- 0.08
0.0
-0.08
52 955
2 855
55 810
49 235
4 090
53 325
7.6
-30.2
4.7
91 383
3 255
94 638
87 986
4 490
92 476
3.9
27.5
2.3
(Fig.
I)
717
www.astm.org
718
720
Viscosity Stability--The coating can be evaluated for longterm stability by placing a sample in an oven at 120~ (48.8~
for an extended time period. Forty days is a typical test
period. The change in viscosity can be evaluated every seven
days using the technique employed to rate initial viscosity. In
addition, settling, agglomeration, or other changes in appearance can be noted.
Density--Density can be measured by using a Gardner
"Weight per Gallon" cup [ASTM Test Methods for Indentation Hardness of Organic Coatings (D 1474)]. The process
involves equilibrating the product to 25~ and pouring it into
a cleaned cup up to the fill mark, taking care to prevent
foaming. The cap is pressed onto the cup and the overflow
carefully wiped from the outside of the cup. The cup is then
weighed on an analytical balance and pounds/gal calculated
by multiplying the number of grams of paint in the cup by 0.1.
Volatile Organic Compounds (VOC)--The determination of
the VOC of a coating requires an analytical balance and an
oven controllable at 110 _+ 5~ [ASTM Test Methods for
Volatile Content of Coatings (D 2369)]. The specimen is
placed in an aluminum dish and after dilution with solvent is
baked for 60 min and the percent weight loss of the sample
determined. This is the percent volatile content.
The volatile organic compound content (VOC) is determined according to Federal Reference Method 24, using the
weight % volatile content, the density of the liquid coating,
and the weight percent water content, using the equations
shown in ASTM Practice for Volatile Organic Compound
(VOC) Content of Paints and Related Coatings (D 3960).
Fineness of Grind--This test is used for the determination
of the fineness of dispersion of pigments in a pigmented
coating. A Hegman Grind Gauge with a double-wedge steel
scraper placed on a flat, nonskid surface is used (ASTM
D 1260). A sample of coating is applied at the deep end of the
groove of the gauge surface so it slightly overflows the total
groove. The scraper is then drawn down over the entire length
of the gauge with sufficient pressure to clean the sides of the
gauge. A reading should be made at this point without delay.
The reading consists of a visual observation made by viewing
the side of the gauge perpendicularly to the drawn coating:
the point where the sample shows a definite speckled pattern
is read from the numbers on the side of the gauge. The quality
of the dispersion is a measure of the effectiveness of the
grinding operation in dispersing of pigments for pigmented
coatings or of additives, such as wax, for clear samples.
Flash Point--The flash point of a coating is the minimum
temperature at which vapor given off by the coating will
ignite when exposed to a spark or flame. The Department of
Transportation standards for shipment places a minimum
flash point requirement for these coatings. A method to determine what is referred to as a closed-cup rating flash point
uses a Seta Flash apparatus [ASTM Test Methods for Flash
Point of Liquids by Setaflash-Closed-Cup Apparatus
(D 3278)]. For an open flash point, a Tag open-cup method is
often used [ASTM Test Method for Flash Point by Tag Closed
Tester (D 56)]. In both methods the substance under test is
heated at a controlled rate (for example, 2~
and a flame
is passed over the surface. The flash point is defined as the
temperature at which definite ignition is observed.
Cure Speed--A variety of methods have been devised for the
determination of this difficult to determine and even difficult
TM
721
722
Mobility/Lubricity--This i m p o r t a n t characteristic of a
coating can be m e a s u r e d using an AltekTM Mobility/Lubricity
Tester (Fig. 4).
The can or flat s a m p l e is m o u n t e d on the unit, and a test
sequence is initiated by sliding a weight across the sample.
The coefficient of friction is d e t e r m i n e d a n d is indicated directly on an electronic analog meter.
Stability to Food Processing and Pasteurization Conditions-Many foods are p a c k e d into containers in an
u n c o o k e d state. Cans are sealed a n d the entire can is processed at an elevated t e m p e r a t u r e for the p e r i o d r e q u i r e d to
c o m p l e t e the food processing. A characteristic test p e r i o d is
1 h at 250~ (121~ in an autoclave. D e t e r m i n a t i o n of the
ability of a coating to w i t h s t a n d this t r e a t m e n t is often m a d e
by careful e x a m i n a t i o n of a section of coated substrate w h i c h
has been m a n d r e l b e n t (ASTM D'1737). The section so
treated is then p e r m i t t e d to cool a n d next exposed to 100%
humidity, at 100~ (37.7~
for 16 to 24 h. After cooling,
visual e x a m i n a t i o n of the surface for discoloration, for film
rupture, a n d for adhesion, especially in those areas w h e r e
film extension has occurred, presents a useful appraisal of the
ability of the coating to w i t h s t a n d food processing conditions.
A less severe test is available for the p a s t e u r i z a t i o n process.
This is r e q u i r e d for some foods a n d for some b e e r packaging.
The t e m p e r a t u r e for this process is 150 to 180~ (65.5 ~ to
82.2~ for 3 h, S i m i l a r visual e x a m i n a t i o n of the surface of
the coated steel o r a l u m i n u m s u b s t r a t e is c o n d u c t e d for disc o l o r a t i o n o r blushing, a d h e s i o n loss, or film failure.
Abrasion Testing--A critical characteristic of an acceptable
exterior film is its ability to protect cans from m a r r i n g a n d
scratching the d e c o r a t i o n a n d identification. As m e n t i o n e d
earlier in the Can P r o d u c t i o n p o r t i o n of this discussion, occasionally a b r a s i o n resulting from cans r u b b i n g against each
o t h e r especially d u r i n g s h i p m e n t can be severe e n o u g h to
actually cause r u p t u r e of the metal.
Several tests are e m p l o y e d to m e a s u r e the coatings ability
to resist abrasion. A simple technique involves r u b b i n g the
coated surface with a s t a n d a r d pencil eraser, counting the
n u m b e r of rubs or d o u b l e r u b s r e q u i r e d to r e m o v e the coating a n d reveal the u n c o a t e d surface.
A c o m m e r c i a l device called a TABER ABRADER TESTER TM [ASTM Test M e t h o d for A b r a s i o n Resistance of Organic Coatings b y the Taber Abraser (D 4060)] is in c o m m o n
use in the i n d u s t r y for a p r e l i m i n a r y evaluation of a b r a s i o n
resistance. In this test, c o a t e d panels are r o t a t e d u n d e r selected weighted abrasive wheels. The value is often r e p o r t e d
as weight loss in milligrams/cycle x 1000. A n o t h e r specific
test requires the use of a Gavarti TM Gv Cat Test Unit (Fig. 5).
This device involves the m o u n t i n g of a limited n u m b e r of
s p e c i m e n s a n d can evaluate c o a t e d metal a b r a s i o n resistance
rapidly. The device vibrates the cans or coated strips at a rate
a n d d u r a t i o n w h i c h can be controlled, e m u l a t i n g the a b r a sion received d u r i n g t r a n s p o r t a t i o n . The cans are visually exa m i n e d after the allotted t i m e of exposure a n d r a t e d according to individual o r c u s t o m e r defined standards.
Pack Testing--A r e q u i r e m e n t for p a c k a g i n g of m a n y food
p r o d u c t s is that no u n d e s i r a b l e effects on the a p p e a r a n c e of
the c o n t a i n e r or to the taste or color of the contents occur
w h e n the p r o d u c t is stored on a shelf for three years or more.
An accelerated test to evaluate this characteristic involves the
actual p a c k a g i n g of the substance in question in a test can.
The can is sealed a n d exposed to the food processing conditions previously described, after w h i c h the p r o d u c t is aged at
an elevated t e m p e r a t u r e for an extended p e r i o d of time. Typical conditions are 120~ (48.8~ with a generally a c c e p t e d
estimate that one m o n t h exposure at this t e m p e r a t u r e relates
to one y e a r of r o o m t e m p e r a t u r e exposure. The coating p r o d uct can be periodically e x a m i n e d b y initiating several containers at zero t i m e a n d w i t h d r a w i n g t h e m selectively at onem o n t h intervals. This test is useful for new p r o d u c t evaluation. A three-year actual test is usually r e q u i r e d by m o s t
c u s t o m e r s before they will accept a new p r o d u c t o r a significant c o m p o s i t i o n a l change in a coating formulation. At the
end of the test period, evaluations include can a p p e a r a n c e ,
food taste, a n d v a c u u m testing. The latter is a c c o m p l i s h e d b y
piercing the c o n t a i n e r with a device such as a h a n d held
v a c u u m unit w h i c h pierces the can a n d seals a gauge a r o u n d
the puncture. This gauge d e t e r m i n e s the p r e s s u r e before c a n
opening. Chemical r e a c t i o n of the food p r o d u c t with coating
or exposed walls can result in a p r e s s u r e change.
Adhesion Test--This test is similar to one used t h r o u g h o u t
the coatings industry. It involves pressing Scotch B r a n d
Tape TM to the surface a n d e x a m i n i n g the surface a n d the
adhesive side of the tape after removal. The surface of the
coated substrate is often scored with a r a z o r in an X p a t t e r n
o r a cross h a t c h p a t t e r n before the tape is a p p l i e d [ASTM Test
Methods for Measuring Adhesion by Tape Test (D 3359-83)].
Flexibility--A test k n o w n as the T-Bend test is c o m m o n
t h r o u g h o u t the metal coating i n d u s t r y [ASTM Test M e t h o d
for Coating Flexibility of P r e p a i n t e d Sheet (D 4145)]. The test
evaluates the flexibility characteristics of a p a i n t on a substrate by d e f o r m a t i o n of the substrate a n d s u b s e q u e n t evaluation of the a d h e r e d coating. A 0-T b e n d is a b e n d in a section
of metal t u r n e d b a c k on itself after a 180 ~ bend. The b e n d
e x a m i n a t i o n can be visual, microscopic, or it can use Scotch
B r a n d TM t a p e o r copper-sulfate exposure. This is usually dep e n d e n t on the customer's stated requirements.
A second 180 ~ b e n d a r o u n d the b e n d a l r e a d y m a d e represents a lesser level of flexure. A coating that satisfactorily
passes e x a m i n a t i o n on this surface, a n d that has a l r e a d y
failed the 0-T test, will be considered a 1-T flexibility coating.
A third b e n d represents 2-T, etc.
A n o t h e r m e t h o d of evaluating the flexibility of the coating
involves the use of an i m p a c t testing device [ASTM Test
M e t h o d for Resistance of Organic Coatings to the Effects of
723
724
REFERENCES
[1] Lamboune, R., Paint and Surface Coatings; Theory and Practice,
John Wiley and Sons, New York, 1987, p. 523.
[2] The Canmaker, Vol. 5, March 1992, p. 10.
[3] Chemical Week, 5 Aug. 1992, pp. 22-26.
[4] Fiedler, J., "Cans Try New Coats," Industrial Finishing, November
1982.
[5] Code of Federal Regulations No. 21, Section 175.300, U.S. Government Printing Office, 1988.
[6] The Canmaker, Vol. 5, December 199I, p. 28.
[7] The Canmaker, Vol. 5, December 1991, p. 7.
[8] "Guide to Tinplate," International Tin Research Institute Publication 622, Lamport Gilbert Printers, Reading, England, 1981.
MNL17-EB/Jun. 1995
ii
Masonry
by Frances Gale 1 and T h o m a s Sliva 2
Unit Masonry (C 270) includes information about compositions and properties of different types of mortar and their
uses for new construction and tuck pointing or replacement
of deteriorated mortar.
Porosity
A physical property that all masonry substrates share is
porosity. Their interior structures are systems of fine, interconnected pores. With some materials the pores are extremely small. However, because of this inherent porosity, all
masonry is somewhat permeable to water. Hence, moisture
can enter them in several ways including through poorly
designed or faulty flashing, vapor barriers, etc. The presence
of excessive amounts of moisture can adversely affect paint
adhesion and thus performance.
Absorption Testing
The sorption of water by a masonry material is an important factor affecting the performance of the coating as well as
the substrates. This is because moisture is a necessary condition for most processes of deterioration. Water absorption by
masonry substrates can be determined by laboratory testing.
ASTM Method of Sampling and Testing Brick and Structural
Clay Tile (C 67) contains methods for testing brick and structural clay tile to determine physical properties such as absorption and saturation coefficient. Absorption is measured
by submersing a representative whole tile or half brick in
water for a 5-h or 24-h period. Percent absorption is determined by comparing the difference between the saturated
and dry weights to the dry weight.
The test procedure for absorption by concrete masonry
units described in ASTM Standard Methods of Sampling and
Testing Concrete Masonry Units (C 140) is similar to that
described in ASTM C 67. Three full-size units are used for
testing absorption. ASTM Test Methods for Absorption and
Bulk Specific Gravity of Natural Building Stone (C 97) provides a standard test method for this type of stone. The test
procedure is also similar to that described in ASTM C 67
except the immersion period is 48 h. ASTM Test Method for
Specific Gravity, Absorption, and Voids in Hardened Concrete (C 642) contains test methods for measuring absorption
and voids in cured concrete. Absorption is calculated after a
48-h immersion and after immersion in boiling water. A
method for determining the volume of permeable pore space
(voids) is also provided.
725
Copyright9 1995 by ASTMInternational
www.astm.org
726
Efflorescence
Surface Finish
Surface pH
The pH of masonry substrates is variable, normally depending on the chemical composition of the material. Some
materials such as brick, tile, and many natural stones have a
neutral or slightly acidic pH. Others, including cement-containing materials such as concrete and calcareous stones
(e.g., limestone and marble) are naturally alkaline. Mortar
used with neutral or acidic masonry units can sometimes
impart alkalinity to the wall surface. If the pH of the substrate
is high, paints that are sensitive to alkalies should be avoided
as the alkalinity saponifies them.
Surface alkalinity is not the only cause of coating failure.
Subsequent migration to the surface of construction water,
condensed interior water vapor through barrier defects, and
capillary water from contact with the earth ("rising damp")
can all result in the presence of alkalies and soluble salts.
A method for measuring surface pH is described in the
ASTM Test Standard Method for pH of Chemically Cleaned
or Etched Concrete Surfaces (D 4262). Although ASTM
D 4262 is intended for determining whether residual chemicals have been removed following chemical cleaning or etching, the procedure for measuring surface pH of the concrete
surface is described. A strip of pH test paper is placed on the
wet concrete surface and compared with the color chart to
determine pH.
COATINGS
Both types of water-borne and organic solvent-borne coatings have been applied to masonry substrates. A brief discussion and examples of each type are provided below. Methods
for determining physical and chemical properties of paints
for masonry substrates appear elsewhere in this manual and
in U.S. Federal Test Method Standard No. 141C. The titles of
federal specifications that specifically refer to application on
masonry substrates are listed in this chapter.
Water-Reducible Coatings
Water-borne or -reducible coatings are or form dispersions
of the pigment, extender, binder, and additive components in
water. A distinctive feature of latex coatings is that the binder
is also dispersed. Consequently, most of the resulting films
are porous or less compact than corresponding solvent-borne
coatings and so are more permeable to water vapor. This
characteristic is important as most masonry substrates contain moisture at the time the paint is applied. Water vapor
permeability is also a factor subsequent to application as it is
virtually impossible to completely prevent access of water to
masonry walls. Transport of this water to the exterior surface,
caused by thermal gradients in the winter, or to below-grade
interior surfaces, caused by hydrostatic pressure, forces impermeable coatings off the surface.
Of the water-reducible coatings, portland cement powder
paints have the longest service record. Cement paints form
hard, flat, porous films that readily permit passage of water
vapor. Cement paints help to seal and fill porous masonry
surfaces. In addition to portland cement, they can contain
specific additives for controlling application, setting time,
water repellency, and color. Federal Specification A-A-1555
Water Paint, Powder covers cementitious type paints for protection, decoration, and waterpi~oofing of interior and exterior masonry, concrete, and plaster surfaces. The corresponding Canadian specification was withdrawn when interior
latex paints were developed. Although once widely used, cement paints have been largely replaced by latex paints.
Other federal specifications for water-reducible paints for
masonry materials are TT-P-19D Paint, Latex (Acrylic Emulsion, Exterior Masonry), and TT-P-55B Paint, Polyvinyl Acetate Emulsion (for Exterior Masonry Surfaces), and TT-P96D Paint Latex Base for Exterior Surfaces.
Block fillers are sometimes required to fill voids or holes in
masonry substrates. TT-F-1098D is a federal specification for
CHAPTER 63--MASONRY 7 2 7
ready-mixed styrene butadiene copolymer resin filler for cinder and concrete block and stucco.
Solvent-Borne Coatings
These materials consist of pigments dispersed in solutions
of resins and additives in organic solvents. Unless
overpigmented, they form smooth, continuous films that are
effective moisture barriers where water intrusion must be
prevented. Solvent-borne paints must be applied to dry surfaces as excessive moisture may interfere with development
of adhesion and, with some coatings, cause blushing. They
are, however, more tolerant than water-borne coatings to
application at temperatures near the freezing point of water.
Solvent-reducible coatings are of both the thermosetting
and thermoplastic type. The former type cures by oxidative
polymerization (oil-modified, air-drying alkyds, and urethanes), by chemical reaction of multi-components just prior
to and/or after application (e.g., epoxies and urethanes), and
by heat just after application (baking alkyd, acrylic and urethane enamel). Thermoplastic coatings form films solely by
solvent evaporation and include acrylic, vinyl, rubber-derivative, and cellulose-derivative resins and are by definition (although not always so called) lacquers. Federal specifications
for solvent-borne coatings are TT-P-24D Paint, Oil, Concrete
and Masonry, TT-P-95C Paint, Rubber, for Swimming Pools
and Other Concrete Masonry Surfaces.
APPLICATION
As with any substrate, masonry surfaces must be free of
dirt, oil, grease, mildew, efflorescence, and other contaminants before being coated. It is generally thought that newly
constructed masonry walls should age six months before
painting, but latex finishes are frequently applied much
sooner. Obviously, on older surfaces, any needed repair work
should be completed prior to painting. Primers are sometimes recommended for previously painted surfaces and
should always be used when specified by the coating manufacturer. TT-P-00620C is a federal specification for conditioner for heavily chalked previous coatings.
Surface Preparation
As with any surface, adequate preparation of masonry substrates is essential for obtaining good adhesion of the
material to be applied. With some surfaces, a simple dusting
is all that is required; with others more rigorous cleaning is
advisable. ASTM Practice for Surface Cleaning Concrete Unit
Masonry for Coating (D 4261) and ASTM Practice for Preparatory Surface Cleaning of Architectural Sandstone (D 5107)
describe procedures for cleaning with broom, vacuum, air
blast, water, detergent water, and steam. ASTM D 5107 also
covers a procedure for chemical cleaning.
If optimum bond of the coating to the masonry substrate is
desired, alteration of the surface profile may be necessary.
For concrete that will be exposed to service conditions such
as continuous or intermittent immersion, temperature cycling or mechanical loading, abrading, or acid etching the
surface is recommended. ASTM Practice for Abrading Con-
Moisture
As stated in the subsection entitled Solvent-Borne Coatings, moisture in the masonry substrate may be detrimental
to those coatings that cannot tolerate moisture at or near the
surface during application. Consideration of this factor is
particularly relevant following cleaning procedures that involve water (e.g., steam cleaning and chemical cleaning).
ASTM Test Method for Indicating Moisture in Concrete by
the Plastic Sheet Method (D 4263) contains a test method to
establish whether sufficient moisture can migrate to the surface to cause problems. In this method a plastic sheet is taped
to the concrete surface and allowed to remain in place for a
minimum of 16 h. Following its removal, the underside is
visually inspected for the presence of moisture.
The methods of sampling and testing concrete masonry
units contained in ASTM C 140 include a procedure for measuring the as-sampled moisture content. As mentioned in the
sections entitled "Water-Reducible Coatings" and "SolventBorne Coatings" above, excessive moisture in masonry may
cause coatings either not to develop initial adhesion or be
subsequently forced off the surface. Annex A4 of ASTM
Method for Preconstruction and Construction Evaluation of
Mortars for Plain and Reinforced Unit Masonry (C 780) provides a test method for determining water content of mortar
sampled at the construction site.
PERFORMANCE TESTS
Field and laboratory testing are useful for evaluating characteristics thought to be essential to good performance of
coatings, hence to predict their performance on masonry
substrates.
Alkali Resistance
Federal Specification A-A-1555 contains a procedure for evaluating the alkali resistance of cement powder
728
Field Testing
Some performance tests rely on exposing coated masonry
test specimens to actual conditions in the field. ASTM Practice for Atmospheric Environmental Exposure Testing of
Nonmetallic Materials (G 7) covers procedures for exposing
nonmetallic materials to natural weather. Practice G 7 is intended to facilitate collection of uniform results of exposure
testing by indicating the variables that should be considered
and specified. Factors determining degradation due to weathering include climate, time of year, presence of industrial
atmosphere, etc. The specifics of weathering, however, can be
accelerated by changing the angle of exposure. ASTM Practice for Conducting Accelerated Outdoor Exposure Tests of
Coatings (D 4141) includes methods for speeding up natural
weathering. The greatest increase occurs when mirrors that
concentrate solar radiation on the specimens also follow the
sun.
Other Tests
Federal Specification TT-C-555B Coating, Textured for Exterior and Exterior Masonry Surfaces contains several procedures for testing paints to be applied to masonry substrates,
including evaluating color, flexibility, impact resistance,
moisture resistance, accelerated weathering, resistance to
wind-driven rain, and moisture vapor permeability.
Federal Specification TT-P-19D is intended to evaluate performance of paints applied to exterior wood and masonry
substrates. Concrete test panels, prepared in accordance with
Federal Test Method Standard No. 141, are used for some of
the test procedures.
CHAPTER 63--MASONRY
Specimens
Obviously, the use of standardized specimens of the masonry substrate is essential to obtaining reliable data in any
testing protocol. ASTM Test Method of Making and Curing
Concrete Test Specimens in the Laboratory (C 192) describes
the practice for making and curing concrete specimens using
precisely controlled materials and conditions. ASTM Test
Methods of Making and Curing Concrete Test Specimens in
the Field (C 31) contains procedures for making and curing
specimens using concrete delivered to the job site.
ASTM Method of Making and Preparing Concrete and Masonry Panels for Testing Paint Finishes (D 1734) contains
instructions for making and preparing concrete panels for
testing coatings designed for portland cement concrete. Panels are molded to fit the artificial weathering apparatus described in Artificial Weathering Tests. The method also
describes how to mold panels for use on outdoor exposure
testing racks.
Method 2051 of Federal Test Method Standard No. 141,
Preparation of Concrete Panels, contains the procedure and
materials required to make concrete and masonry panels for
testing paints. Three procedures are described for panels with
different materials and surface finishes.
SELECTION
There are a number of factors to consider when selecting
paint for a masonry substrate. These include the materials
and type of structure to which the paint will be applied as well
as the desired appearance. As with any application, it is
important to determine the service conditions under which
the masonry paint must perform. Awareness of these factors
should enable selection of a product that will perform effectively on masonry.
REFERENCED STANDARDS
729
C 780 Method for Preconstruction and Construction Evaluation of Mortars for Plain and Reinforced Unit Masonry
D 822 Standard Practice for Operating Light- and WaterExposure Apparatus (Carbon Arc Type) for Testing
Paint and Related Coatings and Materials
D 1653 Test Method for Water Vapor Permeability of Organic Coating Films
D 1734 Method of Making and Preparing Concrete and Masonry Panels for Testing Paint Finishes
D 3361 Recommended Practice for Operating Light- and
Water-Exposure Apparatus (Unfiltered Open-Flame
Carbon-Arc Type) for Testing Paint, Varnish, Lacquer, and Related Products Using the Dew Cycle
D 4141 Practice for Conducting Accelerated Outdoor Exposure Tests of Coatings
D 4259 Practice for Abrading Concrete
D 4262 Test Standard Method for pH of Chemically Cleaned
or Etched Concrete Surfaces
D 4263 Test Method for Indicating Moisture in Concrete by
the Plastic Sheet Method
D 4587 Standard Practice for Conducting Tests on Paint and
Related Coatings and Materials Using a Fluorescent
UV-Condensation Light- and Water-Exposure Apparatus
D 5107 Practice for Preparatory Surface Cleaning of Architectural Sandstone
E 96 Standard Test Methods for Water Vapor Transmission of Materials
E 514 Test Method for Water Permeance of Masonry
Recommended Practice for Atmospheric EnvironG7
mental Exposure Testing of Nonmetallic Materials
ASTM Standards
C31
C 43
C 67
C 97
C 119
C 125
C 140
C 192
C 270
C 642
Practices for Making and Curing Concrete Test Specimens in the Field
Definitions of Terms Relating to Structural Clay
Products
Method of Sampling and Testing Brick and Structural Clay Tile
Test Methods for Absorption and Bulk Specific Gravity of Natural Building Stone
Definitions of Terms Relating to Natural Building
Stones
Definitions of Terms Relating to Concrete and Concrete Aggregates
Methods of Sampling and Testing Concrete Masonry
Units
Method of Making and Curing Concrete Test Specimens in the Laboratory
Specification for Mortar for Unit Masonry
Test Method for Specific Gravity, Absorption, and
Voids in Hardened Concrete
Kapsanis, K. A., "Coating Concrete: A Review of Regulations, Technical Activities, and Resources," Journal of Protective Coatings and
Linings, August 1991, pp. 58-65.
Maslow, P., Chemical Materials for Construction, New York, McGraw
Hill, 1982.
Morgans, W. M., Outlines of Paint Technology, 1990.
NCMA-TEK 10A, "Decorative Waterproofing of Concrete Masonry
Walls," National Concrete Masonry Association, Herndon, VA,
1981.
NCMA-TEK 44, "Maintenance of Concrete Masonry Walls," National
Concrete Masonry Association, Herndon, VA, 1972.
NCMA-TEK 55, "Waterproof Coatings for Concrete Masonry," National Concrete Masonry Association, Herndon, VA, 1973.
Panarese, W. C., Kosmatka, S. H., and Randall, F. A., Jr., Concrete
Masonry Handbook, Portland Cement Association, Skokie, IL,
1991.
MNL17-EB/Jun. 1995
64
Pipeline Coatings
by Loren B. OdelP and AI Siegmund 2
MARKET
EXTERNAL COATINGS
Coal Tar E n a m e l s
731
Copyright9 1995 by ASTM International
7%
17%
14%
32%
30%
year.
www.astm.org
732
Coal tar mastic is heavily filled with clays, silica, fiber glass,
etc., which yields a highly viscous material that is cold applied to thicknesses of 1/2 to 5/8 in. (1.27 to 1.6 cm). This
product can also be field applied as a hot extrusion seamless
coating. A wide range of pipe diameters can be coated for
buried pipeline service.
Polyethylene
This system is generally an extruded film that encapsulates
the pipe using a mastic, two-part epoxy, FBE, or rubberbased primer for adhesion. The polyethylene offers excellent
moisture resistance and mechanical properties. Since polyethylene is an extruded product, its application to pipe is
limited to plant environments.
APPLICATION TECHNIQUES
All of the above-mentioned coatings can be plant applied. A
limited few are suitable for field application, although there
are several good reasons for plant application. The first and
foremost is surface preparation of the steel surface to be
coated. Cleaning techniques ranging from abrasive blasting
to mechanical cleaning can be mechanized and automated,
resulting in a controlled surface ready for acceptance of the
coating system.
This is closely followed by application technique. Automation can result in a more uniform application of the chosen
coating product, resulting in film thickness control and regulation of the bake cycle for heat-cured products. Coatings that
require heat to achieve chemical reaction can most economically be achieved in a plant environment.
~QUALITY CONTROL
Success is related to quality control, a n d the a p p l i c a t i o n of
protective coatings to pipelines is no exception. The very best
coating available can be r u i n e d by p o o r a p p l i c a t i o n o r by
a p p l i c a t i o n to a dirty surface (Tables 1, 2, 3).
A c o m p r e h e n s i v e quality p r o g r a m covers all phases of a
pipeline project, including steel surface quality, coating quality, a n d p r o p e r a p p l i c a t i o n of the product. The j o b does not
e n d there, for i m p r o p e r installation of a pipeline with a g o o d
coating j o b can result in d a m a g e that m i g h t lead to p r e m a ture failure.
The e n f o r c e m e n t of a quality p r o g r a m is m o s t easily acc o m p l i s h e d in a p l a n t environment. Field a p p l i c a t i o n is dep e n d e n t u p o n t e r r a i n a n d w e a t h e r conditions that can
h a m p e r r e q u i r e d processes a n d procedures. A quality prog r a m t h a t includes a representative f r o m each step of the
o p e r a t i o n with full responsibility for their p o r t i o n of the
process is vital. A clear set of specifications, outlined a n d
discussed with all parties in advance of the project, will bypass m a n y problems. C o m m u n i c a t i o n s b e t w e e n all representatives will result in a h i g h e r quality job, resulting in longer
service at a lower cost.
733
Affiliation
Number
Title
API
RP 5L2
API
RP 5L7
NACE
RP T-10D
AWWA
ANSI/AWWAC210
AWWA
ANSI/AWWAC214
AWWA
ANSI/AWWAC215
AWWA
ANSI/AWWAC203
AWWA
ANSI/AWWAC217
partial listing.
Number
Title
D4
D5
D36
D71
D 2415
D 3143
G 17
coatings.
D 1002
D 1044
D 2370
D695
D 257
G6
G8
G9
G 10
G 11
G 12
G 13
G 14
G 19
G 20
Title
Adhesion to Steel (shear)
Abrasion Resistance (Tabor)
Tensile Strength/Elongation
Compressive Strength
Volume Resistivity
Abrasion Resistance of Pipeline Coatings
Cathodic Disbonding of Pipeline Coatings
Water Penetration Into Pipeline Coatings
Bendability of Pipeline Coatings
Effects of Outdoor Weathering on Pipeline
Coatings
Nondestructive Measurement of Film
Thickness of Pipeline Coatings
Impact Resistance of Pipeline Coatings
(Limestone Drop)
Impact Resistance of Pipeline Coatings
(Falling Weight)
Disbonding Characteristics of Pipeline
Coatings by Direct Soil Burial
Chemical Resistance of Pipeline Coatings
734
BIBLIOGRAPHY
Aaboe S. and Grutter A., "A High-Performance Thermal Insulation
Coating for Subsea Pipelines," Pipeline Digest, April 1991.
Banach, J. L., "Evaluating Design and Cost of Pipe Line Coatings,"
Pipe Line Industry, April 1988.
Chapman, G. "New Technology Used On Major Pipeline Rehabilitation Program," Pipeline Digest, November 1988.
Clark, J. R., "Innovations In Rehabilitation," Pipeline Digest, November 1989.
Coates, A. C., "Pipeline Recoating--A Cover Up Story," Pipeline Digest, April 1991.
MNL17-EB/Jun. 1995
i
Sealants
by Saul SpindeP
SEALANTSAREPRODUCTSINSTALLEDinto an opening to prevent
the intrusion of air, water, dust, heat, cold, and other materials such as gases, e.g., radon. The sealant is installed into the
opening by gun or knife. It is then expected to function even
though the space it occupies is stressed because of movement, thereby placing significant strain upon the adhesive
forces that bond the sealant to the substrate to which it is
attached. The sealant is also expected to function regardless
of whether it is applied to a horizontal opening or a vertical
one or whether it is applied to a building facade subject to
rapid expansion and contraction or to a plaza or deck where
it is subject to puncture by spiked heels.
The opening, or gap, into which a sealant is installed is
usually called a joint. The sides of the joint may be made of
similar or dissimilar materials, generally varying in width
from 0.250 to 2.00 in. (0.64 to 5.08 cm) with the depth of the
joint usually about one half the width. When required, preformed joint fillers made of materials such as open or closed
cell rubber or polyurethane foam are installed to control the
joint depth. Primers are sometimes used to improve adhesion.
The typical building materials that sealants are used with
are glass, steel, concrete, mortar, granite, marble, aluminum,
or wood. When the sealant is installed into the joint, the
surfaces the sealant contacts must be clean, dry, sound, and
free of contaminants or loose particles to provide an opportunity for the sealant to perform as intended.
Caulk or sealant compounds are based on oils, latex polymers, butyl, acrylic and blocked styrene solvent-release polymers, and polysulfide, polyurethane, and silicone elastomers.
The oil-based products exhibit relatively little movement capability, generally 5% or less, and thus they are traditionally
installed in relatively static joints. Acrylic latex polymers can
be formulated to possess significant movement, as much as
+25%, whereas the solvent-release butyl, acrylic, and
blocked styrene sealants can move about +_10%. The elastomerics exhibit significant movement, with silicones moving
as much as 150% (+ 100%, - 50%).
thereby dries slowly, though the caulk usually sets up to become paintable within a 24 to 48-h period. Oil-based caulking
compounds are easy to apply, easy to tool, and are available
in a range of qualities. Generally, oil-based caulks exhibit
movement of about 5%. Oil-based caulking compounds are
used primarily by do-it-yourselfers.
Oil-Based Caulks
Butyl Sealants
Butyl sealants are based on polyisobutylene or polybntene,
fillers such as talc and/or calcium carbonate and additives
such as adhesion promoters, antioxidants, and thixotropes.
Butyl sealants dry by solvent release.
Butyl sealants can be formulated to move at about +_71/2 to
+_121/2%. They are widely used in mobile home applications.
In addition, another class of butyl sealants which are prepared without volatile solvents are extensively used as the
primary seal in dual-sealed insulated glass because of their
very low moisture vapor permeation properties.
735
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736
Polyurethane Sealants
Polyurethane sealants are available as single or multi-component products. The one-component sealant is derived from
an in situ reaction of an isocyanate with a hydroxyl component. These components cure by the reaction of the isocyanate (NCO) with atmospheric moisture, forming a polyurea.
The sealants contain fillers, thixotropes, additives, and adhesion promoters.
Two-component polyurethane sealants are usually based
on an isocyanate-terminated polyether reacted with a hydroxyl-terminated polymer. As with other sealants, two-component polyurethane sealants are combined with fillers, adhesion promoters, and other additives and stabilizers.
Polyurethane sealants exhibit good movement capabilities,
easily exhibiting
movement. They generally adhere
well to a variety of surfaces and are widely used in commercial applications, especially where abrasion resistance, i.e.,
traffic applications, is a prerequisite.
TEST PROCEDURES
Polysulfide Sealants
Polysulfide sealants are sold as both one-component and
two-component materials. Two-component sealants are formulated with polysulfide polymers, hiding and color pigments, clays, and mineral thixotropes. The second, or reactive component, consists of a curing agent (e.g., lead
peroxide), adhesion promoters, fillers, and stabilizers. Both
components are mixed just prior to use.
The one-component polysulfide sealants are formulated
with ingredients similar to the two-component material except that the cure chemistry is different. One-component
polysulfides cure by reaction with atmospheric oxygen and
moisture and are generally relatively slow to attain full cure.
Polysulfide sealants can be formulated to move at 25%
and are used on a wide variety of surfaces. Polysulfides are
used widely in insulated glass applications.
Silicone Sealants
Silicone sealants are primarily used as one-component
products usually referred to as RTV (room temperature vulcanizing) materials. They are polysiloxane prepolymers
which react with atmospheric moisture and ultimately cure
to form an elastomer. Silicone sealants are cured generally by
one of three mechanisms, namely:
1. Acetoxy cure--A reaction between methyltriacetoxy silane
with polydimethylsiloxane to form an acetoxy-terminated
polymer "intermediate." This material is then reacted with
atmospheric moisture in order to cure. Acetic acid is liberated during cure, and its odor can readily be noted.
2. Neutral cure--These sealants are the result of a reaction
between polydimethylsiloxane with methyltrimethoxysilane to form the "intermediate." This "intermediate" then
reacts with atmospheric moisture in order to cure. Alcohol
is generally liberated during the cure process.
3. Amine cure--In this cure mechanism, methyltricyclohexylaminosilane is reacted with the polydimethylsiloxane to
form an "intermediate" which cures when reacted with
atmospheric moisture. Cyclohexylamine, a heavy mustyodored material, is released during cure.
Hardness
This test is used to measure the indentation hardness of a
cured sealant using a Shore A Durometer. If a sealant is too
hard, it may be indicative of future problems that can result
in a loss of resiliency, thereby resulting in either cohesive
breaks or adhesive loss.
CHAPTER 65--SEALANTS
cracking, which may affect the durability of the sealant. This
test can be used to predict premature failure. Sealant specimens are cured, then heat aged for 21 days at 158~ (70~
and evaluated for volatility (weight loss), cracking, and hardness.
Tack-Free Time
This is the time required for the surface of a sealant to
attain a tack-free state. This time may be indicative of the
time interval required for the sealant to resist damage from
light surface contact, job-site or airborne dirt pickup, or impinging rainfall.
Adhesion-in-Peel
This test is used to evaluate the adhesive characteristics of a
sealant and its ability to maintain a bond to a substrate. The
737
SEALANT SPECIFICATIONS
Federal Specifications
TT-S-00227E Sealing Compound Elastomeric Type, Multicomponent (For Caulking, Sealing, and Glazing Building and Other Structures).
TT-S-00230C Sealing Compound Elastomeric Type, Single
Component (For Caulking, Sealing and Glazing Building and Other Structures).
TT-S-01543A Sealing Compound, Silicone Rubber Base
(For Caulking, Sealing, and Glazing in Buildings and Other Structures).
TT-C-598B
Caulking Compound, Oil, and Resin Base
Type (For Masonry and Other Structures).
TT-S-001657 Sealing Compound, Single Component-Butyl
Rubber Based, Solvent Release Type (For
Buildings and Other Types of Construction).
ASTM Standards
ASTM C 570 Specification for Oil- and Resin-Base Caulking Compound for Building Construction.
ASTM C 669 Specification for Glazing Compounds for
Back Bedding and Face Glazing of Metal
Sash.
ASTM C 834 Specification for Latex Sealing Compounds.
ASTM C 836 Specification for High Solids Content, Cold
Liquid-Applied Elastomeric Waterproofing
Membrane for Use With Separate Wearing
Course.
ASTM C 920 Specification for Elastomeric Joint Sealants.
ASTM C 957 Specification for High-So|ids Content, Cold
Liquid-Applied Elastomeric Waterproofing
Membrane with Integral Wearing Surface.
ASTM C 1085 Specification for Butyl Rubber-Based Solvent
Release Sealants.
ASTM C 1184 Specification for Structural Silicone Sealants.
738
C 765
Insulating Glass
C 766
C 771
Highway/Bridges
C 772
SS-S-20OE Sealing Compounds, Two Component, Elastomeric, Polymer Type, Jet Fuel Resistant, Cold
Applied.
C 782
C 792
C 712
C 713
C 717
C 718
C 719
C 731
C 732
C 733
C 734
C 736
C 741
C 742
C 794
C 797
C 834
C 836
C 879
C 898
C 906
C 907
C 908
C 910
C 919
C 920
C 957
C 961
C 972
C 981
C 1016
C 1021
C 1083
C 1085
C 1087
CHAPTER 6 5 - - S E A L A N T S
CANADIAN S T A N D A R D S
CAN/CGSB-19.0-M77--Metods of Testing Putty, Caulking
and Sealing Compounds
CAN/CGSB-19.1-M87--Putty, Linseed Oil Type
19-GP-5M--Sealing Compound, One Component, Acrylic
Base, Solvent Curing
CAN/CGSB-19.6-M87--Caulking Compound, Oil Base
CAN/CGSB-19.13-M87--Sealing Compound, One-Component, Elastomeric, Chemical Curing
19-GP-14M--Sealing Compound, One Component, ButylPolyisobutylene Polymer Base, Solvent Curing
CAN/CGSB-19.17-M90--One-Component Acrylic Emulsion
Base Sealing Compound
CAN/CGSB-19.18-M87--Sealing Compound, One-Component, Silicone Base, Solvent Curing
739
AAMA S T A N D A R D S
801.1
802.3
803.3
804.1
805.2
806.1
807.1
808.3
809.2
INTERNATIONAL STANDARDS
ORGANIZATION STANDARDS
The following standards are under the jurisdiction of Subcommittee 8 on Jointing Products, Technical Committee 59Building Construction:
ISO 6927 Building Construction-Jointing Products-Sealants-Vocabulary
ISO 7389 Building Construction-Jointing Products Determination of Elastic Recovery
ISO 8339 Building Construction-Jointing Products-Sealants Determination of Tensile Properties
ISO 8340 Building Construction-Jointing ProductsSealants Determination of Tensile Properties at
Maintained Extension
ISO 8394 Building Construction-Joinfing Products Determination of Extrudability of One-Component
Sealants
740
ISO 9046
ISO 9047
ISO 9048
Building Construction-Sealants D e t e r m i n a t i o n
of Adhesion/Cohesion Properties at Constant
Temperatures
Building Construction-Jointing Products-Sealants D e t e r m i n a t i o n of Adhesion/Cohesion Properties at Variable T e m p e r a t u r e s
Building Construction-Jointing Products-Sealants D e t e r m i n a t i o n of E x t r u d a b i l i t y of Sealants
Using S t a n d a r d i z e d A p p a r a t u s
S O U R C E S OF S P E C I F I C A T I O N S
ASTM Specifications
A m e r i c a n Society for Testing a n d Materials
1916 Race Street
Philadelphia, PA 19103
(215) 299-5400
ASSHTO Specifications
The A m e r i c a n Association of State H i g h w a y
And T r a n s p o r t a t i o n Officials
444 N o r t h Capitol Street, NW, Suite 225
Washington, DC 20001
(202) 624-5800
F e d e r a l Specifications
Business Service Center
General Services A d m i n i s t r a t i o n (Regional Offices)
7th a n d D Streets, SW
Washington, DC 20407
Military Specifications
C o m m a n d i n g Officer
U.S. Naval S u p p l y Depot
5801 T a b o r Avenue
Philadelphia, PA 19120
(215) 697-2000
ANSI Specifications
(Also I n t e r n a t i o n a l S t a n d a r d s Documents)
A m e r i c a n N a t i o n a l S t a n d a r d s Institute, Inc.
1430 B r o a d w a y
New York, NY 10018
(212) 354-3300
REFERENCES
[1] Klosowski, J. S., Sealants in Construction, Marcel Dekker Inc.,
NY, 1989.
[2] Panek, J. and Cook, J., Construction Sealants and Adhesives,
John Wiley & Sons, NY, 1991.
[3] Chu, Sung Gun, Hercules, Inc., "Sealants Based on Block Copolymers," Adhesives and Sealants Short Course, 1989.
[4] Lomax, James Rohm, and Haas Co., "Acrylic Polymer Caulks
and Sealants," Adhesives and Sealants Short Course, 1989.
[5] Klosowski, J.S., "Sealant Materials," Engineered Materials
Handbook.
[6] "Sealants: The Professional Guide," Sealant, Waterproofing and
and Restoration Institute, 1990.
[7] Sherwin, M., "High Performance Acrylic Latex Sealants," Union
Carbide Chemicals and Plastics Company, Adhesives and Sealants Short Course, 1989.
[8] Shah, A., "Selecting Appropriate Caulks and Sealants," American
Painting Contractor, August 1991, Vol. 68, No. 8, pp. 22-34.
[9] Shah, A., "Choosing a Construction Sealant," Adhesives Age, Vol.
33, No. 5, 15 May 1990, pp. 14-16.
[10] Newton, M. V., Halbe, S. D., and Krysiak, G. D., "Butyl Sealants--Formulating, Developing, Processing," Protective Treatments, Inc., Adhesives and Sealants Short Course, 1989.
[11] Prane, J. W., "Sealants and Caulks," Federation monograph,
Federation of Societies for Coatings Technology, September
1989.
[12] Elias, M., Redman, R., and Prane, J. W., "Sealants and Caulks,"
Chap. 37 of Handbook of Adhesives, 3rd ed., I. Skeist, Ed., Van
Nostrand Reinhold, New York, 1989.
MNL17-EB/Jun. 1995
66
by Larry R. Hacker ~
Water-Borne Coatings
Within the last decade, water-borne traffic coatings have
overcome many of their early problems with water sensitivity
and dry time to become acceptable as traffic marking materials. Applied with the same equipment as solvent-borne coatings, favorable environmental conditions are more limited
for water-borne than solvent-borne coatings. Low air and
surface temperatures, high relative humidity, and low air
movement will adversely affect the film formation of the coating. Washout from a rainstorm soon after application can
also be a concern. With the reduction of solvent emission and
hazardous waste, water-borne coatings are the traffic marking material of the future where solvent emission is a concern
and favorable environmental conditions are obtainable during a large part of the striping season.
Polyester
Liquid Coatings
Solvent-Borne Coatings
This is the standard coating in use for traffic marking for
decades. These materials are usually alkyds or chlorinated
rubbers that dry by the evaporation of their solvents, followed
by oxidation of their binders. They are usually applied hot
and under pressure with conventional spray equipment to
achieve fast-drying markings. The advantages of using solvent-borne coatings are the vast body of knowledge and experience with these materials--they can be applied over a wide
range of environmental conditions and have a low cost. The
major disadvantages are the need for frequent applications,
especially in high-traffic areas, the release of large quantities
of solvent to the atmosphere during drying, and the need for
solvent to clean equipment. These solvents contribute to air
pollution and become hazardous waste when used to clean
equipment.
Senior analytical chemist, Virginia Department of Transportation,
1401 E. Broad Street, Richmond, VA 23219.
Epoxy
This is also a two-component, durable, high-quality pavement marking material. Its applications and use are similar
to the polyester material. A variety of cure times can be
achieved through formulation adjustments. Close attention
must be paid to the mix ratio of the components to obtain
optimum performance and durability.
Thermoplastic
Thermoplastic pavement markings are another durable,
high-quality marking material. This is a mixture of either
maleic-modified glycerol resin esters or hydrocarbon resins
with plasticizers, pigments, and glass beads. The formula is
melted at 400~ (204.4~ and can be extruded or sprayed on
the surface to be marked. Thermoplastic may be applied to
741
Copyright9 1995 by ASTMInternational
www.astm.org
742
TESTING
MANUAL
Permanent Tapes
[':"
These tapes can be divided into plastic-backed and foilbacked tapes. Plastic-backed tapes are 60 to 90 mil (0.152 to
0.229 cm) thick and are used as stop bars, crosswalks, arrows,
and long lines in lighted areas only. Foil-backed tapes are
greater than 24 rail (0.061 cm) in thickness. They are used in
unlighted areas that are free of curves, turns, or stops.
.9
"r
**
.q
.-
T e m p o r a r y Tape
NEWLY
~'"i
":::;.Z
"'-'~i
PAINTED
LINE
R e m o v a b l e Tape
This tape is also used on construction sites but on projects
that require the tape to be removed. To facilitate removal, a
plastic mesh or similar material is added between the adhesive layer and the backing material of the tape. Film thicknesses are greater than 30 mil (0.076 cm).
Glass B e a d s
Glass beads are used with pavement markings to increase
night visibility. Without the beads, most marking would be
invisible at night9 Figure 1 gives an excellent explanation of
how glass beads improve visibility. Glass beads must be
round to work. Broken beads or pieces will not refract light.
Beads vary in refractive index (RI) from 1.50 to 1.90. The 1.50
RI beads are most commonly used for highways, while the
1.90 RI beads are found on airport runways. Glass beads also
come in a variety of sizes with a specific size distribution
usually being specified9 The application of glass beads is done
immediately after a pavement marking material has been
applied9 This is usually done by a pressurized spray nozzle so
that many of the beads, about 70%, are buried in the marking
material9 The quantity of beads added to a line will vary with
the marking material from 6 to 25-1b/gal (09
to 3.003 kg/L).
[":'7%:.~9 ~~
~:2..:..'..:~:~o2.::~'.~~:-~ ~.-.-'~'..:~.'.-~..~:":9
MATERIAL
TESTING
Laboratory Testing
Liquid Coatings
Many of the tests performed on liquid coatings are standard coating tests and are referenced where applicable.
Liquid Properties
1. Skinning--Paints that contain binders that dry by oxidation can form skins in a partially filled container. These
must be removed before use. This test can be performed
in accordance with ASTM Methods of Testing Varnishes
(D 154).
2. Fineness of Dispersion--Commonly called "fineness of
grind," this test is not generally specified for traffic marking except in the case of some application equipment. The
test is performed in accordance with ASTM Test Method
for Fineness of Dispersion of Pigment-Vehicle Systems (D
1210).
3. Density or Weight~Gallon--The density is determined for
unbeaded paint by using ASTM Test Method for Density
of Paint, Varnish, Lacquer, and Related Products (D
1475).
4. Consistency--Determine the consistency using a Stormer
Viscometer in accordance with ASTM Test Method for
Consistency of Paints Using the Stormer Viscometer (D
562).
5. Stability--Traffic paints should remain stable in the container for at least six months. Stability can be checked by
heating and cooling a specimen through several cycles or
by storing at room temperature for a period of time. Use
ASTM Test Method for Setting Properties of Traffic
Paints During Accelerated Storage (D 1309) for the accelerated test and ASTM Test Method for Evaluating Degree
of Setting of Paint (D 869) for an aged sample.
6. Chemical Analysis--Identification and quantification of
traffic paint components can be made by several means.
Infrared spectroscopy can be used for resin identification.
Use ASTM Test Method for Infrared Identification of Vehicle Solids from Solvent-Reducible Paints (D 2621) to
aid identification of solvent reducible resins. Oils and oil
acids can be identified by using gas chromatography.
ASTM Test Method for Fatty Acid Composition by GasLiquid Chromatography of Methyl Esters (D 1983),
ASTM Test Method for Identification of Oils and Oil Acids
in Solvent-Reducible Paints (D 2245), and ASTM Test
Method for Preparation of Methyl Esters from Oils for
Determination of Fatty Acid Composition by Gas Chromatography (D 2800) can be determined using either the
Jones Reduction method or the aluminum reduction
method found in ASTM Test Methods for Chemical Analysis of White Titanium Pigments (D 1394). Chrome yellow may be quantified using atomic absorption spectroscopy or by wet chemical methods using ASTM Test
Methods for Analysis of Yellow, Orange, and Green Pigments Containing Lead Chromate and Chromium Oxide
Green (D 126).
7. Pigment Content --ASTM Test Method for Pigment Content of Solvent-Reducible Paints (D 2371) is used for solvent reducible coatings and ASTM Test Method for Pigment Content of Water Emulsion Paints by LowTemperature Ashing (D 3723) is used for water emulsion
743
744
comparison is fast and acceptable although numerical values are not obtained. The advantage of using color difference instruments are that they provide numerical values
that can be compared to later measurements. Visual color
comparison can be made in accordance with ASTM Practice for Visual Evaluation of Color Differences of Opaque
Materials (D 1729). To determine the color in terms of tristimulus values or chromaticity coordinates, use ASTM
Test Method for Computing the Colors of Objects by Using
the CIE Systems (E 308). Color difference measurements
are instrumentally obtained by following ASTM Test
Method for Calculation of Color Differences from instrumentally Measured Color Coordinates (D 2244).
5. Reflectance and Retrorefiectance--Reflectance is the measure of light reflected from the surface of a material. To
determine which of two samples appear lighter when
viewed in average daylight, each sample is illuminated at a
45 ~ angle and viewed at a 0~ angle using the standard CIE
source C, and the Y-tristimulus value is recorded. Determine the reflectance in accordance with ASTM Test
Method E 97. Retroreflectance is a measure of light reflected close to the direction in which it came. In practice,
it simulates the light reflected from a pavement marking by
the vehicles' headlamps. In the laboratory, retroreflectance
can be measured in accordance with ASTM Test Method
for Retroreflectance of Horizontal Coatings (D 4061). Portable retroreflectometers are used to test pavement markings in field evaluations. Although there is not yet a standard procedure to use these instruments, the theory
behind their use is the same as the laboratory procedure.
The Mirolux 12 portable retroreflectometer which is used
by several state Departments of Transportation is shown in
Fig. 3. It has an internal calibration, an illumination angle
of 86.5 ~ and an observation angle of 1.5~ After the instrument is zeroed and calibrated, it is placed over the test line
and the reading is obtained. Testing has shown that there
is a correlation between readings obtained with a portable
retroreflectometer and those obtained in the laboratory using ASTM Test Method D 4061.
6. Resistance to Wear--This is a measure of a pavement
markings' ability to withstand wear from trai~ic, The test
procedure involves dropping sand on a dry test specimen
until the substrate is visible. The test is usually performed
on an unbeaded material that is the appropriate thickness.
A variation of the test is to drop a specific volume of sand
on the specimen and calculate the amount of material lost
by weight. The abrasion resistance can be determined by
using ASTM Test Method for Abrasion Resistance of Organic Coatings by Falling Abrasive (D 968).
Thermoplastic
Thermoplastic material is supplied in a powdered form or
in block form. The material is prepared for testing by melting
a sample at its application temperature under constant agitation. A guideline for testing thermoplastics can be found in
the American Association of State Highway and Transportation Officials (AASHTO) Standard Test Method T-250.
Gravimetric and Chemical Analysis--A melted thermoplastic patty is allowed to cool to room temperature. It is then
broken into pieces and ashed in a muffle furnace at 540~ for
1 h. From this sample, the amount of binder, glass beads,
745
20
30
40
50
80
100
i66
90-100
50-75
0-5
...
746
P A I N T A N D COATING T E S T I N G M A N U A L
Application Process
Location For Tests--Pavements should be selected where
traffic is free flowing without grades, curves, intersections, or
other phenomena that would cause excessive braking or turning. The area should have uniform wear, full exposure to
sunlight throughout the day, and have good drainage. Interstate highways are usually excellent choices for testing.
Wet Film Thickness Measurement--Wet film thickness is
measured with a wet film thickness gage. The most popular
one is a piece of metal with calibrated notches cut at various
mil thicknesses as shown in Fig. 7. The gage is placed in a
freshly applied line and withdrawn. The notch with the highest reading that has paint on it is the wet film thickness.
The wet film thickness is measured and adjusted before the
test line is applied to the pavement. On a piece of roofing
paper, place a rigid metal test panel. Apply a test line to the
panel using a motorized striper. Immediately determine the
wet film thickness. Adjust the pressure and repeat until the
proper thickness is obtained.
747
Evaluation
Periodic inspections of the test stripes are made, usually
monthly. At each inspection, daytime appearance, durability,
and retrorefiectance values are recorded. It is good practice to
obtain data during the winter season.
1. Weighted Rating--An excellent method to compare the relative performance of the test stripes is to assign each stripe
a weighted rating. Each performance criteria that receives
a rating is weighted as a percentage of the entire test. The
weighting system used by the Virginia Department of
Transportation is as follows:
R = 0.1A + 0.2D + 0.7N
where
R
A
D
N
=
=
=
=
Other percentages can be assigned to the rating components according to the importanc e of the user.
2. Length of Useful Life--This can be defined as the projected
or actual useful life in days from the day of application to
the day on which the weighted rating reaches a value of 4
or if any of the rating values (appearance, durability, or
retroreflectance) reaches a value of 3. If the evaluation is
terminated and neither of the above is reached, the projected useful life can be calculated as follows:
L = D(10 - 4)/10 - R = 6D/10 - R
Performance Criteria
Auto-No-Track Time--The auto-no-track time is determined by passing over a freshly applied line in a standardsized passenger car. This is usually done at 25 to 35 mph
(40.25 to 56.35 kin/h) at the specified no-track time. Any
deposit of paint on the roadway or exposure of the pavement
under the test line is considered as not meeting the no-track
requirement. The laboratory no-track time described in
ASTM D 711 has little or no correlation with the field results.
Appearance--This is the general condition of the test lines
when viewed from a distance of 10 ft (3.05 m). It takes into
consideration color, bleeding, darkening, fading, dirt collection, etc. This is done for each wheel track. A numerical value
is usually assigned from 0 to 10 with 10 being the highest
quality.
Durability--The durability is rated as to the percentage of
material remaining on the pavement. The determination is
made in each wheel track. A numerical value is usually assigned from 1 to 10 as determined by the percentage of material remaining, with 10 representing no material has worn
away. ASTM Test Methods D 821 and Test Method for Evaluation Degree of Chipping of Traffic Paint (D 913) are used as
guidelines.
Night Visibility or Retroreflectance--Retroreflectance measurements are made in each wheel path using a portable
retroreflectometer as previously described. On the day of application, the meter reading of a beaded line is assigned a
value of 10 and the reading of an unbeaded line is assigned a
value of 0. Subsequent readings will be assigned a value in
relation to a percentage of the original reading.
where
L = length of useful life,
D = days since application, and
R = overall weighted rating on the termination day.
3. Weighted Cost Factor--A weighted cost factor is useful in
determining which material has the best performance at
the lowest cost. It is calculated as follows
MNL17-EB/Jun. 1995
67
Water-Repellent Coatings
by Victoria Scarborough 1 and Thomas J. Sliva 2
formulated for
the purpose of protecting porous substrates by preventing the
penetration of liquid water. Unlike waterproofing materials
and sealers, water repellents allow the passage of water vapor
and generally are not designed to prevent the intrusion of
liquid water under hydrostatic pressure.
Water is known to penetrate porous materials and contribute to their deterioration [1-3]. Examples include warping
and swelling of wood and cracking and spalling of concrete
and masonry caused by freeze/thaw cycles and dissolved
salts. Further, chloride ions in deicing salts can accelerate the
corrosion of reinforcing steel in concrete. Water repellents
are used to provide protection against such damage.
Water repellents provide protection by depositing hydrophobic compounds on the substrate, thus modifying the surface tension of the treated area. The result is that water no
longer "wets" the surface but is instead repelled. Visually, the
result after the application of water repellents may be beading of water.
WATER REPELLENTS ARE TRANSPARENT COATINGS
Composition
Most water repellents are composed of 1 to 65% monomeric or polymeric hydrophobic compounds suspended or
dissolved in a carrier solvent. The products are generally
classified by the type of compounds used to deliver the water
repellency, e.g., acrylic, siliconate, silane, siloxane, metallic
stearate, etc. The applied material may "cure" by simple carrier evaporation, or a chemical reaction may occur between
the hydrophobic compounds and the substrate.
The carrier solvent used is selected based on its compatibility with the hydrophobic compounds. Organic solvent cartiers can be aliphatic, aromatic, or chlorinated solvents
which can be derived from petroleum distillation. These carriers are considered volatile organic compounds (VOC) and,
in recent years, have been subject to restricted use by state
and federal air emission control regulatory agencies. Thus,
using water as a carrier in water repellents has been the focus
of recent formulation efforts.
Classification
Water repellents can be classified as either film formers or
penetrants. As film formers, the substrate pores are filled and
there is a continuous film on the surface. Examples of film
formers include acrylic polymers or silicone elastomers. In
most cases, the film-forming portion of the water repellent is
a blend of several different hydrophobic compounds.
Water repellents that are penetrants line the pores of the
substrate and generally do not visibly alter the surface of the
substrate. Examples include solutions of metallic stearates or
paraffinic waxes. Penetrants also include reactive chemicals
such as silanes and siloxanes which covalently bond to the
silicate minerals in cementitious substrates. This latter reaction may be catalyzed by moisture and/or alkaline material
present within the substrate.
SCHEDULE OF TESTING
Most of the major laboratory tests used for the evaluation
of water repellents are outlined in the following sections:
Tests on Physical Properties, Tests for Water Repellency of
Treated Wood, and Tests for Application on Treated Masonry. All the tests described may not be required for each
water repellent, and the selection of the tests to be conducted
may be guided by the type and recommended use of the
treatment or as agreed upon by buyer and seller.
www.astm.org
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
D
D
D
D
E
D
E
1475
1200, Ford Cup
2196, Brookfield
1640
1544, Gardner
56, Tag Closed Cup
70
ASTM
ASTM
ASTM
ASTM
ASTM
D
D
D
D
D
2243 Freeze/Thaw
1849 Heat Aging
2369
5095
3960
Dimensional Stability
The relative ability of water repellents to retard dimensional changes in wood submerged in water is measured
using the "wood swellometer test" and is detailed in Federal
Specification TT-W-572b Par 3.7, Water Repellency [4]. This
test compares the swelling of untreated control specimens
with the swelling of treated specimens after each has been
submerged in water for 30 min. Similar procedures are described in: the National Woodwork Manufacturers Association Test Method NWMA-M-2-81 [5]; in ASTM Test Method
D 4446, "Method for Determining the Anti-Swelling Effectiveness of Water-Repellent Formulations and Differential
Swelling of Untreated Wood When Exposed to Liquid Water
Environments"; in American Wood Preservers Association
Standard M-18, "Standard Method of Testing Water Repellency of Pressure-treated Wood" [6]; and in ISO/DIN 4496,
"Wood Test Method-Determination of the Radial and Tangential Shrinkage" [7].
In Federal Specification TT-W-572b, water repellent effectiveness is measured on treated Ponderosa pine sapwood that
is cut into 0.25 by 1.5 by 10-in. (6 by 38 by 254-mm) wafers.
The wafers are cut from two adjacent specimens from each of
five different boards. Specimen pairs of ten wafers are required to make a set for testing, one for the treated wafers and
one for the untreated controls. Five wafers (one from each
board) are immersed in the test water repellent for 30 s. The
wafers are cured under standard conditions for four days or
until constant weight is attained.
The wafers are inserted into a holding device fitted with a
micrometer at one end known as a swellometer gauge. One
end of the wafer touches the base of the gauge, while the
other just touches the plunger dial of the micrometer. The
wafer apparatus is immersed in water for 30 rain, and a dial
reading is made before and after immersion.
The difference between the dial reading of the treated and
the untreated control wafers is divided by the dial reading of
the untreated control wafers and multiplied by 100. The average of these five readings represents the water-repellent effectiveness in percent of the product. Federal Specification TTW-572b requires that a water repellent exhibit a minimum of
60% water repellent effectiveness. ASTM Test Method D 4446
differs from the federal specification in that it requires a
3-rain dipping time for water-based water repellents, and it
specifies that all control untreated specimens must swell a
minimum of 0.325 in. (0.8 cm).
Beading
Water repellents for application on wood can be evaluated
for their ability to form and hold a water bead [8]. A suitable
test is described in ASTM D 2921, "Test Method for Qualitative Tests for the Presence of Water Repellents and Preservatives in Wood Products." After the wood has been treated and
allowed to cure, several water droplets are placed on the
wood with an eye dropper or other device. The time required
for the droplets to lose their spherical shape and flatten out is
recorded. The test can be used to compare water-beading
ability before and after either artificial or natural weathering.
The ability to bead water does not prevent water absorption
as described in ASTM D 540 I, nor does it necessarily correlate with the ability to retard dimensional changes in wood as
described by Federal Specification TT-W-572b.
Paintability
If wood is to be painted and a water repellent is used as an
undercoat, it may be necessary to evaluate the effects of the
water repellent on the primer or topcoat. Evaluations can
include checking the adhesion of the topcoat to the substrate,
observing any changes in color to the topcoat, and measuring
the drying characteristics of the topcoat. These evaluations
may also be made after a periodic weathering of the water
repellent-treated surface before the topcoat is applied.
Weathering
Substrates treated with water repellents can be subjected to
artificial or outdoor weathering, e.g., using ASTM G 53,
"Practice for Operating Light- and Water-Exposure Apparatus (fluorescent UV-Condensation Type) for Exposure of
Nonmetallic Materials," and ASTM D 4141, "Practice for
Conducting Accelerated Outdoor Exposure Tests of Coatings." The substrate is evaluated for appearance properties
like cracking (as shown in ASTM pictoral standards D 661,
"Test Method for Evaluating Degree of Cracking of Exterior
Paints"), discoloration, mold and mildew growth, and dirt
pickup. The substrate may also be evaluated for beading
ability or water repellent effectiveness.
Water Absorption
Water repellent effectiveness can also be measured gravimetrically using ASTM Test Method D 5401, "Evaluating
Clear Water Repellent Coatings on Wood." Water absorption
is tested by cutting matched 2 by 4 by 12-in. (50 by 100 by
305-ram) Ponderosa pine sapwood boards. Five boards are
Water Repellency
Water repellency on masonry is determined following procedures described in Federal Specification SS-W-110c, Par.
750
Chemical Resistance
The resistance of a w a t e r repellent to the i n t r u s i o n of
various chemicals is d e t e r m i n e d following m e t h o d s modified
from p r o c e d u r e s d e s c r i b e d in: ASTM C 267, "Test M e t h o d for
Chemical Resistance of Mortars"; ASTM C 67, "Method of
S a m p l i n g a n d Testing Brick a n d S t r u c t u r a l Clay Tile"; Report
244 of the N a t i o n a l Cooperative H i g h w a y R e s e a r c h Program,
"Concrete Sealers for P r o t e c t i o n of Bridge Structures" [10]
a n d ASTM C 672, "Test M e t h o d for Scaling Resistance of
Concrete Surfaces E x p o s e d to Deicing Chemicals." M o r t a r
cubes are p r e p a r e d a n d t h e n treated, cured, a n d i m m e r s e d in
a specified c h e m i c a l solution. U n c o a t e d control cubes are included in the i m m e r s i o n . Typical chemicals u s e d in this test
include fuels a n d oils, various salt solutions, a n d a c i d a n d
alkaline solutions.
Differences in weight gain or loss over t i m e are m e a s u r e d
a n d plotted as c o m p a r e d to the u n t r e a t e d control. The rate of
weight gain o r loss over t i m e d u r i n g i m m e r s i o n m a y be m o r e
significant t h a n the actual difference. By charting the weight
g a i n or loss over time, the rate of d e t e r i o r a t i o n m a y be determined.
Chloride ion p e n e t r a t i o n resistance is of p a r t i c u l a r interest
in testing for the resistance of w a t e r r e p e l l e n t - t r e a t e d masonry since reinforcing steel in concrete will c o r r o d e a n d
deteriorate after p r o l o n g e d exposure to salt. A m e t h o d of
d e t e r m i n i n g the resistance of concrete to chloride ion penet r a t i o n is d e s c r i b e d in the AASHTO M e t h o d T 259 [11].
Freeze~Thaw Resistance
Freeze/thaw resistance is d e t e r m i n e d b y m e t h o d s modified
f r o m p r o c e d u r e s outlined in ASTM C 67, m e n t i o n e d above
a n d ASTM C 666, "Test M e t h o d for Resistance of Concrete to
R a p i d Freezing a n d Thawing." Treated cubes are subjected to
cycles of freezing a n d thawing, a n d the a m o u n t of w a t e r
a b s o r b e d a n d the change in a b s o r p t i o n with t i m e is determined. The cubes are evaluated for weight loss a n d physical
d e t e r i o r a t i o n such as cracking a n d spalling after each series
of cycling.
Efflorescence
Efflorescence is a crystalline d e p o s i t on the surface of masonry w h i c h is whitish in a p p e a r a n c e a n d often detracts f r o m
the a p p e a r a n c e of the substrate. W a t e r r e p d l e n t s m a y b e
u s e d to prevent the f o r m a t i o n of efflorescence. Their efficiency at preventing efflorescence can be m e a s u r e d using the
m e t h o d d e s c r i b e d in NBS Technical Note 883, Par. 2.2.3.
[12].
REFERENCES
[1] Feist, W. C. and Hon, D. N.-S., "Chemistry of Weathering and
Protection," Chemistryof Solid Wood, R. M. Rowell, Ed., American Chemical Society, Washington, DC, 1983, p. 401.
[2] "Clear Water Repellent Handbook," Sealant, Waterproofing, and
Restoration Institute, Kansas City, MO, 1991.
[3] "Water Repellency and Dimensional Stability of Wood," General
Technical Report FPL-50, R. M. Rowell and W. B. Banks, Eds.,
U.S. Department of Agriculture, Forest Products Laboratory,
Washington, DC, 1985.
[4] "Water Repellent for Use on Wood," General Services Administration, Federal Specification TT-W-572b, Washington, DC, May
1969.
[5] National Woodwork Manufacturers Association, NWMA Swellometer Test, "Standard Method for Determining the WaterRepellent Effectiveness of Treating Formulations," NWMA-M-281.
[6] American Wood Preservers' Association, Stevensville, MD,
Part 14:
Analysis of Paints and Paint Defects
MNL17-EB/Jun. 1995
68
Analysis of Paint
by Darlene Brezinski 1
SAMPLING
The importance of appropriate sampling for analytical
work cannot be overemphasized. Unfortunately, this topic is
often not given sufficient thought, and there is often not
enough training on the subject. A clear understanding of the
nature of the problem or the reason analysis is needed must
be established prior to obtaining a sample. It is extremely
important to know the compositional makeup of the bulk
material from which the sample is being taken. Without this
knowledge, improper sampling can very easily occur. The
homogeneity or heterogeneity of the sample along with its
stability is very important to consider. The composition of a
sample may change once it is removed from its natural matrix or environment due to interactions with a container,
ultraviolet light, or air, for example. One should also know in
advance what level of precision is required of the analysis and
what compositional information is required.
Development of a sampling plan is one of the most important steps in providing reliable samples and consequently
accurate and reliable data. The types of samples usually encountered are:
sampling plans. Because the samples are based on judgement, only judgmental conclusions can be drawn when considering the data. In the case of controversy, decisions on
acceptance of conflicting conclusions may be based on the
perceived relative expertise of those responsible for sampling
[1].
Statistical sampling plans are those based on statistical
sampling of the bulk materials and ordinarily can provide the
basis for probable conclusions. Hypothesis testing can be
involved, predictions can be made, and inferences can be
drawn. Ordinarily, a relatively large number of samples will
need to be measured if the significance of small apparent
differences is of concern. The conclusions drawn from such
samples would appear to be noncontroversial, but the validity
of the statistical model used could be a matter of controversy
[11.
Protocol sampling plans may be defined as those specified
for decision purposes in a given situation. Regulations often
specify the type, size, frequency, sampling period, and even
location and time of sampling related to regulatory decisions.
Not specifically following any part of the protocol could be
reason for discrediting a sample. The protocol may be based
on statistical or intuitive considerations but is indisputable
once established [1].
When decisions are based on identifying relatively large
differences, intuitive samples may be fully adequate. When
relatively small differences are involved and the statistical
significance is an issue, statistical sampling will be required
U].
753
Copyright9 1995 by ASTMInternational
www.astm.org
754
(D 3925) and ASTM Method for Sampling Industrial Chemicals (E 300) should be examined for detailed recommendations.
All the precision in weighing, measuring, calculating, and
so forth has absolutely no meaning if the sample is not a valid
and representative sample. The sample taken for analysis
must totally and accurately reflect the composition of the
bulk material from which it was taken. If there is any doubt
about the integrity of the sample as a representative sample,
the analysis should not be conducted as the data has no
meaning. This becomes extremely important when dealing
with samples where the bulk is large and perhaps not always
completely homogenous [1]. In the real world of sampling, it
is often very difficult to even know if the sample was obtained
properly and if it is representative. The analyst usually has no
control over the sampling step itself. In these cases, it becomes important for the analyst to stress that the data are
only representative of the sample which has been analyzed
and not necessarily representative of the bulk. Rather serious
management decisions can be falsely made if the decision is
based on data which is not representative data.
Care should be taken to assure that all containers, agitators, and sampling apparatus are clean and that they can in
no way contribute to contaminating the sample. Reusable
syringes in particular can pose problems, particularly in trace
analysis, if they are not cleaned extremely well. Contaminant
materials will lead to erroneous test results as the contaminate will be assumed part of the sample. For pigmented
coatings which are dispersions, finely divided pigment particles may settle upon standing. Consequently, very thorough
agitation is necessary at every stage of the sampling and
analysis procedure.
Airtight storage containers are necessary to prevent evaporation of sample material. Volatile solvents may also diffuse
through the walls of plastic containers. The loss of volatiles
subsequently introduces significant error in such tests as viscosity, weight per gallon, and nonvolatile content. If cap
liners are used for samples, they must be made of a nonreactive material. It is also very important in all stages of samplingJanalysis that the samples be kept at fairly constant and
consistent temperatures. Extremes of temperatures may
change the properties of some coatings.
Proper labeling of the sample cannot be stressed enough.
Labeling should be done in accordance with prior established
standard operating procedures (SOPs) for the laboratory. The
more information available on the label, the less likely error
will be introduced either in the handling of the sample or in
the analysis. Formula composition, if known, can be an asset
to the analyst in choosing the best analytical methods and
save valuable and costly analytical time.
Laboratory Protocol
The analytical laboratory today must have standard operating procedures (SOPs). This is standard, acceptable practice
today, and laboratories that have not implemented these procedures will find it more difficult to maintain credibility of the
data with their clients. Standard operating procedures define
clearly how each step of the laboratory operates. Clear SOPs
are necessary for training, logging samples, calibration, quality assurance, receipt of samples, chain-of-custody, report
GENERAL TESTING
Before any tests are run on the coating and prior to separation, testing to establish some basic parameters or con-
C H A P T E R 6 8 - - A N A L Y S I S OF P A I N T
Flash Point
The flash point of a material is defined as the lowest temperature, corrected to a pressure of 760 m m Hg (101.3 kPa,
1013 mbar) at which application of an ignition source causes
the vapor of the specimen to ignite under specified conditions
of test. Flash point is one of the properties used to classify
liquids according to their flammability by governmental regulatory agencies. Several different flash point methods are
available. The analyst must determine which one of these
methods is appropriate for the sample to be analyzed and
then follow the recommended ASTM procedures. Both Tag
open cup and closed cup methods, Pensky-Martens closed
cup, and Setafiash tester methods are commonly used in the
coatings industry. [ASTM Test Method for Flash Point and
Fire Points of Liquids by Tag Open-Cup Apparatus (D 1310);
ASTM Test Method for Flash Point by Tag Closed Tester (D
56); ASTM Test Methods for Flash Point by Pensky-Martens
Closed Tester (D 93); ASTM Test Methods for Flash Point of
Liquids by Setaflash Closed-Cup Apparatus (D 3278)]. Laboratories need to be certain of the shipping requirements and
the appropriate methods prior to analysis of the sample.
755
Density
Density is weight per unit volume. It is a key property in the
identification, characterization, and quality control of a wide
range of paint materials. The density of water at various
temperatures is used to calibrate the volume of the container.
The weight of the paint liquid contents of the same container
at the standard temperature is then determined and density
of the contents calculated in terms of grams per milliliter, or
pounds per gallon, at the specified temperature.
Density measurements in terms of weight per gallon are
commonly used to check paint quality. If the density is not
within specification, there is a good chance that there was a
mischarge or other serious problem. This could indicate further chemical analysis is required to determine the nature of
the problem. ASTM Test Method for Density of Paint, V a r nish, Lacquer, and Related Products (D 1475) is suitable for
the determination of density of paint and related products
and components when in liquid form.
ASTM D 1475 provides for the m a x i m u m accuracy required for hiding power determinations. Automatic equipment for measuring density is available from several manufacturers [see ASTM Test Method for Density and Relative
Density of Liquids by Digital Density Meter (D 4052)]. For
higher precision if working with nonpigmented materials,
ASTM Test Method for Specific Gravity of Drying Oils, Varnishes, Resins and Related Materials at 25/25~ (D 1963) can
be used to determine specific gravity and the corresponding
density.
756
Pigment Content
For most water emulsion paint systems, the pigment content (often called ash) is most often determined following the
determination of the weight percent nonvolatiles. ASTM Test
Method for Pigment Content of Water-Emulsion Paints by
Low Temperature Ashing (D 3723) covers a procedure for the
pigment content determination. After weighing the dishes for
NVM, the dishes are transferred to a muffle furnace and
heated at a low ashing temperature of about 450~ for 1 h. Of
course the analyst must keep in mind that the method is only
applicable to pigments that do not decompose or lose weight
at temperatures below 500~ This would include most metal
oxides, silicates, and a majority of anhydrous inorganic salts.
A note of caution is advised as this may be too low an
ashing temperature for some paints. Each system is different,
and one cannot assume that this temperature will be sufficient.
To separate pigment from solvent-based paints, ASTM Test
Method for Determination of the Pigment Content of SolventReducible Paints by High-Speed Centrifuging (D 2698)
should be followed. Also ASTM Test Method for Pigment
Content of Solvent-Reducible Paints (D 2371) provides a centrifugation method for separation of pigment from the vehicle.
Vehicle Separation
Separation of the vehicle from the pigment in solventreducible paints is desirable and often required in order to
further characterize paint vehicles by chemical or instrumental methods of analysis. ASTM Standard Practice for
Separation of Vehicle from Solvent-Reducible Paints (D
2372) covers the procedure for separating the vehicle from
the pigment by centrifugation.
Solvent Separation
If it is desirable to separate the solvents from the vehicle,
ASTM Standard Practice for Vacuum Distillation of Solvents
CHAPTER 6 8 - - A N A L Y S I S OF PAINT 7 5 7
From Solvent-Reducible Paints for Analysis (D 3272) details a
vacuum distillation procedure. For analysis purposes, however, most people prefer direct injection of paint sample into
the gas chromatograph for solvent identification.
Sample Preparation
For many types of analysis, the previously discussed separation techniques are sufficient. Many chemical analyses require further sample treatment in the form of either extractions or digestions. The standard analytical techniques are
always applicable in these cases. Extractions are often more
attractive techniques for separating inorganic species than
precipitation methods which are more time consuming. Of
course the extent to which inorganic and organic species
distribute themselves between two immiscible solvents differs greatly depending on the species and the extraction solvents.
Decomposition of the organic material for further analysis
requires rather drastic sample treatment and typically involves oxidation techniques. Wet ashing makes use of liquid
oxidizing agents such as sulfuric, nitric, and perchloric acids.
Dry ashing usually implies ignition of the organic compound
in air or in a stream of oxygen.
Sample dissolution is one of the most common operations
in analytical chemistry. Because most quantitative techniques require that samples be introduced in liquid form,
thousands of sample dissolutions are performed every working day in analytical laboratories. Despite the importance and
widespread applicability of sample dissolution, most conventional digestion procedures are tediously labor-intensive, and
a number of them, such as perchloric acid digestion, are
potentially hazardous to laboratory personnel [2].
New microwave dissolution techniques make it possible to
speed the preparation of solid samples by combining the
rapid heating ability of microwave energy with the advantages inherent in the use of sealed digestion vessels. Researchers have found microwave dissolution to be faster,
more controlled, more elegant, and more amenable to automation than conventional open-beaker or closed-vessel techniques [2].
The advantages of microwave dissolution include faster reaction rates that result from the high temperatures and
pressures attained inside the sealed containers. These containers are made of polymers that will not contaminate or
adsorb the sample and do not absorb microwave energy. The
caps are designed to safely vent container gas in case of
excess internal pressure buildup [2].
The use of closed vessels also makes it possible to eliminate
uncontrolled trace element losses of volatile molecular species that are present in a sample or that are formed in the
course of dissolution. Such losses can easily destroy the integrity of a measurement. In the field of elemental analysis,
significant percentages of elements such as arsenic, boron,
chromium, mercury, antimony, selenium, and tin are lost at
relatively mild temperatures with some open-vessel acid dissolution procedures. Several of these elements have already
been shown to be retained when closed vessels are used [2].
Another advantage of closed vessels is a decrease in blank
values as compared to open-beaker work because contamination from the laboratory environment is lower and smaller
Analytical
Data
Structural Analysis
All aspects of coatings manufacture, from the screening of
raw materials to finished product quality assurance, depend
on analysis data. The ultimate goal of analyses is to identify
the chemical species contained in a sample and then determine the amount of each species. As such, both qualitative
(what) and quantitative (how much) analyses must be performed. It is extremely important to try and obtain all the
background information regarding the sample to be analyzed
758
as this information can often save time and expensive analysis costs.
porosity analyses provide useful characterization information about inorganic materials [6].
Inductively coupled argon plasma spectroscopy (ICAP) [5]
allows the determination of numerous elements in aqueous
and organic solvent solutions. ICAP methods rely on the
emission of light by atoms in the sample as opposed to the
absorption of light, the principle behind atomic absorption
(AA) spectrometry. Liquid and/or solid samples are readily
analyzed using ICP techniques after appropriate sample
preparation steps are taken. ICP analytical procedures employ classical sample preparation methods such as acid digestion, fusion, dry ashing, dilution, and extraction. In practical
applications, AA and ICP are quite similar. The major differences are the speed with which ICP handles samples and
most importantly its relative freedom from interferences, The
technique is desirable for: quantitative determination of trace
elements in aqueous and organic solvent solutions, quantitative analysis of pigments in paints and coatings, evaluation of
waste materials and total metals content, and detection of
trace metallic impurities in polymers.
The surface upon which a coating is deposited plays an
important role in the protective properties of a coating system. A single molecular layer of oily contamination can interfere with proper bonding and result in coating adhesion
failure. In addition, the oxide layer that forms in a clean metal
surface is often mechanically weaker than the bulk of the
metal. Under stress, this layer may flake off and carry with it
the coating, Techniques for the examination of surfaces may
take many forms, but all involve bombarding the sample with
atomic or subatomic particles. The bombardment excites the
surface of the sample, releasing energy, which can be used to
determine elemental or molecular composition. Depending
on the technique chosen, the "surface" examined will vary
between the first several atomic layers of a sample down to
the first several micrometers.
Electron beam X-ray analysis (microprobe) is one of the capabilities generally included with a scanning electron microscope (SEM) [5]. High-energy electrons that strike a sample
during the image forming process interact with the atoms
comprising that surface. Among the species formed during
this interaction are X-rays having specific energies depending
on the elements present in the sample. Once detected and
analyzed, X-ray spectra can yield information on the elemental composition of the sample, as well as indicate the quantity
of each element present. Two types of X-ray detectors are in
general use. The energy dispersive detector is useful for detecting elements above sodium in the Periodic Table but is
not suitable for low-level quantitative analysis. A wavelength
dispersive detector observes all elements more massive than
carbon and has significantly improved quantitative analysis
capabilities. An instrument that contains all the imaging ability of the SEM and has full quantitative analysis capability is
called a microprobe. This instrument has sufficient resolution to allow the elemental analysis of a particle less than 1
/~m in diameter. The primary disadvantage of the microprobe
is that X-rays can emerge from atoms several micrometers
below the surface of the sample. Consequently, the signal
from a thin layer of surface contamination can be lost in the
signal from the substrate.
Ion scattering spectrometry (1SS) and secondary ion mass
spectrometry (SIMS) techniques involve bombarding the sam-
760
ple with gas ions and analyzing the products removed from
the surface [5]. Both methods exhibit very high sensitivity for
all elements, including hydrogen, and can analyze a few
atomic layers of exposed surface at a time. Resolution is
normally on the order of millimeters with the exception of
specialized instruments known as microprobes. These techniques are very useful for hazing and chalking problems
where very minute amounts of material cause appearance
problems at the surface of the coating. ISS and SIMS readily
determine the nature and extent of the contaminating material. Cases of substrate contamination leading to adhesion
problems are also more easily solved using the data provided
by these analytical methods.
Electron spectroscopy for chemical analysis (ESCA) and
scanning auger microscopy (SAM) are techniques in which a
sample is irradiated with a beam of X-rays (ESCA) or electrons (SAM) to liberate electrons from the top 2 to 5 nm of the
surface [5]. The energy of the liberated electrons is then
analyzed to provide information regarding the composition
of the surface layers in the sample. In addition to elemental
composition, information can be obtained on the chemical
environment of the elements present on the surface. Through
comparison of spectral fingerprints with the spectra of standard materials or a library of reference spectra, compounds
present on the surface can be readily identified. ESCA has the
capability of observing particles approximately 1 mm in diameter and is well suited to paint films on a variety of substrates. SAM has the ability to study much smaller particles
(approximately 0.2 p~m in diameter), but the surface must be
conductive, limiting its utility to metal surfaces.
B. C h e m i c a l M e t h o d s
In conjunction with titrimetric and gravimetric measurements, analysis of elemental composition provides important
information on coatings systems. Among the many elements
determined are: carbon (%), hydrogen (%), nitrogen (%), sulfur (%), chlorine (%), bromine (%), phosphorous (ppm).
The level of nitrogen in an industrial coatings system is an
important analytical value because nitrogen is present in
melamine, urea, and benzoguanamine oligomers, which are
used as cross-linking agents in many coatings. Correct levels
of cross-linking agent are essential since physical, chemical,
and performance characteristics are directly related to crosslinker levels. Low concentrations of cross-linking agent yield
coatings which are soft, water sensitive, and do not resist
detergent solutions and the weather. Elevated levels of curing
agent have equally undesirable effects since coatings become
brittle and lack sufficient adhesion to the substrate. In addition to cross-linking agent, nitrogen content provides information on the presence of polyamide and urethane polymers,
which also contain nitrogen.
Vehicle Identification
Infrared Spectroscopy
Qualitative infrared spectroscopy is a valuable analytical
tool which allows the examination of the multitude of materials utilized in the coatings industry. It is the primary tool for
vehicle/resin identification in a coating. An infrared spectrum
indicates the overall composition of any unknown material in
terms of its functional groups. With a minimum of back-
Miscellaneous Testing
A host of chemical methods exist for further identification
of resin components by chemical treatment of the resin to
break it down into its original starting components, which
can then be analyzed by conventional methods. For example,
a resin may be subjected to aminolysis to form amides of the
carboxylic acids and to release the polyols. Upon further
treatment, these materials can be readily identified. Scanning
of available ASTM methods and Official Methods of Analysis
of the Association of Official Analytical Chemists (AOAC
Methods) [7] will provide insight into other useful techniques
and procedures.
Thermal analytical data can also aid in the identification
and characterization of a polymer. DTA or DSC can be used
to obtain a melting point, a Tg, and a measure of the thermal
stability of the polymer. XRD analysis of the polymer will
determine if the polymer is partially crystalline, help to
identify the chemical structure of the polymer, and provide
information on the preferred conformation of the polymer
chains in the crystalline regions [6].
Electron microscopy and XRD techniques describe the
submicron morphological features of polymers such as
lamellae and crystallites, while optical microscopy is used to
study large morphological features such as the size and nature of spherulites in a polymer [6].
Electron probe microanalysis (EPMA) is an elemental identification technique associated with SEM. When materials
are bombarded by a high-energy (10 to 50 keV) electron
beam, characteristic X-ray fluorescence radiation is produced. By incorporating either energy dispersive or wavelength dispersive spectrometers directly into the instrument,
it is possible to obtain X-ray spectra directly on the area as
seen by the electron beam. Thus, it is possible to obtain
qualitative and quantitative elemental data from a small volume of material for the elements boron through uranium.
EPMA has been used extensively for impurity and inclusion
identification in polymers [6].
Some unique vehicles may be particularly difficult to analyze, and the determination of residual monomer by gas chromatography often can shed some light on the resin system.
Pigment Identification
The following sections discuss the qualitative and quantitative identification of pigments.
Infrared Spectroscopy
As noted in the discussion on vehicle identification, IR
analysis for the qualitative identification of pigments is most
common. Procedures and reference spectra may be found in
the Infrared Atlas [4]. Infrared is also used for identification
of extender pigments.
762
material. The instrument can provide qualitative and quantitative information and can complete an analysis on numerous elements simultaneously and in a matter of a few minutes. The major strength of the technique, aside from speed,
is the ability to detect trace amounts of elements.
A solution is aspirated into the instrument, where a fine
aerosol is formed. This aerosol is then introduced into a highenergy argon plasma, where the elements present in the sample are raised to an excited state. When these elements return
to ground state, they emit light at wavelengths characteristic
of the elements present. The intensity of the light is proportional to the concentration of the element present in the
sample. Generally, sensitivity is in the low parts-per-million
range for most elements.
The plasma is a highly ionized, chemically inert, hot gas
which achieves a temperature estimated to be 10 000~ A
radio frequency generator provides energy to the plasma
torch by creating an oscillating magnetic field. A sample introduction device, known as the nebulizer, converts the sample solution into fine droplets or aerosol mists which are
transported to the torch by means of argon carrier gas. The
high temperature of the plasma dries the droplets and decomposes the sample into individual atoms which are excited and
emit light as they return to the ground state. The wavelength
of the light produced differentiates one element from another. The intensity of the light produced is a measure of the
concentration of the element present in the sample.
The light emitted from a sample containing many elements
passes through an optical path which separates the spectrum
of light into discrete wavelengths. A detection system, made
from many photomultiplier tubes, each representing a wavelength of an element, measures the intensity of light and
converts it to electrical energy. The electrical energy is converted into concentration by means of a dedicated computer.
The computer performs all instrumental control functions
and prints the data.
Some applications of ICP are the following: pigment composition in coatings, industrial influent and effluent analysis,
soluble cations and anions in electrocoat baths, organo-metallic additives in coatings, driers and catalysts in coatings,
competitive product analysis, quality control of raw materials, and industrial hygiene analysis.
through the flame, the free atoms in the flame will absorb
some of this energy. The decrease in the intensity of the light
beam can then be taken as a measure of the concentration of
that particular element in the sample solution.
Atomic absorption instrumentation requires a light source,
an atomizer, a monochromator, and a detector. The normal
light source used in AA is a hollow cathode lamp. It consists
of a hollow cup made from the element to be analyzed. Application of a high potential causes formation of positively
charged ions which bombard the cathode, forming excited
metal ions which emit light. AA is important since free,
uncombined atoms must be formed before light absorption
occurs. A solution containing the metal ions is heated to a
temperature sufficient to dissociate the ions into atoms. The
heat energy can be provided using an air-acetylene or nitrous
oxide-acetylene flame. The primary function of the monochromator is to isolate a single atomic resonance line from
the spectrum of lines emitted by the light source and direct it
through the flame and onto the detector. Photomultiplier
tubes are employed as detectors. They measure the changes
in light intensity and convert them to electrical signals.
Sample preparation is an essential part of AA. Solid and
pigmented samples are ashed to remove organic species. The
inorganic components are dissolved in acid and diluted with
deionized water prior to introduction into the flame. Nonaqueous AA is an ideal way of determining organometallic
compounds to prevent sample loss or conversion of the metallic species into insoluble components.
Atomic absorption complements ICP techniques for the
analysis of paints, resins, UV curable coatings, and other
materials. It is also a very useful tool in analyzing waste
materials, pigment composition, pollution studies, raw material evaluation, and analysis of organometallic compounds.
Several pigment analysis procedures using AA are standard
ASTM methods. Typical procedural examples of AA analysis
for pigments can be found in the following:
Standard Test Method for the Determination by Atomic
Absorption Spectroscopy of Titanium Dioxide Content of
Pigments Recovered from Whole Paint (D 4563)
Test Method for Detection of Lead in Paint by Direct Aspiration Atomic Absorption Spectroscopy (D 4834)
X-Ray Diffraction
The X-ray diffraction (XRD) pattern obtained from a material is characteristic of that material. The intensity of a diffraction peak is entirely due to one component of a mixture
and is dependent upon the amount of that substance in the
mixture. To a minor extent the peak intensity of the component is also dependent on the mass absorption coefficient of
Chemical Methods
The typical chemical methods using titrimetry and gravimetric procedures are always appropriate for quantitative
pigment determinations. Some of these techniques have been
replaced in recent years by more efficient (not necessarily
more accurate) and time saving instrumental methods; however, there are situations where the traditional testing methods are still most appropriate.
Numerous ASTM methods exist for these types of analysis,
and one needs to check the index of available test methods.
By way of example, the following are noted:
ASTM Test Methods for Chemical Analysis of White Titanium Pigments (D 1394)
ASTM Test Method for Arsenic in Paint (D 2348)
Additive Identification
Infrared Spectroscopy
For samples containing mixtures, the IR spectrum generally gives information only about the major component(s).
However, computerized infrared instrumentation allows one
to subtract spectra of the major constituents from a mixture
and get the resultant spectrum of minor materials such as
additives and contaminants. Thus, it is possible to do a spectral "separation" in just a few seconds rather than a true
chemical separation which may take hours. Water and hexane extractions of dried films followed by IR can point to
some of the following, for example:
9 Cellulosic thickener (which can be confirmed by spot test).
9 Long chain aliphatic hydrocarbon "oil" is indicative of
defoamers.
9 Carboxylate containing component may indicate a polyacrylate salt.
9 Nitrile component may indicate mildewcide.
9 Di-alkyl sodium sulfosuccinate is indicative of a wetting
agent
9 Inorganic sulfate may be a possible persulfate polymerization catalyst.
764
Solvent Identification
Gas Chromatography
Gas Chromatography (GC) is a technique for the separation of any species exhibiting a measurable vapor pressure at
a temperature up to approximately 300~ as well as any
compounds for which a stable, volatile derivative may be
formed. Both qualitative and quantitative information can be
obtained.
Most GC samples are liquids or solutions at room temperature, although instrumentation may be adapted to analyze
solid and gaseous samples. Liquid samples (approximately
0.001 mL) are introduced to the instrument using a syringe
into a flash heating chamber called an injection port. There,
the volatile sample components are quickly and evenly vaporized. In some cases, however, decomposition of sensitive
components can occur when they come in contact with the
hot metal surface. The analytical chemist may be able to minimize or circumvent this problem if proper precautions are
taken. The vaporized components are then carried onto the
column and through the gas chromatographic system using
an inert gas, such as helium or nitrogen, flowing at a constant
rate.
The column is the portion of the chromatograph where the
actual separation of components is achieved. A packed column consists of narrow tubing made from stainless steel,
nickel alloy, glass, or a number of other materials, filled with
fine particles of a packing material. This packing material
may consist of polymeric beads or an inert solid material
supporting a thin film of a non-volatile liquid. It is the varying
degree of interaction between each of the sample components with the packing material that causes the components
to become separated in the column. A large number of packing materials of varying chemical composition are available.
Columns containing other packing materials are easily interchanged so that different separations can be obtained.
Occasionally, samples will contain a number of components of similar volatility and/or chemical composition which
are difficult to separate on packed columns. In these instances, capillary columns are used. Capillary columns are
extremely long (100 to 300 ft, 30.48 to 91.44 m), narrow bore
tubes made from glass, metals, or fused silica. They are internally coated with a thin film of a nonvolatile liquid to effect
separation. A variety of detectors used alone or in combination can be strategically mounted at the end of the column to
monitor the separated components as they exit the column.
The detectors available in GC have varying sensitivity and
specificity. If needed, some may be operated to detect materials in the sub parts-per-million level,
The response of the detector to an eluting component is
electronically converted into a visual representation called a
chromatogram. A chromatogram is a plot of detector response versus time elapsed since sample injection. Eluting
components are represented as peaks in the chromatogram.
The time needed for a component (peak) to elute can be used
to help identify the component. The area produced under the
peak is related to the concentration and is used in the quantitative determination of the component.
Typical applications include: qualitative and quantitative
solvent analysis, odor analysis, pollution studies, purity determinations, determinations of residual monomers, and determination of airborne organic contaminants.
Additional information on gas chromatography may be obtained from ASTM Practice for Packed Column Gas
Chromatography (E 260). ASTM Test Method for Direct Injection of Solvent- Reducible Paints into a Gas Chromatograph for Solvent Analysis (D 3271) describes the techniques
used in many situations. Note should also be made of ASTM
Test Method for Determination of Dichloromethane and
1,1,1-Trichloroethane in Paints and Coatings by Direct Injection into a Gas Chromatograph (D 4457) for exempt solvent
analysis for VOC calculation purposes. ASTM Committee
E l 9 on Chromatography is focused on chromatographic
techniques. There are numerous ASTM gas chromatographic
test methods for the determination of the purity of specific
solvents and for the determination of specific impurities such
as benzene.
CHAPTER 6 8 - - A N A L Y S I S OF PAINT
techniques has unique properties for providing useful analytical information.
Electron impact ionization occurs when electrons emitted
from a hot filament collide with sample molecules causing
the loss of one or more electrons. This results in the formation of positive ions which contain excess energy. The excess
energy causes many of the resulting ions to break apart or
fragment, thus providing the fragmentation patterns used to
determine chemical structure.
In chemical ionization, the mass spectrometer's ionization
source is pressurized with a reagent gas such as methane,
ammonia, or butane. Electrons from the filament collide
with, and impart energy to, the reagent gas. The energetic
reagent gas molecules subsequently collide with the sample
molecules causing the sample molecules to become positively
charged. Ions formed in this manner do not contain as much
excess energy as ions formed via electron impact ionization.
Consequently, very little fragmentation occurs and intact
ions containing molecular weight information are obtained.
Following ionization, the sample and fragment ions are
sorted according to their respective masses. Ion intensities at
each mass are measured by an appropriate detector, and the
corresponding signals are transmitted to a computer for further processing and data storage. Results can then be displayed in graphical or tabular form. Interpretation of the
spectra and comparison with a library containing thousands
of reference compounds allows sample composition to be
determined by the analyst.
Typical problems examined using GC-MS include: the
qualitative identification of volatile organic species and contaminants in coatings and coatings raw materials, quantitative analysis of volatiles at the parts-per-million and partsper-billion level, evaluation of potential odor causing species,
and determination of polymer composition following pyrolysis and chemical degradation. Other uses include: characterization of complex solvent systems; monitoring of waste
streams and ground waters; characterization of polymer
products, by-products, and intermediates; identification of
odor problems; and monitoring of raw materials for potential
contamination.
TRACE ANALYSIS
With the development of sophisticated instrumentation
over the past two decades, the ability to increase sensitivity in
lower detection limits for many materials has increased. This
is particularly true in the areas of metals analysis. As a result,
many regulatory and compliance agencies have changed
their detection limits to reflect this increased capability. For
EPA (Environmental Protection Agency), OSHA (Occupational Safety and Health Administration), and FDA (Food and
Drug Administration) compliance, trace analysis is extremely
important. Many manufacturers require trace analysis to
identify contamination, to verify product purity, and so forth.
Analysts must be prepared to provide data in the parts per
billion (ppb) and sub ppb range when necessary, and this
frequently involves good concentration techniques as well as
good methodology- and instrumentation.
Certainly techniques such as GC, MS, and HPLC are capable of measuring components in solution well below the ppm
765
766
REFERENCES
[1] "Quality Assurance of Chemical Measurements," John Keenan
Taylor, 1987, Lewis Publishers, Inc., 121 S. Main Street, P.O.
Drawer 519, Chelsea, MI 48118.
[2] "Introduction to Microwave Sample Preparation," H. M. Kingston and L. B. Jassie, Eds., ACS Professional Reference Book, American Chemical Society, Washington, DC, 1988.
[3] "Use of Statistics To Develop and Evaluate Analytical Methods,"
G. T. Wernimont, Ed., William Spendley, Association of Official
Analytical Chemists, Arlington, Virginia, 1985.
[4] "An Infrared Spectroscopy Atlas for the Coatings Industry," 4th
ed., D. Brezinski, Ed., Federation of Societies for Coatings Technology Publishers, 492 Norristown Rd., Blue Bell, PA 19422.
[5] Metals Handbook, 9th ed., Volume 10: Materials Characterization,
American Society for Metals, Metals Park, Ohio, 1986.
[6] "A Guide to Materials Characterization and Chemical Analysis,"
1988, J. P. Sibilia, VCH Publishers, Inc., 220 East 23rd Street,
Suite 909, New York, NY 10010.
[7] "Official Methods of Analysis of the Association of Official Analytical Chemists," S. Williams, Ed., Association of Official Analytical
Chemists, Inc., Arlington, VA 22209.
MNL17-EB/Jun. 1995
i
69
by George D. Mills I
767
www.astm.org
768
through the logic that aides one in understanding the potential failure modes. These questions are as follows:
1. What is the actual coating failure?
2. What is the coating system?
3. What was the desired purpose of the coating?
4. How was the coating applied?
5. What evidence is presented by the failure?
ters, but they are usually caused by the production of powdered corrosion products under or within the film [2]. It is
safe to say that the problem cannot be solved and proper
liability placed until the true coating failure problem has
been identified.
Coating
Failure modes tend to follow generic types of coatings. In a
very broad sense, coatings may be grouped into three categories based on the final film. These are coatings with organic
binders, those with inorganic binders, and those composed of
metallic films. The largest category of coatings are those utilizing an organic binder. Organic binders use polymers based
on carbon as the primary atomic makeup of their backbone.
The paint film at application includes polymer precursors
using functional groups such as epoxies, urethanes, vinyls,
acrylics, and alkyds. These must polymerize to reach some
high molecular weight at which they are capable of forming
protective films. Generally, inorganic coatings are those that
utilize elements other than carbon for forming a film. These
may be silicates, sulfates, or cementitious coatings based on
calcium. As a coating, each will have some typical failure
modes. Metallics may be very thin films used on plastics for
affecting gas molecule transmission and abrasion characteristics. They may be thick as from galvanizing or flame/arcsprayed metallics used for corrosion protection.
769
770
ing coatings often produces gas of sufficient pressure to explode the container.
Chemically reactive cross-linking binders include all twopart systems. This includes epoxies and urethanes that have
appreciable reaction rates at room temperature as well as
single-package, cross-linking systems that require heating or
some other energy source to increase the reaction rate significantly and allow a cure to be attained. Some systems will
contain all the reactive polymeric binder precursors that
cross-link with each other to produce the final film. Some
systems may generate the required energetic cross-linking
specie by a reaction brought about by an outside energy
source such as ultraviolet (UV) radiation, electrodeposition,
or high-energy electron beams.
Ambient-cure, two-component, or catalyzed binders such
as epoxies and urethanes require a proper mixing ratio to
allow the finished film to have its desired properties. Improper ratio mixing can lead to a host of final film problems.
These problems include inadequate curing, brittleness, loss
of extensibility, loss of chemical resistance, early extensive
chalking, and many more. Off-ratio coating systqms may be
investigated using GC/MS pyrolysis [1].
Epoxies are often cured by amine functional polyamides,
amine adducts, or aliphatic amines. Polyamides, being manufactured from long-chain fatty acids, are very aliphatic in
nature and, typically, not particularly soluble in the epoxy
side. Because of this poor solubility, it is often necessary to
allow extra time after mixing for the reaction products to gain
solubility characteristics more closely related to each other.
This extra time is called the "induction period" or "sweat-in
time" and allows time for the two resins to partially co-react.
The partially reacted resin solution eventually changes the
solubility characteristics of the binder system sufficiently to
completely solubilize all resin components. A failure to reach
complete solubility will lead to "zone curing" with macro
islands of unreacted polyamide and potentially unreacted
epoxy resin. Additional failure modes include osmotic blister
formation (where the low molecular weight amine is the solute, with condensed water being the solvent), increased
amine carbonate formation and exudation to create intercoat
delamination problems, film brittleness, poor weatherability,
and others.
Application of amine and polyamide systems in cold
weather can present future delamination problems. In cold
weather, when the epoxy-amine reaction slows down, the
amine reaction with carbon dioxide and water vapor from air
does not slow very much. The formation of an amine carbonate "bloom" develops on the coating surface. Additional
amine carbonate within the coating matrix formed during
spray application exudes to the surface. This leaves a weak
boundary layer on the surface. When overcoated, the insoluble "greasy" amine carbonate will not allow adhesion of the
next coat and usually results in delamination in tess than a
year. The interface will be moisture sensitive and potentially
provide the solute for osmotic blister formation. The author
has found a simple test to evaluate for the presence of the
amine carbonates. This is done by applying a drop of 6 M
hydrochloric acid to a suspected surface while watching the
edge of the drop under a microscope. The HC1 will liberate
the carbon dioxide at the edge of the "wetting front" as the
droplet wets the surfaces. The bubbles of gas can be seen in
771
772
Metallic Coatings
Metallic coatings are very thin layers of pure metal, usually
applied to a substrate for appearance, modification of ware
characteristics, corrosion protection, or to disallow the transport of migrating gas molecules through plastic film. They are
important because of their ability to modify physical properties of the substrate such as stopping the migration of oxygen,
carbon dioxide, and other small molecules through plastics.
An example most are familiar with is the shiny metallized
coatings seen on food wrappers containing oxidizable vegetable oils. It is usually assumed that these shiny packages are
for "aesthetics only," however these thin metallized films
serve to stop the migration of oxygen into the food package.
With the trend to eat more unsaturated otis in our foods, the
oxygen would react with the unsaturated bonds in the oils to
produce a rancid taste. This is associated with the product
being old and stale. The bad taste is due to the formation of
aldehydes during the oxidation process.
773
774 P A I N T A N D C O A T I N G T E S T I N G M A N U A L
Quality in the manufacture of the coating products includes both the proper formulation for use in the environment intended as well as the eventual commercial manufacturer. There is usually a lengthy testing program required to
evaluate the coating formulation before a product is commercialized. A few typical failures seen in the formulation and
manufacture include systems formulated to contain low vapor pressure, water-soluble solvents in coatings to be used
under water, formulation without required UV or thermal
stabilizers for exterior coatings, gelation of acidic binders by
reaction with basic pigments, loss of dryer catalysts from a
oxidizable coating system, inclusion of carbon dioxide and
water vapor into the amine side during the manufacturer of
an adduct for a two-part catalyzed coating, and failure to
exclude water contaminants during the manufacture of the
nonisocyanate side of a urethane coating system.
W H A T WAS T H E D E S I R E D P U R P O S E OF
T H E COATING?
Before designing the test regime to evaluate a specification
or starting the investigation of a failed coating, the analyst
should ask why the coating was applied. Often it will be
intuitive or would be stated in the specification. The design of
the testing and evaluation program should include elements
encompassing these objectives. Table 1 lists some of the
ASTM standard test methods used to evaluate a coating's
specific serviceability relative to a particular property. Table
2 lists some of ASTM's standard practices for accomplishing
the objectives.
Coatings provide a renewable surface and allow the engineer to use materials that are more economical or provide a
physical characteristic not attainable from the uncoated surface. While coatings frequently provide a variation in appearance, most coatings serve to protect more than to beautify.
When the protection is not provided for the full design life of
the coating, including the maintenance of all expected and
desired protective properties, a coating failure has occurred.
Frequently the coating will be evaluated for a particular service through a series of tests. These evaluation programs are
designed to assist in predicting failure modes and to assist in
the preparation of specifications. Problems often develop
when the service does not match the initial testing program.
A major reason for applying coatings to many different
types of substrates is to protect the substrate from deterioration. Coatings on steel, when applied properly, have the ability to stop corrosion in hostile environments for a period of
time. Coatings applied to wood have the ability to prevent
fungus growth and rotting, even in damp environments. Hard
metallized coatings protect softer metals from wear. Highly
active metallized coatings such as zinc and aluminum have
the ability to prevent corrosion of steel in adverse conditions
[2]. When coatings are applied to protect the substrate and
the substrate sustains premature damage, a coating failure
has occurred. Test regimes usually address the perceived
problem. Sophisticated a-c impedance and d-c polarization
techniques have the ability to measure actual corrosion currents and represent a very sensitive test method for metal
substrates.
775
tion characteristics over the coating's planned life span constitute a coating failure.
Coatings containing voids or small bubbles have the ability
to adsorb mechanical wave energy such as sound. Changes
with time in these adsorption or dampening abilities usually
constitute a coating failure. Some of these unique physical
properties are impacted by the adsorption of liquids such as
water from condensation and may be the subject of test programs when evaluating this type of failure. Knowledge of the
physics of wave energy transmission and point reflection
through elastic media is necessary to design test programs
evaluating these parameters.
The specification, type of coating being applied and its particular curing requirements, variations in ambient weather conditions, variations in the condition of the substrate, surface
preparation techniques, pretreatments, equipment used during the application, the quality of third-party inspection as
well as the applicator's knowledge and ability all play a major
role in getting the coating properly applied.
Preparation and F o l l o w T h r o u g h o f t h e
Specification
The specification should serve as the "blue print" for getting
the coating properly applied. Its existence implies that someone has surveyed the site to determine any abnormalities that
might exist, evaluated the service requirements, reviewed the
particular problems unique to the structure and service demands, identified a particular coating with the required service characteristics through prior testing, and provided an
adequate application procedure that, theoretically, will meet
the use requirements. The specification assists the applicator
in knowing what is expected of him and serves as a legal
document in times of dispute.
Frequently a coating will be specified by a specific manufacturer's product numbers. Failures in the specification, either in the type of recommended coating or the application
procedures, can result in early failure. As such, the specification must be reviewed when investigating a coating failure.
Coating materials may have been used that were not on the
approved list. Most applicators are not in possession of
proper knowledge to make substitutions and usually do not
want that responsibility. Coating failures in many forms have
resulted from attempts to circumvent the specification. Analysis of very small coating chips by FTIR or GC/MS and com-
776
777
fundamentals and protective techniques; (5) potential formulation problems; (6) potential application problems; (7) the
suitability of the specified coating for the service; and (8) the
instrumentation that can provide sophisticated answers to
the complex questions that exist.
It is rare for all of these disciplines to be found in a single
individual. New coating polymers are being developed routinely and are being incorporated into coating systems. Their
reaction chemistries both with the cross-linkers used to produce the final film and the interfering side reactions with
ambient, local, or solvent species may produce unexpected
results. Because of this, the successful investigator must be
aware of his/her limitations and be willing to seek knowledgeable assistance when necessary.
Those with experience in the formulation of paints and
coatings will often have a distinct advantage over others.
Understanding the potential shortcomings of the polymers
used, the problems forced by the use of environmentally
friendly solvent systems, the functions of the additives, the
physics of adhesion, and the limitations of the analytical
"tools-of-the-trade" will assist in understanding failure mechanisms. Even still, the challenge is tremendous and true
solutions may be elusive. It is important to know when to ask
for help.
While the investigation of a coating failure requires all of
the knowledge discussed, a systematic approach offers the
best chance for a successful conclusion. Before beginning the
investigation, it is important to follow a preconceived procedure that will ensure that each phase of the investigation is
addressed. Since each failure may be somewhat different,
there will be opportunities to veer from the path as evidence
is produced. The investigation should contain the follow elements as a minimum:
1.
2.
3.
4.
5.
778
Hypothesis
At some time after starting the investigation, a hypothesis
can be drawn. A testing program incorporating it may be
developed that will assist in proving or disproving the possibility of a failure mode.
779
CONCLUSION
Coating failure analysis will draw from a multitude of disciplines. To increase effectiveness, one must be willing to have
an open mind during observation and study the basic chemistry and physics controlling the processes. Do not enter an
investigation with preconceived ideas so strongly set so as to
be swayed from seeing the small details that will define the
actual failure mode. Do not be afraid of the "heavy" chemistry
associated with the sophisticated analytical instrumentation
that can give one very powerful insight into the systems.
While there are some coating mistakes that are commonly
made, the reasons for coating failures appear to be limitless.
Just as a good mechanic must know how an engine works to
diagnose its problems, so too must the coatings failure practitioner know how paints work and the tools available for use
in any required investigation. This knowledge of potential
failure mechanisms can be extremely helpful to others, as
well, including the owner, specifier, paint manufacturer, and
applicator. By appreciating potential coating problems, an
awareness of many important details is naturally obtained.
Learning the complex chemistry of urethanes may be beyond
the average applicator, but the knowledge that bubbles in
urethanes may be the result of painting over condensed water
on the surface forces an awareness that is very helpful.
REFERENCES
[1] Mills, G., Bell, R., and Shirey, L., "The Characterization of Coatings Utilizing Thermal Extraction/Gas Chromatography Followed by Fourier Transform Infrared Spectroscopy and/or Mass
Spectrometer," Paper 440, Proceedings, NACE Corrosion 94, National Association of Corrosion Engineers, Houston, TX, 1994;
European Coatings Journal, Vol. 2/95, Hannover, Germany, 1995.
[2] Fischer, K. P., Rosbrook, T., Thomason, W. H., and Murali, J.,
"Performance of Thermal Sprayed Aluminum Coatings in the
Splash Zone and Riser Service," Paper 499, Proceedings, Corrosion 94, NACE, Houston, TX, 1994.
[3] Annual Book of ASTM Standards, Vol. 6.01, American Society for
Testing and Materials, Philadelphia, PA, 1991.
[4] Mills, G., "The Degradation and Stabilization of Polymers used as
Coatings," Handbook of Polymer Degradation, S. Hammad, Ed.,
Marcell Dekker, New York, 1993.
[5] Mills, G., "Modification of the Adhesive Characteristics of Epoxy
Resin to Steel Substrates," Arabian Journal for Science and Engineering, King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia, Vol. 13, No. 4, 1988, pp. 487-490.
[6] Systems and Specifications, 4th ed., Vol. 2, Steel Structures Painting Council, Pittsburgh, PA, 1985.
[7] Mills, G., Sansom, A., and Cox, G., "Modern Analytical Instrumentation used for Determining Coating Quality and Investigating Coating Failures," Paper 439, Proceedings, NACE Corrosion
94, National Association of Corrosion Engineers, Houston, TX,
1994; European Coatings Journal, Vol. 12/94, Hannover, Germany, 1994, pp. 961-967.
[s] Mills, G., "The Interpretation of Differential Thermal Analysis
Data for Fusion Bonded Epoxy Coatings," Material Performance,
Vol. 23, No. 6, National Association of Corrosion Engineers,
Houston, TX, 1984.
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MNL17-EB/Jun. 1995
70
by Dwight G. Weldon I
ELECTROMAGNETIC RADIATION
E=hv
A useful definition of spectroscopy is the study of the interaction of light, or more generally, electromagnetic radiation,
with matter. Therefore, a logical starting place in the discussion of spectroscopic methods is a brief introduction into the
nature of electromagnetic radiation.
Simply put, electromagnetic radiation is energy traveling
through space at enormous velocities that are effectively the
www.astm.org
784
Energy,
common units 100 Me V
L
1 keV
4
1014
Frequency, Hz
Wavelength,
common units
8OO nm
200 nm 400 nm
o.IA
1A
.____L
Spectral region
y Ray
X-ray
Optical method
y Ray spectroscopy;
M6ssbauer
spectroscopy
X-ray
spectroscopy
Inner-electron
transitions
Source
Nuclear
reactions
Atomic reactor,
particle
accelerators
Monochromator
Pulse-height
discriminator
Crystal
grating
Transition
occurring
Detector
33 cm 1
Ultraviolet
Vacuum uv Near
Geiger-Muller tube,
scintillation counter, film
1012
L
I
251Jm
Microwave
s.Reck.roscoe;
eeciron spin
resonance
spectroscopy
Outer-electron
transitions
Molecular
vibrations
Hydrogen or
Xe arc
~
Quartz prism
grating
Salt prisms:
LiF, NaCI, KBr, CaBr
Phototube, I ~
photomuitiplier I ~...~
~
Microwave
N e a r / M~d Far
Ir / '
ir
ir spectrophotometry
101~
L
Infrared
/ uvl h
~, spec~oham~W ~ [ ~
X-ray tube
1 cm "1
Thermocouple,
bolometer
10 e
lm
Radio
Nuclear magnetic
resonance
spectroscopy
/ Electronic oscillator
L
Monochromatic source
Crystal
diode
Diode, triode,
transistor
FIG. 2-The electromagnetic spectrum and corresponding spectroscopic methods [1]. (Printed with permission of McGraw-Hill,
Inc., from Olsen, E.D., Modern Optical Methods of Analysis, 1975.)
ATOMIC ABSORPTION
(AA)
SPECTROSCOPY
CHAPTER
70--ATOMIC
ABSORPTION
785
BURNER
CATHODE
LAMP
_
/If
I
LAMP
r 9
~'TI
]
MONOCHROMATOR
I
.
~
FUEL
DRAIN
ELECTRONICS
METER
[
OR
RECORDER
SAMPLE
AIR
Flame Characteristics
Although the processes taking place within a flame are very
complex, the flame serves three basic functions:
9 sample volatilization
9 decomposition of molecular compounds to the elements of
interest
9 excitation of the individual atom (AE only)
The flame consists of three regions: an inner core, an interconal zone, and an outer cone. The analytical measurement is generally carried out in the interconal zone, which is
the hottest part of the flame. The height of this zone above the
burner varies with the type of gases being burned, their flow
rate, and the burner type.
A very important property of the flame is its temperature,
since thermal energy is responsible for decomposing samples
into individual atoms and, in the case of AE, for exciting the
atoms thus formed. The most common flame type is the airacetylene flame, which achieves an interconal-zone temperature of approximately 2200~ If a nitrous oxide-acetylene
flame is used, the temperature is approximately 2900~
Hotter flames are usually more advantageous because they
reduce the number of chemical interferences. One primary
source of chemical interference is compound formation
within the flame, resulting in broad-band absorption and
emission. As flame temperature is increased, many of these
compounds are decomposed into the free atoms and the
problem is eliminated. Also, hot flames are desirable in AE
since they will provide more energy for the excitation of an
increased number of elements. Too high a temperature
should be avoided since it is possible that a significant portion of the neutral atoms may become ionized rather than
simply excited.
786
Graphite Furnace
A modification of AA involves the use of a graphite furnace
rather than a flame to achieve excitation. Small graphite
tubes or boats that have electrical contacts through which an
electrical current can be passed are the basis of this technique. A small amount of sample is precisely measured into
the graphite furnace, the current flow is begun, and a very
high temperature is achieved, resulting in the production of
an atomic vapor.
The graphite tubes are usually about 5 cm in length and
about 1 cm in diameter. The sample is introduced with a
micropipette through a hole in the top of the tube. The radiation from the hollow cathode lamp is focused through the
axis of the tube. Heating is usually accomplished in stages.
The first stage is a low-temperature step that has the purpose
of volatilizing any water or solvent in the sample. The second,
somewhat higher temperature, step is used to ash the sample,
and this is followed by a rapid increase in current to achieve
temperatures of 2000 to 3000~ and atomization of the unknown elements whose absorption is then measured.
The main advantage of the graphite furnace technique is
improved detection limits due to greater sampling efficiency.
Flames have low efficiency because flow down the drainage
tube (see Fig. 3) results in most of the sample never getting to
the flame, and also because the residence time of the atoms in
the analytical portion of the flame is very brief. In contrast,
graphite furnace atomizers utilize almost all of the sample
and residence time is greatly increased.
A T O M I C E M I S S I O N S P E C T R O S C O P Y (AE)
Instrumentation for atomic emission spectroscopy is very
similar to that used for AA. In fact, the same instrument can
usually be used for both methods. AE relies on detection of
energy emitted from excited atoms as they relax to their
ground state configuration as opposed to measuring the decrease in signal strength due to absorption of energy by
ground state atoms being raised to an excited state. Since in
AE the source of the measured light is the analyte itself, there
is no need for an external light source such as the hollow
cathode lamp used in AA. For this reason, the technique is
more readily adaptable to multi-element analysis than AA.
SOURCES OF INTERFERENCE
Spectral interference can affect AA and AE results. It can be
caused by the overlapping of a line or band originating from
an impurity element with the line being measured. For example, in emission analysis of sodium, the presence of calcium
can give rise to spectral interference since thermally stable
calcium hydroxide can form in the flame. This compound
emits a band of radiation that overlaps the characteristic
590-nm line of sodium. This can be reduced to a certain
degree if a monchromator of high resolution is used in AE.
Such spectral interferences are less common in AA than in
AE. In AA the line source is the extremely narrow line produced by the hollow cathode lamp, and, therefore, monochromator resolution is less important in AA. However, there
are still a few cases of spectral interference in AA. For example, both iron and platinum have absorption lines very near
272 nm, and manganese and gallium have lines near 403 nm.
Problems can be caused by chemical interference, which
can decrease the population of free metal atoms and thereby
yield an artificially low result. For example, many elements
form stable oxides or hydroxides within a flame. Lithium is
known to form a hydroxide in the flame. Such interferences
can be minimized by increasing flame temperature.
Other types of interference include broad-band absorbance
that is caused by molecules that have either formed or not
been completely dissociated in the flame or by particulate
matter in the flame.
B a c k g r o u n d Correction
Instrument manufacturers have devised a variety of instrumental methods for background correction. Background correction with a deuterium lamp relies on the fact that this
lamp provides broadband continuous radiation in the ultraviolet region. By having a relatively wide slit width, the fraction
of this radiation absorbed by the analyte is very small compared to the broadband absorbance due to molecular species
in the flame or by scattering. Therefore, this type of interference can be corrected by simply subtracting the absorbance
of the deuterium lamp from the absorbance of the hollow
cathode lamp.
Another type of background correction utilizes the Zeeman
effect. When vapor phase atoms are subjected to a strong
magnetic field, a splitting of the electronic energy levels occurs. This produces, in the simplest case, three lines separated by a fraction of a nanometer and is termed the "Zeeman
effect." The central, strongest line only absorbs radiation that
is plane-polarized with the magnetic field, while the two
weaker lines do not absorb radiation of this polarity. By
mounting a rotating polarizer after the hollow cathode lamp,
absorption by the analyte occurs only during the proper orientation of the polarizer. When the polarizer is in the opposite orientation, no analyte absorption occurs. Since background absorption and scattering occur during both cycles, it
can now be subtracted to give only the absorbance due to the
analyte.
787
In simultaneous spectrometers, a series or bank of detectors, such as photomultiplier types or diode arrays, are positioned at fixed points about the grating so that light at several,
preselected frequencies is measured simultaneously. This is a
much faster technique than the sequential method, especially
if ten or more elements are being determined per sample. A
disadvantage with the simultaneous instruments is their lack
of flexibility. Since only a limited number of detectors can be
used, only a limited number of preselected analytical lines
can be measured. Typically, instruments can be set up to
determine approximately 30 to 40 elements, although some
can accommodate more than this.
Therefore, although able to detect more elements at somewhat better detection limits with an extended linear calibration curve compared to AA and AE, the biggest advantage of
ICP spectroscopy is speed and especially so when multielement analyses are performed. However, speed comes at a
price. Conventional AMAE spectrometers can be purchased
for $15,000 to $30,000, whereas sequential ICP instruments
are typically $50,000 to $75,000, and simultaneous instruments are well over $100,000. Therefore, if only a few samples are being analyzed per day for two or three elements,
which is often the case in most coating laboratories, AA or AE
is probably the most cost effective choice.
APPLICATIONS
Approximately 70 elements can be detected in a practical
sense with either AA or AE. Detection limits are typically subpart per million. Thus, the techniques are both versatile and
sensitive. Although several hours may be required for sample
preparation, the actual analysis step is usually extremely
rapid. Samples must be introduced into the instruments as
liquids of low viscosity with the material to be analyzed in a
dissolved state. Some limited work has been done on fine
suspension samples.
One of the most common uses of AA spectroscopy in the
coating industry is determination of lead. Lead had become a
major health concern, and its presence can greatly impact the
cost of removal and disposal of old paint from various structures. The commonly accepted method for lead determination is ASTM Test Method for Low Concentrations of Lead,
Cadmium, and Cobalt in Paint by Atomic Absorption Spectroscopy (D 3335). In this method, the dried paint is ashed to
burn off the organic materials and then digested in hot nitric
acid. The method is also used to determine cadmium pigments and cobalt contained in some driers.
ASTM Test Method for Low Concentration of Mercury in
Paint by Atomic Absorption Spectroscopy (D 3624) is used
for the determination of mercury that is contained in many
common fungicides used in paint. The sample is decomposed
at elevated temperature, dissolved in sulfuric and nitric acids,
diluted, and analyzed using a cold-vapor AA technique.
ASTM Test Method for Low Concentrations of Chromium
in Paint by Atomic Absorption Spectroscopy (D 3718) involves ashing dried paint followed by digestion with potassium permanganate and sulfuric acid, dilution, and analysis.
ASTM Test Method for Low Concentrations of Antimony in
Paint by Atomic Absorption Spectroscopy (D 3717) involves
788
Analytical Chemistry, "Application Reviews," usually published in the June 15 edition of every odd-numbered year
since 1987 and in the April editions prior tO: 1987. For instance, the 1989 review [6] listed ten AA and AE methods for
coatings and related products. These included determination
of lead content in household paints, of nickel and cobalt in
coatings for brass, of sodium and silicon in surfactants, and
of metallic elements in poly(vinyl chloride). The 1993 review
[7] lists 13 AMICP methods.
REFERENCES
[1] Olsen, E. D., Modem Optical Methods of Analysis, McGraw-Hill,
New York, 1975.
[2] Analytical Methods for Atomic Absorption Spectroscopy, PerkinElmer, Norwalk, CT, 1982.
[3] Skook, D. A., Principles of Instrumental Analysis, Saunders College Publishing, Philadelphia, 1984.
[4] Routh, M. W. and Paul, K. J., "A Fixed Grating Sequential ICP
Spectrometer," American Laboratory, June 1985, pp. 84-97.
[5] Demko, P. R., "Second Generation Sequential ICP Spectrometers," American Laboratory, November 1985, pp. 97-103.
[6] Anderson, D. G., "Coatings,"Analytical Chemistry, Vol. 62, No. 12,
15 June 1989, pp. 33R-45R.
[7] Anderson, D. G., "Coatings,"Analytical Chemistry, Vol. 65, No. 12,
15 June 1993, pp. 1R-11R.
MNL17-EB/Jun. 1995
i
Chromatography
by Rolando C. Domingo I
CHROMATOGRAPHY IS A TERM THAT DENOTES a myriad of laboratory separation processes based on a differential migration
phenomenon. It is particularly effective for the resolution of
complex mixtures; hence, it can be used as a chemical preparatory method or, more importantly, as an analytical tool.
This potent analytical technique has been widely used in the
paint industry for a broad range of coating applications from
everyday routine analysis to fundamental research into the
nature of organic coating systems. Its use has been so extensive that virtually every type of material used in paint has
been affected by chromatography.
Chromatography possesses certain inherent features that
offer distinct advantages over conventional analytical techniques: complex mixtures, including isomers and homologs,
can be separated; most of the equipment is relatively simple
and inexpensive; chromatographic procedures are applicable
to a broad spectrum of chemical types and are adaptable to
both micro- and macro-size samples; and chromatography is
capable of both qualitative and quantitative functions even
when applied to multicomponent systems.
The term chromatography was coined by Tswett [1] who, in
1906, used powdered chalk and petroleum ether to separate
plant pigments into colored zones of isolated pigment. As
early as 1930 the technique was applied successfully to colorless materials, but the name remained unchanged. The term
is currently used to signify a broad group of separation techniques, most of which are independent of color.
GENERAL PRINCIPLES
Considered simply, the chromatographic process involves
the differential migration of sample components as they are
moved through a chromatographic system. The rates of migration for various components are related to their unequal
distribution between two phases, a moving phase and a stationary phase. Distributions are determined by driving and
resisting forces that are exerted between the two phases and
the components in the sample. These forces are influenced by
the chemical structure and the size and shape of molecules
present in the chromatographic system and in the sample.
Generally, the stationary phase is a finely divided solid serving as an adsorbing surface or a liquid supported by some
inactive porous media; the mobile phase is usually liquid or
gas. The effectiveness of a chromatographic separation de-
GENERAL METHODS
Frontal, displacement, and elution analysis are the three
basic methods for conducting chromatographic separations,
and each has its own unique function. Separations are determined by adsorption or partition interplay between sample,
stationary phase, and moving phase.
789
Copyright9 1995 by ASTM International
www.astm.org
790
Frontal Analysis
Adsorption Chromatography
Displacement Analysis
In this method, a concentrated portion of a sample is adsorbed onto a column, foIlowed by the addition of a solvent
(developer) that is adsorbed more strongly than any of the
components in the sample. As the developer passes through
the column, the components are displaced and forced ahead
of it. Components will also displace one another so that the
one least strongly adsorbed emerges from the column first,
followed by the others in the order of increasing adsorption
affinity. The component with the greatest adsorption affinity
elutes last, immediately ahead of the displacing solvent. Under optimum conditions, each component will move through
the column as a "belt" of pure material. A graph, obtained by
plotting volume against some physical property of the
effluent, will contain a series of steps. Under standardized
conditions, the height of each step is used for identification,
and the length of each plateau is used to determine relative
amounts. When put to practice, all reversibly adsorbed components are moved through the column, but they are not
resolved completely. The trailing edge of one component will
overlap the leading edge of the following component, and,
although it is not possible to completely separate each component in its pure form, normally a relatively pure fraction of
each is attainable.
Elution Analysis
Elution processes are conducted by introducing a concentrate of the sample onto a column followed by the addition of
an unadsorbed moving phase. As the sample mixture is
washed through the column, components are selectively retarded and separated into discrete zones that are isolated by
the presence of the moving phase between zones. This procedure contrasts with displacement and frontal methods by
having the eluting solvent pass through the sample. Theoretically, complex mixtures can be completely resolved; hence,
elution chromatography has the potential of being a good
procedure for qualitative and quantitative analysis.
Of the three processes discussed, elution chromatography
is the most efficient method for resolving mixtures, which
accounts for its being the most widely used form of chromatography.
Partition Chromatography
Partition chromatography is distinguished from adsorption chromatography by the presence of a liquid that is positioned in the system by sorption to an inactive solid support.
The liquid layer is the stationary phase, and the solid merely
serves as a support. Separation of compounds is related to
their differential solubility in two immiscible phases. Hence,
a compound demonstrating a solubility preference for the
stationary liquid phase will have its passage through the colu m n retarded. Those that are less soluble in the stationary
liquid phase, but readily soluble in the mobile phase, tend to
move unimpeded through the column. In a static experiment
with a given set of phases, a compound will be distributed
between phases in a characteristic manner. This property is
referred to as its partition coefficient, k, and may be defined
as follows:
[concentration of compound in 1
k = [- stationary liquid phase (g/mL) J
concentration of compound in 1
moving phase (g/mL)
]
Since components are separated by virtue of differences in
LIQUID CHROMATOGRAPHY
Of the various forms of chromatography, the form using a
liquid eluent came first. Liquid chromatography (LC) is characterized by the employment of a liquid moving phase; the
stationary phase may be either liquid or solid. The separation
of molecules is based on their preference for a liquid or solid
stationary phase relative to a liquid moving phase. LC encompasses established techniques such as paper, thin layer, "classical column," and gel permeation chromatography, all of
which have been used extensively for routine and research
purposes. For the purpose of clarity and continuity, the different chromatographic techniques will be discussed as separate entities, but, in some cases, there has been a fusion of
techniques. For instance, papers have been impregnated with
ion exchange materials; gels, the material commonly associated with gel permeation chromatography, have been spread
on thin plates for thin-layer separations.
"Classical Column"
Chromatography
792
Fractions are collected and titrated with 0.01 N sodium hydroxide solution.
Swannet al. [6] used carbon black and asbestos to separate
phthalate plasticizers from phthalate resins. Phthalate resins
were retained selectively on the column, and phthalate plasticizers were detected and measured by saponification of the
effluent.
ii
I.o,-., ! l,o.vE,, I
IRESE.vo,R I I~Es~.vo,. !
9
NO.I
,o. 2
WASTE
NO, 3
PUMP
PRESSURE
FRAC~ONATING
FILTER
COLUMN
PULSATION
DAMPER
PRE~OLUMN
INJECTOR
REFERENCE VALVE
CHAPTER 71--CHROMATOGRAPHY
At the present time, refractive index comes closest to being
the universal detector for liquid chromatography. Detection
depends on the difference in the refractive indexes of pure
solvent flowing through the reference side of the detector and
of the effluent from the analytical column; measurement is
nondestructive to the sample, the level of sensitivity is good,
and operation is simple. Use of the refractive index detector
in liquid chromatography is discussed in ASTM Practice for
Refractive Index Detectors Used in Liquid Chromatography
(E 1303-89). As with other nondestructive detectors, when
used in conjunction with an automated fraction collector, the
sample can be isolated and subjected to further treatment.
The heat of adsorption detector is also applicable to a wide
range of materials since it responds to an almost universal
property of materials, heat of adsorption. Thermal changes,
induced by the adsorption and desorption of the sample, are
sensed, amplified, and recorded as positive and negative
peaks on a chromatogram.
The flame ionization detector, also called chain, cord, and
belt detectors, combines high sensitivity and quantitative
analysis with wide dynamic range. In flame ionization detection, all of the carrier leaving the column can not be directed
through the detector; instead, a small wire or belt is passed
continuously through the eluting stream collecting a portion
of the sample. The carrier solvent is flash evaporated in one
chamber, and the sample residue is then moved into a pyrolysis zone where the sample is decomposed thermally and detected with a flame ionization detector. Since the carrier solvent is removed completely, this type of detector is not
affected by gradient analysis, but at the same time, its use is
restricted to nonvolatile compounds. Obviously, this type of
detector is well suited for the analysis of resins, polymers, and
oils.
Photometric detectors measure the difference in ultraviolet
light adsorption between a sample and reference stream.
Since ultraviolet adsorption is parameter-specific, this type of
detector is limited to chromophores. This property, of course,
can be advantageous when nonultraviolet and ultraviolet adsorbing compounds emerge from a fractionating column together.
Applications--Bombaugh et al. [11] were able to separate
ethylene glycol, diethylene glycol, and triethylene glycol using a column packed with porous silica beads; the eluting
solvent was water in methyl ethyl ketone, and the eluted
compounds were detected using a differential refractive index detector. Poulson and Jensen [12] used an adsorption
column composed of 100 to 200-mesh silica gel for the separation of alkene-alkane hydrocarbons. Diatomaceous earth
coated with various liquids was used to separate and determine aromatic hydrocarbons [13]. The compounds were
sensed with a differential photometric detector. ASTM Practice for Testing Fixed-Wavelength Photometric Detectors
Used in Liquid Chromatography (E 685-79) discussed the use
of the fixed wavelength photometric detectors in liquid chromatography.
PAPER CHROMATOGRAPHY
Paper chromatography, as the name implies, uses paper as
the separation media. A strip of filter paper is spotted with the
sample near one edge and is arranged so that developing
793
794
THIN-LAYER CHROMATOGRAPHY
In thin-layer chromatography (TLC) an aqueous slurry of a
finely divided adsorbent mixed with a binder is spread on a
glass plate so that a uniform, coherent film adheres to the
Paper Support~
*,~
Ni
Filter'Paper
Filter .,....am
Paper
Solvent
F~
Developing
Solvent
Solvent
Air Tight C h a m b e r
Flow
Developing
Solvent
,,. S a m p l e
9
ed
,.
,, ,,,
Ascending Technique
Descending Technique
FIG. 2-Apparatus for paper chromatography.
CHAPTER 71--CHROMATOGRAPHY
its polarity can be altered to enhance or suppress the movement of the components. For example, if a sample moves
with the solvent front, the polarity of the mobile phase should
be reduced by choosing a solvent of lower polarity or by
mixing solvents of different polarity. Conversely, if a sample
shows little tendency to move, the polarity of the eluting
solvent is increased by selecting a solvent occurring lower in
the eluotropic series or by changing the ratio of polar and
nonpolar solvents, favoring the polar solvent. The eluotropic
series, solvents arranged in order of polarity, and other solvent activity have been described in books [19,20].
The preparation of chromatoplates is relatively easy and
can be accomplished by using several techniques: pouring,
dipping, spreading, or spraying. The first two methods require no special equipment, but they lack the refinement
needed to provide uniform films. The spray technique is
messy and does not always yield films of uniform thickness.
By far the most popular technique is that which uses a draw
bar.
Films are prepared by mixing adsorbent, binder, and water
until a homogeneous slurry is obtained. Glass plates, usually
2 by 8-in. (5.08 by 20.32 cm) or 8 by 8-in. (20.32 by 20.32 cm),
are aligned on a perfectly flat surface. A spreader is positioned on the end plate, charged with the slurry, and drawn
across the plates with constant pressure and speed. For analytical purposes, film thickness should be in the range of 0.2
to 0.5 ram. Chromatoplates are air dried and, if desired, activated by heating at elevated temperatures. Although glass is
the most common substrate, plastic and fiber glass sheets
have been used successfully. TLC sheets from plastic and
fiber glass can be cut and shaped with scissors. Precoated
glass plates and plastic sheets can be purchased from several
commercial sources, and, although the price per plate is in-
.$2
795
~;
FIG. 3 - T L C analysis of oils on silicic acid with 15% diethyl ether in petroleum
ether containing 1% glacial acetic acid. (Courtesy of Official DigesL) S--Hormel
Institute standards: lecithin (R~ = 0), cholesterol (Rf = 0.17), oleic acid (R~ = 0.52),
triolein (Rf = 0.67), cholesteryl oleate (Rr = 0.80). I - - l i n s e e d oil, 2--safflower seed
oil, 3--castor oil, 4 - - t u n a oil, 5--olive oil, and 6--menhaden oil.
796
GAS C H R O M A T O G R A P H Y
Of the various forms of chromatography, that using a gaseous moving phase has proved to be the most effective for the
analysis of organic coating materials. As in most chromatographic processes, the separation of compounds may occur
by partition or adsorption activity--GLC and GSC, respectively. The equipment for, and the execution of, both forms
are similar; however, due to its versatility and effectiveness,
GLC has made a much greater impact on paint analysis, and
for that reason it will be emphasized and discussed at considerably greater length. A glossary of GC terms can be found at
the end of this chapter.
The primary object of this discussion is to impart to the
reader a basic concept of GC processes and to focus attention
on the many applications to paint analysis. Within the scope
also published Practice for Direct Injection of Solvent-Reducible Paints Into a Gas Chromatograph for Solvent Analysis
(D 3271-87) and ASTM Test Method for Analysis of Dichloromethane and I, I, l-Trichloromethane in Paints and Coatings
by Direct Injection Into a Gas Chromatograph (D 4457-85).
Gas-LiquidChromatography
Various terms such as gas-partition, vapor-phase-partition,
gas-liquid-partition chromatography, and vapor fractometry
have been used interchangeably when referring to GLC. However, the name GC, which stands for gas chromatography, is
probably the most commonly used.
GLC is characterized by the presence of a stationary liquid
phase, usually a nonvolatile liquid or solid that is liquid at the
operating temperature, supported by the wall of a tube or by
sorption to an inert porous material such as diatomaceous
earth. In GLC, the components to be separated are vaporized
at the entrance of a partition column and moved through the
column by a continuous flow of inert gas. For the most part,
the rate of migration exhibited by components is dependent
upon their degree of solubility in the immobile liquid phase.
Very soluble molecules are dissolved readily by the stationary
phase, and their passage through the column is retarded.
Compounds that have poor or moderate solubility in the liquid phase spend more time in the carrier gas and move
through the column rapidly. Ideally, the multiplicity of variable conditions can be regulated so that each compound will
reach the end of the column at different times where they are
detected electronically as they leave the column.
The distribution of a compound between phases is referred
to as its partition coefficient. Although the partition coefficient difference may be very small in a static experiment
where only one equilibrium occurs, separation is possible
through magnification of that difference by a continuous
series of equilibria that is the normal occurrence during chromatographic separation. Since the partition coefficient is affected directly by the solubility characteristics of the liquid
phase, the equilibrium for a given compound can be shifted
by using stationary phases at different chemical structures.
Liquid phases of varying polarity are available in great number, and it is the exploitation of their different selectivities
that accounts for the tremendous flexibility and effectiveness
of GLC.
Carrier
Gas
;~
,IL
~
Injection
, Port
.....
Columns
.....
~
FIG. 4 - S c h e m a t i c diagram of a gas chromatograph.
Detectors
~
I
I ~ . ~
9 i t I
1
I
.I
i
L....
798
Columns
The successful practice of GLC depends primarily on the
proper selection and preparation of a suitable column. The
availability of hundreds of liquid phases and numerous solid
supports in addition to parameters such as length, diameter,
amount of liquid phase, and mesh size offers an almost infinite number of possibilities. Fortunately, most separations
can be performed on relatively few columns involving only a
few liquid phases. Columns are divided into two major
classes, packed and open tubular. Packed columns consist of
tubing filled with size-graded support material impregnated
with a nonvolatile liquid. Generally, higher-column performance is obtained with small-column-diameter and light-stationary-phase loading. Four to ten-foot (1.22 to 3.048 m) columns of 1/8 or 1/4 in. (3.175 or 6.350 mm) outside diameter
containing 10 to 20~ liquid phase are common.
With Golay's development of the capillary column or open
tubular column [55], the separations possible in GLC were
greatly increased. These columns are prepared by coating the
inside surface of small-diameter tubing with a thin layer of
nonvolatile liquid. Capillary columns are generally much
more efficient than packed columns, but, owing to their low
capacity, high-sensitivity detectors and special sampling
techniques are necessary to accommodate the small samples
used. Fortunately, the split/splitless injector ports introduced
by GC manufacturers the late 1980s and early 1990s are able
to handle normal-sample-size injections without much difficulty.
The readers may find the chemically cross-linked and surface-bonded stationary phases made using fused silica capillary tubing (30 m by 0.25 m m ID) quite useful to have in their
gas chromatography laboratory (see Table 1).
CHAPTER 71--CHROMATOGRAPHY 7 9 9
TABLE lnCommonly used stationary phases in the gas chromatography laboratory.
Stationary Phase
Composition
Comparable to
DB|
DB|
Rtx|
Rtx|
HP|
HP|
Rtx|
OV|
SPB-20, 007-7
DB|
Rtx|
OV|
DB|
17
DB|
DB|
DB|
Rtx|
HP-17, OV|
1,007-11
SP-2270, 007-
SP-2330, 007-CPS-1
SP-2410, RSL-700
Rtx|
HP-225, OV|
DB|
007-624, AT-624, OV|
volatiles
DB|
Rtx|
OV|
Rtx|
Rtx |
007-1701
SP-2340, OV|
DB|
HP-FFAP, 007-FFAP, SUPEROX|
OV|
STABILWAX|
DB|
STABILWAX| HP-20M, 007-CW,
SUPEROX| II, SUPELCOWAX|
NOTE:
Company
Trademark
DB |
J&W Scientific
OV|
Rtx|
STABILWAX~
SUPEROX|
SUPELCOWAX|
Teflon|
Tubing
Solid Support
Tubing materials should be stable with respect to the sample, packing, and c a r d e r gas, and be of uniform diameter,
Tubing made of copper, stainless steel, monel, glass, and
plastic have all been used for the construction of packed
columns. The two most widely used materials are stainless
steel and copper--stainless steel for its inertness and copper
for its low cost. The most c q m m o n tubing material used in
capillary column gas c h r o m a t o g r a p h y is fused silica, primarily due to its flexibility and inertness. Special attention was
given to the wide-bore, 0.53-ram inside-diameter columns
because they have been reported [47] as a packed column
alternative. Readers are also referred to a 1990 review coveting the fundamentals, characteristics, and selection of open
tubular columns in gas c h r o m a t o g r a p h y [48].
White
ASTM Code 60
Chromosorb G
ASTMCode 70
Celatrom
Gas Chrom S
Pink
ASTMCode 80
Anakrom P
Chrompak P, Regular
Chromosorb P
Columpak
Firebrick, C-22
Gas Chrom R
GC Super Support
Sterchamol
Ultraport
800
Column Efficiency
The selection of liquid phase is one of the most vital judgments made in selecting a chromatographic system, for it is
the degree of selectivity of the partitioning liquid that most
strongly influences the separating capability of a GLC column. Theoretically, any liquid can be used as a liquid phase,
but there are some limiting factors. A liquid phase must be
nonreactive to the system and sample, have reasonable thermal stability, and be liquid at the operating temperature.
Although materials of low vapor pressure are favored, the
main criterion regarding volatility is that the liquid phase be
relatively nonvolatile (vapor pressures 0.01 to 0.10 mm) at
operating temperature. Finally, a liquid phase must be soluble in some volatile solvent to allow coating of the support.
Terms such as substrate, partition liquid, stationary phase,
and solvent are synonymous with liquid phase.
Considerable effort has been expended in an attempt to
permit advance prediction of the most suitable liquid phase
for a given problem, but most often the analyst must rely on
experience, published procedures, and certain generalizations. Although solute-liquid phase activity such as chemical
interaction, hydrogen bonding, and other cohesion forces all
affect the selectivity of the liquid phase, in practice the most
distinguishing characteristic is polarity. The polarity of the
Column efficiency may be defined by considering the narrowness of a peak relative to time spent in the column. Provided there are no instrumental deficiencies, column efficiency is a function of packing type, packing technique, and
operating conditions and is usually expressed in terms of the
number of theoretical plates. The plate concept, a carryover
from countercurrent extractions, implies a series of complete
equilibria or "theoretical plates." The better the performance
of a column, the higher is its number of theoretical plates.
Inasmuch as distinct stages are not observed in chromatographic separations, the number of theoretical plates for a
column is calculated from the relative peak sharpness shown
on the chromatogram. A good packed column should have an
efficiency of at least 400 plates, and it is not u n c o m m o n for a
well-prepared column to have over 1000 plates. The number
of theoretical plates, N, equals 16(x/y) z, where x is the distance in millimeters from injection to peak maximum, and y
is the baseline in millimeters cut by the two tangents as
shown in Fig. 5.
Column efficiency can be expressed per unit of column
length. The height equivalent to a theoretical plate (HETP) is
calculated by dividing L, the length of the column in centimeters, by N; thus, HETP = L/N. High HETP indicates that the
CHAPTER 7 1 - - C H R O M A T O G R A P H Y
START
X
NR
[641.
Interpretation of Chromatograms
Fundamentally, the object of a chromatographic analysis is
the resolution of sample components for identification and
quantitative measurement. Fortunately, GC has tremendous
capacity for resolving mixtures, but, unlike many other instrumental techniques, the record of an analytical run tells
very little about the chemical nature of separated compounds. In addition, components in a sample mixture may
not completely separate on a given column; consequently, the
number of peaks on a chromatogram is not always an indication of the number of compounds in a sample.
When background information concerning the sample is
available and when sample components are few, the interpretation of GC data is fairly simple. However, the interpretation
of a chromatogram from a multicomponent sample, where
background information is limited, is a formidable task. In
this section, qualitative and quantitative analysis will be
briefly discussed; for a more complete treatment of the subject, the reader is referred to the work of others [65,66].
801
rc,~ = t'R,c/t'R,s
where c refers to component in the sample, and s indicates
the reference standard. Relative retention times are independent of column length, liquid loading, and flow rate, but they
are dependent on the type of liquid phase. The reference
material may be one that is known to be in the original
sample, or it can be mixed prior to the chromatographic
analysis. In practice, relative retentions are obtained usually
by computing the ratio of the distance from air peak to standard and air peak to component.
Once a peak has been tentatively identified from its retention time, the sample may be "spiked" with the suspected
compound to see if it superimposes and shows up as one
peak. If the two materials emerge together, this is good evidence of its presence in the original sample, but this does not
constitute positive identification since more than one com-
START
ta
Qualitative Analysis
For a given set of operating conditions, the amount of
carrier gas required to elute a compound from a column is
characteristic for that compound and is not influenced by the
presence of other compounds. Accordingly, the time from
injection to peak maximum is a property peculiar to a compound. This type of information, represented as retention
volume (VR) and retention time (tR), has been the basis for
most schemes of qualitative analysis. The use of such infor-
AIR
FIG. 6-Retention time (t~) and adjusted retention time (tR).
802
pound may have the same retention time for a given column.
The next step is to go through the same procedure using a
different column having a packing of completely different
polarity. It is not likely that two materials will have the same
retention time on widely different columns, but, if doubt still
persists, the compounds can be trapped at the exit of the GC
unit, and the isolated materials can be subjected to instrumental or chemical analysis. Walsh and Merritt [67] trapped
eluted materials in a neutral solvent and applied a battery of
chemical tests to determine chemical functionality. Methods
have been described for direct trapping of fractions on a disk
of potassium bromide and fraction trapping with subsequent
transfer to a microcell; the isolated components were then
subjected to infrared (IR) analysis. Although somewhat limited in versatility and flexibility, table top GC-mass-spectroscopic and GC-FTIR units do an outstanding job of routine
identification and for quality control purposes. Prices of these
integrated instruments vary from 60,000 to approximately
$100,000.
Success in any research laboratory is highly dependent on
the timing upon which unknown chromatographic peaks are
identified. While infrared (IR) and mass spectroscopy (MS)
have been proven to be important qualitative tools, each has
its inherent weaknesses. When used together, these techniques reinforce each other, producing a richer body of useful information than either technique used alone [68]. The
use of mass spectrometers as detectors for capillary column
gas chromatography has also been discussed by Clement [69]
in his 1992 publication. Another 1992 review [70] with several references is given on gas chromatography, including
column types, injection methods, detection means, data systems, supplementary apparatus, and future prospects.
Quantitative Analysis
The analog signal generated by the presence of a compound in the carrier gas is proportional to its concentration,
and quantitative analysis is obtained by conversion of this
signal to some form of digital data. For the most part, quantitative data are obtained from peak area measurements, but
significant use has been made of peak heights.
Peak areas can be measured by: (1) use of a planimeter, (2)
cutting and weighing chart paper, (3) triangulation (A =
WH/2), (4) height times width at half height (H X W at H/2),
(5) ball-and-disk type of integrator, and (6) electronic digital
integrator. The planimeter yields good results, but its use is
tedious, and accuracy is dependent on the shape of the peak
and the skill of the operator. Cutting and weighing peaks
from chart paper is time consuming, and it is practically
impossible to accurately cut and weigh cutouts of narrow
peaks. Triangulation and height times width at half height are
both relatively simple methods, and each will yield satisfactory results with symmetrical peaks, but the methods are
unsuitable with asymmetric or very narrow peaks. The balland-disk type of integrator, which is attached to the drive
mechanism of the recorder pen, has found widespread application. Since peak areas are integrated as they are recorded,
the operator need only count the integrator units under the
appropriate peak. With an electronic integrator, the output
from a gas chromatograph is fed to the measuring unit that
converts the analog signal to digital, which is eventually converted to peak areas using appropriate algorithm. The inte-
area of C
9100
total of peak areas
B.S
where
C = peak area of component,
B = peak area of internal standard,
W = weight of internal standard, and
S = weight of sample.
If the determination is to be calculated on a volume basis,
simply substitute volume for weight in W and S. Complete
elution of all components is not necessary; in fact, the percent
of sample hangup can be determined by calculating the total
percent represented by all the peaks eluted and subtracting
the total from 100.
A direct weight-to-area relationship does not exist for all
compounds. Detector response is a function of structure and
molecular weight; the detector response for a given compound is not the same with all detectors since various detector types operate on different principles. Once determined,
however, response factors are generally interchangeable between instruments having the same type of detector. Messner
et al. [71] published thermal conductivity factors for a large
variety of compounds and also provided a formula for calculating factors. Deitz [72] tabulated a lengthy list of TC and
FIn detector response factors for various classes of compounds. For certain applications, peak height measurements
CHAPTER 71--CHROMATOGRAPHY
are more convenient and reliable than peak area. Such is the
case when peaks are tall and narrow and where errors in area
measurements are likely to be maximized. Peak height determinations are affected to a greater extent by variations of
operating conditions than are peak area determinations. This
effect is greatly diminished through the use of an internal
standard.
To increase accuracy and precision of peak area measurements, the use of electronic integrators is highly recommended. The initial cost for such an investment can easily be
recovered within a short period of time primarily through
labor cost savings. Current integrators are so versatile that
they can perform difficult peak integration that normally
would take a less experienced analyst a lot of time to perform.
Some can perform reintegration and recalculation using a
variety of methods. In the 1990s, most integrators are capable
of being interfaced to a personal computer to enhance data
crunching and for information storage and retrieval purposes. This is especially useful where data documentation is
critical.
Applications--Applications for GLC in the paint industry
exist at almost every level of manufacture and product development. Its rapid acceptance by the industry is due to several
inherent features, principally, versatility and speed. Initially,
analyses were solvent oriented, but applications to virtually
every class of material used in surface coatings have been
reported in the literature. At present, GLC is used for a variety
of analytical operations including both routine and research
functions. It is unexcelled as a routine quality control tool for
defining raw materials to be used for the manufacture of
paint products. Batches of solvent, plasticizers, polyols, fatty
acids, and other materials can be examined simply and rapidly to determine conformance to acceptable standards. Information regarding vehicle composition of a whole paint
can be obtained in great detail and with reasonable accuracy.
Moreover, GLC can be used to monitor drying processes,
solvent release from films, and the chemical curing of polymeric materials. In a 1991 publication, K. Takahashi [42]
described a simple and sensitive method for the measurement of the leaching rate of tributyltin and triphenyltin compounds from antifouling paint by gas chromatography using
flame photometric detection. Static headspace analysis by
combined gas chromatography-mass spectrometry for the
analysis of organic solvents in printing inks was recently
studied [43].
Because of the multiplicity of published papers relevant to
GC coatings analysis (well over 1000), complete coverage of
all applications is beyond the scope of this chapter. A review
[46] describing basic GC processes and applications includes
approximately 150 references to coatings analysis. In his
monograph on GC application to polymer analysis, Stevens
[44] refers to several hundred analytical procedures and, in
many cases, presents operating conditions, tables of retention times, and chromatograms. Readers are directed to the
second part of a 1992 article by Ettre [45] on the evolution of
chromatography since the development of GLC by Martin
and James 40 years ago and HPLC by Moore and Horvath 25
years ago.
A partial list of references is shown in Table 3; examples
were selected to illustrate the variety of coating problems
amenable to GLC analysis. Methods directed to the analysis
803
of oils and fats are listed separately, but most are also applicable to fatty acids isolated from alkyd resins. A compilation of
ASTM methods that have been evaluated and accepted as
standard or tentative procedures is presented in Table 4.
Other GLC procedures are currently being evaluated for
ASTM acceptability.
One facet of GLC that often goes unrecognized is the
pretreatment of substances to alter their structure, thereby
permitting the examination of materials that would not respond normally to GLC analysis. Such is the case with the
analysis of paint binders and very polar materials such as
polyols and dicarboxylic acids. Many of the methods of sampling and techniques for preparing derivatives described by
Cavagnol and Betker [73] and Schupp [74] have application
to the analysis of surface coatings. Beroza and Coad [75]
attack the same general problem but in a different way; for
the most part, samples are altered within the instrument and
not externally.
In the following discussion of analytical methods, special
emphasis will be directed to the broad range of usefulness
within the paint field, and, wherever possible, basic principles
and equipment will be stressed.
Solvents
A major consideration in GLC is sample volatility. Materials to be analyzed must possess sufficient vapor pressure to
permit vaporization at the point of sample introduction.
Since enamel and lacquer solvents fulfill this requirement, it
is only natural that GLC would be rapidly utilized in this area.
Solvents may be encountered in two forms: as raw material to
be formulated into a surface coating or as an ingredient of a
coating. In the latter event, the analysis is complicated by the
presence of pigment and binder, which usually necessitates
the isolation of solvent through distillation. To alleviate problems associated with solids or nonvolatile components of the
paint or coating, a removable glass liner or glass insert can be
installed in the injection port of the gas chromatograph. Such
glass liners can be occasionally solvent-cleaned or ovencleaned overnight at 400~ Another, but less desirable alternative, is through the use of a precolumn. The precolumn
should be made from the same stationary phase as the analytical column.
An important aspect of production control is the analysis of
individual solvents for impurities. Relatively small amounts
of impurity may seriously affect the performance characteristics of a paint, and such impurities can be easily detected and
determined using GLC. Batches of solvent can be rapidly
screened by subjecting them to GLC analyses and comparing
the resulting chromatograms to those obtained from reference materials of acceptable quality. Relative amounts of
each solvent can be quickly ascertained from ratios of peak
heights or peak areas. If significant deviation from the reference material is observed, a more thorough and precise GLC
analysis can be then conducted. In 1993, Vonk [78] described
the use of wide-bore fused silica columns for the analysis of
solvents.
Petroleum fractions, such as mineral spirits and VM&P
naphtha, are extremely complex mixtures of hydrocarbons,
and it is virtually impossible to completely separate all the
components. Nevertheless, valuable information regarding
804
References
37, 38, 39, 40, 41, 44, 45, 46, 47, 48, 68, 70,
138
76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87,
88, 89, 90, 137
91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101
102, 103, 104
105,10~ 107
108,111, 112, 113, 114
t 0 8 , 1 t Z 113, 11~ 11~ 117
10~ 11~ ll& 11~ 12~ 121, 12Z 12~ 12~
125, 126
127, 12& 129, 130
131, 132, 133, 134, 142
ASTMD 3792, ASTMD 3960, ASTMD 4457
43, 135, 136, 137, 13~ 14~ 141, 14Z 143,
14~ 145
TABLE 4--Summary of ASTM test methods for paints, related coatings, and aromatics using gas chromatographyf
D 1983
D 2245
D 2306
D 2360
D 2455
D 2456
D 2743
D 2800
D 2804
D 3008
D 3009
D 3054
D 3257
D 3271
D 3329
D 3362
D 3432
D 3457
D 3545
D 3626
D 3760
D 3792
D 3797
D 3798
D 3893
D 3960
D 4367
D 4457
D
D
D
D
4492
4534
4735
5135
Test Method for Fatty Acid Composition by Gas-Liquid Chromatography of Methyl Esters
Method for Identification of Oils and Oil Acids in Solvent-Reducible Paints
Methods for Cs Aromatic Hydrocarbon Analysis by Gas Chromatography
Test Method for Trace Impurities in Monocyclic Aromatic Hydrocarbons by Gas Chromatography
Test Method for Identification of Carboxylic Acids in Alkyd Resins
Test Method for Identification of Polyhydric Alcohols in Alkyd Resins
Practices for Uniformity of Traffic Paint Vehicle Solids by Spectroscopy and Gas Chromatography
Test Method for Preparation of Methyl Esters from Oils for Determination of Fatty Acid Composition by Gas Chromatography
Test Method for Purity of Methyl Ethyl Ketone by Gas Chromatography
Test Method for Resin Acids in Rosin by Gas Chromatography
Test Method for s
of Turpentine by Gas Chromatography
Test Method for Purity and Benzene Content of Cyclohexane by Gas Chromatography
Test Methods for Aromatics in Mineral Spirits by Gas Chromatography
Methods for Direct Injection of Solvent-Reducible Paints into a Gas Chromatograph for Solvent Analysis
Test Method for Purity of Methyl Isobutyl Ketone by Gas Chromatography
Test Method for Purity of Acrylate Esters by Gas Chromatography
Test Method for Unreacted Toluene Diisocyanates in Urethane Prepolymers and Coating Solutions by Gas Chromatography
Test Method for Preparation of Methyl Esters from Fatty Acids for Determination of Fatty Acid Composition by Gas-Liquid
Chromatography
Test Method for Alcohol Content and Purity of Acetate Esters by Gas Chromatography
Test Method for Tar Acid Composition by Gas-Liquid Chromatography
Test Method for Analysis of Isopropyl Benzene (Cumene) by Gas Chromatography
Test Method for Water Content of Waterborne Paints by Direct Injection Into a Gas Chromatograph
Test Method for Analysis of o-Xylene by Gas Chromatography
Test Method for Analysis of p-Xylene by Gas Chromatography
Test Method for Purity of Methyl Amyl Ketone and Methyl Isoamyl Ketone by Gas Chromatography
Practice for Determining Volatile Organic Content (VOC) of Paints and Related Coatings
Test Method for Benzene in Hydrocarbon Solvents by Gas Chromatography
Test Method for Determination of Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by Direct Injection Into
a Gas Chromatograph
Test Method for Analysis of Benzene by Gas Chromatography
Test Method for Benzene Content of Cyclic Products by Gas Chromatography
Test Method for Determination of Trace Thiopene in Refined Benzene by Gas Chromatography
Test Methods for Analysis of Styrene by Capillary Gas Chromatography
CHAPTER 71--CHROMATOGRAPHY
the nature and identity of such solvent systems may be obtained by comparison with reference chromatograms obtained using identical operating conditions. No attempt is
made to identify the individual peaks; instead, observations
are made to determine if the unknown and control have
similar distillation ranges and if peaks are proportional.
Chromatograms of this type are referred to as "fingerprints"
and will often suffice for quality control purposes.
The percentage of aromatic species in mineral spirits may
be determined by using columns prepared from highly selective liquid phases such as N,N-bis(2-cyanoethyl) formamide
(CEF) and 1,2,3-tris(2-cyanoethoxy) propane. These very polar liquid phases are capable of eluting high boiling aliphatic
solvents well in advance of low boiling aromatics, thereby
providing the means for aliphatic-aromatic group separation.
Such columns provide the basis for the analysis of aromatics
in enamel thinners and solvents [79,80] yielding information
that relates to the photochemical reactivity of hydrocarbon
solvents, a factor of importance in air pollution studies.
The problem of determining solvents in whole paints and
lacquers by GLC is compounded by the presence of nonvolatiles, and special provisions must be made for sampling. No
universal method for isolating solvent from paint and lacquer
is available. Vacuum distillation and collection in a cold trap
[86] works well in many cases, but this scheme is time-consuming and difficulties arise when very light or very heavy
solvents are present. Introduction of a coating from a syringe
onto an adsorbent pad [36] in the injection port has been
used, but viscous samples require dilution, and thermally
unstable resins are decomposed in the injection port, resulting in the appearance of extraneous peaks on the chromatogram. To avoid or significantly minimize thermal degradation of certain resins, it is advisable to decrease the
injection port temperature below its decomposition temperature. A good injection port temperature for most solvent
analysis is 200~ As previously indicated, use of a removable
glass liner or insert is a must if direct injection of the whole
paint is to be performed. Again, the glass insert can be occasionally cleaned using an appropriate solvent or by overnight
oven cleaning at 400~ Precipitation of lacquer resins with
pentane and subsequent analysis of the supernatant liquid by
GLC works well with most automotive lacquers [77], but the
nonuniform occlusion of certain solvents has been reported.
For the most part, the means of sample handling will be
determined by the type of material encountered and the extent of analytical information desired.
Several comprehensive schemes have been proposed that
are particularly useful for the analysis of unknown samples.
Haken and McKay [87] used GLC in conjunction with solubility tests in various media along with functional group analysis for the characterization of solvent systems. The New York
Society for Paint Technology published a paper [81] on the
subject of solvent analysis that included a comprehensive
tabulation of retention data for a broad spectrum of solvents.
A procedure for the identification of plastic and lacquer solvents was described by Haslam et al. [86]. The solvents were
isolated by vacuum distillation in a sealed "H-tube" and subsequently separated on tritolyl phosphate and paraffin wax
columns. Chromatographic data were supplemented by infrared spectroscopy where necessary.
805
Since no single column will separate all solvents, separation on one liquid phase can be very misleading. When
examining an unknown solvent mixture, it is best to conduct
the analysis on at least two liquid phases of different polarity,
and in some cases supplementary chemical or instrumental
testing will be also necessary.
GLC has been also used to study the retention of solvents in
paint films during drying processes [88,89]. It has been demonstrated that solvent retention is related to the chemical
structure of the film and solvent, as well as the boiling point
of solvents. Perrone [90] also described a GC method for the
determination of residual solvents in pressure sensitive tapes
as a quality control step in the manufacturing process.
Oils
The drying and nondrying oils used in the production of
paints and varnishes can be identified through the application of GLC. The GLC analysis is preceded by the saponification of sample and isolation of the fatty acids. Free fatty acids
may be examined directly [100], but they are generally analyzed as their methyl esters, which are more volatile, less
polar, and less susceptible to isomerization. Any of several
acid-catalyzed esterification techniques, for example, hydrochloric acid (HCL), sulfuric acid (H2504), or boron trifluoride
(BF3) in methanol, will provide adequate conversion to the
ester; the BFa-rnethanol reagent, however, offers the advantages of a high yield combined with rapid ester conversion.
The difficulty in handling BF 3 gas can be circumvented by
using boron trifluoride etherate in methanol. The reagent is
easy to prepare, stable, and will convert fatty acids to their
corresponding methyl esters within a few minutes.
Many of the fatty acids found in oils are of the same carbon
chain length, differing only in position and number of double
bonds. Most polyester liquid phases will differentiate between Cls fatty acids, but polyesters having the highest oxygen-to-carbon ratio provide the best separations. Of the
polyester liquid phases, diethylene glycol succinate has received the most attention. Six-to-eight-foot (1.83 to 2.44 m)
columns containing 10 to 20% polyester on white diatomaceous earth supports are most common.
Zielinski et al. [105] considered the analysis of reacted and
unreacted oils and made provisions for their complete analysis. Fatty acids were identified from the relative retention
time ratio (RTR) values. RTR values were defined as the
numerical ratio of the corrected retention time of a given
methyl ester peak to that of the methyl palmitate peak. With
the exception of licanic and eleostearic acids, all the fatty
acids can be readily separated and identified.
Linseed, soybean, tall, safflower, and cottonseed oils can be
identified from their characteristic fatty acids distributions.
With other oils, identification may be achieved from an inspection of only one or two acids. For example, marine oils
contain respectable amounts of palmitoleic and myristic
acids, castor oil consists mostly of ricinoleic acid, coconut oil
is rich in lauric acids, and oiticica and tung oils contain
appreciable amounts of licanic and eleostearic acids, respectively.
Complete details for the identification of oils in organic
coatings by GLC may be found in ASTM Test Method for
Fatty Acid Content of Alkyd Resins and Resin Solutions
806
Resins
The GLC analysis of resins constitutes a special problem
inasmuch as the analyst must rely on some means of forming
volatile products, either by derivative formation or through
thermal decomposition. Thermal decomposition techniques
will be discussed in greater detail in the following section;
this section will be concerned with methods for converting
nonvolatile resinous materials to volatile derivatives.
Alkyd and polyester resins account for a large portion of
polymeric material used in organic coatings. The identification of the oil component in alkyd resins by GLC has been
already described. The remaining classes of material, dicarboxylic acids and polyols, can be analyzed by chemically
degrading the resin so as to regenerate the acids and alcohols,
which are then derivatized and subsequently analyzed by
GLC. If butylamine is used to degrade the resin, polyols may
be analyzed qualitatively [115] as their acetates or qualitatively and quantitatively as trimethylsilyl ethers [117]. The
latter method involves a minimum of sample manipulation,
and it is applicable to all of the polyols normally found in
alkyd resin. Both procedures are relatively uninvolved and
capable of analyzing more than one polyol simultaneously.
When alkyd or polyester resins are subjected to a catalyzed
equilibrium reaction in a large excess or methanol, methyl
esters of mono- and dicarboxylic acids are formed in good
yield.
MeOH (large excess) + alkyd or polyester
>
methyl ester + glycol
A method [111] has been developed for the identification of
mono- and dicarboxylic acids in alkyd and polyester resins
where lithium methoxide was employed as the transesterification catalyst. Two columns, one polar and the other nonpolar, were used to obtain retention data. Identification was
made possible by comparing the relative retention times of
peaks from a sample to those obtained from pure compounds. Percival [108] reported a similar method using sodium methoxide as the catalyst; semiquantitative results for
polyols and dicarboxylic acids were presented.
Pyrolysis
Thermal degradation, when used in conjunction with GLC,
can be applied to the analysis of a wide range of polymeric
Plasticizers
One of the most desirable properties of a plasticizer is low
volatility, and for this reason it would be expected that the
analysis of such materials by GLC would not be easy. Indeed,
the vapor pressures of many plasticizers are so low that they
have been recommended as stationary liquid phases for GLC
analysis where moderate operating temperatures are adequate. However, by a suitable choice of operating conditions,
most nonpolymeric plasticizers may be chromatographed
without great difficulty.
In general, reasonable emergence times of high boiling
compounds may be achieved by the use of short columns,
rapid flow of carrier gas, high operating temperatures, or
low-liquid-phase concentration. Since each of these operating conditions can produce undesirable effects such as poor
resolution, reduced column longevity, and tailing, a compromise must be reached that will allow the resolution of high
boiling mixtures within a reasonable time span. A 9-in.
(22.86-cm) silicone grease column [127] was found to be adequate for the quality control of incoming stocks of butyl
benzyl phthalate. Differences in the manufacturing processes
of this plasticizer leads to products of variable composition,
and, although a high yield is the desired end product, appreciable amounts of dibutyl and dibenzyl phthalate are sometimes encountered. When incorporated with acrylic resins,
dibutyl phthalate tends to distill out of a lacquer on exposure,
a condition that may ultimately lead to resin embrittlement.
A method for the analysis of plasticizers was presented
[128] in which a 6-ft (1.82-m) silicone grease column was
used to separate a broad range of plasticizers. A rapid flow of
carrier gas, 120 mL/min, and a high terminal column temperature, 290~ were used in conjunction with temperature
programming for the separation of low, medium, and high
boiling plasticizers.
Miscellany
Ghanayem and Swann [135] separated glycols on polar
columns without resorting to derivative formation. A method
of this type is useful where the purity of low-boiling,
uncombined polyol is under consideration. High-boiling
polyols, however, normally require derivatization prior to the
chromatographic step. The ever-increasing popularity of
aerosol packaging has generated considerable interest in
methods for the chemical analysis of aerosol propellants. The
performance characteristics of various propellants may vary
808
Gas-Solid Chromatography
Gas-solid chromatography (GSC) represents a gas chromatographic technique where components are separated on a
solid rather than on a liquid phase. Its application to the
analysis of coating materials has been extremely limited, and
for this reason only a very brief description of GSC processes
will be presented with special emphasis being directed to new
developments and potential applications to paint analysis.
Instrumentation and interpretation of data are basically
the same as in GLC, the only departure from GLC convention
being the absence of a liquid stationary phase. Initially, GSC
methods were used primarily for the analysis of very volatile,
inert materials, but with the introduction of new packing, the
technique has been extended to the analysis of a much
broader spectrum of chemical types. Alumina, silica gel, molecular sieve, organoclay, and porous polymers are the most
widely used GSC packing materials. GSC with silica gel, alumina, or organoclay preclude the analysis of polar solutes
E 1151-87
E 1303-89
adsorption chromatography.
integrator--A mechanical or electromechanical device for
producing a continuous summation of detector output with
respect to time, yielding a measurement of included area of a
chromatographic band.
ionization detectors--Chromatographic detectors in which
the measurement of a sample is derived from the current
produced by the ionization of sample molecules induced by
thermal, radioactive, or other excitation sources.
phy.
p e a k - - T h e portion of the chromatogram recording the detector response while a single component emerges from the
column. (If the separation of a mixed sample is incomplete,
two or more components may appear as one peak.)
peak a r e a - - T h e included area formed by the ascending and
descending arms of a chromatographic-recorded band and
the baseline of the chart.
potentiometrie reeorder--A readout device in which a pen,
whose deflection is proportional to the voltage output of the
chromatographic detector, writes on a paper chart that is
moving at a constant speed.
pyrolysis--A technique in which nonvolatile samples are
thermally decomposed in the absence of oxygen in the inlet
810
REFERENCES
[1] Tswett, M., in Berichte der Deutsche Botanische Gesellschaft,
BEDBA, Vol. 24, 1906, pp. 316, 384.
[2] Martin, A. J. P. and Synge, R. L. M., "A New Form of Chromatography Employing Two Liquid Phases. I. A Theory of Chromatography. II. Application to the Microdetermination of the
Higher Monoamino Acids in Proteins," Journal of Biological
Chemistry, JHCHA, Vol. 35, 1941, p. 1358.
[3] Strain, H., Chromatographic Adsorption Analysis, Interscience,
New York, 1942, pp. 15 and 16.
[4] Strain, H., Chromatographic Adsorption Analysis, Interscience,
New York, 1942, p. 12.
[5] Loeblich, V. M. and Lawrence, R. V., "Chromatographic Investigation of Disproportionated Rosin," Journal, American Oil
Chemists' Society, JOACA, Vol. 33, 1956, p. 320.
[6] Swann, M. H., Adams, M. L., and Esposito, G. G., "Analysis of
Lacquers Containing Nitrocellulose, Alkyd Resins, and Phthalate-Type Plasticizers," Analytical Chemistry, ANCHA, Vo]. 27,
1955, p. 1426.
[7] Lambert, S. M., "An Instrument for Precision Liquid-Liquid
Chromatography," Analytical Chemistry, Vo]. 37, 1956, p. 959.
[8] Stouffer, J. E., Oakes, P. L., and Schlatter, J. E., "A Liquid
System for the Analysis of Macromolecules," Journal of Gas
Chromatography, JCHSB, Vol. 4, 1966, p. 89.
[9] Jentoft, R. E. and Gouw, T. H., "A High Resolution Liquid
Chromatography," Analytical Chemistry, ANCHA, Vol. 40,
1968, p. 923.
[10] Huber, J. F, K., "Evaluation of Detectors for Liquid Chromatography in Columns," Journal of Gas Chromatography, Vo]. 7,
1969, p. 172.
[11] Bombaugh, K.J., Dark, W. A., and King, R. N., "Analytical
Liquid Chromatography," Research~Development, Vo]. 19,
1968, p. 28.
[12] Poulson, R. E. and Jensen, H. B., "Vapor Pressure Detector for
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CHAPTER 71--CHROMATOGRAPHY
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MNL17-EB/Jun. 1995
ii
Electron Microscopy
by John G. Sheehan 1
THERE ARETWOMAINTYPESof electron microscopes, the scanning electron microscope (SEM) and the transmission electron microscope (TEM). Today both SEM and TEM are used
for microstructural examination in nearly all disciplines of
science and engineering. The resolving power of electron
microscopes is three orders of magnitude greater then lightoptical microscopes. Modern SEMs with field-emission electron guns resolve better than 1 nm, and modern TEMs resolve
better than 0.2 nm [1]. Contrast develops in SEM by electrons
emitted at or near the surfaces of bulk specimens and therefore topography and composition are examined. Contrast develops in TEM by electrons transmitted through thin specimens and therefore variations in structure and composition
are examined.
Types of signals generated in a sample of varying thickness
by incident electron beam are illustrated in Fig. 1. The SEM
collects secondary electrons (SE), backscatter electrons (BE),
and X-rays from surfaces of bulk specimens. The TEM collects X-rays, elastically scattered electrons, and inelastically
scattered electrons from thin and ultra-thin specimens. Hybrid TEMs have SEM capabilities: they collect BE that exit
the incident-beam side of thin specimens, and they collect SE
and X2rays from both sides. These are known as scanning
transmission electron microscopes (STEM) or analytical
electron microscopes (AEM).
SEM and TEM were both invented in the 1930s in Germany. TEM quickly became widely used to image replicas of
surfaces at resolution far better than was possible with the
first SEM and therefore further attempts to develop SEM
were regarded as a waste of time. SEM did not become
available commercially until 1965, when Cambridge Instrument Company marketed the "Stereoscan" [2]. Immediately
SEM became widely used to examine coatings, as seen in
American Chemical Society Symposia on SEM of coatings in
1968 [3] and again in 1972 [4]. Today the higher resolution
available from SEMs has mostly replaced TEM of surface
replicas, since TEM is no longer needed to see sub-micrometer pigment and latex particles. Therefore SEM will receive
most of the attention in this chapter.
This chapter has three main parts: SEM, TEM, and applications to coatings. The SEM section begins with a discussion
of image formation and signal collection; these must be
understood to correctly interpret SEM images. Then, the
electron-optical column that includes the electron gun, the
condenser lens system, the scan coils, and the objective lens
lUnilever Research, 45 River Road, Edgewater, NJ 07020.
Image Formation
Most SEMs are equipped to detect secondary electrons
(SE), backscatter electrons (BE), and characteristic X-rays as
the electron beam scans across sample surfaces. The SE signal is produced when bound electrons are removed as a result
of inelastic scattering of the electron beam. The intensity of
815
Copyright9 1995 by ASTMInternational
www.astm.org
816
e-
le-
le-
X-rays,
Secondary and
Backscatter e-
ULTRATHIN
Inelastlcally
Elastically
Scatterede-
Scattered e-
BULK
FIG. 1-Signal types generated by electron beams impinging on a sample of
varying thickness. Adapted from Thomas [I].
the SE signal depends partly on the orientation of the sample
with respect to the electron beam, which is why SE images
are topographical.
Backscatter electrons (BE) result from elastic scattering.
Electrons are elastically scattered when they penetrate the
electron clouds of atoms and change direction, a result of
coulombic interaction with the positively charged nuclei,
known as Rutherford scattering. An electron is backscattered
after a series of direction-changing elastic events that cause
the electron to exit the sample. The probability of a hackscatter event depends on the size of the nuclei and therefore
backscatter contrast depends on the distribution of average
atomic number in the sample. The depth in a sample from
which BE information emerges ranges from about 80 nm for
gold to about 600 nm for aluminum with an accelerating
potential of 20 kV [6]. The yield of BE varies by only about
10% over an accelerating-potential range of 10 to 50 kV [5].
Most SEM images are collected with the Everhart-Thornley
(ET) detector, shown in Fig. 3. The ET detector collects
mostly SE and some BE. The main components of the ET
detector are a collector grid, a scintillator, and a photomultiplier. SEs, whose average energy is about 3 to 5 eV [5], are
pulled toward the scintillator by a 300-V p6tential on the
collector grid. A 10-kV bias on the scintillator accelerates SEs
enough to cause photon emission in the light pipe. The collection grid also protects the electron beam from deflection by
the 10-kV bias on the scintillator.
Secondary electrons are classified into four types, shown
schematically in Fig. 3. SE-I are generated by direct interaction with the primary beam and therefore carry the highest
resolution information. SE-2 are generated by backscatter
electrons as they exit the sample surface and therefore generate sub-surface atomic number contrast. In 1940, before the
first SEM images were collected, yon Ardenne correctly predicted that SE-2 would limit resolution: SE-2 cannot be de-
particles are barely visible because the exit depth of BE, and
therefore contrast from SE-2 and SE-3, is less than 100 nm at
5 kV. Comparison of Figs. 4A and 4B demonstrates the strong
dependence of accelerating voltage on the appearance of
SEM images: sometimes more than one accelerating voltage
is needed for correct interpretation. Also, SE images at lower
accelerating voltage better represent topography because the
exit depth of BE is smaller.
The micrograph in Fig. 4C shows the same area as Figs. 4A
and 4B, this time recorded with an annular solid-state BE
detector that was attached to the bottom of the objective lens.
Because no SEs were detected, the latex binder at the sample
surface generated no contrast. Instead, contrast was generated by the distribution of calcium carbonate particles beneath the latex-film surface. This example illustrates the importance of understanding image formation in the SEM in
order to correctly interpret images. Observation of only Fig.
4A would lead one to the false conclusion that the latex film
does not cover all of the calcium carbonate particles.
X-Ray Microanalysis
Inner shell ionization is the event that triggers characteristic X-ray production. An X-ray photon is produced when an
electron from an adjacent shell drops to an inner shell to
replace the ionized electron. Each element has its own set of
characteristic X-rays and therefore elements present in a
sample can be identified qualitatively or quantitatively if a
spectrum of emitted X-rays is collected.
There are two types of X-ray detectors, the wavelength
dispersive spectrometer (WDS) and the energy dispersive
spectrometer (EDS). In WDS, a small portion of the emitted
X-rays hit a crystal. X-rays that satisfy Bragg's law for the
crystal are diffracted to a proportional counter. X-ray spectra
818
Electron Guns
The ultimate resolution of an SEM is determined by the
type of cathode in its electron gun. The main measures of
electron gun performance are current density and diameter
of the first crossover. High current density and a small first
crossover are needed for high-resolution imaging.
There are two types of cathodes, thermionic and field emission (FE). Thermionic excitation occurs when a filament is
heated to near its melting point, allowing electrons to overcome their work function and eject themselves into the vacuum. Tungsten and lanthanum hexaboride (LAB6) are the
most common thermionic cathode materials. Tungsten cathodes consist of a wire bent like a hairpin. They are easy to
operate, and moderate vacuum prevents oxidation (1 to 5 x
10-3 Pa). However, they require frequent replacement: every
2 to 40 h. LaB6 cathodes consist of a crystal of the material,
CHAPTER 7 2 - - S H E E H A N ON E L E C T R O N M I C R O S C O P Y
usually soldered to refractory metal strips. One advantage of
LaB 6 over tungsten is its higher current density, 20 to 50 M
cm 2, compared to tungsten at about 3 A/cm 2. Another is the
smaller diameter of the first crossover, about 10/zm for LaB6
and 50 ~zm for a tungsten hairpin. Together, these make the
resolution of LaB6-equipped SEMs higher. Another advantage of LaB 6 cathodes is their longer lifetimes, 200 h or more.
However, LaB6 guns require more frequent and more precise
alignment than tungsten guns. Better vacuum (< 10 -4 Pa) is
required to slow evaporation that results from reactions of
LaB 6 material with oxygen-containing residual gases [6].
Field emission occurs when a huge potential gradient
(>107 Wm) is applied to a tungsten tip of about 0.1 /zm in
diameter, causing electrons to tunnel through their potential
barrier. No thermal energy is needed to lift the electrons over
the barrier. The combination of high current density and
small diameter of the first crossover in FE guns makes possible ultra-high resolution (< 1 nm) SEM imaging, not possible
with thermionic cathodes. The current density is around 10~
A/cm 2, three orders of magnitude greater than LaB 6 cathodes.
The diameter of the first crossover from a field emitter is only
about 10 nm and therefore only one condenser lens is needed
to demagnify the probe enough for high-resolution imaging.
Gas molecules that strike the tip cause the work function to
rise and the emission to fall. Field emitters that operate at
room temperature (known as "cold-field" emitters) require
vacuum better than 10 -s Pa. Even in a clean vacuum, gas
molecules eventually cover the tip. The tip is cleaned by rapid
heating to around 2300 K. Field emitters that operate at
around 1200 K are less susceptible to gas molecules, and
field-emission is stable at pressures up to 10 -7 Pa [6].
SEM at low accelerating voltages (1 to 5 kV) has advantages
of high topographic contrast, less specimen damage, and less
surface-charge buildup. Until recently, low-voltage SEM was
limited in resolution mainly by large chromatic aberrations
in objective lenses, which arise from the large energy spread
of electron beams from thermionic cathodes. This problem
has been overcome by FE cathodes, whose energy spread is
more than ten times smaller than in thermionic cathodes.
The merits of low-voltage SEM with FE cathodes were discussed by Pawley [8].
819
820
PAINT A N D COATING T E S T I N G M A N U A L
continuous films with smaller grains were needed. D-c magnetron sputtering is one of them.
In d-c magnetron sputtering, films are formed when
ionized, inert gas atoms strike a metal cathode to eject metal
atoms, which strike the sample. Ionization efficiencies and,
hence, sputtering rates are increased with an annular magnetic field that surrounds the cathode to concentrate electrons in the cathode area [11]. Films made with d-c magnetron sputtering have smaller grains than thermally
evaporated films. However, grain size is sensitive to contamination [12], and artifacts are often present [13]. The d-c magnetron coater is now standard equipment in the SEM lab.
Many models are available and prices vary widely. Inexpensive models are evacuated with rotary mechanical pumps.
Care should be taken not to allow rotary-pumped coaters to
reach their ultimate pressure, otherwise pump oil can disrupt
nucleation when it contaminates the target and the sample.
State-of-the-art magnetron coaters are evacuated with oilfree turbomolecular pumps and equipped with cold stages
because low sample temperatures promote nucleation.
A more recent development in metal coating for high-resolution SEM is ion beam sputtering. Films are formed by ion
beam sputtering when a collimated ion beam strikes a metal
target to eject metal atoms [14]. Mean grain sizes of 1 nm
have been obtained for both gold and platinum [15], too small
to be resolved with SEM. Dislodged metal atoms have about
100 eV of kinetic energy. It is speculated that high kinetic
energy metal atoms implant themselves into sample surfaces,
causing increased nucleation density and small grains. Ion
beam sputtering is becoming widely used for ultra-high resolution SEM.
Metal film thickness should be measured to insure that
only enough metal is deposited on the sample to form a
continuous film. The quartz microbalance is the most widely
used instrument to measure film thickness on electron microscopy specimens. Film thickness sensitivity is equivalent
to about 0.05 nm of gold. Methods of film-thickness determination were discussed by Flood [16].
C r y o g e n i c SEM
Conventional electron microscopes have a vacuum better
than 10- 3 Pa in their specimen chambers. This limits conventional SEM to dry samples. When volatile samples like paints
are placed in the SEM specimen chamber, their solvents
quickly evaporate, damage the vacuum pumps, and cause the
electron beam to scatter. One solution is to lower vapor pressures by freezing and examine samples in an SEM equipped
with a stage cooled by liquid nitrogen. The technique is
known as cryogenic SEM (cryo-SEM), described by Sheehan
[17-19] for examining paper-coating formulations. The
reader is also referred to Echlin [20] for more on techniques
of cryo-electron microscopy.
The procedure of cryo-SEM is to fast-freeze each sample
and transfer it into a vacuum chamber attached to the SEM
specimen chamber. There each sample is fractured, sometimes etched, and then coated with a thin metal film. Then
each sample is transferred to the cold stage in the SEM. The
challenges of high-resolution cryo-SEM are to freeze fast
enough to prevent noticeable growth of ice crystals, transfer
without condensing water vapor on the fracture surfaces,
coat frozen-hydrated samples with an ultra-thin, continuous
metal film, and image in the SEM without too much buildup
of contaminants.
Wet microstructures of coating formulations can be examined with cryo-SEM after freezing and fracturing. Complementary fracture faces of a frozen-fractured pigment/latex
coating formulation are shown in Fig. 5. Kaolin and calcium
carbonate particles can be identified by their morphologies.
The dark areas between the particles are ice. Close examination of the complementary faces shows that fracture propagated around the pigment particles.
The stages of drying can be fixed by freezing and examining
with cryo-SEM. A cross section of a fractured drop of a 20
wt% aqueous suspension of styrene-butadiene latex is shown
in Fig. 6. The drop was placed on a glass slide, air-dried for 3
rain, and plunge-frozen into liquid ethane. The lower part of
FIG. 6-Cross section of a partly dried drop of styrene-butadiene latex. The lower part (CS) is the cross section, and the
upper part (S) is the drop's surface. Bar = 1 p.m.
Fig. 6 is the cross section (CS), and the upper part is the
drop's surface (S) that was exposed to air during drying.
Latex that was deformed during fracture is seen on the cross
section. Hexagonal close packing of latex is seen on the surface.
of wet, volatile specimens without freezing is known as environmental SEM (ESEM) [21]. In ESEM, samples are imaged
in a gaseous environment at pressures up to 2.7 kPa. This is
made possible by a combination of a differentially pumped
vacuum system, small travel distances for the electron beam
in high-pressure gas, and a new biased specimen current
detector known as a gaseous detector device (GSD). The gas
in the specimen chamber is a medium for SE signal multiplication, and it neutralizes charge buildup on samples. Therefore, metal coating is not required for electrically insulating
samples. Ultimate resolution is near that for a conventional
SEM, about 5 nm. But one cannot expect this resolution from
electrically insulating samples without metal coating because
SE contrast is low from electrical insulators in ESEM.
The main advantage of ESEM compared to conventional
SEM is that hydrated samples can be examined at saturated
vapor pressures of water. This makes accessible dynamic imaging of wetting and drying by controlling sample temperature and water-vapor pressure. An ESEM image of dry paper,
taken in 800 Pa of water vapor at 20~ is shown in Fig. 7A.
Water was condensed on the same area by raising watervapor pressure to 1.3 kPa and lowering sample temperature
to 12~ An image is shown in Fig. 7B. Most of the fibers are
covered with water.
Care must be taken during ESEM of hydrated specimens to
avoid specimen damage by radiolysis products of water. Water molecules are radiolyzed by the electron beam into mainly
hydrogen and hydroxyl radicals, which diffuse into specimens and sometimes damage them [22-24].
FIG. 7-Two ESEM micrographs of the same area of paper (A) before wetting; (B) wet.
Bar = 50/Lm.
822
Types o f Contrast
Electron beam-specimen interactions in thin and ultra-thin
samples that lead to contrast in the TEM are shown in Fig. 1.
Electrons are elastically scattered by coulombic interactions
with positively charged nuclei as they travel through TEM
specimens. Scattering contrast is also known as mass-thickness contrast because the amount of scattering depends on
specimen thickness and atomic number. Scattering contrast
in TEM can be imaged in the bright-field mode and in the
dark-field mode. In the bright-field mode, electrons that are
scattered at larger angles are intercepted by the objective
aperture. Others pass through the objective aperture and
form the image. In the dark-field mode, only the electrons
that are scattered at large angles are used to form the image.
This is accomplished by tilting the electron beam off axis or
by moving the objective aperture off axis.
Another type of contrast caused by elastic scattering is
known as phase contrast, the result of interference between
the scattered and the unscattered electrons. Phase contrast
varies as the objective lens focus is varied above or below the
specimen.
Diffraction contrast results when Bragg reflections from
crystalline planes interfere with the primary beam. The interference image gives information about crystal structures.
Inelastic interactions in TEM are plasmon excitations and
inner-shell ionizations. Some TEMs are equipped with electron spectrometers that measure the energy loss spectrum,
known as electron energy loss spectroscopy (EELS). Electronic structures are indicated by plasmon losses, whose energies are less than 50 eV. Chemical compositions are indicated by losses from inner shell (K, L, and M) ionizations
[25].
Optics
A schematic of an electron-optical column of a TEM is
shown in Fig. 8. The electron-optical column of the TEM
differs from the SEM in several ways. First, the electron beam
is not scanned across the sample. Instead, the condenser lens
system illuminates the entire area to be imaged and a set of
projector lenses beneath the sample focus the transmitted
electrons on a phosphor screen, where the image can be
viewed. This points to the second major difference: the purpose of the condenser lens system is not to produce a finely
focused probe at the sample, as in SEM. Instead, the condenser lens system in TEM illuminates the entire area of
interest with the highest electron density that will not damage
the sample. Third, the TEM has a projector lens system,
making imaging more difficult than in SEM. Fourth, higher
APPLICATIONS TO COATINGS
Film Thickness Measurements
Film thickness measurement requires cross sections. There
are several ways to cross-section a dried coating. The simplest
is to cut by hand with a razor blade. However, the cross
section will be smoother if the cut is with a microtome
equipped with a diamond knife. Cross sections of coated paper are made with a microtome after embedding the paper in
epoxy [26]. A BE image of microtome-sectioned, coated paper is shown in Fig. 9. The coating appears lighter than the
fibers because of its greater average atomic number.
ASTM Test Method for Microscopic Measurement of Dry
Film Thickness of Coatings on Wood Products (D 2691) states
that the specimen may be sliced with a microtome or a razor
blade. Whitehead [27] pointed out that brittle paint films can
be shattered when cut with a microtome. Also, the diamond
knife in a microtome is easily damaged by hard paint films.
Grinding and polishing of epoxy-embedded specimens is one
solution.
Identification o f P i g m e n t s
FIG. 9-Microtome-sectioned paper showing thickness of the coating and its penetration into the sheet.
Bar = 10/.m. From H. Matsubayashi [26].
chord. It was also shown that the EDS identified plaster dust,
fly ash, and S02 as contaminants that caused adhesive failure
in other samples.
FIG. 10-Kaolin clay imaged in (A) SEM; (B) TEM. Bar = 0.5/~m. Photo by R. P. Gursky.
Acknowledgments
Thanks go to H. Matsubayashi (Nippon Zeon Co., Ltd.,
Kawasaki, Japan) for supplying the SEM micrograph of
cross-sectioned, coated paper and R. P. Gursky (Unilever
Research, Edgewater, N J) for supplying the TEM micrograph
of kaolin clay.
REFERENCES
825
[24] Sheehan, J. G., "Assessment of Environmental Scanning Electron Microscopy for Coating Research," 1990 TAPPI Coating
Conference, TAPPI, Technology Park/Atlanta, 1990, pp. 377383.
[26] Matsubayashi, H., Miyamoto, K., Takagishi, Y., and Kataoka, Y.,
"Study on Blistering by Coating Structure Analysis," 1990 TAPPI
Coating Conference, TAPPI, Technology Park/Atlanta, 1990, pp.
419-430.
MNL17-EB/Jun. 1995
73
Infrared Spectroscopy
by Jack H. Hartshorn ~
INFRARED ABSORPTION
All matter either emits or absorbs radiant energy in response to its atomic and molecular structure. The electromagnetic spectrum, Fig. 1, represents that relationship. The
most familiar region of the spectrum is the visible portion
because that is the part we see and the paint formulator
utilizes to produce his aesthetics. Immediately adjacent is the
longer wavelength infrared region. This is of particular interest to the coatings analyst since organic chemicals have
unique absorption bands in this range. These products include solvents, resins, polymers, additives, and a host of paint
constituents. Many inorganic materials used as pigments absorb here as well. The region from 2.5 to 25/xm (or 4000 to
400 cm-~) is particularly informative since here the structural bonds in organic molecules have fundamental vibrational modes. Thus, molecular compositions can be deduced
from IR spectral band assignments. Structural interactions
produce spectral signatures or "IR fingerprints" that can be
~Retired from Du Pont Automobile Products, Marshall Laboratory,
Philadelphia, PA 19146; current address: Hartshorn Associates, Inc.,
Paoli Technology Enterprise Center, 19 East Central Avenue, Paoli,
PA 19301.
used to identify those materials. Examination of the IR spectrum thus produces important information as to the composition of a paint film and the chemistry of a coating.
An in-depth discussion of IR spectroscopy theory and practice is beyond the scope of this chapter. However, there are a
number of excellent texts on vibrational spectroscopy and IR
band assignments for those interested in pursuing the subject
[1-3]. The most useful discussion for the paint chemist is the
recently updated and expanded An Infrared Atlas for the Coatings Industry published by the Federation of Societies for
Coating Technology [4].
DISPERSIVE INSTRUMENTATION
Infrared spectroscopy became a practical contributor to
the coatings laboratory with the development of double beam
instrumentation shortly after World War II [5]. This instrumental design directs an IR beam through the sample and
compares it with a corresponding reference beam. The spectrum is incrementally scanned to produce a graphic output of
the sample's transmission characteristics. Figure 2 shows a
simplified double beam IR spectrophotometer depicting the
essential elements. An electrically heated wire or ceramic rod
source irradiates an IR continuum. Two spherical mirrors,
M1 and M v focus that energy to form two equivalent rays, one
for the sample and the other a reference beam. Mirrors M3
and M4 recombine the two at the "chopper," which alternately
views each beam. The chopped beam is then routed through
the monochromator, which examines each wavelength sequentially. S~ is the entrance slit, and $2 is the exit slit. Their
function is to provide spectral resolution and to compensate
for variations in source intensity and detector response. Originally, the dispersive element was a rock salt prism, but this
was superseded by more energy-efficient gratings. Two or
more gratings are usually required to cover the entire IR
range. The detector alternately "sees" and compares the sample and reference beams. When an absorption band is detected in the sample, the reference beam is attenuated by
interposing an optical wedge to match the sample's transmission. Some recent instruments have employed electronic
compensation rather than mechanical blockage. The attenuator is linked to the vertical displacement of the chart pen,
while the monochromator is coupled with the horizontal
chart drive to produce a transmission versus wavelength or
frequency presentation. An in-depth discussion of this instrumentation is available in IR texts [4,6] and in manufacturers'
literature.
826
Copyright9 1995 by ASTMInternational
www.astm.org
Wavelength (Z in Meters )
Angstroms
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Nanometers
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Microns
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10 "s
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10 "2
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10 "s 10"*
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'
EMERGENCE OF FTIR
A new approach to producing infrared spectra became
commercially available in the 1970s. Interferometry, or Foutier transform infrared (FTIR) spectroscopy as it is more
popularly known, acquires data based upon an entirely different principle. Figure 3 shows the essential elements of a FTIR
interferometer. Mirror M~ collimates the energy from an IR
source onto a beamsplitter, where the energy is divided between a stationary mirror, M2, and a moving mirror, M3. The
two reflections are combined at the beamsplitter to produce a
harmonically modulated beam. The mirror motion is precisely driven by a linear motor, and its location accurately
tracked by a helium-neon laser. Its optical path (M6 and laser
detector, DE) retraces the beam to produce that information.
The interferometer's output goes through the sample compartment and is focused onto the IR detector by M4 and M5.
Figure 4 shows a typical interferogram. A digital computer
mathematically transforms the interferogram via the Fourier
relationship into a traditional IR spectrum. The sample spectrum is then ratioed against a reference spectrum, which is
usually taken immediately prior to the sample scan and
stored in the computer. That results in the familiar transmission versus wavelength or frequency presentation. This
equipment is much faster and more sensitive than dispersive
instruments, and it also produces spectra with much greater
precision and reproducibility. While the optics are fairly sire-
828
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SAMPLE PREPARATION
IR became popular in the paint laboratory because of the
useful information that can be obtained by merely spreading
the binder on a salt plate, evaporating the solvent, and scanning it [8]. This is still the method of choice whenever possible. However, not all samples can be examined as cast films,
CHAPTER 7 3 - - I N F R A R E D SPECTROSCOPY 8 2 9
so additional techniques have evolved to fulfill much broader
requirements. Gases, which have very sharp, well-resolved
spectra, need only be confined in a cell with appropriate
windows to be analyzed. Gas cells are available with path
lengths from a few centimeters to tens of meters. The volume
is matched to the concentration of the gases to be measured.
Liquids can be studied merely by squeezing them between
two salt plates to produce a capillary film. These films make
excellent spectra, and the intensity can be varied by changing
the compression. Cells of known path length can be formed
by introducing spacers of controlled thickness between the
plates. Solids such as pigments are often ground with potassium bromide (KBr) powder and pressed under vacuum to
produce clear pellets. Alternatively, solids can be ground in
mineral oil or fluorolube and examined as mulls smeared
onto salt plates. These techniques continue to be the sample
preparations of choice because they are the simplest, most
convenient, and have the best reproducibility. The quantity
and value of the data generated are unfortunately highly dependent on the skill and experience of the operator. The best
applications of this technique rely on the spectroscopist's
faculty for pattern recognition and a good spectral library
such as the more than 2500 spectra collected by the Infrared
Spectroscopy Atlas Working Committee of the Federation of
Societies for Coatings Technology [4].
SAMPLING ACCESSORIES
The preferred sampling method is to spread a material on a
salt plate, flash the solvent, and run a transmission spectrum
[8]. When this is not feasible, the procedures previously described are the first choices. However, our ability to examine
coatings has been enhanced by a host of accessories. Their
utility is greatly enhanced by FTIR's speed and sensitivity.
The most successful of these techniques is attenuated total
reflectance (ATR). Here, the sample is pressed against a special crystal which carries the IR beam. The optical interaction
between the two appears similar to a transmission spectrum.
There are, however, some major differences in band shape
and intensity, which are dependant on the wavelength. ATR
units are available in many configurations so that liquids,
powders, films, dry panels, and almost any physical form can
be accommodated.
With the advent of FTIR, a wide variety of new techniques
have been developed for dealing with difficult samples and
unique applications. Thin films on reflective surfaces may be
investigated via specular reflectance, and rough surfaces or
powders are examined by diffuse reflectance. Solids that can
be heated may even be studied using their emission spectra.
Dry solids and films have been investigated by detecting the
sounds they produce when exposed to the FTIR beam (photo
acoustic detection). Recently, infrared microscopes have become available which can focus on areas as small as 10 ~m.
Any of these approaches can be of great benefit to the coatings analyst, but it should be recognized that each has its own
unique advantages and limitations.
DATA P R O C E S S I N G
The digital computer, which performs the Fourier transform to convert the interferogram into a normal spectrum,
can also be utilized for additional tasks important to the
coatings analyst. Some of these were previously thought impossible. Since the transformed spectrum is already in digital
form, a variety of data processing operations, such as baseline correction, scale expansion, plot modification, smoothing, etc., can be readily performed. The computer can also
execute a number of mathematical operations such as conversion to absorbance, band deconvolution, peak height measurement, and area quantitation. However, the most valuable
asset is its ability to subtract one spectrum from another.
This feature can be used to make separations that would be
very difficult to perform chemically. The spectra are stored on
magnetic disks for examination at any time and can be retrieved later without any loss in precision or integrity. Thus,
samples for comparison need not be run at the same time.
The computer can also rapidly compare one spectrum with a
whole library of reference spectra and display the most likely
choices. This can be a great blessing to the fledgling spectroscopist trying to gain experience. Finally, the computer can be
preprogrammed to carry out nearly all the instrumental operations automatically. This allows the operator to concentrate
on sample preparation and spectral interpretation. It also
permits essentially "black box" operations by technicians.
APPLICATIONS TO R O U T I N E PAINT
PROBLEMS
Every paint laboratory is confronted at times by crises. The
analytical laboratory is usually called upon to contribute to
its resolution by answering questions like "What is this
stuff?," "Where did it come from?," "What's the matter with
this batch?," and "Why is this different from what we expected?." Such questions orginate from all parts of the organizat i o n - f o r m u l a t o r s and polymer chemists, plant support personnel, and customer service representatives. All these
requests are important and require immediate attention. Infrared is usually the first step in executing an analysis program since it provides the most qualitative information in the
shortest amount of time with the least sample preparation.
Fourier transform spectroscopy makes this process considerably easier because it allows the spectroscopist to obtain a
useful spectrum from almost any material. A spectrum can be
obtained from nearly any amount of material that can be
visually detected and isolated. If the amount is too small to
see with the unaided eye, one is never certain that it is within
the IR beam. With the development of IR microscopes, even
this constraint is minimized. Once a spectrum is acquired,
much can be learned about the material and an analysis
scheme can be formulated to identify it, to isolate it, to
determine its properties, and to trace the problem to its
source.
For example, a common problem results when a component separates while standing in the shipping container. Figure 5 shows the spectrum of such a "float" found on the
surface of a paint can. Using a micropipette, the material was
drawn off and spread onto a KBr plate. Even though there
830
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FIG. 5 - M a t e r i a l
was only a tiny a m o u n t of material, it was sufficient to produce a s p e c t r u m with a b o u t 10% absorption. Using scale expansion, it was identified as m i n e r a l oil. This clue led to the
discovery that a s h i p m e n t of cans h a d not been adequately
degreased.
Another c o m m o n p r o b l e m is the "scum" that develops on
the surface of panels d u r i n g exposure testing. It m a y be
c a u s e d b y an exudate from within the film o r it m i g h t be
d e p o s i t e d from the environment. The a m o u n t of m a t e r i a l is
very small a n d is easily lost. The m a t e r i a l can be transferred,
examined, a n d identified b y s i m p l y rinsing the exudate from
the p a n e l with a solvent a n d evaporating the rinse solution
onto a salt plate. Figure 6 shows the s p e c t r u m of such an
exudate. The infrared s p e c t r u m is that of a polyester t h a t was
not s u p p o s e d to be in that f o r m u l a a n d r e p r e s e n t e d a c o n t a m inant.
DIFFERENCE SPECTROSCOPY
P r o b a b l y the m o s t useful c o n t r i b u t i o n of F o u r i e r transform spectroscopy, as far as the coatings analyst is concerned, is its ability to r e m o v e k n o w n o r u n w a n t e d
c o m p o n e n t s so that h i d d e n o r m a s k e d m a t e r i a l s are exposed
[9]. Spectral s u b t r a c t i o n allows the analyst to p e r f o r m separations that w o u l d be difficult a n d time c o n s u m i n g o r even
impossible b y c h e m i c a l means. Interactive s u b t r a c t i o n prog r a m s n o w p e r m i t the spectroscopist to m a n i p u l a t e subtrac-
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SPECTRAL SEARCHING
Fourier transform instruments are usually offered with
spectral searching algorithms as a part of their software package, either included with the equipment or as an additional
option. Several third party search packages are also available.
These can be very helpful to the coatings spectroscopist, particularly the novice. They provide a quick way to eliminate
the majority of possibilities so that one can concentrate on
the best fits in their quest to discover what an unknown spectrum is chemically. Several approaches, such as peak match-
832
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centrificate (8B), the pure spectrum of the haze can be isolated (8C). A search of several libraries indicated the best
match would be a silica. Silica flock is very often used as a
filter aid. Apparently a small hole had developed in one of the
process filters, allowing the filter aid to leak through and
contaminate the batch.
TIME LAPSE S P E C T R O S C O P Y
Digitized Fourier transform spectra are readily stored on
magnetic disks media and can be retrieved at some later time
without any lose of accuracy or integrity. This allows spectra
to be accumulated over a period of time and compared at
leisure. Thus, cure studies may be carried out over hours,
days, or weeks, while durability and weathering tests may
extend to years. By repeatedly examining the same point
within a film, very subtle chemical changes can be detected.
This technique is used to determine cross-linking reactions
taking place during cure and the degradation resulting from
QUALITY A S S U R A N C E
Fourier transform spectroscopy's greatest contributions to
the coatings industry have just begun. The recent increased
emphasis on product quality makes automated analytical
techniques not only practical but necessary to remain competitive. Using computerized spectral subtraction, a fraction
of a percent of a foreign material can be detected and identi-
t00
~
50
Resin "Cloud"
gT
~ - -
4000
I
3500
t
3000
2500
2000
1750
cITr 1
1500
1;~50
t000
750
450
i250
t000
750
450
750
450
Resin
Centrtficate
t00
gT
50
4000
3500
3000
2500
2000
i750
i500
CffH
'Cloud ~
Isolated
t03.i9
ZT
67.70
C
32.22
'
4000
3500
I
3000
2500
2000
1750
i500
t250
O
i 00
cm-~
CONCLUSIONS
Infrared spectroscopy has proven over the years to be one
of the most valuable problem-solving tools available to the
coatings analyst. It is usually the first technique applied to
difficult analytical problems because it provides unique information about samples in almost any physical state. The extent of the problem can then be assessed and a plan of attack
formulated. The advent of FTIR has removed most restrictions imposed by sample size and form. A wide variety of
attachments is available that greatly expands the range of
samples amenable to examination. Its associated computer
allows the analyst to strip away known components to reveal
minor additives and contaminants. Spectral subtraction can
thus perform separations which would be difficult if not impossible by other means. Data-handling techniques are proving to be the most valuable contributions of this technology
for the paint industry. Spectral identification of unknown
materials via computer pattern matching has become common place. Digital spectral storage and retrieval permits
comparison of films as a function of time so that the chemistry taking place during cure and exposure can be followed. It
can also determine when and at what rate those reactions are
taking place. The ability to preprogram the spectrometer allows relatively unskilled operators to perform very sophisticated analyses without being burdened by spectroscopic
functions. The instrument can then become an automated
"black box" quality assurance analyzer.
834
REFERENCES
[1] Bellamy, L. J., The Infrared Spectra of Complex Molecules, Vol. I,
3rd ed., Chapman and Hall, London, 1975.
[2] Bellamy, L. J., The Infrared Spectra of Complex Molecules, Vol. II:
Advances in Group Frequencies, 2nd ed., Chapman and Hall,
London, 1980.
[3] Socrates, G., Infrared Characteristic Group Frequencies, John
Wiley & Sons, Ltd., New York, 1980.
[4] An Infrared Spectroscopy Atlas For The Coatings Industry, Vols. I
& II, D. R. Brezenski, Ed., Federation of Societies for Coatings
Technology, Blue Bell, PA, 1991.
[5] Shreve, O. D., Analytical Chemistry, Vol. 23, 1951, p. 441.
[6] Conley, R. T., Infrared Spectroscopy, 2nd ed., Allyn & Bacon,
Inc., Boston, MA, 1972.
[7] Griffiths, P. R., Chemical Infrared Fourier Transform Spectroscopy, Wiley-Interscience, New York, 1975.
MNL17-EB/Jun. 1995
i
THE BINDERS USED IN COMMERCIAL COATINGS a r e o r g a n i c p o l y m e r s , the molecular weights of which greatly influence the
MOLECULAR W E I G H T D E F I N I T I O N S
While the molecular weight of a single molecule is a simple
concept, there are several ways to calculate the molecular
weight of a mixture. The most useful values are number average molecular weight, Mn and weight average molecular
weight, Mw
E FliMi
M--'~= i~ng
i
M E T H O D S FOR D E T E R M I N A T I O N OF
N U M B E R AVERAGE MOLECULAR W E I G H T
End Group Analysis
E wiMi
Mw - "~ wi
835
9
www.astm.org
836
PAINT AND
COATING
TESTING
MANUAL
is not limited to polyurethane raw materials. Amine or carboxylic acid functional groups may be determined by acidbase titration, often in non-aqueous solvents, but the parameters of solvent, titrant, and apparent pH at the end point must
be worked out for each compound.
End groups may also be determined by spectroscopic
methods, usually infrared and nuclear magnetic resonance
spectrometry. For example, see ASTM Method for Testing
Polyurethane Raw Materials: Determination of Primary Hydroxyl Contents of Polyether Polyols (D 4273).
Even polymers which are not usually thought of as possessing functional end groups may be analyzed. This is because
molecules are often terminated by fragments of the catalyst
which initiated the reaction. An example is polyacrylonitrile,
which may be terminated by a sulfate or sulfonate group. The
analyst familiar with the mechanism of polymerization
(which should not involve a high percentage of chain terminations which do not leave the desired end group) can often
devise a way to measure the molecular weight based on determination of these residues.
Accurate measurement of M-~, by end group analysis is limited to polymers of molecular weight less than about 20 000,
since the end group concentration is too low for precise measurement above this range.
Mn -
KC
AX
For determination of molecular weight by m e m b r a n e osmometry, a solution of the test substance is separated from
pure solvent by a semi-permeable membrane, i.e., a membrane which is permeable to low molecular weight solvent
molecules but impermeable to molecules of the test substance. Because of the lowered activity of solvent containing
the polymer, solvent molecules will tend to travel across the
membrane from the pure solvent. The pressure which must
be applied to the solution to equalize this flow is equivalent to
the osmotic pressure. Because the change in osmotic pressure is dramatic compared to the small temperature changes
observed with the other colligative property methods, membrane osmometry is useful for higher molecular weights, up
to about M---~= 106, although accuracy fades at the highest
values. The technique cannot be used for low molecular
weights because commercial membranes are not sufficiently
selective: typically, manufacturers quote cutoff values of 5000
to 20 000 for various membranes, indicating that molecules
below that value can permeate the membrane. This property
can actually be an advantage in that it is not necessary to
purify the polymer to remove low molecular weight additives:
their concentration is quickly equalized on each side of the
membrane, so that their presence does not affect the molecular weight value. Elevated temperatures may be used with
less soluble polymers, but choice of membranes becomes
limited as the temperature is increased and as less common
solvents are selected.
Vapor pressure osmometry actually is unrelated to osmometry, consisting simply of the measurement of vapor
pressure depression in order to determine molecular weight.
Commercial instruments measure the vapor pressure indirectly: the vapor pressure difference between a dilute polymer solution and pure solvent is measured by monitoring the
temperature difference between drops of each liquid in equilibrium with solvent vapor. Although in principle this is an
absolute measurement, in practice these instruments are calibrated with standards of known Mn. Vapor pressure osmometry complements membrane osmometry in that it is suitable
for materials with Mn in the range below 20 000, with accuracy dropping off at higher molecular weights because of the
very small temperature differences observed.
The experimental procedure is described in ASTM standard D 2503 (Test Method for Molecular Weight of Hydrocarbons by Thermoelectric Measurement of Vapor Pressure),
although the manufacturer's literature for the specific apparatus must be considered definitive.
D E T E R M I N A T I O N OF W E I G H T A V E R A G E
M O L E C U L A R W E I G H T BY L I G H T
SCATTERING
Unlike ~/n, Mw is not much affected by the presence of
small quantities of low molecular weight impurities. The only
common method for direct determination of Mwwis light scattering. Light is scattered by polymer solutions in a manner
which is well understood theoretically and which depends
upon the size of the polymer molecules in solution. Classical
measurement of M w by light scattering is described in an
ASTM standard [Practice for Determination of Weight-Average Molecular Weight of Polymers by Light Scattering (D
CHAPTER 7 4 - - M E A S U R E M E N T OF P O L Y M E R MOLECULAR W E I G H T
4001)]. The technique is usually performed by specialists
because of the attention to detail required for accurate values:
(1) Traces of dust and other particles must be removed from
the solutions; (2) Light scattering measurements formerly
needed to be made manually at several angles.
Modern laser light sources make possible measurement of
light scattered at angles less than 10~ [2]. At such low angles,
the equations defining the relation of M Wto scattered light are
reduced such that measurement at a single fixed angle is
sufficient. Simple measurement of a set of dilute solutions of
the polymer to determine scattered light and the concentration dependance of the solution refractive index (RI) suffice
to determine M--~.Instruments are also available which make
measurements at multiple angles automatically, so that the
radius of gyration as well as the molecular weight of the
substance may be determined. With either the low-angle or
multiple-angle instruments, operation is no more tedious
than if a single measurement were made on each solution. An
advantage of the laser light sources is that their intensity
makes the sample size requirement lower, so that much less
solution need be filtered free of particulates. If the instrument
is designed so that the sample solution flows through the cell,
interference from particulates is apparent as random sharp
spikes, which may be corrected electronically before performing molecular weight calculations.
Light scattering is less suitable for analysis of polymers of
Mw lower than about 20 000. However, the low-range sensitivity increases as the RI difference between solvent and polymer increases. Methods for molecular weight determination
for light scattering are well described in the literature [2-5],
but the instructions of the instrument manufacturer are most
relevant.
837
SEC Instrumentation
SEC instrumentation consists of a basic HPLC system, including a constant volume pump, injector, column set, detector, and computerized data handling system. HPLC is
discussed in another chapter. The pump must be capable of
delivering solvent with greater precision than is necessary for
ordinary HPLC, preferably within 0.1%. This is because of the
semilogarithmic SEC calibration curve, where small differences in elution volume result in a large difference in apparent molecular weight. Alternatively, some device may be used
to continuously monitor flow rate so that experimental data
may be replotted in terms of elution volume rather than
elution time. Another approach is use of an "internal standard," usually of very low molecular weight, to permit correction of experimental retention times. Such devices are rarely
used nowadays, since the variations they introduce are of the
same magnitude as the variations in flow of modern, wellmaintained HPLC pumps. Control of the temperature of the
system is desirable since fluctuations in ambient laboratory
temperature add variation to retention times and, more seriously, cause drift in the baseline of the refractive index detector. Ideally, the entire unit is encased in a constant temperature chamber. Unfortunately, these enclosures usually must
be constructed by the user because of the limitations of
commercial units. Many users make do with temperature
control of only the column chamber and the detector, which
suffices if the laboratory temperature remains somewhat
constant.
SEC columns are usually filled with styrene/divinylbenzene
copolymer and are always purchased pre-packed. Modern
instrument manufacturers supply columns of a uniform high
performance. For increased resolution, more than one SEC
column is used in series, with as many as four or five 30-cm
columns being preferred by many operators. These may consist of diverse columns, each containing packing of a specific
pore size, or each may contain packing of broad pore size
distribution.
Various detectors are used in SEC. The most common is
based on detection of changes in refractive index (RI) of the
solvent as the solute elutes. This property is closely related to
concentration and such a detector is suitable for any material
with an RI which differs from that of the solvent. Commercial
detectors are designed to minimize temperature fluctuation
since RI is strongly dependant upon temperature. Temperature control can be either active (electronic heating devices)
or passive (massive metal block surrounding the cell). The
mass response of the refractive index detector varies by only a
few percent with molecular weight, and it is thus assumed to
be a linear concentration detector. It is well to check this
assumption if analyses will straddle a broad molecular
weight range, particularly at the low end of the range. Caution must be used in the analysis of copolymers since the RI
of copolymers changes with composition.
Other detectors are used for special purposes. A UV absorbance detector, usually in series with an RI detector, is suitable
for analysis of polymers with strong chromophores, such as
those containing styrene, terephthalate, or bisphenol A
groups. Infrared absorbance detectors are used to track particular components of the polymer, but limitations in useful
wavelengths and solvents prevent their general use. Another
838
weight of many common polymers. The method of calibration should always be reported when SEC molecular weight
values are given.
A universal calibration system has been devised based on
the relationship between viscosity and SEC retention time,
since each is a function of the size of the solvated polymer.
When using universal calibration, standards and samples
may be quite different polymers; it is only necessary that the
Mark-Houwink coefficients for standards and samples be
known. Of course, the Mark-Houwink coefficients must be
known for the polymer in the particular SEC solvent at the
temperature used. Obtaining these coefficients is not as demanding a task as preparing narrowly distributed standards
of a new polymer, and universal calibration has found widespread use. The approach is sufficiently popular that it is
described in an ASTM standard: ASTM Test Method for Molecular Weight Averages and Molecular Weight Distribution
of Certain Polymers by Liquid Size-Exclusion Chromatography (Gel Permeation Chromatography-GPC) using Universal
Calibration (D 3593).
Most analysts use computerized data systems for evaluation of SEC data. These systems are reasonably priced and
aid the operator in all phases of data treatment, from preparation of the calibration to determination of molecular
weight averages to preparation of attractive graphs of molecular weight distribution. Caution must be used in their application; not all systems will give the same results as an intelligent operator performing manual calculations. The greatest
difficulty is in mathematical representation of the calibration
curve of retention time versus molecular weight. Use of
higher order equations to represent the calibration can introduce large errors compared to simply connecting the experimental data points.
SEC data for narrow molecular weight distributions must
be corrected for dispersion contributed by the instrumentation. This correction is not significant for the broad
molecular weight distributions typically found in coatings.
Band broadening corrections become more important if a
molecular weight-sensitive detector is used, such as a viscometer or light-scattering instrument.
SEC procedures and calculations are thoroughly described
in ASTM Test Method for Molecular Weight Averages and
Molecular Weight Distribution of Polystyrene by Liquid Exclusion Chromatography (Gel Permeation Chromatography--GPC) (D 3536).
Application of SEC
SEC may be performed with either aqueous or organic
solvents. Non-aqueous systems are more reliable, but, of
course, water-soluble compounds such as polyacrylates are
more readily analyzed in aqueous solvents. Non-size exclusion interactions between the column and sample are more
common with aqueous systems. These undesirable interactions include adsorption and ion exclusion/ion retardation
and can often be controlled by adding salts or a low percentage of organic solvent.
Elevated temperature is necessary for the analysis of some
polymers because of their low solubility or because of the
high viscosity of the solvents which they require. In general,
C H A P T E R 7 4 - - M E A S U R E M E N T OF P O L Y M E R M O L E C U L A R W E I G H T
this is not a consideration for the relatively low molecular
weight polymers used in coatings raw materials.
SEC has long since spread from the specialized central
laboratory to the laboratory of the synthetic and formulating
chemist. Central analytical laboratories select the SEC colu m n set and mobile phase for optimum resolution of a particular polymer and molecular weight range. Central laboratories also typically perform extensive calibration. Practice in
synthesis laboratories is usually different, with a single system used in a comparative fashion for all analyses. Indeed,
when SEC is used routinely by resin chemists to follow polymerization reactions, the fine details of calibration are typically ignored and molecular weight is estimated by simple
comparison to polystyrene standards, either by visual estimation of "peak" molecular weight or by uncritical acceptance of
the default computer-generated report. For most troubleshooting applications, it is enough to overlay the chromatograms of a "good" and a "bad" polymer in order to determine
whether differences in molecular weight distribution contribute to a problem. In the case of a product which does not have
a single smooth molecular weight distribution but rather
consists of two or more discrete distributions, visual comparison of peaks is often more valuable than comparison of
numerical values. To monitor a polymerization reaction, it
may be enough to watch the gradual disappearance of the
peaks due to monomers.
839
~l
t/to
where t and t o are the efflux times for polymer solution and
pure solvent, respectively. R e d u c e d viscosity takes concentration into account:
T~ r e d
--
t -- t o
toC
VISCOMETRY
Rheology of paint components is discussed in Chapter 33.
We will discuss here only viscosity measurement to determine molecular weight.
S o l u t i o n v i s c o m e t r y is the method of determining molecular weight most suitable for routine quality control. The
viscosity/concentration relationship of a polymer solution is
a function of the chain length of the polymer, so viscosity can
be used as a measure of molecular weight.
As with other methods, determination of true molecular
weight by solution viscosity requires purification of the polymer and extrapolation to zero concentration of a series of
ratios representing measured values. The zero intercept, representing the limit of the viscosity/concentration relation as
zero concentration is approached, is the intrinsic viscosity,
[~?]. It is related to ~ by the relationship expressed in the
Mark-Houwink equation
[-q] = KM~
The constants for the Mark-Houwink equation must be
determined experimentally using well-characterized polymer
standards of narrow Mw/M .. (Mw/M. must be small for valid
calibration since ~ is numerically different than ~ or Mw.)
Since viscosity is determined by the hydrodynamic volume
of the polymer, the relationship with molecular weight is
specific for the polymer, the solvent, the temperature, and, of
course, the concentration. A relationship determined for a
linear polymer will not be accurate if branched molecules are
also present. This means that the constants in the MarkHouwink equation change with various solvents and with
polymers having various degrees of branching. Measurements are made at high dilution to minimize the effect of
MNL17-EB/Jun. 1995
Coatings Characterization by
Thermal Analysis
by C. Michael Neag ~
improvements allow technologists to complete complex experiments involving multistep heating programs and several
purge gases. At the same time, calibration routines were also
simplified and the accuracy and precision of the results improved. All of these advances came with the additional benefit
of unattended operation. In fact, several commercial suppliers offer instruments with robotic control that permit the
analysis of scores of samples at the touch of a button.
The simple yet highly sophisticated character of these instruments has a major drawback: their simplicity significantly increases the potential for misinterpreting experimental results. With advances in automation, thermal analytical
techniques have moved closer to simple "turn-key" operations and have reduced considerably the technical demands
on the user. TA has become a marvelously simple process that
unfortunately requires little understanding of the instrumentation or the results. A few minutes in sample preparation yields a raft of data from sophisticated data analysis
software, considerably increasing the potential for error in
data interpretation or analysis. The improvements in instrumentation and software demand greater caution from the
scientist in experimental design and results interpretation.
Wendlandt [2] and Earnest [3] discuss the advent of automation in thermal analysis, and two volumes edited by T.
Provder [4,5] describe laboratory automation and computer
applications in polymer science more generally.
Coatings and TA
In the coatings industry--limited here to commercial
paints and industrial coatings--TA has proven to be a cost
effective means for understanding the interrelationship between a coating's synthesis, formulation, and end-use performance [6]. Techniques historically important in coatings
characterization can be broadly grouped under the headings
of differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermomechanical analysis (TMA), dynamic mechanical analysis (DMA) and thermogravimetry
(TG). Techniques such as dielectric analysis (DEA) and
evolved gas analysis (EGA) have gained popularity as tools for
coatings characterization as well. Although results are easily
obtained using these techniques, they are grounded in complex thermodynamic and kinetic principles. Excellent overviews of the foundations, instrumentation, and applications
of thermal analysis can be found in reviews by Wendlandt [2],
Wunderlich [7], and Turi ]8, 9]. The International Confederation for Thermal Analysis (ICTAC) also provides an overview
of TA and a list of reference articles [56].
841
Copyright9 1995 by ASTM International
www.astm.org
842
EXPERIMENTAL TECHNIQUES
Scans were made using the TA Instruments' (formerly
DuPont) 990, 9900, 2000, or 2100 temperature programmer
controller. Nonisothermal studies were completed at heating
rates varying from 5 to 15~
isothermal temperatures
will be noted as required. All scans were made under dry
nitrogen or air. Each instrument was calibrated and operated
using the manufacturer's recommended procedures. The typical operating conditions for each instrument are described
below, with other important key experimental variables
noted where necessary. A general overview of running experiments with each instrument is included at the end of each
section.
DSC--Nonisothermal scans were made variously using the
TA Instruments' 910 and 2910 DSCs, typically with 5.0 _+
0. l-mg samples. Materials were usually scanned twice, initially to establish uniform thermal histories and again to
learn about specific physical properties. Runs were generally
made at heating rates of 15~
between - 125~ and 250~
under a 50 mL/min nitrogen or air purge. In some instances,
latex samples were introduced into liquid drop pans and
dried in a controlled humidity chamber for a minimum of
24 h before analysis.
DSC Reaction Kinetics--Similar conditions to those described above were used, although heating rates were generally held to about 5~ per minute. Samples of unreacted
material weighing about 10 mg were placed in special pans
for liquid samples. In the residual heats of reaction experi-
ments, heats of reaction were determined for samples removed from a batch reactor at lO-min intervals throughout
the reaction process. The residual heats were measured under nonisothermal conditions using commercially available
software. The ratio of partial heats of reaction to total heat of
reaction as the polymerization progressed was given as the
percent chemical conversion.
DMA--DMA scans were made variously in vertical and horizontal modes on TA Instruments' 981,982, and 983 DMAs.
All studies were completed at 5~
usually under nitrogen
purge. Cure studies employed either fiberglass braid supplied
by TA Instruments or stainless steel mesh (Cleveland Wire
Cloth & Mfg., Cleveland, OH). In cure studies, 100-/zL wet
samples were applied to substrates mounted in the DMA
using analytical pipettes [50 mL _+ 0.5% to deliver (TD)].
Isothermal temperatures were typically attained by mimicking the come-up time in an oven. For example, if a coated
panel required 4 min to reach bake temperature in a production scale oven, then a similar time schedule was programmed into the DMA.
TMA--Thermomechanical and dilatometric experiments
were made using TA Instruments' 942 and 943 TMAs. Scans
were made at 5~
under nitrogen or air between about
- 5 0 and 250~ In general, the sample was cooled at least
50~ below the expected transition temperature. TMA scans
were typically made directly on coated substrates, while dilatometric experiments were completed on samples varying between 0.1 and 0.6 mm in thickness. In the penetration experiments, loads were typically about 5 g (0.05 N).
DEA--The TA Instruments' 2970 DEA and either the
parallel plate or ceramic single surface sensors were used in
the dielectric experiments. Parallel plate sensors were used to
study thin films removed from various substrates. Ram force
varied from a few newtons to 175 N depending on the coating. The ceramic single-surface sensor was used to study
resins and powders. 100-/~L samples were spread uniformly
on the sensor and dielectric measurements recorded from 0.1
Hz through 100 kHz in order-of-magnitude increments.
Heating rates were selected to ensure that an entire set of
frequencies (0.1 Hz through 100 kHz) could be recorded for
each 1~ increase in the sample temperature. Samples were
typically scanned at 1 to 2~
between - 125 and 200~
under nitrogen.
TGA--TA Instruments' 950, 951, and 2950 TGAs were used
in the examples described here. Samples used in typical thermogravimetric experiments usually weighed between 3 and
10 mg. Scans were made at 10~
under nitrogen beginning at room temperature (RT) and ending at 600~ The
high-resolution thermogravimetric analysis described here
was completed at 50~
in nitrogen at a resolution factor
of 5; sample weights ranged between roughly 10 and 12 mg.
Exotherm
D eg rad ation
"-'X r --<',
',,
Endotherm
i
Temperature
FIG. 1 -Schematic DSC curve illustrating common transitions
observed by DSC (Aq = heat flow),
Glass Transition Temperatures--Probably the best understood and most commonly used property of polymers, glass
transition temperatures are important in virtually every
phase of a coating's development and manufacture. The Tg
marks a polymer's transition from an amorphous glass to a
rubbery solid and defines the limits of processability for most
polymers. In a nonisothermal or rising temperature DSC
experiment, the glass transition coincides with a relatively
sharp increase in heat flow to the polymer and a corresponding increase in the polymer's specific heat. Several techniques
can be used in the assignment of a DSC Tg, including the
onset, midpoint, and endpoint of the transition; in practice,
the Tg is most commonly assigned to the extrapolated onset
of the transition.
Sample Preparation and Tg Measurement--Measuring the
glass transition temperature usually means nothing more
than removing a sample from a substrate, placing it in a
sample pan, and heating through the glass transition temperature in the DSC. Either of two techniques can be used to
determine the Tg. When the "product" Tg (including all processing and thermal history effects) is of interest, Tg's are
obtained with a single temperature sweep. Where thermal
history effects are unwanted complicating factors, two temperature sweeps are used. The first sweep removes thermal
history effects (for example, sample preparation or aging
effects) while the second sweep gives the Tg. The latter technique works very well provided that there are no chemical
changes, solvent losses, or morphological alterations during
the first sweep.
Sometimes, inconsistencies in sample preparation or a
seemingly unimportant detail can significantly influence the
interpretation of the results--particularly when first run
transitions are required. In the example below, two latexes-one scraped from a glass slide and placed in a vented pan and
the other dried directly in a liquid drop p a n - - p r o d u c e d considerably different results. The samples were dried side by
side in a dessicator before analysis.
The sample scraped from the glass slide shown in Fig. 2
exhibits a large endothermic peak centered around 75~
Normally, this endotherm would suggest the loss of a volatile
component or an important morphological feature. However,
the results for the latex dried directly in the liquid drop pan
suggest that something else is influencing the results. The
heat flow curve for the latter sample exhibits no endotherm
and has a Tg some 15~ higher than the sample removed from
the glass slide. High-resolution videography resolved the issue, showing that the difference in Tg and the endothermic
"event" was probably brought about by the softening and
subsequent relaxation of the latex pieces scraped from the
glass slide. What appeared as a significant morphological feature was nothing more than an artifact of the sample preparation process. In a typical two-sweep Tg measurement, this
endotherm most likely would have been ignored and only the
second run Tg reported, but, in studies that require the firstrun data (as was the case here), the wrong conclusions could
have been drawn.
844
,,-0.4
-0
0.2
95~
\\
0.0
~-~ - 0
~.
~ /'--~
:~
o
,,'7
o
u_
-0.2'7
5"
12.~0~
I
I
-0
\
\
-0
,-
-~oo
-40
c~
-0.4
~
Temperature
vented pan
Ic~o
~o
200
-0.6
(~
FIG. 2-Characteristics of the glass transition in identical latexes prepared by different methods.
-0.3
0.05
ACRYLIC A
Tg (a4 c)
A
-0.05-
.......
-0.4
Tg ( 4 8 C)
S
ti
Q
m
O)
tl
r
Ul
-0.15-
-0.5 ~,0
ACRYLIC C
3
0
r-~
h
ILl
"r
-0.25-
-0.35
ACRYLIC D
2b
-0.8
Tg ( 3 4 C)
4b
6b
ab
Temperature (~
FIG. 3-Glass transition temperatures for four acrylic copolymers.
100
-0.7
DSCTg
Fox Tg
A
B
C
D
34
48
48
34
60
65
70
75
[12] of these copolymers. The polymers used in this experiment were all low-molecular-weight tetramers (number average molecular weight < 5000) composed of various combinations of methylated and butylated acrylics. Van Krevlan [1]
provides a more comprehensive overview of polymer properties which could have an influence on the assignment of the
glass transition temperature.
REACTION KINETICS
A number of techniques have been developed for measuring the kinetic parameters of chemical reactions from DSC
data. The primary advantage of these techniques over traditional wet chemical techniques is their speed and simplicity.
Research in reaction kinetics analysis by DSC includes studies focused on isothermal techniques [13-15], nonisothermal
(also known as temperature variant, rising temperature) or
dynamic methods [16-17] and multiple scan methods
[18-19]. Each method uses the rate of heat evolution as the
computational parameter, implicitly assuming that the reaction is not autocatalytic, has one rate-limiting step, and is
unaffected by changes in reactant concentration or volume.
The validity of kinetic data obtained using nonisothermal
procedures has been the source of considerable technical
effort and discussion in the literature (see, for example, Refs
20 and 21).
Nonisothermal reaction kinetics analysis plays an important role in the characterization of coatings. Differential
methods based on the work of Borchardt and Daniels [16] are
the most commonly used in obtaining reaction kinetics parameters by DSC. These methods assume that the heat
evolved during a reaction is proportional to the extent of
reaction. The order of reaction, n, the activation energy, E
(kJ/tool), and the Arrhenius constant, A (s-~), are determined
using an equation based on a general nth order rate expression
dF(t,T)
- - k[l - F(t,T)] ~
dt
(1)
(2)
where R is the ideal gas constant (J/tool K). The methods used
here have been described in detail elsewhere [22-23].
In nonisothermal kinetics experiments, autocatalytic reactions and first-order reactions are virtually indistinguishable
845
because both reactions produce a uniform, monomodal, exothermic peak as the experimental temperature increases. The
only way to determine the nature of the reaction mechanism
is by running an isothermal experiment. An isothermal experiment will clearly differentiate between the two reaction
types because the exothermic peak marking the maximum
rate of reaction will occur at very different points, depending
on the nature of the reaction. In a reaction that obeys firstorder kinetics, this peak will occur immediately after reaching the isothermal temperature. In an autocatalytic reaction,
the maximum rate of reaction--and therefore the peak maxim u m - o c c u r s well after reaching the isothermal temperature.
E p o x y - A m i n e R e a c t i o n Kinetics
Maximizing the efficiency of a reactor and minimizing raw
material waste in a chemical reaction depends inherently on
knowing how a reaction proceeds and, more specifically, how
long the reaction takes to reach completion. Unfortunately,
measuring the rate and degree of conversion in reactors holding hundreds or even thousands of gallons is a prohibitively
expensive process during product scale-up. Small-scale laboratory DSC experiments representative of a production reaction can significantly reduce reactor time and process costs.
Modeling the extent of reaction using DSC kinetics analysis
can further shorten the development process and can be used
to predict the extent of reaction under widely varying temperatures and reaction times. In the example that follows, these
techniques were used to optimize reactor time and improve
productivity in manufacturing. The reaction involved a typical diglycidyl ether of bisphenol A (DGEBPA) epoxy and an
amine.
In this example, chemists arbitrarily placed the time to
form an epoxy adduct at 8 h, a substantial manufacturing
cost when considering reactor time and labor. However, predictions based on nonisothermal DSC reaction kinetics
showed that the reaction should actually reach completion
much faster than 8 h. In fact, DSC reaction kinetics parameters (n = 1.1, E = 72.0 J/tool, and In A = 19.2) indicated that
the process should take about 2 h under the specified polymerization conditions. These results were then corroborated
by measuring the residual heats of reaction (see experimental
for details) observed in small samples taken from a 100-gal
reactor. Figure 4 compares predicted conversion with the
residual heats of reaction measurements. While neither
method was extended to show the actual time required to
reach 100% conversion, extrapolation to 100% conversion
indicates the reaction should reach completion after about
2 h. Table 2 compares selected data from Fig. 4 at specific
reactor times. These results show that the reaction reached a
higher level of conversion (based on DSC residual heats) in
the manufacturing process (88%) than predicted by DSC
(67%). Nonetheless, the extrapolated end-point from the DSC
kinetics analysis--although a bit high at 2.5 h - - i s much better than the 8-h reactor time set arbitrarily by the chemists.
The discrepancies between the measured and calculated
degrees of conversion are probably related to competing side
reactions that could occur in DSC experiments (i.e., at elevated temperatures) but not during manufacturing and also
to the vast difference in the reaction conditions: DSC kinetics
846
.o
.g
o
ov-4
t.m
.oi
I
/
/
II
1-4
V
r=3
i/
zoO.
fl~
a,
Actual
o
L)~o
r~d"
o
L)
[-,
<r
Predicted
o
Br.]
~..
o.
~
~
'5"
I
20
I
40
.o
I
60
TIME (minutes)
80
100
FIG. 4 - A comparison of actual and predicted degree of conversion in an epoxyamine reaction. The predicted degree of conversion at each point was based on DSC
kinetics analysis, while the actual degree of conversion at each point was based on
the residual heat of reaction on samples removed from the reactor.
analyses were m a d e using fresh 5-mg samples, while the residual heat studies were m a d e with samples taken f r o m a
100-gal reactor.
Actual %
Conversion
Predicted %
Conversion
...
10
20
30
40
50
60
14
31
49
61
81
88
19
33
43
53
61
67
the p a n and, m o s t i m p o r t a n t l y , r e m a i n very flat on the bott o m of the pan. Liquids are a n o t h e r m a t t e r a n d usually require a special c o n t a i n e r for analysis. No m a t t e r w h a t the
form, limit y o u r s a m p l e size to s o m e w h e r e b e t w e e n 5 a n d
10 mg. Large s a m p l e s (>10 mg) m a y not heat uniformly,
with the o u t e r layers heating m o r e r a p i d l y t h a n the center of
the sample. You can also get results with s a m p l e s in the 1-mg
range, b u t using s m a l l e r m a s s e s c a n reduce resolution. F o r a
m o r e a c c u r a t e a s s i g n m e n t of the Tg, use high s a m p l e weights
(ca. 20 mg) a n d slow heating rates (l~
E i t h e r o p e n o r closed pans can be used. We prefer d o s e d
p a n s with p e r f o r a t e d (use a fine needle) lids. Lids help keep
the DSC oven o r cell clean; the p e r f o r a t i o n s prevent p r e s s u r e
b u i l d u p caused by solvents o r low-molecular-weight r e a c t i o n
products. M a n y others use only open pans.
Liquid p a i n t a n d latex s a m p l e s are treated s o m e w h a t differently in t h a t they are p l a c e d in open p a n s (especially
designed for ]iquids) a n d allowed to dry (24 h m i n i m u m )
before analysis. This a p p r o a c h prevents the d e v e l o p m e n t of
artifacts that s o m e t i m e s o c c u r w h e n a d r i e d s a m p l e is
s c r a p e d from a s u b s t r a t e a n d p l a c e d in the pan.
847
[26].
848
Glassy
State
12"
(3-
11.4
/-\
\
--._...,\
\ ".--..
1t .2
,-7,,, \
/',,,
..,'\i
(3.
....................... ~ , ,
t l .0
O~
O
_J
TS~,banTsgt,ons
0
J
10.8
Rubbery
Region
Glass
Transition
Region
-4o
5b
TI
I
t0.6
\
,,
\..__i..I
10
-150
LLI
18o
~--
10.4
t0.2
T e m p e r a t u r e (~
FIG. 5-Typical viscoelastic response in polymeric systems, log relative modulus (E') and log relative loss
(damping, E").
200
25
EPOXY
cO
._1
- 1 5 0 (5
Z
20-
a
O
<(
a
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rr
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0
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._1
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rr
-0
I
-100
I
-50
I
0
I
50
I
100
I
150
-5O
I
200
25O
Temperature (C ~)
20
160
-140
ACRYLIC
o')
~
--J 1 5 Q
O
-
(5
-120 z
I1.
<(
-100a
UJ
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iii
>
<~10._J
LU
rr"
._1
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-60
m
-40
-20
0
-150
I
-100
I
-50
I
0
I
50
I
100
I
150
I
200
Temperature (C ~)
FIG. 6-Dynamic mechanical properties of epoxy/acrylic copolymers.
250
rr
849
850
time allows, the best way to control thermal lag in the sample
is by using step-change experiments. This kind of experiment
combines slow heating rates (1 to 2~
and isothermal
"steps" (1 to 5 min), which allow the sample to equilibrate
before heating to the next isothermal step. For thin coatings,
shorter isothermal periods (1 to 2 min) are satisfactory, while
thicker samples require longer (e.g., 5 min) isothermal steps.
Strain or Oscillation Amplitude and Frequency: In general, the greater the applied stress, the longer the relaxation
time. Ideally, the sample should come close to full recovery
from one applied stress before the next one begins. This
means the experimenter should choose well-matched amplitudes and frequencies. For example, choosing a large mechanical deflection means that the time between the applied
stresses should be longer. Conversely, higher-frequency experiments should have correspondingly smaller applied
stresses. The proper relationship between the test frequency
and oscillation amplitude will ensure that the sample has
come close to mechanical equilibration between "events." In
most instruments, the amplitude of the deflection is based on
controlled strain. In these instruments, the maximum applied
strain should be at 0.1% or less. This is particularly important
in filled systems (like coatings), which will exhibit nonlinear
responses more readily than unfilled systems.
Because mechanical relaxation times vary widely in polymers, there are no specific rules governing the selection of
oscillation amplitudes and test frequency. As a general rule,
oscillation amplitudes of a few tenths of a millimeter at 1 Hz
are commonly accepted practical "standards." In very hard
(brittle) or very soft materials, however, it's generally best to
perform a controlled stress (stress relaxation or creep) experiment rather than an oscillating stress experiment.
THERMOGRAVIMETRY
(TGA)
120
I00-
Sample
100
Sample
-...
%\"~,,
BO'
80
60-
6O
4J
TI
Z
40
4 0 84
20
1do
2do
3do
4do
Tempepatune
5do
General
20
V4.tC
600
OuPont
2000
FIG. 7A-Weight loss curves for waxes with ostensibly identical compositions.
-1.0
1.0
Sample
B
0.8
0.8
0.6
0.6
o
4J
0.4
Sample A
>
0.2
\"\"
/ ~k
0.2
c~
-r
g~
/L
0.0
0.2
0.4
@J
"T
0.0
1do
2do
3do
Temperature
4do
(~
~do
General
-0.2
V4.tC
600
OuPont
2000
851
852
Condition
A
B
Control, dry
Suspect, dry
T m - l(~
87.7
87.4
Total
AHm
Decomposition
Onset-l, ~
% Char
75.7
46.1
172
150
38
43
LATEX
NV
100
80
IZ
w
t.1 so
uJ
Q.
!.1.
O
m 40
W
24%
20
11%
0
0
40
80
I
120
160
TEMPERATURE
(~
FIG. 8-Polystyrene nonvolatile (NV) content measurement obtained through TG.
AT 2 5 0 ~
co
I
40
8L
0
J
120
I
160
T I M E (hours)
FIG. 9 - T h e r m a l stability of vinyl-ester resin.
Temperature Range and Heating Rate (i~): In most compositional analyses, o u r e x p e r i m e n t s are run between r o o m
t e m p e r a t u r e a n d 600~ This t e m p e r a t u r e range suits m o s t
coating systems because, as a rule, p o l y m e r s (coating
binders) usually begin to d e c o m p o s e s o m e w h e r e between
250 o r 350~ a n d are gone by 450~ W h e n r u n n i n g liquids,
p a y very close attention to the i n s t r u m e n t ' s set-up time before
it begins to collect data. In highly volatile materials, as m u c h
as 10% of the volatile m a t e r i a l can be lost before the first d a t a
p o i n t is collected in the experiment. The difficulties with int e r p r e t a t i o n in this situation should be obvious.
The m o s t i m p o r t a n t c o n s i d e r a t i o n in selecting a heating
rate for y o u r experiments is heat transfer a n d the steady-state
c o n d i t i o n of the sample. F o r r o u t i n e analysis, a 10~
n o n i s o t h e r m a l t e m p e r a t u r e r a m p offers a good c o m p r o m i s e
b e t w e e n run t i m e a n d resolution. Keep in m i n d that high
heating rates can p r o d u c e t h e r m a l lag within the sample,
w h i c h in turn will b r o a d e n t r a n s i t i o n regions. In instances
where a s a m p l e exhibits two o r m o r e weight loss transitions,
they will tend to r u n together at h i g h e r heating rates. Slower
heating rates are usually used w h e r e there is a need for
i m p r o v e d resolution a n d r u n t i m e is not a concern. W h e r e
i s o t h e r m a l t e m p e r a t u r e s are necessary, choose an experim e n t a l t e m p e r a t u r e m o s t representative of the end use requirements.
A few i n s t r u m e n t vendors offer "high o r e n h a n c e d resolution" capabilities, a technique which, in essence, c o m b i n e s
the virtues of a rising t e m p e r a t u r e e x p e r i m e n t with the benefits of a n i s o t h e r m a l experiment. W h a t e v e r the m a n u f a c turer's r e c o m m e n d a t i o n , m a k e certain that the gas flow rates
are identical for each p a r t of y o u r experiment. Analyzing the
s a m e s a m p l e with even small variations in gas flow (less t h a n
5 m L / m i n ) can p r o d u c e d r a m a t i c changes in the weight loss
curves or the weight loss derivative curves. In fact, one mate-
853
Instrumentation--The kind and quality of information obtained from a thermomechanical analyzer depends primarily
on the arrangement of the sample and probe type. The penetration mode is probably the most commonly used arrangement in TMA and is usually used in assigning transition
temperatures, such as the glass transition temperature or
softening point temperature, in polymeric materials. In this
mode of operation, substrate effects become increasingly important as the sample thickness decreases. This is particularly
true in the analysis of thin films and coatings [38]. Tension
tests are often used in characterizing the properties of thin
films. In fact, improvements in instrumentation, particularly
in controlling the applied force and fully automated operation, make possible the characterization of more fundamental viscoelastic properties such as creep and stress relaxation.
These improvements have also increased the resolution of
these instruments considerably. The resolution of these instruments ranges from about 500 nm in first-generation commercial instruments (ca. 1975-80 and earlier) to claims of
less than 5 nm in second-generation instruments.
Dilatomet~--This method has broad applicability in coatings technology, such as in determining the coefficient of
thermal expansion (CTE). It is particularly valuable in failure
analysis. For example, mismatches in CTE appear to play a
role in the failure of two-coat systems such as gel coats.
Gel coats are polyester/styrene systems that are sprayed
directly onto a mold surface and allowed to advance to a tackfree state. A fiberglass mat is then placed onto the partially
cured gel coat and a reinforcing laminating polyester resin
applied to the fiberglass mat. The laminate is removed from
the mold after reaching optimum cure under ambient conditions. If the gel coat or laminating resin is improperly formulated or undercured, differences between the CTE values
may be large enough to cause delamination at the interface.
Ideally, the CTE values for the members of the part should
be the same or only slightly different. In this instance, however, the differences in CTE values shown in Table 4 led to
d~elamination and the eventual failure of the part. Subsequent
analysis of residual heat of reaction by DSC showed that the
gel coat was improperly cured. Inadequate cure led to appreciable differences between the CTE values of the gel coat and
laminate, and ultimately, to the failure of the system. Figure
10 provides a comparison of the CTE curves for the gel coat
and polyester laminating resin.
Material
No, of
Runs
Avg
CTE
Standard
Deviation
Range
Gel Coat
Laminating Resin
4
5
5.0
5.9
0,2
0.1
5.0-5.3
5.8-6.1
854
P A I N T A N D COATING T E S T I N G M A N U A L
TMA C O E F F I C I E N T
OF
EXPANSION
While free films are probably best--provided that they lay flat
and retain their shape during the experiment--it's usually
more practical to run TMA experiments with coated substrates. If you use a coated substrate, pay close attention to
sample thickness, the dimensional stability of the substrate
during the experiment, and the size of the sample in relation
to the probe tip. The larger the sample in relation to the probe
tip, the better.
Substrates, like the coating, can change with experimental
conditions and consequently influence experimental results
that an experimenter might attribute to coating properties
alone. The best way to avoid substrate effects is to increase
the thickness of the sample. Ideally, samples should be about
500/~m (20 mils) thick, but films this thick are rarely found in
any application. Moreover, increasing the thickness of the
sample may improve resolution at the expense of validity. In
practice, films measuring 20/~m (about 1 mid will yield
excellent quantitative results. In general, if you can make the
sample thicker without compromising the validity of the
results, you should. The need for thick samples doesn't mean
that thin samples may not be tested. In fact, significant qualitative results can be obtained at film thicknesses as small as
5/xm provided that the sample preparation conditions are
extremely well controlled.
If you have doubts about potential substrate effects, analyze the uncoated substrate and try to determine if the substrate will contribute to changes in the TMA's response. Some
software packages will allow you to subtract baseline effects
from the total response of the coated substrate. As with the
DMA, ensure uniform thermal histories by preparing specimens in a controlled environment.
GEL COAT R
Z
9e)
z
LU
LAMINATING RESIN
I,
-60
~
-20
i
20
I.
60
T E M P E R A T U R E ( d e g C)
FIG. 10-A comparison of the CTE curves for the gel coat and
polyester laminating resin.
Thermomechanical Analysis
Softening point temperatures (SPT) and total probe displacement obtained using thermal mechanical analysis provide valuable insight into a coating's performance, particularly in comparing the relative degrees of cure in production
materials. For example, when cure levels in two container
coatings were c o m p a r e d - - o n e of which failed QC tests after
manufacture--TMA results strongly suggested that the failed
coating was undercured. The TMA results in Table 5 show
that the failed coating had a lower softening point temperature and greater total displacement than the coating that
passed, gebaking the failed coating led to an increase in SPT
and a decrease in probe penetration. While the changes in
SPT and probe displacement indicate an improvement in performance, they still failed to match those of the coating that
passes the QC test. Intentionally undercured coatings yielded
similar results, strongly suggesting that the coatings that
passed reached a higher degree of cure than the coating that
failed. Perhaps more importantly, these materials were characterized directly on the container substrate, indicating the
TMA's value in situations not amenable to characterization
using more routine analytical methods.
Applied Force:
This only applies to penetration experiments because dilatometric experiments require that the
probe be brought into very light contact with the sample. In
penetration experiments, applying very low forces may not
provide adequate change in the sample to accurately monitor
subtle transitions during an experiment; conversely, large
forces may actually damage the sample during an experiment. In instruments that use weights, the applied force
should be between 5 and 20 g. In servomotor-controlled
TMAs, use 0.05 to 0.2 N forces for probe tips with a 0.4-mm
radius.
Gas Flows: As with all of the instruments, purge gases provide a stable test environment and ensure uniform heat transfer to the sample. Use the manufacturer's recommended
purge rates for all experiments.
100
91
1.1
4.8
104
99
0.3
0.9
DIELECTRIC ANALYSIS
Dielectric thermal analysis (DEA) is a convenient nondestructive test that relates fundamental molecular motions to a
variety of polymeric properties. Applications in coatings science include the characterization of new materials and processes, cure studies, film formation studies, formulations
optimization, applications development, performance prediction, competitive product evaluation, and QC/QA applications. General descriptions of dielectric properties can be
found in a variety of papers [27,39-41].
Because engineering limitations prohibit the characterization of the complete continuum of dielectric properties, there
are a number of commercial dielectric analyzers available,
each offering advantages in their potential range of applications. The operating principle of all of these instruments,
however, is the same: a polymeric system is polarized in an
electrical field and the time, temperature, and frequencydependent dielectric relaxations monitored. Commercially
available instruments may be divided into two broad categories: those polarizing samples with an alternating current (ac)
and those using a direct current (dc). Each instrument may
also have one or more sensors or analytical configurations;
these include remote single-surface, ceramic-single-surface
or parallel plate geometries.
All dielectric analyzers measure two fundamental electrical
characteristics of a material--capacitance and conductance.
Capacitance measures a material's ability to store electrical
charge, and conductivity measures its ability to transfer electric charge. These components are used to determine geometry-independent values for the material's permittivity (e') and
loss factor (e"), serving as molecular probes that correlate
with the changing chemical and physical states of the material. Permittivity corresponds tO the alignment of dipoles in
the electrical field; permittivity values are relatively low at
temperatures below Tg or in highly cross-linked polymers
and relatively high above the Tg. The loss factor corresponds
to the amount of energy required to align dipoles and move
ions in the electrical field. The latter term is frequently used in
monitoring rheological changes during processing or for
monitoring the progress of a cure reaction. More complete
descriptions of the use of dielectric analysis in thermal analysis [9], film formation [42], and thermoset cross-linking
[43-45] can be found elsewhere.
Thermally stimulated current (TSC) represents a relatively
new approach where dipole moments are polarized in a d-c
field at temperatures above the sample's main transition temperatures [46]. Following polarization, the sample is quench
cooled to a low temperature, and then scanned at a constant
heating rate through the polarization temperature. As the
855
856 P A I N T A N D C O A T I N G T E S T I N G M A N U A L
0.6
Epoxy-Ester Ionomer
DEA @ 0.1/10/100/10K Hz
0.4-,-,
O~
0
..J
0.2
O_
0.0
Powder Melt/Flow
Crosslinking
.... -..~
,.
-1_
-2
~'~.~
\jI
I
40
N~. / /
-0.2
,,.~
50 ~ C
-3
( H20 loss )
"\
II
DSC
- -0.4
123~
I
80
Temperature
I
120
I
180
-0.6
I
200
(C ~)
a difficult subject to characterize and understand. Improvements found in newly available dielectric analyzers indicate
that DEA will offer, at the very least, a significant step forward in our ability to follow film formation. Figure 13 follows
the change in the dielectric constant (complex permittivity)
in two latexes, one catalyzed and the other uncatalyzed, after
they were applied to a DEA sensor. By comparing the changes
in log e* with the observations from optical microscopy, DSC
and TGA (results not included here), some inferences about
the nature of the film formation process were made. In the
catalyzed sample, the drop in e* over the first 20 min of the
experiment correlates to the loss of free water. Between
roughly 20 and 30 min, the latex particles begin to deform
and pack tightly together. Finally, over the next hour or so,
there is a loss of ionic mobility that probably coincides with
polymer interdiffusion at the particle-particle interface. The
catalyzed latex had formed a clear, uniform film by the end of
the experiment.
The dielectric behavior of the uncatalyzed film was far
different. While changes in permittivity associated with water
loss and particle packing were evident, the lengthy period
thought to correlate with interdiffusion was missing. In fact,
this latex was a poor film former, leaving an opaque, severely
cracked film on the surface of the sensor.
free films, while film formation studies would typically employ single-surface sensors. As with other approaches, free
films should be made in well-controlled environments and
m u s t meet the minimum film thickness specifications of the
manufacturer. Whenever possible, though, the sample thickness should closely approximate the thickness of the coating
after application. As noted earlier, free films can be made by
coating low-energy surfaces like PTFE or polypropylene or
coating thin aluminum sheet stock and dissolving the aluminum (after the film has formed, of course) with an alkali.
Single surface sensors can be used for any material, but
they are especially useful for studying liquids or materials
that require a gas/polymer interface for proper analysis. Applying liquids, for example in film formation studies, often
requires special preparation to ensure that the electrode surface is completely and evenly covered. For example, when
studying low-viscosity liquids, we first calibrate the sensor,
then build a low silicone polymer border at the edge of the
electrode to keep the sample in place. The volume of liquid
applied should leave a final film roughly twice as thick as the
distance between electrodes when the sensor uses interdigitated comb electrodes. Always use analytical pipettes
to ensure that the applied volume is uniform from experiment to experiment. While absolute measurements of dielectric properties may be in doubt using this approach, it is a
valid way to make relative comparisons provided that each
material is prepared and handled in exactly the same way.
Frequency Selection: In general, there are two components of the dielectric response to an applied electrical field:
dipole polarization and free charge migration. The former is
most frequently associated with high frequencies (1 O0 kHz or
857
3
@ 01. Hz
t~
.-I
Manufacturer I ,
1
/
/
/
O_
58 ~
-1
Manufacturer 2
62 ~
Melt
-2
'
'
40
I
80
I
120
i
160
Temperature (C ~
FIG, 1 2 - A comparison of the dielectric properties in identically formulated resins from two manufacturers.
THERMOSET
CURE
STUDIES
The interrelationship between the network formation process and performance properties make cure process studies
critically important in product development. A thermoset
coating's performance properties depend inherently on cure
conditions. Important characteristics of the cross-linking reaction include the gel point, Tg, and the kinetics of the crosslinking reaction. These properties establish a quantifiable
link between the cure reaction and the development of thermoset properties. In essence, they provide a way to "picture"
the cure process and a tool for optimizing materials handling,
processing, and cure.
Characterizing cure behavior also helps to distinguish between complete cure and optimum cure, an important distinction in thermoset applications. Completely cured thermosets are "ideal systems" where the cross-linking reaction has
reached 100% conversion and properties are constant for
practical purposes. Optimally cured thermosets are "nonideal" systems where the cross-linking reaction is incomplete
and satisfactory performance properties rather than 100%
858
DEA
Sample:
Size:
2.500
RCR0327
mm
Si Chemistry
File: C: SIDEA.03
Operator: Neag
Run Date: 2-Feb-90 10:06
Method: Si DEA
Comment: Catalyzed vs Uncatalyzed Si-latex System
8
.1 Water Loss
7"
0
'~
\\
0
._1
(1)
t-.,.i
-6
(ZD
O
._J
-2
Uncatalyzed
"x
'
0
I
40
I
80
T i m e (min)
I
120
0
160
DEA V4.2A
DSC Cure Studies--DSC cure studies have been particularly beneficial in optimizing cure schedules for gel c o a t s - polyester/styrene thermoset coatings used in marine and sanitary applications. The initiation of the cure reaction in gel
coats begins with the decomposition of a peroxide and the
subsequent copolymerization of styrene with unsaturated
groups in the polyester resin backbone [49]. When fully
cured, these systems are highly cross-linked. Elementary kinetics analysis [50] indicates that the reaction order should
be 1.5, first order in monomer and half order in initiator.
Evaluation of the kinetics of the gel coat cross-linking
reaction using DSC and FT-IR agreed remarkably well. The
data in Table 6 also show that the order of reaction obtained
by both DSC and FT-IR almost match the value of 1.5 obtained using a theoretical kinetics approach.
E, kJ/mole
In A, s 1
1.56
1.54
105.0
107.6
28.4
29.2
DSC studies revealed that the onset of the gel coat cure
process corresponds to the decomposition of the peroxide
initiator; according to these results, the reaction began at
about 75~ and ended just prior to 150~ The temperature
range (72 to 148~ selected for the kinetics evaluation using
DSC was based on FT-IR spectra. These results showed that
the reaction of styrene, and presumably its reaction with the
polyester, began and ended at similar temperatures in the
DSC and FT-IR. FT-IR reaction kinetics were based on the
disappearance of the styrene vinyl group (779 c m - i ) . While
both methods produced excellent results, the DSC results
were obtained in a single temperature sweep, while the FT-IR
results required significantly more experimental effort to produce and analyze. Results for gel coat cure by DSC, FT-IR,
and also DMA are covered in detail elsewhere [51,52].
RELATIVE MODULUS
RELATIVE DAMPING
E
REGION OF CURE
!
I
!
_c
-1()0
(~
1(30
300
200
(~
TEMPERATURE
FIG. 14-Generalized dynamic mechanical cure response,
glass transition r e g i o n - - b e t w e e n roughly - 8 0 and 20~ the relative modulus of the sample decreases until it reaches
a minimum. Between 50 and 180~ the coating is really a
low-viscosity liquid that has little measureable dynamic mechanical response. The only measurable mechanical response in this region is due to the substrate used in the experiment. As the temperature increases, cross-linking (or film
coalescence) begins and the relative modulus begins to rise.
When the reaction is complete, about 220~ in this example,
the development of mechanical properties reaches a plateau.
Cure studies by DMA can also help explain the interrelationship between cross-linker characteristics and the cure
process. Figure 15 shows the change in the rate and degree of
cure in relation to the reactive groups on melamine crosslinkers. As the imino ( - - N H ) concentration increases, the
rate and degree of cure both increase. At low imino levels, the
rate and degree of cure are low; beyond about 15% - - N H , the
rate of cure changes significantly, while the DOC appears to
reach an asymptotic limit.
INDUSTRIAL W A T E R B O R N E S Y S T E M
M E L A M I N E CURE
1.0
.,s. I ~
0.6
==
s, .s
=
0.4
ss~l~*rs
0.0
<r
s S
0.2
ps
I
0
I
8
I
10
I
15
I
20
I
25
I
30
FIG. 15-The relationship effects of cross-linker characteristics on the rate and degree of cure of a waterborne coating.
859
When the experimental objective is to make a quick comparison of the effects of formulation variables like crosslinker levels or catalyst levels, simple cure curves like these
offer an excellent way to make qualitative judgments about
the cure process. Sometimes, however, customers may dem a n d more than simple "faster/slower" or "more/less" comparisons. For example, a customer may want to know how
long the film formation process will take under a variety of
cure conditions different, often substantially different, from
those used in past experiments. In cases like these, models of
the film formation process are a valuable tool for predicting
the time required to complete the film formation process. The
virtue of modeling lies in its ability to provide a well of information from a relatively small database or, in this case, a few
film formation experiments.
The time-temperature superposition (TTS) approach,
while somewhat more demanding experimentally, is a far
more versatile method for characterizing the cure process
than individual cure scans. This approach uses a series of
isothermal cure curves (usually four) to determine the activation energy for the cross-linking process. Once the activation
energy is known, an Arrhenius model is used to predict relative rates of cure at different isothermal cure temperatures.
The curves shown in Fig. 16 illustrate portions of the storage
modulus curves typically used in TTS cure studies. These
curves were obtained for an epoxy-polyester powder cured at
four isothermal temperatures. The characteristic form of
these "cure" curves discloses several important aspects of the
cross-linking process, such as the time to gelation, the rapid
increase in relative modulus during cure, and a plateau region that marks the end of the cross-linking process.
From a processing perspective, the onset of the rise in
modulus about 3 min into the "bake" scan represents the
most important feature of the curve. The onset of the rise in
frequency in these curves approximates the time to gelation,
or the point where the polymer transforms from a viscous
liquid to an elastic gel; this point marks the processing limit
of the thermoset. Beyond this point, cross-link density increases, approaching a plateau which marks the end of the
cross-linking process. In Fig. 16, these powder coatings fail to
reach this plateau, even at the highest cure temperatures
and/or longest cure times. The continued rise in relative modulus indicates incomplete network formation, even after 100
min at temperatures as high as 210~ Longer cure times or
higher cure temperatures would eventually establish the endpoint of the cure process. The modest increase in relative
modulus at later cure times may be related to annealing
effects or some combination of cure and annealing. Generally, thermosets cured to the plateau will possess less damping, have higher Tg's, and are more brittle than thermosets
cured to a point below the plateau.
Degree of cure curves for powder coatings were obtained
from DMA data by measuring the increase in relative modulus (measured as a frequency increase here) occurring as
cross-linking proceeds. The DMA degree of cure was calculated from Eq 1 below. This equation allows the estimation of
the relative degree of cure between the gel point (0% DMA
DOC) and the fully cured thermoset (100% DMA DOC). In
these experiments, the gel point is defined by the initial rise in
the modulus curves. This point in the modulus curve marks
the formation of an intractable gel. Full cure is defined by the
860
DMA
EPOXY-POLYESTER
POWDER
COATING
4.0"
__.- 210~
_______--~--~
191~
~ 1 6 3 ~
"N 3 . 6 "I"
>O
150~
Z
IJJ
03.2UJ
n"
LI.
2.8
40
60
80
100
120
TIME (rain)
FIG. 1 6 - D y n a m i c mechanical cure response of an epoxy polyester powder coating at four
isothermal temperatures.
Hzmi
-
HZmi
(1)
different baking conditions. For example, in Fig. 18, simulated DMA degree of cure curves were generated at three bake
temperatures and compared with the DOC at minimum impact resistance. The time required to reach a minimum performance level varies considerably; at 150~ the coating fails
to reach the minimum DOC even after 90 min. At 177 and
204~ minimum DOC is reached after roughly 15 and 30
rain, respectively. Obtaining the same information by a conventional experimental approach would require a considerable amount of time and effort in the laboratory. Moreover,
techniques like the DMA TTS methods described here can
predict the time required to reach a specified level of performance for any isothermal cure schedule.
C O M B I N E D T E C H N I Q U E S IN P R O B L E M
SOLVING
Thermal techniques usually reserved for routine analysis
and characterization or research support are also useful for
solving problems that arise in process or production. Because
problems in manufacturing present unusual experimental
difficulties, solving them usually requires several methods for
adequate characterization. A solitary piece of evidence, whatever the quality, usually needs corroborating information
from other sources. Multiple techniques are particularly valuable in settling financial or legal claims where the need for
undisputable evidence becomes preeminent. In the example
described below [54], quality control tests in manufacturing
indicated that container coatings sprayed on the interior of
aluminum beverage cans were improperly cured, the cus-
861
POWDER COATING
210~
t . ~
100-
_.....-
80
191~
O
O
r
I.- 60
Z
LU
o
n,.
Q. 4 0 -
163~
20-
20
40
60
0
TIME ( m i n )
FIG. 1 7 A - E p o x y polyester powder coating degree of cure curves.
DMA M A S T E R C U R E CURV E
EPOXY-POLYESTER
POWDER
COATING
E=18.5
kcal/mole
100.......-,,--
8O
O
O
r
I'Z60
UJ
O
nUJ
I1. 4 0 '
1 9 1~
---~/~/
163~
210~
20-
150~
i
20
i
40
610
i
80
lOO
T I M E (rain) AT 1 9 1 ~
FIG. 1 7 B - E p o x y polyester powder coating DMA mastercurves for cure at 191~
and an activation energy of 18.5 kcal/mol,
862 P A I N T A N D C O A T I N G
TESTING MANUAL
oo
O 177~
o~,.
/ - -
15
30
45
60
75
90
(rain)
TIME
AT TEMPERATURE
FIG. 18-Predicted time to minimum acceptable impact resistance at three isothermal bake temperatures.
EXO
PRODUCTIONSTANDARD
At
REBAKEDPROBLEM
N
-80
O
0
~
80
~PROBLEM
160
240
TEMPERATURE ( ~
FIG. 19-Comparison of the DSC heat flow characteristics of a production standard, a
problem coating, and the rebaked problem coating (Aq = heat flow).
SUMMARY
Thermal analysis occupies a unique place in research and
development. In most instances, the utility of an analytical
technique is strictly limited by its output. For example, spectroscopic tools like NMR or IR tend to be viewed as standalone operations that provide a specified result. TA differs
from other analytical operations because the instruments
offer greater versatility. In fact, thermal analysis is generally
recognized as a broad technology encompassing many instruments and many more applications. Depending on the
need, the resuks delivered by TA can range from the straightforward, like Tg's, to the complex, like reaction kinetics parameters.
TA realizes its greatest value, however, when more than
one instrument is focused on a research or production problem. In combination, these instruments can provide tremendous insight into the relationship between formulation, processing, and the ultimate performance of material, often
clarifying hard-to-understand relationships [55]. When applied throughout the product development cycle, these instruments can reduce product development time, manufacturing costs, and, in the end, help shape the best possible
product.
Acknowledgment
Thanks are due to the many coworkers at Glidden for their
contributions to the work described in this paper. The author
is particularly indebted to Leo Tischer, Tony Parker, Mary
Logue, Tammy Chalmers, Sharon Chang, and Patti Wilson
for their diligence in obtaining much of the experimental data
described here and also to Richard Holsworth for his
thoughtful contributions to experimental design and the
analysis of the results over many years. In addition, Mark
Koehler, Ted Provder, Ted Niemann, and Ann Kah deserve
recognition for their pioneering efforts in the automation of
the DSC and DMA. Without the time savings acquired in data
acquisition and analysis made possible through their efforts,
much of this work would have been a practical impossibility.
Thanks also to Ann for redrawing many of the figures used in
support of the text. Finally, I'm indebted to Dr. Stephen
Cheng (University of Akron), Dr. Richard Chartoff (University of Dayton), Dr. David Kranbuehl (William & Mary), Dr.
Don Burlett (Goodyear), Dr. Charles Earnest (Berry College),
and Dr. Peter Kamarchik (PPG Industries) for their valuable
comments and insights on instrument operation and experimental detail.
863
REFERENCES
[1] Van Krevlan, D. W., Properties ~ Polymers, 3rd ed., Elsevier,
New York, 1990, p. 49.
[2] Wendlandt, W.W., Thermal Analysis, P.J. Elving and J.D.
Winefordner, Eds., John Wiley & Sons, New York, 1986.
[3] Compositional Analysis by Thermogravimetry, STP 997, C.M.
Earnest, Ed., American Society for Testing and Materials, Philadelphia, 1988.
[4] "Computer Applications in the Polymer Laboratory," T. Provder,
Ed., ACS Symposium Series 313, American Chemical Society,
Washington, DC, 1985.
[5] "Computer Applications in Applied Polymer Science," T.
Provder, Ed., ACS Symposium Series 404, American Chemical
Society, Washington, DC, 1988.
[6] Holsworth, R. M., Journal of Paint Technology, Vol. 41, 1969, p.
167.
[7] Wunderlich, B., Thermal Analysis, Academic Press, New York,
1990.
[8] Thermal Characterization of Polymeric Materials, 1st ed., E. A.
Turi, Ed., Academic Press, New York, 1981.
[9] Thermal Characterization of Polymeric Materials, 2nd ed., E. A.
Turi, Ed., Academic Press, New York, in press.
[10] Fox, T. G., Bulletin of the American Physics Society, Vol. 1, 1956,
p. 123.
[11] Johnston, N.W., Journal of Macromolecular Science-Revious
Macromolecular Chemistry, Vol. C14, No. 2, 1976, pp. 215-250.
[12] Cowie, J. M. G. and Toporowski, P. M., European Polymer Journal, Vol. 4, 1968, p. 621.
[13] Acitelli, M. A., Prime, R. B., and Sacher, E., Polymer, Vol. 12,
1971, p. 335.
[14] Widmann, G., Thermochimica Acta, Vol. 11, 1975, p. 331.
[15] Sourour, S. and Kamal, M. R., Thermochimica Acta, Vol. 14,
1976, p. 41.
[16] Borchardt, H. J. and Daniels, F., Journal of the American Chemical Society, Vol. 79, 1957, p. 41.
[17] Fava, R. A., Polymer, Vol. 9, 1968, p. 137.
[18] Kissenger, H. E., Analytic Chemistry, Vol. 29, 1957, p. 1702.
[19] Ozawa, T., Journal Thermal Analysis, Vol. 2, 1970, p. 301.
[20] Bamford, C. H. and Tipper, C. F. H., Comprehensive Chemical
Kinetics, Vol. 22, Elsevier, New York, 1980.
[21] Benoit, P. M. D., Ferrillo, R. G., and Granzow, J., Journal of
Thermal Analysis, Vol. 30, 1985, p. 869.
[22] Provder, T,, Holsworth, R. M., Grentzer, T., and Kline, S. A.,
"Polymer Characterization: Spectroscopic, Chromatographic
and Physical Instrumental Methods," C. Craver, Ed., "ACS Advances in Chemistry," No. 203, American Chemical Society,
Washington, DC, 1983, p. 234.
[23] Neag, C. M., Provder, T., and Holsworth, R. M., Journal of Therreal Analysis, Vol. 32, 1987, p. 1833.
[24] Nielsen, L. E., Mechanical Properties of Polymers, 2nd ed., Dekker, New York, 1974.
[25] Nielsen, L. E., Mechanical Properties of Polymers, 2nd ed., Dekker, New York, 1974.
[26] Ward, I. M., Mechanical Properties of Solid Polymers, 2nd ed.,
Wiley, New York, 1983.
[27] McCrum, N. G., Read, B. E., and Williams, G., Anelastic and
Dielectric Effects in Polymeric Solids', John Wiley & Sons, London, 1967.
[28] Ferry, J. D., Viscoelastic Properties of Polymers, 2nd ed., Wiley,
New York, 1980.
[29] Chartoff, R. P., Weissman, P. T., and Sircar, A. K. inAssignment
of the Glass Transition, STP 1249, R.J. Seyler, Ed., ASTM,
Philadelphia, 1994, p. 88.
[30] Williams, M. L., Landel, R. F., and Ferry, J. D. in Journal of the
American Chemical Society, Vol. 77, 1955, p. 3701.
[31] Hill, L. W. inJournalofCoatings Technology, Vol. 64, 1992, p. 28.
864
[37] Earnest, C. M., "Assignment of the Glass Transition Using Thermal Mechanical Methods," Assignment of the Glass Transition,
ASTM STP 1249, American Society for Testing and Materials,
Philadelphia, 1994, p. 75.
[47] Neag, C. M., Ibar, J. P., and Denning, P., Journal Coatings Technology, Vol. 65, No. 826, pp. 37-42.
[48] Kumins, C. A., Knauss, C. J., and Ruch, R. J., Journal of Coatings Technology, Vol. 66, No. 835, pp. 79-84.
[49] Saunders, K. J., Organic Polymer Chemistry, Chapman and Hall,
Ltd., London, 1973, Chapter 10.
[38] Skrovanek, D. J. and Schoff, C. K., "Thermal Mechanical Analysis of Organic Coatings," Progress in Organic Coatings, Vol. 16,
[51] Provder, T., Neag, C.M., Carlson, G.M., Kuo, C., and
Holsworth, R. M., Analytical Calorimetry, Vol. 5, P. S. Gill and R.
[52] Neag, C. M., Carlson, G. M., Provder, T., Kuo, C., and Eley,
R. R., ACS Preprints, Polymer Materials Science and Engineering,
Vol. 49, 1983, p. 404.
[54] Neag, C. M. and Holsworth, R. M., American Laboratory, January 1986, pp. 48-54.
[56] For Better Thermal Analysis, J. Hill, Ed., 3rd ed., ISTAC, 1991.
MNL17-EB/Jun. 1995
Ultraviolet/Visible
Spectroscopy
by George D. Mills ~
865
Copyright9 1995 by ASTMInternational
www.astm.org
866
P A I N T A N D COATING T E S T I N G M A N U A L
ELECTROMAGNETICRADIATION
Electromagnetic radiation is a form of energy that possesses both wave-like characteristics and particle-like characteristics. The wave-like nature allows the radiation to travel at
extremely fast velocities and to be refracted. Unlike sound,
this energy form may be transmitted through the vacuum of
space without a supporting medium. As a particle, when
radiation interacts with matter, it is absorbed in discrete
packets of energy called photons. The radiation is composed
an electrical field of oscillating field strength superimposed
on an oscillating magnetic field at right angles to one another.
If the vectorial values for the electrical and magnetic field
strength are plotted as a function of distance from the moving
point charge that is generating the EMR, the graphical presentation in Fig. 1 is obtained. In this plot, the magnetic field
strength, I~I,is represented as a vector in the xz plane, and the
overlapping plot of the electric field strength, 1~, is presented
as a vector in the xy plane. The direction of propagation is
down the x axis. This represents the plot of a plane polarized
wave. If all waves coming from a collection of similar radiators are in the same spacial orientation, we call the radiation
plane polarized light. In nature, radiation coming from a collection of point sources will usually be randomly oriented and
therefore will not be polarized. It is useful to note that when a
beam of polarized light passes through a collection of absorbing species that has at least one area of asymmetry, polarized
light will be rotated to some degree. This principle is used to
obtain information about the shapes of particular molecules
and quickly gather information on their concentration.
The wavelength, ),, is usually expressed in units of centimeters, microns, millimicrons, or angstroms. The frequency
the oscillations, v, is the number of cycles that occur in 1 s
and is therefore equal to the speed of the radiation divided by
the wavelength.
of
of
v = c/X
(1)
of
~=
of
BASIC INSTRUMENTATION
The basic optical path or layout of modern scanning instruments has not changed appreciably over the past decade or
two. The optical diagram of a modern instrument is presented in Fig. 3. Low-cost computers for doing sophisticated
calculations and better diffraction gratings have allowed important enhancements. Increased electronic noise suppression has allowed lower cost-to-benefit ratios in the newer
instruments. Software now provides full instrument control,
enhanced data analysis including rapid graphics, and considerable options in report generation. Three-dimensional plotting enables easy representation of reaction mixtures, allowing kinetics studies of active systems. While following the
(2)
1/x
wavelength, ;~, cm
10'0 10~ 10~ 10~ 10.2 1
ELECTROMAGNETIC
RADIATION
I| ~
Y
I
'~"
~ ~ f -
!0
cycles/sec
Directionof
L----~P"-~OPxagation
Ii,
~.~
,-
visable region
~-
FILTERWHEEL
DOUBLE
SOURCEMIRROR "
r REFERENCEBEAM
CHOPPER
MIRRO~~
~..~/
DETECTOR
920: PHOTOMULTIPLIERTUBE
\,.t
L SAMPLEBEAM
Calibration of Instruments
The calibration of instruments having absorptions in the
UV/VIS/NIR wavelengths may follow ASTM Practice for Describing and Measuring Performance of Ultraviolet, Visible,
and Near Infrared Spectrophotometers (E 275) [3]. Here, a
mercury arc provides twelve very unique peaks having extremely precise wavelengths for comparison with the values
reported by the instrument. Figure 6 presents the mercury
arc emission spectrum in the UVNIS region showing the
reference wavelengths.
Another useful standard that provides established specific
reference peaks is holmium glass (Coming No. 3130). This
standard has the advantage over the mercury arc in that it
may be conveniently placed within the instrument with minim u m problems. That spectrum is presented as Fig. 7.
SPECTRAL INTERPRETATION:
QUALITATIVE AND QUANTITATIVE
INTERPRETATION OF SPECTRA
The output of the UV/VIS spectroscopy instrument will
usually be a plot of absorbance versus wavelength and is
called the absorption spectrum. Absorption of the UVNIS
radiation usually occurs when an electron within the active
specie absorbs the energy of a photon. The molecular conse-
ENERGY SLIT
DISPERSER i
~ I
I OUTPUT I
DEVICE
SOURCE
MONOCHROMATOR
SAMPLE
CELL
DETECTOR
868
PAINT AND
COATING
TESTING
MANUAL
ENERGY
I ~ [
I OUTPUT
DEVICE
SOURCE
SAMPLE
CELL
MULTIPLE
DIODE
DETECTORS
FIG. 5 - C o m p o n e n t arrangement of the modern UV/VIS instrument using a diode array detector.
dP/P = - k dN
rl
tY
,r162
IJJ
Z
m
,,J
(3)
-kPAN
, I
,,ll,2
O
Z
>O9
Z
UJ
I-Z
m
110
200
250
300
350
400
450
500
550
WAVELENGTH,
600
nm
bne Number
Wavelength, nm
Line Number
Wavelength, nm
Line Number
Wavelength, nm
Line Number
Wavelength, nm
1
2
3
253.65
296.73
302.15
4
5
6
313.16
334.15
365.01
7
8
9
404.66
407.78
435.84
10
11
12
546.07
576.96
579.07
FIG. 6 - T h e mercury arc emission spectrum in the UV/VIS region with the corresponding reference wavelengths (from
A S T M E 275).
CHAPTER
2.0Ik~
1.5
1.0
0.5
0.21--
r,*
0
tn
m
I
4
76--ULTRAVIOLET/VISIBLE
SPECTROSCOPY
I
550
I
600
I
650
869
12
~ /
14
13
O'I t
0
250
I
300
350
I
500
400
450
WAVELENGTH, nm
Band Number
Wavelength, nm
Band Number
Wavelength, nm
Band Number
Wavelength,nm
Band Number
Wavelength,nm
3
4
5
279.4
287.5
333.7
7
8
9
360.9
385.9
418.7
10
12
13
453.2
460.0
484.5
14
15
5362
637.5
FIG. 7-Spectrum of holmium glass (Coming No. 3130) showing reference wavelengths (from ASTM E
P0
In (P/Po) = - k N
(6)
(7)
w h e r e c is c o n c e n t r a t i o n in m o l e s p e r liter, b is the p a t h
length in centimeters, a n d s is the cross-sectional a r e a in
square centimeters. W h e n the constants are combined, this
yields
log (P/Po) = e b c = A (the a b s o r b a n c e )
(8)
(9)
where
A
a
b
c
=
=
=
=
275).
POTENTIAL
PROBLEMS
870
REFERENCES
[1] Bower, D. R., "Chemical Criteria for Durable Automotive
Topcoats," Journal of Coatings Technology, Vol. 66, No. 835, 1994,
pp. 5-65.
[2] Cazaux, F., Coqueret, X., Lignot, B., Loucheux, C., Rousseau, P.
Flat, J. J., Leroux, S., and Verge, C., "Epoxidized Polybutadiene: A
Novel Prepolymer for Cationically UV-Curable Coatings," Journal
of Coatings Technology, Vol. 66, No. 838, 1994, pp. 2-34.
[3] AnnualBook of ASTM Standards, Vol. 14.01, American Society for
Testing and Materials, Philadelphia, 1993.
[4] Robinson, J. W., Ed., Practical Handbook of Spectroscopy, CRC
Press, Boca Raton, FL, 1991.
MNL17-EB/Jun. 1995
X-Ray Analysis
by A. Monroe Snider, Jr. 1
X-RAY DIFFRACTION(XRD) and X-ray fluorescence spectrometry (XRFS) are powerful, well-established tools used by analytical chemists in many areas of technology. They have great
utility in the coatings industry. In areas where they are applicable, they are frequently the quickest and easiest technique
available. XRD is convenient for the identification of diverse
crystalline solids encountered in paint research laboratories
and production plants. It is particularly well suited for use in
the identification and quantitative analysis of crystalline pigments and extenders, either when they are alone or present in
paste or paint. XRFS is useful as a stand-alone technique for
elemental analysis and as a complementary tool for use with
other analytical techniques. X-ray spectrometers typically
can analyze all elements with an atomic number of about 11
(sodium) and higher, but some units can reach as low as
atomic number 5 (boron). XRFS can span the concentration
range from parts per million to high percentages for most
elements in liquid or solid samples. Dedicated XRFS units,
much lower in cost than scanning spectrometers, can be set
up to detect and quantify one or a few specific elements.
Portable XRFS units are available for field investigations. The
present section summarizes the principles and methodology
of XRD and XRFS.
X-RAY D I F F R A C T I O N
Application
Types of Samples
X-ray diffraction is widely used for the analysis of analytes
that are crystalline or polycrystalline solids, i.e., solids comprised of atoms or ions arranged in a three-dimensional lattice pattern [2]. The sample may be totally crystalline or may
contain one or more crystalline components interspersed
with noncrystalline material. Common types of materials
analyzed include pigments and extenders (alone, in grind
pastes, in liquid paints, or in dried paint chips), miscellaneous crystalline solids, and pretreatment on metal. X-ray
diffraction also has important uses in the study of amorphous
materials such as polymers and inorganic glasses [2]. In the
case of scanning X-ray diffractometers, a flat surface of the
specimen must be presented to the X-ray beam.
X-ray diffraction analysis permits qualitative and quantitative analysis of crystalline components. It can indicate the
degree of crystallinity, crystallite orientation, and long-range
order in polymers. Long-range order in liquids has also been
studied [2].
Range of Concentrations
As a rule, crystalline components can be analyzed by routine methods at concentrations ranging from 100% down to
approximately 1 or 2%. However, the limit of detection varies
widely with the identity of the analyte of interest, the number
and identity of other components, the quality of the instrumentation used for analysis, and the instrument operating
conditions. Analysis of components at concentrations as low
as 0.01% has been reported [3].
Physical Principles
X-ray diffraction experiments are performed by irradiating
a specimen of crystalline or polycrystalline material with a
beam of X-rays of known wavelength and determining the
angle 20 between the incident beam and each diffracted beam
of X-rays and measuring the intensity of each diffracted
871
Copyright9 1995 by ASTM International
www.astm.org
872
where
n = a positive integer (usually one),
)~ = the wavelength of the X-rays used,
d = the distance between layers of atoms of a set of lattice
planes, and
0 = the angle between the incident X-ray beam and the
lattice plane [5].
The wavelength of the X-rays is determined by the choice of
the X-ray tube target material, usually copper, and is thus
known. The wavelength of copper K s radiation, the principal
component of X-rays from a copper target, is 1.541 78 ,~. It is
common practice to use a crystal monochromator or absorption filter to prevent unwanted wavelengths of X-rays from
contributing to the diffraction pattern. Angle 0 is half of the
diffraction angle 20 that is determined experimentally. The
distance between layers of atoms in a set can be calculated by
using the Bragg equation. The distance, d, is determined by
the diameter of atoms comprising the crystal, the three-dimensional arrangement of the atoms in the crystal, and the
set of lattice planes in the crystal that produced the "reflection" of X-rays. Thus, crystallites of different compounds or
different crystal modifications of a single compound will give
different sets of d-spacings. Each crystalline phase will produce a unique X-ray diffraction pattern that can be used as a
"fingerprint" for identification. Detailed discussions of the
Bragg equation and the physical basis of X-ray diffraction are
available in various treatises on X-ray diffraction, such as the
classic work by Klug and Alexander [2].
Analysis by X-ray diffraction requires that a specimen be
placed in the primary beam of a diffractometer and the diffraction angle and the intensity of each diffracted beam be
measured. Diffractometers use either an electronic detector
or photographic film to indicate the position of the diffracted
beams of X-rays. Most diffraction units in industrial laboratories today use an electronic detector, usually a proportional
counter. Figure 1 is a simplified diagram of a diffractometer.
Here, the specimen is placed in a holder at the center of a
goniometer system. A receiving slit and detector slowly sweep
around an arc at a fixed distance from the center of the
goniometer, facilitating determination of the intensity of Xrays scattered at each angle, 20, on the arc. While the detector
moves through angle 20, the specimen rotates about the same
axis through angle 0. A plot of the intensity of scattered
radiation as a function of 20, a diffractogram or diffraction
pattern, is thus produced. Figure 2 shows the diffraction
pattern of the rutile form of titanium dioxide.
A relatively new variation of the electronic detector is the
position-sensitive detector (PSD) that uses an arc-shaped
solid state detector to sense both the position and intensity of
the diffracted radiation [6, 7]. The PSD is stationary during
data collection, but may be moved to different locations on
the goniometer circle, as required, so that its surface can
intercept X-rays at all 20 positions of interest. Compared to a
conventional scanning unit, a PSD can markedly shorten the
time required to collect data.
The oldest method for collection of diffraction patterns,
photographic, is still useful today, with the Debye-Sherrer
X-ray
Tu be
"
Slits"" . , x-,/ ~( / / D e t e c t o r
/ ~ -
l'S,,ts
9
Specimen
~.,~'
Experimental Procedure
Specimen Preparation
Specimens for X-ray diffraction can be any crystalline containing solid that can be mounted to permit collection of a
diffraction pattern. For scanning diffraction units, the surface of the specimen should be flat and must be positioned in
the focal plane of the instrument's X-ray optical system. The
latter requirement can be met by mounting the specimen
with its surface flush with the face of the specimen holder
designed for the instrument. Failure to do so causes a systematic error in the observed 20 angle and d-spacing of all peaks
in the diffraction pattern. Figure 5 shows a photograph of
specimen holders used in some commercial X-ray diffractometers.
Common types of samples encountered in the coatings
industry and the recommended modes of mounting them in a
scanning diffractometer are summarized in Table 1.
A Debye-Sherrer camera is useful for analysis in cases
where there is too little sample for analysis using a conventional scanning diffraction unit. For small amounts of powder, the specimen is prepared by loading the powder into a
thin-walled glass capillary or by mixing the powder with
noncrystalline glue and rolling the mixture to form a filament. The capillary or filament after hardening is mounted in
the center of the camera on a motor-driven rotating stub.
Rotation presents a more nearly random orientation of crystallites to the incident X-ray beam. A single small chip or
crystal may be analyzed by attaching it by glue to the end of a
CHAPTER 7 7 - - X - R A Y A N A L Y S I S
N
B
40
~5
20
;25
30
35
40
e~
45
873
.z,:
50
55
60
65
TWO THETA
FIG. 2-X-ray diffraction pattern of futile TiO2 with the peaks labeled with the d-spacing of the corresponding sets of crystallographic planes.
FIG. 3-Debye-Sherrer camera with the front cover removed displayed with a
developed X-ray film.
thin films of crystalline coating or contaminant on fiat surfaces [8,9]. They also give better results than conventional
diffractometers when only a small amount of powder is available. Thin film units operate exactly as conventional scanning
diffractometers except the surface of the specimen is irradiated with X-rays at a fixed but selectable grazing angle. In
comparison to conventional X-ray diffraction analysis, this
approach reduces the depth of penetration of the X-ray into
FIG. 4-Debye-Sherrer film with diffraction pattern of rutile TiO2. The d-spacings of selected diffraction arcs are marked for
comparison with peaks shown in Fig. 2.
874
FIG. 5-Specimen holders for three common commercial X-ray diffractometers, each with a different
type of specimen: (left) powder in a depression, (center) powder sprinkled on petroleum jelly smeared on a
zero background quartz plate, and (right) disk cut from
a drawdown of paint.
Sample
Method of Mounting
Powder
O p e r a t i n g conditions should be b a s e d u p o n r e c o m m e n d a tions of the m a n u f a c t u r e r of the X-ray diffraction unit, req u i r e m e n t s of the analytical m e t h o d being used, a n d
practical l a b o r a t o r y considerations. As a general rule, X-ray
t u b e s w i t h c o p p e r targets are c o m m o n l y o p e r a t e d with a
potential of a b o u t 40 to 45 kV and a filament c u r r e n t of a b o u t
35 to 45 mA. If o t h e r factors are held constant, t h e n h i g h e r
p o w e r settings can be used to s h o r t e n analysis time, lower the
limit of detection, a n d i m p r o v e signal-to-noise ratio, b u t at
the expense of s h o r t e n e d tube life. F o r routine, general-purpose analysis by scanning X-ray diffraction units, the comm o n choice for slits u s e d to define the d i m e n s i o n s of the Xr a y b e a m illuminating the s p e c i m e n a n d reaching the detect o r are as follows: 0.15 ~ for the receiving slit a n d 1.0 ~ for all
o t h e r slits. If o t h e r factors are held constant, then larger slits
can be used to s h o r t e n analysis time, lower the limit of detection, a n d i m p r o v e signal-to-noise ratio, b u t at the expense of
r e d u c e d ability to resolve closely spaced peaks. Conversely,
s m a l l e r angle slits should be u s e d if h i g h e r resolution is
required. F o r analysis of u n f a m i l i a r paints, pigments, a n d
o t h e r materials, diffraction p a t t e r n s should be collected over
a range scanning at least from 5 to 65 ~ 20. Use of a s h o r t e r
scan range m a y cause the o m i s s i o n of i m p o r t a n t diffraction
peaks. However, scans s p a n n i n g a n a r r o w 20 range m a y be
satisfactory for r o u t i n e tests b a s e d on peaks located within a
chosen p o r t i o n of the diffraction pattern. F o r r o u t i n e qualitative and semiquantitative analysis, satisfactory results can be
achieved with m o s t step scanning i n s t r u m e n t s b y progressing
in steps of 0.02 ~ 20, with 1.0 to 1.2 s p e r step. L o n g e r count
t i m e m a y be required for quantitative analysis. I n the case of
older diffractometers with analog scanning motors, a scan
rate of l~
is satisfactory for r o u t i n e qualitative a n d semiquantitative analysis.
Qualitative Analysis
Interpretation of X-ray Diffraction Patterns
Preparation of d-Spacing Intensity Table--After the X-ray
diffraction p a t t e r n of a test s a m p l e is recorded, the analyst
m u s t o b t a i n a list of all diffraction peaks with t h e i r d-spacing
a n d relative intensity. The peaks should be listed in descending o r d e r of d-spacing. The intensity is expressed as a percentage of the strongest peak, taken as 100. If the X-ray unit lacks
d a t a processing capability, then the analyst m u s t r e a d the 20
of each p e a k from the p a t t e r n a n d calculate the d-spacings
from the 20 values of the peaks using the Bragg equation.
Likewise, the height of each p e a k m u s t be m e a s u r e d by h a n d
a n d the relative intensity d e t e r m i n e d . However, d-spacingintensity tables can be o b t a i n e d a u t o m a t i c a l l y from diffraction units e q u i p p e d with even the m o s t basic c o m p u t e r capabilities.
General Comments--Identification of pigments, extenders,
a n d o t h e r crystalline phases by X-ray diffraction is a c c o m plished by m a t c h i n g the peaks of the diffraction p a t t e r n of a
s a m p l e u n d e r analysis with the sets of diffraction peaks
exhibited by reference s a m p l e s of k n o w n c o m p o s i t i o n
[2,10,11]. X-ray diffraction provides no c h e m i c a l i n f o r m a t i o n
a b o u t a test s a m p l e o t h e r t h a n the identification of each corn-
CHAPTER 7 7 - - X - R A Y A N A L Y S I S
ponent that is achieved when a full match of its set of peaks is
found. Either manual or computer-assisted searches can be
done. Manual methods rely on the numerical comparison of
d-spacings and intensities of diffraction peaks. Recent computer search methods also begin by matching the d-spacings
of peaks, but rely in part on the analyst to do visual matching
of peaks on a video screen.
Several instrument manufacturers and after-market suppliers offer computerized search-match programs. Operated
on personal computers, these programs use diffraction data
files stored on compact disk or magnetic medium. The data
files are available from the International Centre for Diffraction Data (ICDD), formerly known as the Joint Committee for
Powder Diffraction Standards (JCPDS) [12]. Use of these
computer programs and data files can greatly speed qualitative analysis [13].
Manual Search Procedures--Diffractionists who are experienced in the analysis of paints, but who do not have
computerized search-match facilities, usually employ a qualitative analysis procedure that has the two following steps.
First, the diffraction pattern is inspected for the presence of
sets of peaks that are characteristic of commonly used pigments and extenders, or other phases suspected of being
present. Sets of peaks found in the pattern that are suspected
of resulting from common components are compared to the
peaks on reference diffraction patterns. The comparison may
be done directly by comparing diffraction patterns or indirectly by comparing the d-spacings and relative intensities
calculated from reference patterns. Partial or even complete
identification of components may be achieved by this procedure. Second, peaks that were not identified by the first approach are subjected to a systematic search using compilations of X-ray diffraction data, such as the Powder
Diffraction File from ICDD. The first approach is most useful
when the analyst, because of information available from
other sources such as elemental analysis, the appearance,
knowledge of the intended use of the paint, or experience,
suspects the presence of certain crystalline components.
Figure 6 shows the X-ray diffraction patterns of several
common paint pigments. For brevity, the term pigment will
be used to mean both pigments and extenders. The pigments
are readily distinguished from each other and from all other
crystalline material by the positions of the peaks on the 20
scale and by the relative intensities of the peaks. Since the
diffraction pattern of each crystalline phase is unique, it may
be used as a "fingerprint" for identification. The patterns in
Fig. 6 were collected under identical conditions from powder
specimens. Although some pigments originally gave patterns
with greater peak heights, they are all plotted to about full
scale for convenience.
Figure 7 shows diffraction patterns of dried paint films of
two test paints of known composition. Each crystalline component in the paint film contributes its own set of peaks to the
pattern, with the position and relative intensity unaltered by
the other components. Resin and other noncrystalline components produce only a broad, weak h u m p in the baseline.
Some crystalline components of the two paints represented
by Fig. 7 can be identified by comparison with the diffractograms of individual pigments in Fig. 6.
Table 2 lists 37 pigments and extenders commonly used in
paint, with the d-spacings and relative intensities of their five
875
QUARTZ
>p-
is.
~o.
~B.
zo.
aB.
so.
TWO
ses.
4o.
4B.
Bo.
eses.
Iso.
Ises.
THETA
FIG. 6-X-ray diffraction patterns of several c o m m o n pigments and extenders run as powder.
876
R
Y
T
Z
RUTILE. 28X
YELLOW IRON OXIDE,
TALC, 24%
ZINC OXIDE. 20%
28X
1750
S
E
C
1150
R
R +
+ Y
YT
YY
+/~
Z
~
Y
+
+R
~+
SSO
!
4gs0
CC
C 3gs0
RUTILE,
CALCITE,
CC -
S 2950
35%
30X
CHINA CLAY,
28%
CC R
1950
II
II
I
15.00
25.00
A
I
35.00
oR
c
I
45.00
+
I
55.00
65.00
2 THETA
FIG. 7-X-ray diffraction patterns of drawdowns of two paints with the principal peaks of the
constituent pigments labeled.
nent, then the analysts should note the ICDD file number
listed for the phase in the last column. The file number may
then be used to locate the full set of diffraction data provided
by ICDD (and JCPDS) compilations. Using the ICDD data, all
peaks attributed to the identified component may be marked
on the pattern of the test sample. The identification process is
then repeated with unassigned peaks in the pattern, working
progressively from the peaks with the highest d-spacing, particularly the strongest ones, to the peaks with low d-spacing.
In an alternative use of Table 2, the analyst searches the list
for crystalline phases that he suspects may be present in the
test sample. If the strongest peaks listed in Table 2 for the
suspected component are present in the diffraction pattern of
the test sample, then the analyst notes the ICDD file number
and proceeds as described in the previous paragraph.
The printed Alphabetical Index & Search Manual and its
computer compact disk counterparts from ICDD provide an
alphabetical listing by name of a large collection of crystalline
phases, their formula, the d-spacing and relative intensity of
the three strongest peaks, and their ICDD file number. These
references are an extremely useful starting point in peak identification when the analyst knows or suspects the presence of
certain phases in the test sample. If the three strongest peaks
of a candidate are found in the pattern of a test sample, then
the analyst should use the ICDD file number to locate the full
set of diffraction data on the compact disk or in the equivalent printed volumes. For positive identification, all peaks
listed for the candidate in the full data set must be present
with appropriate intensity in the test pattern. However, the
weaker peaks of a low-concentration component may be unobservable.
Peaks that remain unassigned after the information in Table 2 and the alphabetical files has been used must be
identified by using the ICDD Powder Diffraction Files and
either the Hanawalt or Fink search methods, or other search
system. The Hanawah method is based on the three strongest
peaks in the diffraction pattern. The Fink method is based on
the eight strongest diffraction peaks of each phase without
use of intensity information. The Fink index lists each phase
eight times with a cyclic permutation of the eight peaks.
Instructions in the Hanawalt and Fink search manuals
should be studied carefully before attempting to use either
method [12]. Although still used in many laboratories, sale of
Fink search manuals has been discontinued.
Computer-Assisted Searches--Analysts using computer
programs for qualitative analysis must rely on instruction
from the program supplier. In general, computer search routines provide a list of crystalline phases that have peaks that
match, or approximately match, the 20 positions of the peaks
of the test sample. Unfortunately, since more than one phase,
perhaps many, may have peaks at the same 20 position as the
test sample, a search-match program may suggest phases
that are not actually present. "False hits" are especially
common when the diffraction pattern of the test sample is
complex. Recent computer search routines provide the
opportunity for the analyst to include information about
elemental content of the sample and a variety of additional
physical and chemical data to exclude implausible candidates. They also permit the analyst to adjust the d-spacing
range spanning each test sample peak to account for possible
error in the d-spacings of test sample and reference data. The
analyst can widen the d-spacing "search window" to reduce
the possibility of missing a component of the test sample or
877
9.05
4.499
Name
9.34x
4.669
7.63x
7.36x
7.3 lx
7.17x
4.568x
4.18.
4.040
3.52x
3.445x
3.39x
3.38x
3.342,
3.310x
3.28x
3.260~
4.283
4.565
4.575
4.3666
9.126
2.694
3.1361
2.3702
3.3197
6.322
2.9035
4.2572
3.1298
4.963
9.796
4.498
3.666
3.116x
3.0658
3.668
3.657
4.1865
4.4102
2.455
2.8411
1.8924
3.103x
2.9868
2.7875
2.4571
2.9269
4.383
5.7712
3.584
3.36.
2.4767
2.8735
2.4517
2.273
3.5798
3.4603
2.192
2.4871
1.7002
2.1218
2.8404
2.6323
1.8181
1.91038
3.486
4,2512
1.5046
2.5659
1.8704
2.6854
1.5317
1.5355
2.4955
2,853v
2.4860
1.6672
2.106 s
2.2692
1.7553
1.5421
1.76425
3.037
3.1305
3.260x
3.247x
3.22x
3.160x
3.142 x
3.030
2.886x
2.700~
2.666x
2.623x
3.452s
2.4875
4.893
3.5838
4.5712
3.8523
2.1923
3.6843
3.6338
4.476
3.0066
2.1883
4.723
3.3676
3.4943
2.2842
2.0152
2.5197
2.480 x
4.256
2,5436
1.6876
3.12x
2.0686
3.1742
2.0943
1.8042
1.84064
2.1764
3.619
2.3085
1.6242
2.6682
1.7615
3.1188
1.87263
1.7863
1.69415
1.6729
3.299
1.722
2.609x
7.029
3.319
3.089
2.5503~
2.87663
2.38467
1.63614
2.8967
1.43764
2.543.
2.532,
2.476,
2.443,
2.9844
2.9673
2.8146
2.8647
2,1092
2.09932
2.6034
2.0262
1.6243
1.61583
1.6253
1.56024
1.4914
1.48454
1.4773
1.4244
2.338.
2.091x
2.0245
2.4735
1.4312
2.3084
1.2212
1.6873
0.92891
1.3423
bentoniteb
micab
talcb
gypsum
chrysotile-20rcl
chrysotile-2Mcl
kaoliniteb
zinc phosphate b
yellow iron oxide
crystobalite
anatase
barium sulfate
chrome orange
red lead
quartz
zinc sulfide
lead chromate
lead oxide sulfate
hydrate
strontium chromate
rutile
moly orange
cadmium yellow
antimony oxide
calcite
dolomite
red iron oxide
chrome oxide green
lead carbonate
hydroxide
zinc yellow
copper chromium
oxide
tan iron oxide
black iron oxide
zinc oxide
cobalt aluminum
oxide
aluminum metalb
zinc metalb
Formula
Nao.3(A1Mg)2Si4010(OH)2.H20
KAlaSi3A1010(OH)2
MgaSi4010(OH)2
CASO4.2H20
Mg3SiEOs(OH)
4
Mg3Si2Os(OH)4
A12Si2Os(OH)4
Zn3(PO4)2.H2
O
FeO(OH)
SiO2
TiO2
BaSO 4
Pb2(OH)2CrO4
Pb304
SiO2
ZnS
PbCrO4
Pb403SO4.H20
SrCrO4
TiO2
Pb(Cr19Mo11)O
4
CdS
Sb203
CaCO 3
CaMg(CO3) 2
ICDD
File No.
12-219
7-25
13-558
33-311
25-645
31-808
14-164
37-465
29-713
39-1425
21-1272
24-1035
8-437
8-19
33-1161
36-1450
8-209
29-781
Cr203
Pb3(CO3)2(OH)2
15-356
21-1276
19-685
6-314
11-689
24-27
11-78
33-664
6-504
13-131
K2Zn4(CrO4)2.3H20
CuCr204
8-202
34-424
ZnFe204
Fe304
ZnO
CoAl204
22-1012
19-629
36-1451
10-458
Fe203
A1
Zn
4-787
4-831
~Subscripts represent the relative intensity (rounded to the nearest integer) of the diffraction peaks of a phase with the most intense peak taken as 10 and
represented by "x."
bparticles of this material frequently exhibit preferred orientation in paint films, thus causing the observed relative intensities to differ significantly from
intensities listed in this table.
878
crystalline phases producing a complex pattern and diffraction is the only technique being used for analysis. Examples
of potentially confusing coincidences or near coincidences
are the strongest peaks of red lead, quartz, and zinc sulfide,
with d-spacings of 3.38, 3.34, and 3.31 A, respectively, a secondary peak of barytes at 3.319 A, and a strong peak of mica
at 3.36 A. The 3.247 A peak of rutile may conceal the 3.260
peak of strontium chromate. The 3.446 peak of barytes may
conceal the 3.452 P, peak of strontium chromate. Many other
similar peaks can be found for common pigments in Table 2.
Third, low concentration components may be overlooked,
especially if they scatter X-rays weakly or if their strongest
peaks are overlapped by major components. For example,
small amounts of zinc oxide may be overlooked if its strongest peak at 2.476 A is overlapped by a peak of rutile at 2.487
/~ or talc at 2.476 A, particularly when the latter phases are
major components. Fourth, the relative intensity of peaks in
the pattern of certain phases may differ significantly depending on their history, the degree of preferred orientation of the
particles, the specimen preparation techniques, and the instrument used to collect the pattern. Anomalies especially
arise from pigments that consist of platelet or acicular particles that exhibit preferred orientation and from clays that
have been changed by chemical, thermal, or mechanical processing.
The speed and reliability of analyses can be greatly improved if information is available about what elements and
functional groups are present in the sample. X-ray fluorescence and optical emission spectroscopy are convenient techniques for qualitative elemental analysis. Plasma emission,
atomic fluorescence, and atomic absorption spectrometry
can also be used for elemental analysis. Infrared spectroscopy can provide functional group information and, through
spectral matching, may provide independent corroboration
of pigment identification. Elemental analysis data are particularly useful in detecting and identifying crystalline components that are present at low concentrations. Elemental
analysis and infrared spectroscopy results are useful for identifying noncrystalline pigments.
Quantitative Analysis
Theory o f Quantitation
Quantitative analysis by X-ray diffraction is based on the
principle that the intensity of a diffraction pattern of a crystalline substance is directly proportional to the concentration
of that substance in the sample. This relationship and several
complicating factors are discussed in detail by Klug and
Alexander [2]. The intensity of X-rays diffracted from a given
set of crystallographic planes in component i in a mixture is
given by the equation
I~ = K~f~/I.~
where
I~ = the intensity of diffracted X-rays,
K~ = a constant that depends on both the nature of component i and the characteristics of the apparatus,
f~ = the volume fraction of component i, and
/z = the absorption coefficient of the mixture.
Since the absolute intensity Ii is influenced by the composition of the matrix, the absolute concentration of an analyte
cannot be determined unless a calibration curve is established with an internal standard.
However, using the "matrix flushing" method described by
Chung, the relative concentration of crystalline components
in a mixture can be determined without knowledge of the
absorption coefficient [14,15]. This approach is based on the
fact that all components under analysis are in the same matrix and thus are equally influenced by X-ray absorption. The
intensity of X-rays diffracted from a component i is given by
the equation
1i = kiXi
where
ki = a constant that depends on component i and the
apparatus, and
X i = the mole fraction of component i.
The ratio of the intensity of X-rays diffracted from two components i and R is given by the equation
li -- ki S i
IR kRXR
where
kR 1R
by measuring the intensity of X-rays diffracted from two crystalline components i and R in a 1:1 binary mixture. Peak
area, rather than height, should be used to represent intensity
since the former is less influenced by differences in particlesize distribution. Quantitative analysis of a multicomponent
mixture requires that the identity of all components be
known. One component is arbitrarily chosen as an internal
reference, R. Binary I : I by weight mixtures are prepared
with the reference component and each of the other components. The intensity ratio Ig/IR of a peak, usually the strongest,
of each component is then measured. The ratio of the intensities of the diffraction peaks defines the ki/kR of each pair of
components. The ratio k i / k n is called a reference intensity
ratio or RIR [16-20]. Corundum, the most commonly used
reference material, is the basis of all RIR values given in
ICDD Powder Diffraction Files. Davis, Smith, and coworkers
published RIR values for some common materials, including
several that are used as pigments or extenders in paint
[20,21]. Published reference intensity ratios must be used
with care since material other than corundum may have been
used as the reference and intensity may have been measured
as peak height instead of area.
Example:
The diffraction pattern of a sample indicated the presence
of three components: rutile, quartz, and tan iron oxide. The
analyst determined that the RIRs for these phases are:
879
Limitations
Intensity
100.0
19.1
1.8
Intensity
100.0
19.1
1.8
RIR
3.20
2.96
2.32
Quotient
31.3
6.45
0.78
Percent
81.1
16.8
2.1
Two important points about quantitation by X-ray diffraction analysis should be noted. First, the results do not include
noncrystalline components such as carbon black, amorphous
silica, or highly processed days. Second, the results do not
represent percent by weight on either a dry film or a liquid
paint basis.
The absolute weight percent of crystalline pigments and
extenders can be determined by either:
1. Using a variation of the above method that includes an
internal standard [14,15,22] added in known concentration to the paint.
2. Taking into account the total percent pigment in the paint
if no amorphous pigment is present. The percent pigment
880
X-RAY F L U O R E S C E N C E S P E C T R O S C O P Y
Application
Types of Samples
X-ray fluorescence spectrometry is applicable to any liquid
or solid that can be placed at the focal point of the X-ray
optics system. Permissible specimen size differs widely with
instrument type. Common commercial laboratory units can
accept specimens as large as a cylinder about 4.0 cm in diameter and 2.5 cm in height to as small as 1 or 2 mg of powder.
Some laboratory models can analyze specimens up to several
centimeters in each dimension. There is no maximum size
limit for bench top or portable units with hand-held X-ray
probes.
Range of Concentrations
Analysis can be performed on elements ranging in concentration from 100% down to a few parts per million in favorable cases. The limit of detection differs widely with the
o
o
i
TALC
' 'ALC
~-
}--o.
Z"
ZD
u~
~"
CHINA CLAY
A
TALC
~
CHINA CLA~
~"
05"00
17.659
T~
.
9.09
9.719
.
13.18
6.7it
I~.27
5.129
2~.3B
4.156
TWO -
. 5.45
2
3.496
THETA
--
2 9 .. 5 5
3.021
.
33.84
2.862
3~.73
2.382
4t .B2
2.t58
45,91
1.975
50.00
1,823
d SPACING
FIG. B-X-ray diffraction patterns of drawdowns of two paints: one known to be good, one of suspect
identity.
881
o
o
HOPEITE
m
0
A j ~
* o~ . . _ _ . . . . _ ]
U)
I--
SCHOLZlTE
i7.659
1i.042
t19
8.036
TWO -
THETA
t4.00
t7.00
6 . 3 2 0 5.2tt
20.00
4.436
--
23.00
3.863
26.00
3.424
d SPACING
Physical Basis
When X-ray photons of sufficient energy are directed onto
a specimen, some photons are absorbed in a process that
causes ejection of electrons from core atomic orbitals. The
x190 kcps
l.ee
r
t
0.75
o.5e
'
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
..............
,D
~I
U.
I::
.......
..............................
......1...............i....................................... ...................
Z
H
0.25
0.00
20
3~
44
TWO
56
68
8e
THETA
FIG. IO-Pe~ of a WLD X-ray fluorescence spectrum of paint containing rutile, yellow iron oxide, talc,
and zinc oxide9
882
Vert=
5~0B
counts Dis~= I
Elapsed=
f~ secs
p-
Zn
AOFeAA
] ~'
t ^,1
P/
~-
0.80B
Range= 10.230keV
. . . .
. . . .
Vert=
I
IIII
. . . .
3.~--"~
II II
Col,, tor-
Range-
40.9"~]
keY
. . . .
Elapsed=
f~ secs I
I I
, F' lt,rJ/tl
"
Integral 0
5.038 -~
393194
..Integral 0 =
. . . .
~-
, ll
23.7~3 ~
3~41~ I
10
15
20
ENERGY, teV
FIG. 11-X-ray fluorescence spectrum, recorded using an energy dispersive spectrometer, of the paint used for Fig. 10.
tion of the X-ray detector that moves at twice the angle of the
diffraction crystal used in some instruments to separate different wavelengths to produce a spectrum.
On-line
Products and process materials may be analyzed on-line by
specially adapted dedicated X-ray fluorescence units with
remote analyzer heads [32]. The heads house the X-ray
source and detector. Flow-through heads can be used for
liquids. Fixed or moving heads can be used for moving sheet
stock or other solid material. Bulk composition or the composition or thickness of a coating on a substrate can be determined by this method. The apparatus and methodology are
custom-designed for each application.
Portable
Types of X-ray Fluorescence
Spectrometers
Scanning
Scanning X-ray fluorescence spectrometers permit the
acquisition of spectra spanning a broad wavelength or energy range. These spectrometers, usually floor-standing, are
versatile instruments for both qualitative and quantitative
analysis. Scanning spectrometers, most using X-rays from
Coolidge-type tubes, can be further classified as either wavelength or energy dispersive.
Wavelength-dispersive (WLD) instruments produce a spectrum by using a crystal to diffract the fluorescent X-rays, a
single wavelength at a time, onto a detector that measures
their intensity. By rotating the crystal through an angle defined as 0 as the detector moves around an arc through angle
20, only those X-rays that satisfy the Bragg equation reach the
detector. The resultant spectrum is usually plotted as intensity as a function of 20 angle, but could in principle be plotted
as intensity as a function of wavelength. By use of several
[33].
Electron Beam Excited X-ray Spectroscopy
Spectroscopic analysis can be performed with X-rays generated by bombardment of a specimen with an electron
beam, as in a scanning electron microscope (SEM) or an
electron microprobe (EMP) [27]. The spectrum may be produced by either energy-dispersive or wavelength-dispersive
means. SEM units, commonly equipped with energy-dispersive X-ray capabilities, are extremely useful tools for the
study of surfaces and small features, especially defects such
as craters, voids, pinholes, mars, and stains. In addition to
providing images, such instruments can perform qualitative
and quantitative elemental analysis. EMP units, usually
equipped with both energy-dispersive and wavelength-dis-
Experimental Procedures
Specimens may be any solid or liquid that can be presented
to the X-ray beam. The size of the specimen holder of the
spectrometer is the principal practical limitation. Sample
preparation methods have been discussed by Bertin and
Leyden [27,34]. Figure 12 shows two types of specimens.
Many of the recommendations given in Table I for X-ray
diffraction also can be used to prepare specimens for qualitative analysis by X-ray fluoresence spectroscopy. However, the
analyst is cautioned that the X-rays used for X-ray fluorescence spectroscopy are commonly more penetrating than
those used for diffraction analysis. Unless care is taken, the
fluorescence spectrum may show elements in the backing
material used to support the intended specimen material. The
analyst must either use a specimen that is sufficiently thick to
prevent X-ray fluorescence from the backing from reaching
the detector or use a backing (such as a metal-free polymer)
that is free of conflicting elements. It is common practice to
place liquid or powder in a disposable plastic cup, the bottom
of which is covered with a thin plastic film that transmits Xrays. (Liquids and powder are most conveniently analyzed in
spectrometers that irradiate the specimen from below. For
instruments of the opposite configuration, the specimen cup
must be filled so that there is no bubble when the cup is
inverted in the analysis chamber.) Paint chips may be placed
directly in the specimen cup, and drawdowns of paint on
metal-free plastic sheets such as Mylar may be cut to fit the
specimen holder.
For quantitation, powders may be pressed into disks in a
binding agent such as orthoboric acid, granular cellulose, or
883
Qualitative Analysis
Qualitative elemental analysis can be conveniently done using a scanning X-ray fluorescence unit. Elements in a specimen can be identified by the position of the peaks on the
spectrum expressed as photon energy (kilovolts), 20 angle, or
wave length. Peak identification tables can be found in manuals provided by manufacturers of the spectrometers or in
treatises on X-ray spectrometry [27]. Modern X-ray spectrometers have computer programs that can indicate what
elements are present in a specimen. For instruction in use of
these programs, the analyst should refer to the instrument
operation manual.
Figure 10 shows part of an X-ray fluorescence survey spectrum (collected using a wavelength-dispersive instrument) of
a drawdown of a tan paint, the same one used to produce the
diffraction pattern in Fig. 7a. Note the corroborative nature
of element content indicated in Fig. t 0 and the identity of the
pigments determined from the diffraction pattern in Fig. 7a.
For comparison, Fig. 11 is an X-ray fluorescence survey spectrum, recorded by an energy-dispersive instrument, of the
same sample.
Quantitative Analysis
General Principles
The principles of quantitative analysis by X-ray fluorescence spectrometry have been discussed in detail by many
workers including Bertin [27,28]. The basic equations show
that the intensity of the fluorescent X-rays is proportional to
the amount of element that produced the X-rays, but is influenced by other factors such as the density and absorption
coefficient of the specimen. Nevertheless, the linear proportionality between analyte concentration and fluorescence intensity shows that common analytical methods such as
standard addition can be readily employed in X-ray spec-
884
Empirical Methods
The empirical methods require the use of a set of reference
samples that span the concentration range of all elements of
interest. All modern high-priced and most mid-price X-ray
spectrometers can perform analyses using one or more variations of this approach when equipped with suitable software.
The analyst must follow the instructions from the instrument
supplier. Empirical methods are well suited for routine multielement analysis of large numbers of samples of the same
type. A different program, with its own set of reference samples, must be established for each class of samples and choice
of elements. High accuracy and precision are achievable
when the reference samples properly represent the test samples.
885
Intensity, e / s
1.5
1.0
0.5
0.0
-aoo
-loo
I
o
L
loo
Concentration,
, i
200
a00
ppm
FIG. 1 3 - A plot of the intensity of the sulfur K . peak as a function of the concentration of sulfur in the analysis of an aqueous solution by a standard addition method,
Applications
of X-ray Fluorescence
Spectroscopy
Surface Analysis
Foreign substances may sometimes be detected on surfaces
by X-ray fluorescence spectroscopy, eliminating the need to
resort to X-ray photoelectron spectroscopy and other "surface analysis" techniques. To be detectable, the contaminant
must contain an element that is not present in significant
amounts in the surface itself. Figure 14 shows a silicon peak
in the high-resolution X-ray fluorescence scan of the surface
of a piece of aluminum extrusion from which poorly adhering
paint was peeled. Comparison of Figs. 14a and 14b, respectively, prove that washing the peeled surface with hexane
significantly reduced the amount of silicon present. The elevated silicon signal on a substrate to which paint adhered
poorly and the ready removal of the silicon material by hex-
Quality Control
Dedicated X-ray fluorescence units that can determine the
concentration of a single element have great utility in production plants for monitoring the composition of raw materials,
intermediates, and products. One application is the monitoring of batches of paints to ensure compliance with federal
regulations that limit lead content to no more than 600 parts
per million based on nonvolatile content. A common tech-
886
IS.OOO"
12,008"
6.888
3. OOO '
O.OOO
(b)
s.eee
9.000-
G. 008
i~'.eee.
9
lOG.O
3. B@8
,eo.s
~1.0
e.e~ele~,, o
l~o.s
2 e ~I~GLB
~'....
iiz.e
2 e ~I~G~.~.
FIG. 14-The K. peak of silicon on extruded aluminum from which poorly adhering paint
has been peeled: (a) peeled only; (b) peeled and washed with hexane.
nique for determining lead content has been atomic absorption spectroscopy using ASTM Test Method for Low
Concentrations of Lead, Cadmium, and Cobalt in Paint by
Atomic Absorption Spectroscopy (D 3335) [23] or a similar
method. X-ray fluorescence offers a quick alternative to
atomic absorption spectroscopy, which may be too laborious
and time-consuming for routine plant use. Lead content of a
sample of paint can be determined by placing a drawdown or
liquid specimen in the analysis chamber and directly reading
either the content or signal count rate of lead. Dedicated Xray fluorescence analyzers are available that give direct readout of concentration once a calibration curve has been established using samples of known concentration. The principal
drawback of this method is the need for a separate calibration
curve for every type of paint analyzed. Differences in the
paint composition such as the type and amount of pigment
can influence the intensity of the lead signal. In addition,
interference from other elements such as bromine can produce large errors in apparent lead concentration.
Figure 15 is a plot of lead count rate from ten consecutive
batches of paint measured with a dedicated X-ray fluorescence analyzer. The count rate that corresponds to 0.06%
lead, the legal limit, is indicated by a horizontal line. To
provide leeway for error, a lead limit of Lmax (taking into
account the precision of the method) may be chosen as the
highest "passing" count rate. The dotted line represents Lm~.
Any sample that gives a count rate between Lmaxand the legal
limit is considered suspect. Suspect batches of paint should
be analyzed by ASTM Method D 3335 or other independent
method, to determine the concentration of lead. Batches with
unacceptable lead content may be scrapped or "blended-off."
TABLE 3--Concentration of silicone, determined by XRFS, in
batches of resin used in batches of paint of known extent of
cratering.
Extent of Cratering
None
None
None
Bad
Bad
Worst
3
4
7
13
13
40
600
XPb0.00%
500I
Lmm<
4o0(-
220
. . . . . .
200
U~
t/O~
X = 0.002%Pb
................................
I
I
5
Li
I
I
10
SAMPLE
FJG. 15-A plot of the intensity of the lead signal for consecutive batches of latex paint as measured by a dedicated X-ray
analyzer.
[36].
Guidance on the use of X-ray analyzers to determine the
coating thickness is given in ASTM Standard Test Methods A
754-90, Coating Thickness by X-Ray Fluorescence [37], and B
568-90, Measurement of Coating Thickness by X-Ray Spectrometry [38].
SUMMARY
X-ray diffraction a n d X-ray fluorescence spectrometry,
u s e d alone o r in c o m b i n a t i o n , c a n provide valuable i n f o r m a tion a b o u t coatings, coating ingredients, impurities, a n d substrates. S a m p l e p r e p a r a t i o n effort is m i n i m a l for b o t h
techniques. X-ray diffraction offers easy qualitative a n d
quantitative analysis of crystalline m a t e r i a l s in general a n d
p i g m e n t s in particular. X-ray fluorescence s p e c t r o m e t r y is
widely useful for qualitative analysis and, w h e n suitable stand a r d s are used, for quantitative analysis. Attractive features
of X-ray fluorescence s p e c t r o m e t r y for quantitative analysis
include its suitability for all e l e m e n t s except a few with lowest
a t o m i c n u m b e r , applicability over a b r o a d c o n c e n t r a t i o n
range, tolerance of chemically reactive specimens, a n d applicability to s a m p l e s of diverse physical states. Both X-ray
diffraction a n d X-ray s p e c t r o m e t r y are suitable for applications including basic research, p r o d u c t a n d process development, quality control, a n d practical p r o b l e m solving. The
a r e a of greatest potential g r o w t h is the use of d e d i c a t e d X-ray
fluorescence s p e c t r o m e t e r s in p r o d u c t i o n plants for quality
control, p a r t i c u l a r l y for on-line monitoring.
REFERENCES
[1] ANSI N43.2-1988, "Radiation Safety for X-ray Diffraction and
Fluorescence Analysis Equipment," American National Standards Institute, 1430 Broadway, New York, NY 10018.
[2] K.lug, H. P. and Alexander, L. E., X-ray Diffraction Procedures,
John Wiley & Sons, New York, 1974.
[3] Schreiner, W. N., Applications Note, September 1989, p. 1, IC
Laboratories, P.O. Box 721, Amwalk, NY 10501.
[4] Bragg, W. L., Proceedings of the Cambridge Philosophical Society,
Vol. 17, 1912, pp. 43-57.
[5] Bragg, W. H. and Bragg, W. L., Proceedings of the Physical Society (London), VoL A88, 1913, pp. 428-438.
[6] Foster, B. A. and Wolfel, E. R., Advances in X-ray Analysis, Vol.
31, 1988, pp. 325-330.
[7] Tissot, R. G. and Eatough, M. O., Advances in X-ray Analysis,
Vol. 34, 1991, pp. 349-355.
[8] Goehner, R. P. and Eatough, M. O., Powder Diffraction, Vol. 7,
No. 1, 1992, pp. 2-5.
887
[9] Huang, T. C., Advances in X-ray Analysis, Vol. 33, 1990, pp.
91-99.
[10] Scott, R. W., Journal of Paint Technology, Vol. 41, No. 534, 1969,
pp. 422-430.
[11] Scott, R. W., Treatise on Coatings, VoL 2, Part II, Marcel Dekker,
New York, 1976, pp. 591-624.
[12] ICDD Powder Diffraction File, International Centre for Diffraction Data, 12 Campus Boulivard, Newton Square, PA, 190733273.
[13] Jenkins, R. and Holomany, M., Powder Diffraction, Vol. 2, No. 4,
1987, pp. 215-219.
[14] Chung, F. H., Journal of Applied Crystallography, Vol. 7, 1974,
pp. 519-525.
[15] Chung, F. H., Journal of Applied Crystallography, Vol. 7, 1974,
pp. 526-531.
[16] Camden, R. H. and Snyder, R. L., Powder Diffraction, Vol. 3, No.
2, 1988, pp. 74-77.
[17] Davis, B. L., Kath, R., and Spilde, M., Powder Diffraction, Vol. 5,
No. 2, 1990, pp. 76-78.
[18] Snyder, R.L., Powder Diffraction, Vol. 7, No. 4, 1992, pp.
186-193.
[19] Smith, D. K., Johnson Jr., G. G., Scheible, A., Wims, A. M.,
Johnson, J. L., and Ullmann, G., Powder Diffraction, Vol. 2, No.
2, 1987, pp. 73-77.
[20] Davis, B. L. and Smith, D. K., Powder Diffraction, Vol. 3, No. 4,
1988, pp. 205-208.
[21] Davis, L. D., Smith, D. K., and Holomany, M. A., PowderDiffraction, Vol. 4,tNo. 4, 1989, pp. 201-205.
[22] Goehner, R. P., Advances in X-ray Analysis, Vol. 25, Plenum
Press, New York, 1981, pp. 309-313.
[23] Annual Book of ASTM Standards, Vol. 06.01.
[24] Karlak, R. F. and Burnett, D. S., Analytical Chemistry, Vol. 38,
1966, pp. 1741-1745.
[25] Dyakonov, J., Mischenko, K., Hering, A., Unger, G., Korecky, J.,
Melka, K., Zoubkova, J., Raynov, N., Thekhlanova, N., Rischak,
G., Sidorenko, and Volkov, M., Powder Diffraction, Vol. 7, No. 3,
1992, pp. 137-141.
[26] Kamarchik, P. and Rat_lift,J., Advances in X-ray Analysis, Vol. 26,
1983, pp. 129-135.
[27] Bertin, E.P., Principles and Practices of X-ray Spectrometric
Analysis, Plenum Press, New York, 1970.
[28] Bertin, E. P., Introduction to X-ray Spectrophotometric Analysis,
Plenum Press, New York, 1978.
[29] Campbell, W. C., Analyst, Vol. 104, 1979, pp. 177-195.
[30] Kunz, F. W., Spectroscopy, Vo]. 3, No. 8, 1988, pp. 16-23.
[31] Valkovic, V., Markowicz, A., and Haselberger, N., X-ray Spectrometry, Vol. 22, No. 4, 1993, pp. 199-207.
[32] Kalnicky, D. J. and Ramanujam, R. S., Analytical Division, Vol.
25 (Edmonton Spring Symposium, 1991, Part 2), 1991, pp.
262-274.
[33] Piorek, S. and Rhodes, J. R., Advances in Instrumentation, Vol.
41, No. 3, 1986, pp. 1355-1368.
[34] Leyden, D. E., Fundamentals of X-ray Spectrometry as Applied to
Energy Dispersive Techniques, Tracor X-ray, Inc., Mountain
View, CA, 1984, pp. 39-45.
[35] Spex Industries, Inc., 3880 Park Avenue, Edison, NJ, 38820.
[36] Kamarchik, P. and Cunningham, G. P. in Progress in Organic
Coatings, Vol. 8, 1980, pp. 81-107.
[37] Annual Book of ASTM Standards, Vol. 01.06.
[38] Annual Book of ASTM Standards, Vol. 02.05.
[39] Rasberry, S. D., Applied Spectroscopy, Vol. 27, No. 2, 1973, pp.
102-108.
MNL17-EB/Jun. 1995
S O U R C E S OF P A I N T S P E C I F I C A T I O N S
SPECIFICATIONS
CONSIDERATIONS
Federal G o v e r n m e n t S o u r c e s
The U.S. Department of Defense (DOD) Index of Specifications and Standards (DODISS) indexes government standardization documents (military specifications, standards, and
handbooks; federal specifications, standards, and commercial item descriptions; qualified products lists; and industry
documents adopted for DOD use); as well as alphabetic, numeric, and Federal Supply Class (FSC) listings. The DODISS
is available to civil agencies and private sector industry by
subscription, as either hardcopy from the Government Printing Office, or as microfiche from the Defense Printing Service
Detachment Office (DPSDO) at 700 Robbins Avenue, Building 4D, Philadelphia, PA 19111-5094. Individual government
documents may be ordered, generally without charge, from
DPSDO; by telephone 215/697-2667, by fax 215/697-2978, or
by mail from the Standardization Documents Order Desk,
same address as previously stated. Automatic distribution of
standardization document also is provided by DPSDO by
subscription for new or revised issues in requested FSCs.
Non-Government Sources
Technical Societies
Committee D-1 on Paint and Related Coatings, Materials,
and Applications of ASTM, the American Society for Testing
891
www.astm.org
892
Organization
IHS
Address
Subscriptions
700 Robbins Avenue
Building 4D
Philadelphia, PA 19111-5094
Informational Handling Services
15 Inverness Way East
P.O. Box 1154
Englewood, CO 80150
GED
GPO
Superintendent of Documents
U.S. Government Printing Office
Washington, DC 20402
GSA Specifications Unit, Suite 8100
4700 L'Enfant Plaza
Washington, DC 20024
GSA
MFMA
NACE
NIBS/CCB
NPFD
Telephone
Fax
Criteria/services
Form
Microfiche
Hardcopy
Microfilm,
microfiche, compact
disk system
Hardcopy
Hardcopy
Hardcopy
Hardcopy
Hardcopy, volume
Compact disk
system, with
executable software
Hardcopy,
microfiche hardcopy
reduce corrosion. SSPC, the Steel Structures Painting Council (4400 5th Avenue, Pittsburgh, PA 15213, 412/268-3326),
has developed paint specifications and other standards for
the preparation of metal surfaces for painting, painting systems, and paint application. CSI, the Construction Specifications Institute (601 Madison Street, Alexandria, VA 223141791,703/684-0300), has prepared several SpecGuides as part
of 'construction documentation covering the preparation of
technical specifications for paints and painting.
Underwriters Laboratories Inc. (333 Pfingsten Road,
Northbrook, IL 60062, 312/272-8800) is used to obtain UL
listing, classification, and recognition. Testing sites are also
located in California, North Carolina, and New York.
Nongovernment standards that have been adopted by the
DOD and that are listed in the DODISS are issued by the Navy
Publishing and Printing Service Office to DOD activities only
[4].
Electronic Database Sources
A powerful database, the Construction Criteria Base (CCB),
is available in compact disc format by subscription from the
National Institute of Building Sciences (1201 L Street NW,
893
TABLE 1--Continued.
Organization
SSPC
AAMA
AASHTO
AIA
ASTM
CSI
DPSDO
Address
Telephone
Fax
Criteria/services
Form
Hardcopy, volumes
Hardcopy
Hardcopy, volumes
Hardcopy,
computerized
services
Hardcopy, volumes
Hardcopy,
computerized
services
Hardcopy
Library Sources
Some standardization documents, indexes, databases, and
services listed above may be available in government, state,
city, industry, university, or federal depository libraries.
Table 1 summarizes construction/coatings criteria sources,
access, and types of information available [5].
REFERENCES
[1] ASTM Terminology, D 123-92.
[2] SpecGuide 09900, Painting, February 1988.
[3] Form and Style for ASTM Standards, 1989.
[4] DODISS Notice, Vol. 9, No. 91, 6 May 1991, p. 1.
[5] Source: Naval Construction Battalion Center, Port Hueneme, CA,
1992.
MNL17-EB/Jun. 1995
Appendix
www.astm.org
o.
~,~
:,)
).
~,1
gD
! ~ ~ ~ E ~ E ~ E ~ E ~ E E ~ - ~
I
I
I
I
I
I
I
I I
~n
~nl
~mn
~n
0.
~ 0
C~
,ui,,
mum
|
|
mun
nmqi
0~
5"
r-
4)
'
= t ~ 4 - 1 ~ ~ - 4 -x
I
-
4-
I'0
-I--
II
-,,4
II
rrll
MNL17-EB/Jun. 1995
Author Index
A
Ashton, Harry E., 696
Athey, Robert D. Jr., 415
Austin, M. Jay, 238
Aviles, Julio I., 507
Pellowe, Don, 53
Perera, Dan Y., 585
Petraitis, D. J., 95
Price, Martin B., 717
Pulley, David F., 683
H
B
C
Campbell, David L., 654
Carlozzo, Ben J., 15
Crewdson, Michael J., 619
Curtis, L. G., 23
S
Santer, J. Owen, 60
Scarborough, Victoria, 748
Schaeffer, Leonard, 481
Schmitt, Thomas M., 835
Schnall, Marvin J., 30
Shay, Gregory D., 268
Sheehan, John G., 815
Sherbondy, Valerie D., 643
Siegmund, A1, 731
Sliva, Thomas J., 439, 725, 748
Smyrl, William H., 609
Snider, A. Monroe, Jr., 871
Spadafora, Stephen J., 683
Spindel, Saul, 735
Spinelli, Frank R., 179
M
E
T
Tan, Peter, 115
W
N
899
MNLI7-EB/Jun.
1995
Subject Index
A
A-A-1555, 726, 727-729, 729
AAMA 801.1,739
AAMA 802.3,739
AAMA 803.3, 739
AAMA 804.1,739
AAMA 805.2, 739
AAMA 806.1,739
AAMA 807.1,739
AAMA 808.3, 739
AAMA 809.2, 739
AASHTO M-247, 745
AASHTO T 250, 744, 745
AASHTO T 259, 750
Ablative coatings, testing, 675
Abrasion, mechanism, 526
Abrasion resistance
air blast abrasive, 527-528
architectural coatings, 703
balanced beam tester, 531-532
Bell Laboratory Rotating Disk
Abrasion Test, 528
camp abrasion tester, 529
coin mar test, 532
comparison of wear abrasion testers,
531
correlation with end-use performance,
525-526
definitions, 525
falling abrasive test, 526-527
FDC wear test, 529-530
fingernail test, 532"
gloss reduction test, 527
gravel projecting machine, 528-529
impinging abrasive method, 532
less well-known tests, 532-533
pebble abrasion wear test, 527
PEI abrasion tester, 533
Peters abrasion block, 533
Princeton scratch tester, 532
rain or water erosion, 532
RCA tape tester, 531
relation to hardness, elasticity, and
tensile strength, 525
Roberts jet abrader, 527-528
Schiefer abrasion testing machine,
529-530
straight-line reciprocating machines,
531
Taber Abraser, 530
mar test, 532
traffic marking materials, 744
traffic paint tests, 532
901
902
P A I N T A N D COATING T E S T I N G M A N U A L
SUBJECT I N D E X
A S T M C 5 3 9 69,71
A S T M C 554 69
A S T M C 556 69
A S T M C 5 7 0 737,738
A S T M C 584 69
A S T M C 603 738
A S T M C 609 69
A S T M C 6 1 4 70-71
A S T M C 633 72
A S T M C 63~ 738
A S T M C 642, 725, 729
A S T M C 650, 69
A S T M C 661, 738
A S T M C 666, 750
A S T M C 669, 737, 738
A S T M C 672, 750
A S T M C 675 71
A S T M C 676 71
A S T M C 679 738
A S T M C 681 738
A S T M C 690 216
A S T M C 703 71
A S T M C 711 738
A S T M C 712 738
A S T M C 713 738
A S T M C 717 738
A S T M C 718 738
A S T M C 719 738
A S T M C 724 71
A S T M C 731 738
A S T M C 732 738
A S T M C 733, 738
A S T M C 734, 738
A S T M C 735,71
A S T M C 736, 738
A S T M C 738, 69
A S T M C 741,738
A S T M C 742, 738
ASTMC 743,70-71
A S T M C 756, 70-71
A S T M C 765, 738
A S T M C 766, 738
A S T M C 771,738
A S T M C 772, 738
A S T M C 777, 71
A S T M C 780, 727, 729
A S T M C 782, 738
A S T M C 792, 738
A S T M C 793, 738
A S T M C 794, 738
A S T M C 797, 738
A S T M C 824, 71
A S T M C 834, 738
A S T M C 836, 738
A S T M C 839 71
A S T M C 8 7 2 70-71
A S T M C 879 738
A S T M C 895 69
A S T M C 898 738
A S T M C 907 738
A S T M C 908 738
A S T M C 910 738
A S T M C 919 738
A S T M C 9 2 0 737-738
A S T M C 927, 71
A S T M C 957, 737-738
A S T M C 961,738
A S T M C 972, 738
A S T M C 978, 71
A S T M C 981,738
A S T M C 988, 523
A S T M C 1016,738
A S T M C 1021, 738
A S T M C 1027, 69
A S T M C 1028, 603
A S T M C 1034, 69
A S T M C 1070,216
A S T M C 1083,738
A S T M C 1085, 737-738
A S T M C 1087, 738
A S T M C 1109, 788
A S T M C 1111, 788
A S T M C 1193, 738
A S T M D 12,28
A S T M D 21,604
A S T M D 4, 15, 19, 733
A S T M D 5, 19, 733
A S T M D 26, 692
A S T M D 36, 19, 733, 745
ASTM D 41, 20
ASTM D 43, 20-21, 20
ASTM D 56, 755
aerospace a n d aircraft coatings, 686
can coatings, 720
plasficizers, 117
so~ents, 142
wate~repellent coatings, 748
ASTM D 61, 19
ASTM D 70, 19
ASTMD71,19,733
A S T M D 86, 116, 140-141
A S T M D 88, 19
A S T M D 92, 19, 117
A S T M D 93,755
aerospace and aircra~ coatings, 686
architectural coatings, 699
plasticizers, 117
so~ents, 143
ASTMD 95,19,226
A S T M D 115, 362
A S T M D 130, 116, 153
A S T M D 140, 19
A S T M D 153
colored organic pigments, 208
extender pigrnents, 221
solids, 301-302
traffic marking materials, 745
A S T M D 154, 743
A S T M D 156, 149, 462
A S T M D 185
aerospace and aircraft pigments, 684
architectural coatings, 698
artist's paints, 707
ceramic pigments, 216
metallic pigments, 226
A S T M D 212, 720
A S T M D 233 127
A S T M D 234 2 8 , 2 5 2 - 2 5 3
A S T M D 235 126,153, 226
A S T M D 255 20
A S T M D 256 745
A S T M D 257 733
A S T M D 262 5O8
A S T M D 267 226
A S T M D 269 428
A S T M D 270 294
A S T M D 281
ceramic pigments, 216
colored organic pigments, 207
extender pigments, 221
oil absorption, 253
white pigments, 169
ASTM D 287, 146
ASTM D 304, 130
ASTM D 312, 19
ASTM D 319, 130
ASTM D 323, 135
ASTM D 329, 128
ASTM D 330, 129
ASTM D 331, 129
903
904
686
692
683
688,
SUBJECT I N D E X
ASTM D 2240, 97
ASTM D 2243, 20, 685,748
ASTM D 2244, 465, 771
aerospace and aircraft coatings, 687
archictectural coatings, 702
artist's paint, 708-709
traffic marking materials, 744
natural weathering, 641
ASTM D 2245 743, 804, 806
A S T M D 2247 20, 692,714
A S T M D 2248 43,532
A S T M D 2249 738
A S T M D 2268 151
A S T M D 2288 97
A S T M D 2306 151,804
A S T M D 2318 19
A S T M D 2319 19
A S T M D 2320 19, 301
A S T M D 2348, 763
A S T M D 2360, 152,804
A S T M D 2363, 277, 302
A S T M D 2364, 276, 362
ASTM D 2369, 5 - 7
aerospace and aircraft coatings, 684
amino resins, 62
architectural coatings, 713
bituminous coatings, 20
can coatings, 720
nonvolatile content, 756
traffic marking materials, 743
water-repellent coatings, 748
ASTM D 2370, 733
bituminous coatings, 20
dynamic mechanical properties, 536
tensile properties, 543
aerospace and aircraft coatings, 664
architectural coatings, 704
ASTM D 2371, 743, 879
A S T M D 2372 684, 756
A S T M D 2373 35
A S T M D 2374 35
A S T M D 2375 35
A S T M D 2376 738
A S T M D 2377 738
A S T M D 2393 362
A S T M D 2414 188
A S T M D 2 4 1 5 19, 733
A S T M D 2416 19
A S T M D 2444 723
A S T M D 2448 221
A S T M D 2450 738
A S T M D 2451, 738
A S T M D 2452, 738
A S T M D 2453, 738
A S T M D 2455, 804
A S T M D 2456, 804
A S T M D 2485, 667
A S T M D 2486, 705
A S T M D 2503, 836
A S T M D 2521, 19
A S T M D 2556, 362
A S T M D 2569, 19
A S T M D 2571, 662
ASTMD 2574,267,657
A S T M D 2613,35
A S T M D 2616,465
A S T M D 2621, 100, 743,771
A S T M D 2627, 128
A S T M D 2634, 129
A S T M D 2635,130
A S T M D 2669, 362
A S T M D 2697, 771
aerospace and aircraft coatings, 684
automotive products, 713
displacement, 302
b i t u m i n o u s coatings, 20
can coatings, 722
natural weathering, 642
peel adhesion, 517-518
ASTM D 3360, 221, 321
ASTM D 3361, 728-729
ASTM D 3362, 804
ASTM D 3363, 771
aerospace and aircraft coatings, 690
can coatings, 721
cure, 412
driers, 32
hardness, 559-560, 564
natural weathering, 642
ASTM D 3423, 20
ASTM D 3432, 685, 804
ASTM D 3447, 151
ASTM D 3450, 704, 705
ASTM D 3456, 267, 659
ASTM D 3457, 804
ASTM D 3459, 680
ASTM D 3461, 19
ASTM D 3465, 117
ASTM D 3468, 21
ASTM D 3505, 148, 299
A S T M D 3506, 130
A S T M D 3536, 838
A S T M D 3539 135
A S T M D 3540 129
A S T M D 3545 129, 151,804
A S T M D 3593 838
A S T M D 3619 221
A S T M D 3622 130
A S T M D 3624 787
A S T M D 3626 804
A S T M D 3698 130
A S T M D 3717 787
A S T M D 3718 685,787
A S T M D 3719 705
A S T M D 3720 1 6 4 , 7 6 3 , 8 8 0
A S T M D 3723 7 4 3 , 7 5 6 , 8 7 9
A S T M D 3728 129
A S T M D 3730 420, 523,697
A S T M D 3735 126
A S T M D 3742 151
A S T M D 3760 151,804
A S T M D 3792 6 - 7 , 7 5 5 , 8 0 4
A S T M D 3797 151, 8O4
A S T M D 3798 151,804
A S T M D 3804 35
A S T M D 3805 2O
A S T M D 3806 670-672
A S T M D 3893 128, 151, 804
A S T M D 3894 674-675
A S T M D 3925 753-754, 774
A S T M D 3928 702
A S T M D 3934 144
A S T M D 3941 143
ASTM D 3960 6, 8, 774
aerospace and aircraft coatings, 684
architectural coatings, 699
automotive products, 714
bituminous coatings, 20
can coatings, 720
chromatography, 809
gas chromatography, 804
water-repellent coatings, 748
ASTM D 3961, 154
ASTM D 3964, 464, 702
ASTM D 3969, 35
ASTM D 3970, 34
ASTM D 3988, 35
ASTM D 3989, 35
ASTM D 4001, 836-837
ASTM D 4017, 6-7, 226, 685, 755
905
906
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
D 4715, 19
D 4735, 8O4
D 4746, 19
D 4752, 411,664
D 4758, 756
D 4764, 762
D 4773, 129, 151
D 4796, 745
D 4797, 744
D 4798, 19
D 4799, 19
D 4828, 705
D 4834, 762
D 4835, 129
D 4836, 129
D 4837, 129
D 4838, 508, 708
D 4866, 20
D 4875, 109
D 4883, 302
D 4890, 109
D 4892, 19, 302
D 4893, 19
D 4941, 707
D 4946, 42, 704
D 4951, 788
D 4958, 274, 702
D 4960, 744
D 4989, 19
D 5008, 130
D 5009, 8
D 5018, 20
D 5031, 680, 865
D 5066, 8
D 5076, 20
D 5087, 8
D 5095, 8, 748
D 5098, 707, 708
D 5107, 727, 729
D 5135, 804
D 5137, 129
D 5146, 696, 697
D 5150, 503, 703
D 5162, 774
D 5178, 580
D 5179, 519-520, 771
D 5200, 8
D 5201, 8, 710
D 5286, 8
D 5324, 696, 697
D 5325 8
D 5326 700
D 5327 8
D 5328 9
D 5383 709
D 5398 709
D 5401 749
D 5403 9
D 5478 363
D 5531 464
E 11,317
E 12, 145
E 20, 318-319
E 70, 221, 714, 748
E 84, 670, 672-674
E 96, 19, 728-729, 750
E 97, 463, 744
E 100, 297
E 102, 19
E 108, 19
E 119, 675
E 136, 668
E 161,317
E 162, 670, 672, 674
E 167, 474, 688
SUBJECT INDEX
ASTM G 19, 733
ASTM G 20, 733
ASTM G 26, 648, 680
ASTM G 42, 771
ASTM G 50, 613
ASTM G 53, 774
aerospace and aircraft coatings, 692
automotive products, 715
accelerated weathering, 649-650
water-repellent coatings, 749
ASTM G 85, 690
ASTM G 90, 639-640, 652
ASTM G 95, 771
ASTM G 104, 613
ASTM gage, particle-size measurements,
327-329
Atmospheric corrosion, metals, 611-612
Atmospheric exposure testing, inorganic
anti-corrosive pigments, 248-249
Atomic absorption spectroscopy, 784786
applications, 787-788
background correction, 786-787
coating failure analysis, 779
cold vapor technique, 786
flame characteristics, 785
graphite furnace, 786
pigment identification, 762
sources of interference, 786-787
Atomic emission spectroscopy, 786
applications, 787-788
background correction, 786-787
sources of interference, 786-787
Attapulgite clays, 281-282
Attenuated total reflectance, 829
Automobile industry, VOC standards, 8
Automotive products, 711-716
coatings, 554
hiding power, 713
identification, 711-713
material requirements, 713-714
paints, waterborne amino resins, 66
pearlescent pigments, 230-231
performance requirements, 714-715
pretreatments, 711
primer, 711-712
process requirements, 715-716
surface cleaners, 711
topcoats, 712-713
viscosity, 714-715
Azam method, oil absorption
determination, 253
Azo-based oranges, 200-201,203-204
B
Bacteria
associated with paint, 654-655
resistance of liquid paints, 657
Bactericides, 261-267, 657
analysis and decontamination, 265266
definition of terms, 261
methods for determination of efficacy,
267
mode of action, 262-265
reactive with acetylacetone, 263,265
strategies for minimizing resistant
strains, 265
Bake latitude, automotive products, 715
Balanced beam tester, abrasion
resistance, 531-532
Barium metaborate, 240
Barium sulfate, 219-220
907
908
SUBJECT INDEX
Cobalt blue pigments, 214-215
Cobalt phosphate violet, 215
Code of Federal Regulations, subchapter
topics, 11
Coefficient of friction, 600
Canadian government standards, 603,
605
concept of, 601
determination, 601-602
determination methods, 603-605
measurement, 604-605
Coefficient-of-Friction Mar Test, 582
Coefficient of thermal expansion, 853854
Cohesion, versus stress, 594, 596
Cohesion energy, 385
Cohesive energy density, hydrocarbons,
389
Coin mar test, 532, 582
Cold checking resistance, automotive
products, 715
Cold crack resistance tests, 554
Cold vapor technique, atomic absorption
spectroscopy, 786
Cold weather, extreme, 629
Cole method, critical pigment volume
determination, 255
Colligative properties analyses, 836
Color
aerospace and aircraft coatings, 687
architectural coatings, 702
automotive products, 714
change
artists' paints, 707
sealants, 737
colored organic pigments, 207
compatibility, architectural coatings,
700
constancy, 451
feasibility, automotive products, 715
industrial measurement, 462-465
commercial instruments, 464-465
instrument selection and calibration,
463-464
instruments using eye as detector,
462
spectrophotometers, 462-463
tristimulus colorimeters, 463
liquid, mixing time, 510
matching, 467-468
measurement, can coatings, 723
metamerism, 451-452
mixing, 466-467
perceived, variables, 451-452
temperature, 456
terminology, 447
tolerances, 465-466
traffic marking materials, 743-747
uniform spaces, 456-457
variation, artists' paints, 708
(see also CIE system)
Colorcurve system, 460
Color differences
calculations, 465
instrumental measurements,
architectural coatings, 702
visual comparison, architectural
coatings, 702
Colored inorganic pigments, 209-212
blues, 210-211
browns, 212
classification, by chemistry, 209-210
greens, 212
oranges, 212
reds, 209-210
violets, 210
yellows, 211-212
Colored organic pigments, 190-208
bleed test, 207
blues, 197-198
classification, by chemistry, 191
color and tint strength, 207
Colour Index, 190
exposure testing, 207-208
fastness tests, 207
greens, 203-204, 206-207
health and environmental concerns,
204-206
oil absorption, 207
oranges, 200-201,203-205
reds, 191-197
high performance, 194-196
metallized azo, 191-192
non-metallized azo, 192-194
novel high-performance, 196-197
specific gravity, 208
testing, 206-208
yellows, 198-203
benzimidazolone, 199, 201
diarylide, 199-201
heterocyclic, 199-200, 202-203
monoarylide, 198-199
Colored pigments, 484
hiding power, 487
Colorimeters, 687
pearlescent pigments, 231
tristimulus, 463
Colorimetry, definition, 452
Color-matching booths, 448
Color order systems, 457-462
colorcurve system, 460
cylindrical systems, 451
DIN system, 459-460
ISCC-NBS system, 458
Munsell system, 457-458
natural color system, 459, 461
opponent systems, 451-452
OSA-UCS system, 459-461
Ostwald system, 459
printed systems, 460
scales for liquids, 462
universal color language, 458
whiteness indices, 461-462
yellowness indices, 462
Colour Index, 190, 507
Combustibility, tests for, 668-670
Commercial Standard 98, Section 6.6,
707-708
Compartment fire tests, full-scale, 674675
Compatibility, titanium dioxide
pigments, 174
Condensation
controlled testing, 679
effect on natural weathering, 627-628
Conductivity, automotive products, 714
Conical Mandrel tests, 548-549
Consistency
architectural coatings, 700-701
artists' paints, 707
Constant depth gage, particle-size
measurements, 328
Construction Criteria Base, 892-893
Contact angle, 372-373, 514
measurement, 378
Contaminants, titanium dioxide
pigments, 169
Continuous flow method, particle-size
measurements, 313
Contrast, visual observations, 482
909
910
Diethylenetriamine, 85-86
Difference spectroscopy, 830-832
Differential scanning calorimetry, 759,
761, 842-845
coatings characterization, 846-847
epoxy-amine reaction kinetics, 845846
glass transition temperatures, 843-844
purge gas, 846
sample preparation, 846
Differential thermal analysis, 759, 761
Diffusion theory, 514
Digital electromagnetic thickness gages,
432-433
Dilatancy, 339-34l
Dilatometry, 853
Diluent dilution ratio, solvents, 133
Diluents, 131-132
Dilution limit, solvents, 133
Dilution stability, architectural coatings,
699
Dimensional stability, water-repellent
coatings, 749
Dime scrape, automotive products, 715
DIN 33 157, 574
DIN 35 152, 550
DIN 50 101,551
DIN 50 102, 551
DIN 53 150, 442
DIN 53 153, 563
DIN 53 162, 505
Dinitroaniline orange, 200
DIN system, 459-460
Dip coating, 421-422
surface energetics, 379
Dipentene, 127
DIPPR database, 390
Directionality, gloss, 471-472
Direct tensile testing, adhesion, 519-523
Dirt pickup, architectural coatings, 705
Disazo condensation reds, 196
Disbonding method, 560
Disk centrifuge, 321-323
Dispersibility, titanium dioxide pigments,
171-172
Dispersion
carbon blacks, 186-187
fineness of
aerospace and aircraft coatings, 684
architectural coatings, 698-699
artists' paints, 708
can coatings, 720
traffic marking materials, 743
interactions, 385
pigments, 508-509
rheology, 351-352
solubility parameter, 387, 389-391
white hiding pigment, 500
Displacement analysis, chromatography,
790
Displacement technique, 294-295
Dissolution
anodic, 610-61 l
microwave, 757
Distillation
plasticizers, 116-117
range, solvents, 137, 139-140
Distinctness of image, automotive
products, 714
Doctor Test, 153
Drainage equation, 353-354
Drawdown, thin-film, oversize particles,
326-327
Drawdown bars, 418-420
Drier acids, description, 31
Driers, 30-35
function, 30-31
levels in coatings, 32
liquid paint
specifications, 33-34
testing, 34-35
metals, description, 31
miscellaneous, 31-32
recommendations, 33
testing of drying efficiency, 32-33
Drop weight, 374
Dry film
appearance, m-chitectural coatings,
702-703
printing, vinyl resins, 105
Drying oils. 26-29
classification by iodine value, 26
physical characteristics, 26, 28
Drying time, 439-444
aerospace and aircraft coatings, 686
artists' paints, 708
ASTM D 1640, 439-440
B.S. 3900, 441-442
circular drying-time recorder, 443-444
DIN 53 150, 442
environment, 439
Federal Test Method Standard 141C,
Method 4061.2, 440-441
I.C.I. drying time recorder, 444
ISO 9117, 441
no pick-up lime traffic paint roller, 444
specimen preparation, 439
straight line drying time recorder, 444
Dry-powder pulse jet disperser, 315-316
Dry to-recoat, aerospace and aircraft
coatings, 686
Du Nuoy ring, 374-375
Du Pont Scratch Testing Machine, 557
Durability
sealants, 737
testing, titanium dioxide pigments in
coatings, 173
traffic marking materials, 747
Dynamic coefficient of friction, 600
Dynamic mechanical analysis, 842, 847850
applications, 847
automated instruments, 538
coatings characterization, 848, 850
cure, 413
studies, 858-860
description, 538-539
glass transitions, 847
heating rate, 848
plot interpretation, 539-541
sample preparation, 848
synthetic variables and morphological
character, 847-849
Dynamic mechanical and tensile
properties, 534-545
cross-link density, determination, 541542
definitions, 534-536
dynamic property relation to other
mechanical properties, 542
free film sample preparation, 537-538
stress-strain curves, interpretation,
543-544
tensile properties, 543-545
relation to other mechanical
properties, 544-545
tensile versus shear tests, 534-535
Dynamic mechanical thermal analyzer,
548
SUBJECT INDEX
E
cover coat, 70
ground coat, 70
End group analysis, molecular weight,
835
Energetic deposition techniques, 615
Energy dispersive spectrometer, 817-818
Energy dispersive X-ray, coating failure
analysis, 768, 778
Energy of vaporization, for straight
chain hydrocarbons, 389
Engine oils, aerospace and aircraft
coatings resistance, 692-693
Environmental impact
amino resins, 66-67
colored organic pigments, 204-206
inorganic anti-corrosive pigments, 245
pearlescent pigments, 235-236
polyamides, 87-88
Environmental Protection Agency
federal environmental laws
administered by, 3
regional offices, 11
Environmental scanning electron
microscopy, 821
Envirotest, 651
Epoxides
coal tar, 732
coating failure analysis, 770
fusion bond, 732
Epoxy
reactive crosslinking, 410
traffic marking materials, 741
Epoxy/acrylic copolymers, dynamic
mechanical properties, 847, 849
Epoxy-amine reaction kinetics, 845-846
Epoxy polyester powder coating, cure,
859-861
Epoxy resins, 74-78
coatings, 75
cross-linked with acid-functional
acrylics, 43
curing agents, 74-75
electrodeposition coatings, 77
ester, ambient cure coatings, 76
heat-cured solvent-borne coatings, 7677
heat-cured waterborne coatings, 77
powder coatings, 78
properties, 75
reactions with polyamides, 87
two-package, ambient-cure coatings,
75-76
types, 74-75
Equivalent circle diameter, 310-311
Equivalent spherical diameter, 310
Erichsen cupping tester, 551
Erichsen Hardness Tester, 557-558
Erichsen Lacquer Testing Instrument,
723
Erichsen Scar-Resistance Tester, 581582
Esters, 128
purity, 151
Ester value, plasticizers, 117
Ethoxylate urethanes, hydrophobemodified, 278
Ethyl alcohol, 129
Ethyl hydroxyethyl cellulose, 277
hydrophobe-modified, 280-281
Evaporation rate
analysis, cure, 413
solvents, 135-139
Everhart-Thornley detector, 816, 818
Exposure frames, 634-636
Exposure testing
911
912
SUBJECT INDEX
qualitative analysis, 801-802
quantitative analysis, 802-803
resins, 806
retention parameters, 801-802
solid support, 799-800
solvent identification, 764
solvents, 149-151,803, 805
stationary liquid phase, 800
robing materials, 799
weaknesses, 801
Gas chromatography-mass spectrometry,
solvent identification, 764-765
Gases, 293-294
adsorption, particle-size
measurements, 313
as concrete materials, 295-296
displacement, 302
supercritical, as solvents, 400-401
Gas phase dipole moment, 392
Gassing test, metallic pigments, 227-228
Gas-solid chromatography, 790, 808809
Gavarti Gv Cat Test Unit, 722-723
Gearhart-Ball solvent resistance, 663664
Gel coat, thixotropy, 343
General Electric Impact Flexibility Tool,
553
General Electric Indention Tester, 566
Gibbs equation, liquids, 370
Gibbs free energy, 609
liquids, 370
Glass
beads
adhesion, pavement marking tape,
745
traff marking materials, 742
bonding, automotive products, 715
enamels, 71
insulating, sealants, 737
panels, as hiding power test substrate,
490
Glass transitions
dynamic mechanical analysis, 847
temperature
differential scanning calorimetry,
843-844
thermoplastic acrylic resins, 40-42
Glazes
ceramic, 68-69
lead-containing, 69
leadless, 68-69
matte, 69
satin, 69
Gloss, 470-479
aerospace and aircraft coatings, 688
architectural coatings, 702-703
artists' paints, 709
automotive products, 714
can coatings, 723
carbon blacks, 186, 189
definition, 470
directionality, 471-472
goniophotometry, 474-475
haze, 471
image clarity, 471
measurement, 477-478
Landolt ring use, 472-473
orange peel
measurement, 477
visual evaluation, 473
percentage, 581
pigment effects on, 173-174
reduction test, 527
913
914
P A I N T A N D COATING T E S T I N G M A N U A L
SUBJECT INDEX
Isocyanates
in polyurethane coatings, 90-91
reactive cross-linking, 410
ISO/DIN 3494, 530
ISO/DIN 4496, 749
ISO/DIN 4584, 530
ISO TC 35, 551
J
Kaolin, 217-218
electron microscopy, 823-824
Karl Fischer reagent method, solvents,
154
Katharometers, 797
Kauri-Butanol value, solvents, 132
Kelvin-Voigt model, 347-348
Ketimine, curing agents, 76
Ketones, 128
purity, 150-151
Kinetic stability, 610
Knife scrape, automotive products, 715
Knoop hardness number, 412, 564, 567
Knoop Indenter, 567-569
Krebs diamond-stripe hiding power
chart, 485-486
Krebs method, hiding power, 485-486
Krebs-Stormer viscometer, 683-684
Krieger-Dougherty model, 351-352
Kubelka-Munk equations, 170-171
Kubelka-Munk relation, 467
Kubelka-Munk two-constant theory, 491499
equation symbols, 491-492
hiding power
calculation from tinting data, 498499
general method, 492-493
relative, untinted white paints from
tinting data, 499
results, 495-496, 498
Judd graph, 493-495
Mitton graph and table, 495-497
original equations, 492
scattering coefficient and scattering
power, 492
theoretical problems and practical
considerations, 496-498
Laboratory testing
coating failure analysis, 778-779
traffic marking materials, 743-746
Lab roller mill, 416
Lacquers
coating failure analysis, 769
cure mechanisms, 408
915
Magne-gage, 429-430
Magnetic recording media, vinyl resins,
106
Magneto resistor, 431-432
Maintenance coatings, acrylic emulsion
polymers, 49
Mandrel bend tests, 542, 548-550
can coatings, 722
aerospace and aircraft coatings, 689
Manganese-doped ruffle, 214
Marangoni effect, 357-358
Marine atmosphere, 629-630
Marine finishes, vinyl resins, I05-I06
Mark-Houwink equation, 41,839
Mar resistance testing, 579-582
aerospace and aircraft coatings, 690
impinging abrasive method, 581
scuffing methods, 581-582
single scratch methods, 579-580
Martin's diameter, 309, 311
Masonry, 725-730
absorption testing, 725
alkali resistance, 727-728
application, 727
artificial weathering tests, 728
coatings, 726-727
definition, 725
efflorescence, 726
field testing, 728
moisture in, 727
performance tests, 727-729
pH, 726
porosity, 725
resistance to wind driven rain, 728
selection, 729
solvent-borne coatings, 727
specimens, 729
surface
finish, 726
pH after cleaning, 727
preparation, 727
treatments, VOC standards, 8
water-reducible coatings, 726-727
water-repellent coatings, 749-750
water vapor permeability, 728
Mass, 291
Mass color, definitions, 507
Mass spectrometry, 758
Masstone, 507
Mastic, coal tar, 732
916
Object colors
cylindrical systems, 451
opponent systems, 451-452
Obstructed-flow devices, 360-361
Odor
architectural coatings, 699
artists' paints, 708
automotive products, 713
plasticizers, 117
solvents, 149
Ohmic drop, 611
Oil
absorption
colored organic pigments, 207
titanium dioxide pigments, 169
pigments, 252-258
characterization of dispersions at oil
absorption point, 257-258
critical pigment volume, 253-256
SUBJECT INDEX
Asbeck-Van Loo method, 254-255
Cole method, 255
Pierce-Holsworth method, 255-256
critical pigment volume
concentration and, 256-257
determination methods, 252-255
mechanism, 252
gas chromatography, 805-806
vegetable, used in alkyd manufacture,
56
(see also Drying oils)
Oiticica oil, 27
Olefins, in solvents, 153
Opacity, 481
aerospace and aircraft coatings, 687
artists' paints, 708
carbon blacks, 183
dry, Federal Test, 489
titanium dioxide pigments, 170-171
Optical density, carbon blacks, 183
Optical measurement methods, contact
angles, 378
Optical properties
aerospace and aircraft coatings, 687688
pearlescent pigments, 230
Orange peel
measurement, 477
visual evaluation, 473
Orange pigments, 200-201,203-205
inorganic, 212
Orchard equation, 356
Organic coatings
deadhesion, 616
drying time, 439-440
on plastics, pull strength, 521
resistance to rapid deformation effects,
412
structural analysis, 758-759
(see also Architectural coatings;
Protective overlayers; Stress)
Organic paints, ceramic pigments, 214215
Organic pigments (see Colored organic
pigments)
Organic solvent resistance, aerospace
and aircraft coatings, 692
Organoclays, 282
Organosilica, as thickeners and rheology
modifiers, 282-283
Organosols, 104-105
Orifice cups, 359-360
Orthonitroniline orange, 200
OSA-UCS system, 459-461
Oscillating jet, 376-377
Osmometry, vapor pressure, 836
Ostwald-deWaele model, 337
Ostwald system, 459
Outdoor exposure, aerospace and aircraft
coatings, 691
Oxidative binders, coating failure
analysis, 769-770
Oxidative cross-linking, polymers, 408409
Oxidative drying, theory of, 30-31
Oxidative passivation, inorganic anticorrosive pigments, 239
Oxygen, weathering effect, 647-648
Oxygenated solvents, 127-130
Ozone
control in atmosphere, 9
effect on copper and silver corrosion,
612
nonattainment areas, 9
standard, 5
stratospheric protection, 11
917
918
SUBJECT INDEX
phenolics as cross-linking agents, 8283
reactive cross-linking, 409-410
solubility parameters, 393, 398-399
solutions viscosity, 350-351
used in sealants, 735-736
viscoelasticity, 572-573
viscosity, 547
Polymerization
emulsion, vinyl resins, 100
post processing, vinyl resins, 100
suspension, vinyl resins, 100
Polymethacrylates, properties, 39
Polyols, 108-109
Polysulfides, 111
sealants, 736
Polyurethane coatings, 89-94
catalysts, 91
chemistry, 90-93
definitions, 89-90
markets, 93-94
powder coatings, 93
radiation-curable, 93
raw materials, 90-91
reactions, 91-92
thermoplastic, 92-93
water-borne, 93
Polyurethane sealants, 736
Porcelain enamels, 69-71
Porosity, masonry, 725
Position-sensitive detector, 872
Pot life, aerospace and aircraft coatings,
686
Pour point, plasticizers, 117
Powder coatings, xiii-xiv
dielectric analysis, 855-856
epoxy polyester, cure, 859-861
epoxy resins, 78
pearlescent pigments, 231
polyurethane coatings, 93
vinyl resins, 106
Power law, 337
Precision Spectral Pyranometer, 632
Preservation, in-can, 261-262
Pretreatments, automotive products, 711
Primer, automotive products, 711-712
conductive, 712
electrodeposited, 711-712
nonconductive, 712
weatherable, 712
Princeton scratch tester, 532, 580
Print resistance, 572-573
architectural coatings, 704
Protective overlayers, 609-616
corrosion control, 615-616
thin metal films and microstructures,
612-615
Pseudoplastic, 339
Pull strength, organic coatings on
plastics, 521
Purge gas, differential scanning
calorimetry, 846
Putrefaction, artists' paints, 707
PVC latex, vinyl resins, 106
Pycnometers
helium gas, 297, 302
liquid, 298
methods, solvents, 147-148
solid density, 301
Pyrazolone orange, 200-201
O
Quality assurance
919
920
Slumping, 353
Smog, 3-4
Smoke characteristics, automotive
products, 713
Snell's law of refraction, 483
SNV 37 112, 574
Soap titration, emulsion particles, 313314
Sodium aluminosflicates, 220
Sodium carboxymethyl cellulose, 277
Softening point
coating, 547
thermoplastic marking material, 744745
Soil, preparation for aerospace and
aircraft coatings cleaning tests,
693-694
Solids, 293-294
as concrete materials, 295-296
content
total, in aerospace and aircraft
coatings, 684
by volume, paint, 756
by weight, paint, 755-756
density, 301-302
paint volume, 303
Solid support, gas chromatography, 799800
Solubility, 385
cellulose esters, 24
inorganic anti-corrosive pigments, 247
of solvents in water, 154
Solubility parameters, 383-402
applications, 393, 397, 399-401
dispersion, calculation, 387, 389-391
Hansen solubility parameters, 384-385
Hildebrand parameters, 384
hydrogen bonding
calculation, 392
temperature effects, 397
nomenclature, 383
partial, determination, 385-388
polar, calculation, 390, 392
polymers, 393, 398-399
solvents, 134
supplementary calculations and
procedures, 392-393
Solutes, adsorption onto pigments, 313
Solvency, solvents, 132-134
Solvent-borne coatings, traffic marking
materials, 741
Solvent/fuel resistance, 663-664
Solvent-reducible coatings, masonry, 727
Solvent reflux process, alkyds, 54-55
Solvent rub resistance, 411,542, 664
Solvents, xvi, 125-154
acidity, 152
acid wash color, 152
active, 131
alkalinity, 152
aniline point, 132-133
approved, 4
aromatics, nonaromatic hydrocarbons
in, 152
balance, 132
benzene content, 152
classification by chemical type, 125131
chlorinated hydrocarbons, 130
hydrocarbons, 125-128
nitrated hydrocarbons, 130
oxygenated, 127-130
supercritical carbon dioxide, 131
classification by function, 131-132
coalescing, 393
SUBJECT INDEX
color, 148-149
copper strip corrosion, 153
density and specific gravity, 144-148
calculations and conversion tables,
147-148
definitions, 145-146
digital density meter, 147
hydrometer methods, 146-147
pycnometer methods, 147-148
significance, 144-145
diluent dilution ratio, 133
dilution limit, 133
effect on stress in organic coatings,
593-596
electrical resistivity, 149-150
emissions, automotive products, 713714
failure modes associated with, 772773
gas chromatography, 803, 805
Heptane Miscibility Test, 154
identification, paint, 764-765
Karl Fischer Reagent Method, 154
Kauri-Butanol Value, 132
latent, 131
nonvolatile residue, 152
odor, 149
o|efins content, 153
organic, resistance, aerospace and
aircraft coatings, 692
oxygenated, 393
purity and composition, 149-151
esters, 151
gas chromatography, 149-151
ketones, 150-151
liquid chromatography, 150
refractive index, 149
selection using solubility parameters,
393, 397, 399
separation from vehicle, 756-757
solubility parameters, 134
solvency, 132-134
sulfur content, 153-154
supercritical gases, 400-401
tolerance, amino resins, 62
viscosity reduction, 133-134
volatility, 134-144
boiling point/distillation range, 137,
139-140
evaporation rate, 135-139
flash point, 140-144
vapor pressure, 134-135
water content, 154
water solubility, 154
(see also Hydrocarbons, solvents)
Sonic frequency shifts
liquid density, 299-301
solid density, 302
Sonic sifter, 317-318
Soybean oil, 27
Spatula and hand muller, 509
Spatula rub-out method, oil absorption
determination, 253-255
Specialty paints and coatings,
bituminous coatings, 16, 20-21
Specifications
considerations, 891
sources, 891-893
Specific gravity, 289-303, 290
colored organic pigments, 208
definition, 146
plasticizers, 117-118
solvents, 144-148
thermoplastic marking materials, 745
Spectrocolorimeters, 463
Spectrophotometers, 687
color measurement, 462-463
double beam, 826-827
pearlescent pigments, 231
techniques, particle-size
measurements, 323-324
Spectroradiometers, 463
Specular glass, 470-471
Spin coating, 422
Spinel brown pigments, 214
Spinning riffler, 308-309
Spoilage, artists' paints, 707
Spray application, architectural coatings,
702
Spray outs, 421
Spray rack, accelerated natural
weathering, 639
Spreading rate
contrast ratio at, 493
determination, 492-493
hiding power, 489-490
hiding power, 482
SS-A-118, 676
SSPC PA2, 435, 437
SSPC-VIS1, 435
SS-S-200E, 737
SS-W-110c, 749
Stain chambers, 659
Staining, 662-663
sealants, 737
Stainless steel flakes
grade classification, 225
properties, 224
State implementation plans, 5
State operating permit program, 10
Static coefficient of friction, 600
Statistics
in film thickness measurement, 437438
inorganic anti-corrosive pigments, 249
Steel flake, 245
Steel Wool Scratch Tester, 561-562
Step-shear method, thixotropic recovery,
342-343
St. Louis gage, particle-size
measurements, 327
Stokes equation, 361
Stokes E. S. D., 3t0
Stokes' law, particle-size measurements,
320-321
Stokes-Smoluchowski-Einstein theory,
338
Stopped method, 428-429
Storage stability
aerospace and aircraft coatings, 685
artists' paints, 706-707
can coatings, 722
traffic marking materials, 743
Stormer viscometer, 359-360
Straight line drying time recorder, 444
Straight-line reciprocating machines, 531
Strain
definition, 334-335
internal, 586
oscillating, stress response, 345-346
in tension and shear tests, 534
Strain rate
definition, 334-335
effect on flexibility and toughness, 548
Strand Gauge, 721
Stress
definition, 335
internal, 592
in organic coatings, 585-598
921
922
amino resins, 64
measurement, 373-378
dynamic, 376-378
static, 374-376
Surface thermodynamics, 370-373
liquid/solid interfaces, 372-373
liquid surfaces, 370-372
Sward hardness, 412
Sward Rocker Hardness Test, 573
Sward Rocker Hardness Tester, 575-578
calculation of number of rocks, 576
compared with K6nig and Persoz
hardness values, 578
comparison of rockers, 577
uses, 578
Swelling, 385
Syneresis, thickeners and rheology
modifiers, 274-275
Synthetic brown oxide, 212
T
Taber Abraser, 530
aerospace and aircraft coatings, 690
can coatings, 722
mar test, 532, 581
Table sampling, particles, 308-309
Tack-free time, sealants, 737
Tag Closed Cup Tester, 142, 144
Tag Open Cup Flash Point test, 142, 144
Tag tester, 686
Talc, 218
Tall off, 27
fatty acids, 85
Tape and wrap systems, 732
Tape test
adhesion, 517-519
aerospace and aircraft coatings, 688
can coatings, 722
TAPPI Method T649sm, 321
Technical societies, specification sources,
891-893
Teledyne Taber Shear/Scratch Tester,
561-562
Temperature
critical, 390
effect on
flexibility and toughness, 548
natural weathering, 624-626
variation, stress in organic coatings,
586
weathering effect, 647
Temperate climate, with pollution, 629
Tensile adhesion test, aerospace and
aircraft coatings, 688-689
Tensile creep experiment, 537
Tensile loss modulus, 535
Tensile modulus, relation to shear
modulus, 534
Tensile properties
definitions, 536-537
dynamic (see Dynamic mechanical and
tensile properties)
Tensile storage modulus, 535
Tensile strength
pavement marking tape, 745
relation to abrasion resistance, 525
Tensile stress relaxation experiment, 537
Tensile tests, aerospace and aircraft
coatings, 689
Terpenes, 127-128
Thermal analysis, 841-863
classification of material properties,
841
SUBJECT INDEX
Total solids, traffic marking materials,
743
Total ultraviolet radiometer, 632
Touch-up uniformity, architectural
coatings, 702
Toughness, 547-554
aging and weathering effects, 554
automotive products, 715
cold crack resistance tests, 554
cupping tests, 551-552
effect on coating performance, 547548
forming tests, 552-553
humidity effects, 548
impact resistance tests, 553-554
interpretation, 547
Mandrel bend tests, 548-550
strain rate effects, 548
t-bend tests, 550-551
temperature effects, 548
Toxicity
amino resins, 66-67
colored organic pigments, 204-206
evaluation, artists' paints, 710
inorganic anti-corrosive pigments, 245
pearlescent pigments, 235-236
polyamides, 87-88
Trace analysis, paint, 765
Traffic marking materials, 741-747
appearance and physical
characteristics, 743-744
auto-no-track time, 747
epoxy, 741
field evaluation, 746-747
glass beads, 742
laboratory testing, 745-746
laboratory testing, 743-746
liquid coatings, 741
laboratory testing, 743
pavement marking tape, 742
laboratory testing, 745
permanent tapes, 742
polyester, 741
removable tape, 742
solvent-borne coatings, 741
temporary tape, 742
thermoplastic material, laboratory
testing, 744-745
thermoplastic pavement markings,
741-742
water-borne coatings, 741
Traffic paint, abrasion resistance tests,
532
Transfer efficiency, automotive products,
715
Transmission, light, 448-449
Transmission electron microscopy, 822824
electron-optical column, 822-823
particle-size measurements, 319-320
types of contrast, 822
Transportation industry, staining in, 662
1,1,1-Trichloroethane, staged phaseout,
11
Tristimulus (filter) colorimeters, 463
Tristimulus values, 507
calculation, 453-454
from spectral data, 463
TT-C-555B, 728-729
TT-C-598B, 737
TT-F-1098D, 726, 729
TT-P-19, 658
TT-P-19D, 726, 728-729
TT-P-24D, 727, 729
TT-P-29, 700
923
characteristics, 99
definition, 99
dry film printing, 105
emulsion polymerization, 100
FDA status, 100
formulation, 101, 103
history, 99
inks, 105
magnetic recording media, 106
maintenance and marine finishes, 105106
manufacture, 99
market, 105-107
organosols, 104
packaging, 105
pigmentation, 103-104
plasticizers, 102-104
plastisols, 104
polymerization, 99
post-polymerization process, 100
powder coatings, 106
primers for plastisols and organosols,
104-105
properties, 101
PVC latex, 106
solubility, 101-102
solution characteristics, 102- 103
solution process, 100
suspension polymerization, 100
trends, 106-107
vinyl chloride copolymer coating
resins, 100-102
waterborne dispersions, 106
wood finishes, 106
Vinyltoluene, 43
Violet pigments, inorganic, 210
Viscoelasticity
industrial processes and, 348-350
polymers, 572-573
(see also Elastic liquids)
Viscoelastic models, 346-348
Viscoelastic parameters, 345-346
Viscoelastic properties, measurement,
548
Viscometers, 683-684
Viscometry (see Rheology and
viscometry)
Viscosity
aerospace and aircraft coatings, 683684
alkyds, 55
amino resins, 62, 64
artists' paints, 708
automotive products, 714-715
can coatings, 720
cellulose esters, 24
changes
artists' paints, 707
definition, 335
dynamic, 536
high-shear, thickeners and rheology
modifiers, 274
low-shear
architectural coatings, 700-701
thickeners and rheology modifiers,
274-275
medium-shear, thickeners and
rheology modifiers, 273-274
melt, 839
plasticizers, 118
polymer, 547
reduction, solvents, 133-134
relative, 839
shear-dependent, 337-339
solution, 839
924
Wetting, 372-373
Wetting-contact theory, 514
White hiding pigments, 499-501
concentration, 500-501
crystal and particle size, 499-500
dispersion, 500
film porosity, 500-501
microvoids, 501
Whiteness indices, 461-462
White paints
tinting strength, 508
untinted, relative hiding power from
tinting data, 499
White pigments, 159-178
calcium carbonate, 176-177
economics of hiding, 161- 162
extenders, 176
manufacture, 159-160
market, 159
research and development, 160
substance, 161-162
void pigments, 177-178
(see also Titanium dioxide pigments;
White hiding pigments)
Wilhelmy plate, 375, 377-378
Wilson/Tukon Hardness Tester, 571-572
Wire-wound rods, 420-421
WMO instrument house, 634
Wolf abrasion method, 529
Wolff-Wilborn Scratch-Hardness Tester,
562-563
Wollastonite, 220
Wood
finishes, vinyl resins, 106
treated, water repellency, 749
X
SUBJECT INDEX
electron beam excited X-ray
spectroscopy, 882-883
empirical methods, 884
field analysis, 886-887
film thickness measurement, 438
fundamental parameter methods, 884
on-line units, 882
physical basis, 881-882
pigment identification, 762
portable units, 882
procedures, 883
qualitative analysis, 883
quality control, 885-886
quantitative analysis, 883-884
scanning, 882
standard addition method, 884-885
surface analysis, 885
X-ray microanalysis, scanning electron
microscopy, 817-818
X-ray photoelectron spectroscopy coating
failure analysis, 768, 778
925