Professional Documents
Culture Documents
CORROSION CONTROL
COATING TECHNOLOGY
A JPCL eBook
iStockphoto/curraheeshutter
i
Advances in
corrosion control
coating technology
A JPCL eBook
Contents ii
FEVE RESIN
Contents
iv Introduction
1
FEVE Technology for Higher Performance Coating Systems on Bridges
Bob Parker, AGC Chemicals Americas
6 Technology
Mike ODonoghue Ph.D. and Vijay Datta MS, International Paint LLC
19
Paint & CoatingsWhere Are We Now?
Brian Goldie, JPCL
24
Improving Polyurethane Pipe Coatings for Harsh Conditions
Andreas aus der Wieschen, Matthias Wintermantel, Todd Williams and Ahren
Olson, Bayer MaterialScience AG
Raw Material Suppliers Answer Calls for Green and Smart Coatings
Introduction
This eBook features articles from the Journal of Protective Coat-
ings & Linings (JPCL) about technological advancements in
heavy-duty coatings for corrosion control.
iStockphoto/Bim
T he history of coating system types used on steel bridges has always paralleled the evolution
of coatings technology as a whole. When breakthroughs have occurred, the bridge coating
market has paid attention and embraced these advancements. Sometimes, regulations have
played a significant part in altering this course of evolution, but the goal of the stewards responsible for
bridge maintenance and preservation has never changed. The ideal coating system will always be the
one that offers the best protection of the substrate at a reasonable cost, with due respect for compli-
ance with regulations.
The most popular long-life coating system in place at this time for bridges with challenging applica-
tions and environments is a three-coat system consisting of a zinc-rich primer, an epoxy midcoat and a
polyurethane topcoat. Other less expensive coating systems still exist, but many provide lesser protec-
tion and have a shorter lifetime. Depending on the available funding for any specific bridge project,
these options may be the only choice. However, if the goal of the bridge steward is the ultimate protec-
tion of the bridge against structural degradation for the longest period of time, the standard three-coat
system is the preferred choice.
Fluoroethylene vinyl ether (FEVE) fluoropolymer technology has proven to be a successful addition
to the global bridge coating market (Fig. 1). In the U.S., there is a growing interest from state DOTs,
Performance Properties
Both accelerated exposure testing and real-life exposure testing have been per-
formed on coatings using FEVE technology. Figures 4 (p. 40) and 5 show com-
parisons of FEVE resin-based coatings with different coatings also used as
topcoats for bridge coating systems.
The graph in Figure 4 shows two different FEVE resin-based coatings a
100% FEVE polyol, and a 78% FEVE polyol blended with 22% polyester polyol.
FEVE solvent-based resins, like the FEVE emulsions, have a wide range of com-
patibility with other polyols. Laboratory work is being done to measure the per-
formance capabilities of these blended formulations. Some physical properties of
the paint film, such as flexibility, can be improved when non-FEVE polyols be-
come part of the formulation. As this graph shows little change with the 60-de-
gree gloss at 3,000 hours, the exposure is still in progress.
The second test exposure was done at the Equatorial Mount with Mirrors for
Acceleration with Water (EMMAQUA) test site in Arizona (Fig. 5). The meas-
urement of UV exposure is in megajoules per square meter (MJ/m2). Again,
the FEVE coating showed the best gloss retention percentage of all the coat-
ings tested.
Certain bridge applications are being monitored for their performance. The
The Tokiwa bridge is located in Japan (Fig. 6). This bridge was recoated in
1986, using two coats of an epoxy primer and two coats of a FEVE-based top-
coat. The changes in 60-degree gloss and color over 25 years of exposure are
shown in Table 1 (p. 3).
Additional Considerations
Because the main function of FEVE resin-based coatings is to extend the life of
the coating system, it is important to point out other proposals for bridge coating
longevity that should to be considered in order to achieve this goal. Some
thought has been given to expanding the procedure for coating a bridge so that
the critical components of the bridge get the best protection from the coating sys-
tem. Conversely, the remaining components, which are not prone to early coating
failure, can be given a lesser degree of protection. This idea is explained in detail
in a JPCL article written in 1984 by Clive Hare, entitled Specific Utility In the De-
sign of Coating Systems for Steel Bridges. Hare states that, The ever-increas-
ing demands on bridge paint systems (fed by increasing traffic loadings, salt
usage, and years of neglect) must be met by the use of heavier duty coating sys-
Fig. 6: These photos show the Tokiwa Bridge in Japan, which was tems applied with great exactitude over better surfaces.
coated with a FEVE-based topcoat in 1986. The photo on the top
The article goes into detail about specific areas of bridges that have historically
was taken in 1988, the middle photo in 1993, and the photo on
the bottom in 2014. Clearly, there has been very little change in experienced premature coating failure resulting in damaging corrosion of the
the coating's gloss and appearance over the years. steel. The seams, edges, bolts and rivets of bridges are most susceptible (Fig. 7).
These are the areas that need coating systems that are more functional for corro-
sion resistance. In many instances, these areas do not receive the level of UV radiation experi-
enced by other parts of the bridge, but the need for recoating is still critical.
The use of a FEVE resin-based topcoat has demonstrated the ability to resist the penetration
of chloride ions through energy-dispersive X-ray microanalysis testing. However, the difficulty of
attaining success lies in the morphology of certain bridge components and the challenge of
coating application on these components. Although FEVE technology can offer greater
longevity of the topcoat on a bridge, the protection of every steel surface, for up to thirty years,
is still a significant challenge.
Conclusion
Although FEVE technology has shown itself as a viable alternative to standard topcoats for the
three-coat system for bridges, research is continuing on the utilization of this technology in
combination with zinc-rich primers or epoxy primers to create an effective two-coat system.
The elimination of an entire coat will significantly lower the final cost of the coating project.
As the evolution of coatings for bridges continues, the ultimate goal will always be the most
Fig. 7: Certain bridge components such as efficient protection of the steel substrate at the most reasonable cost. If we can succeed in pro-
seams, edges, bolts and rivets still present
coating and life cycle challenges, even for
longing the life of an important part of our nations infrastructure, much will be gained from this
FEVE-based coatings. success.
JPCL
T he demand for enhanced productivity, cost reduction, fast throughput, and optimization of
life cycle costs associated with high-performance lining applications is often met using
two-component, solvent-free polyurethane, polyurea, and polyurethane/polyurea hybrids.1-3
Moreover, these thermoset technologies can readily comply with todays stringent environmental regu-
lations, as exemplified by their low- or zero-VOC content and absence of oxygen-depleting substances
(ODSs).
The genesis of polyurethanes hails back to the pioneering work on isocyanates by Otto Bayer in
1937. As a result of Bayers work, thin-film polyurethane finish coats later became for decades the de
facto finish coat of choice on structural steel. It was not until the early 1980s when thick-film and single-
coat solvent-free aromatic polyurethane linings were formulated
for use on girth welds, valves, and pipe. By the mid-1980s, ad-
vanced versions of these polyurethane linings were being used on
large-scale pipe rehabilitation projects in Western Canada.4 Then,
by the late 1980s, an innovative generic class of thick-film and sin-
gle-coat solvent-free coatings and linings emerged on the
scenepolyureas.57 Like their fast-reacting and fast-curing
polyurethane predecessors, the even faster gel time and cure time
of the polyureas necessitated that these linings be applied by plu-
ral-component spray equipment.
In the early 1990s, further advances led to new and improved
polyurethane and polyurea linings in which properties could be
customized. Later, various hybrids of both technologies were de-
veloped and touted by some to have a combination of the best
properties of multiple technologies.8 Interestingly, many of todays
so-called polyurethanes are actually hybrids, and the implied ter-
minology distinctions among polyurethane, polyurea, and
polyurethane/polyurea hybrid descriptions has become somewhat
blurred.9 For example, a coating may be described as a
polyurethane, but it is actually a hybrid.
This article will focus primarily on very fast-cure, solvent-free
polyurethanes, polyureas, and polyurethane/polyurea hybrid tech-
nologies, many of which are well-suited to immersion service: the
veritable Titans of the Abyss.
The chemistry, cure mechanism, safety aspects, strengths, and
weaknesses of each technology will be discussed. Case histories
will be provided for each technology.
In todays fast-track lining projects, the gel time and cure time of
a given lining might vary from a few seconds to a few hours. Coat-
ing formulators and polymer chemists can utilize these technologies to carefully tailor elas-
tomeric or high-tensile strength rigid linings for specific tank and pipe internals or externals.
Depending on the chemistry of a polyurethane, polyurea, or hybrid, the applications for
these linings are diverse.
Examples of applications include the following:
penstocks, riveted and welded;
potable water processing, transportation, and storage;
aquariums;
pipelines exposed to raw sewage and erosion degradation;
Fig. 1: Polyurethane formation
concrete digesters;
cooling water intakes;
primary and secondary containment;
rail cars;
oilfield pipelines;
icebreakers (underwater hulls);
platforms;
barges;
syntactic foams for sub-sea projects;
and
Fig. 2: Polyurea formation
food storage.
Each service represents conditions in which one or more factors, such as corrosion and
erosion resistance, flexibility, immersion resistance, and wear resistance are important. All three lining
technologies have been used on carbon steel, galvanized steel, ductile iron, and concrete substrates.
Definitions
In terms of chemistry and cure mechanism, a more thorough definition of polyurethane, polyurea, and
hybrid technology is available from the Polyurea Development Association.12
Polyurethane: For reference purposes, a polyurethane coating/elastomer is that derived from the
reaction product of an isocyanate component and a resin blend component. The isocyanate can be
aromatic or aliphatic in nature. It can be a monomer, polymer, or any variant reaction of isocyanates,
quasi-prepolymer, or a prepolymer. The prepolymer, or quasi-prepolymer, will be made from hydroxyl-
terminated polymer resins.
The resin blend must be made up of hydroxyl-terminated polymer resins, being diol-, triol-, or multi-
hydroxyl polyols, and/or aromatic or aliphatic hydroxyl-terminated chain extenders. The resin blend
may also contain additives, or non-primary components. The resin blend will contain catalyst(s) for sys-
tem reactivity.
Polyurea: A polyurea coating/elastomer is that derived from the reaction product of an isocyanate
component (as described for a polyurethane) and a resin blend component. The isocyanate can be
aromatic or aliphatic in nature.
The resin blend must be made up of amine-terminated polymer resins, and/or amine-terminated chain
extenders. The amine-terminated polymer resins will not have any intentional hydroxyl moieties. Any hy-
droxyls are the result of incomplete conversion to the amine-terminated polymer resins. The resin blend
may also contain additives, or non-primary components. These additives may contain hydroxyls, such as
pre-dispersed pigments in a polyol carrier. Normally, the resin blend will not contain a catalyst(s).
Disadvantages
Advantages of Polyurethane Linings of Polyurethane Linings
Rapid productivity in shop and field applications, e.g., pipelines Moisture sensitivitysusceptibility to
Elimination of solvents and compliance with stringent air pollution regulations (VOCs) thickening, gelation, and foaming
Single coat, high-build applications up to 250 mils (~6,000 microns) Relatively low alkali and solvent resistance
Formulated in a broad spectrum of cure timesminutes to hours Potential allergic reactions due to any
Rapid curing even at sub-zero temperatures free isocyanate content
Formulation diversity based on vast selection of polyol and isocyanate raw materials Susceptible to undercutting and peeling
when immersed linings are
Customized water and chemical resistance, flexibility, and impact resistance
mechanically damaged when not
Coated pipes are readily inspected and buried within minutes of application formulated properly for this service
Low surface frictionexcellent hydraulic characteristics for pipeline internals Poor cathodic disbondment resistance
Good cathodic disbondment resistance at temperatures below 50 C at temperatures above 50 C
Can be used with geotextiles Poor hot water adhesion
Abrasion resistance can be superior to AR steel Poor color retention in aromatic
Repairable by hand within minutes (kits available) polyurethanes with UV exposure
Table 2: General Comparison of Polyurethane, Polyurea, for ambient temperature water and wastewater
and Hybrid Properties in the Coatings and Linings Industry immersion service (domestic waste and indus-
trial waste at a pH from less than 1 to 14).
Property Polyurethane Polyurethane Polyurea Polyurethane Hybrid
Certain hybrid linings use hydroxyl- and
Hybrid Advantage
amine-containing resins that have very little to
Gel time Seconds Instant set Instant set Superior
to hours to minutes substrate wetting no oxygen atoms, or other atoms that would in-
crease polarity in the resin backbones. This
Tack free Minutes One minute 630 Rapid return
to hours to hours seconds to service chemical make up causes the hybrids to be
Tensile Up to Up to Up to Higher tensile much more hydrophobic than polyurethane
strength 7,000 psi 7,000 psi 4,000 psi strength and polyurea linings. The hybrids also resist
Tensile Up to 500% Up to 500% Up to 700% Lower elongations chemicals as much as, or better than, many
elongation however, significantly polyurethane and polyurea linings.
lower permeability
Shore 50A to 85D 5OA to 85D 50A TO 85D Harder, better General Discussion
hardness D impact resistance
Table 2 provides a general comparison of
Abrasion Pure As low as 76 mg loss Hybrids often
polyurethane, polyurea, and
resistance polyurethanes 30 mg (H18 wheel) have better
typically (H18 wheel) abrasion resistance polyurethane/polyurea hybrid properties in the
have best coatings and linings industries.
AR props A high degree of surface preparation must
Tear resistance Up to 500 pli Up to 500 pli Up to 500 pli Similar tear be done in order to ensure that the solvent-
resistance
free and high-build polyurethane, polyurea,
Moisture vapor Too low Too low 42 Significantly better
and hybrid linings will perform well for many
transmission to detect to detect g/m2/24hrs resistance to
the passage years and provide the owner with a good re-
of moisture turn on his investment. For optimum results,
steel surfaces should be free of surface con-
taminants such as soluble salts, grease, and oil; be abrasive blasted to a minimum SSPC-SP 10;
and have a deep and jagged profile of 35 mils (75125 microns).
By virtue of their short pot lives and fast curing properties, these linings are applied using plural-
component, hot airless spray equipment. Humidity control is important, and the surface temperature
should be at least 3 degrees C above the dew point.
One of the key areas where polyurethane and hybrid technology have demonstrated long-term
immersion performance has been in the lining of potable water tanks and pipes. Certified to the
ANSI/NSF 61 standard, these coatings have a long track record when applied to steel substrates.
The same is true for polyurethane coatings applied to the interior and exterior of steel per AWWA
C222-99. The rapid curing characteristics of this technology, coupled with the need to use special-
ized equipment, behooves owners to select qualified applicators and ensure that third-party inde-
pendent inspection is provided to ensure a successful application.
Lining and relining steel penstocks is another application where polyurethane and hybrid
polyurethanes excel.14,17 Of particular note is that a single-coat application of these films can provide
long-term corrosion protection to rivets in penstocks, some designed and installed in the 1940s.
Another immersion environment where polyurethane and hybrid polyurethane linings have been
used is the underwater hulls of ice breakers.18 The excellent abrasion resistance and low frictional
resistance indicate that these coatings would be well suited to resist abrasion and ice impact. While
these characteristics proved to be the case on many icebreakers, in more recent years, epoxy lin-
ings have become favored more than polyurethane and hybrid polyurethane linings for icebreaker
underwater hulls.
Table 3: Transmission Pipeline Coating Testing The low temperature cure of some
polyurethanes and hybrid urethanes is very
Solvent-Free Hybrid Polyurethane: Testing in Accordance with Qualification Protocol for Liq-
uid Epoxy Coatings useful in cold climates. In the Canadian oil
Test Test Method Test Results patch, for instance, where several fast-set
28 day cathodic disbondment @ 20C 35.9 mm epoxy coatings are used for transmission
28 day cathodic disbondment @ 65C CSA Z245.20-06 1.8 mm pipeline externals, some owners prefer the
28 day cathodic disbondment @ 80C Clause 12.8 0.6 mm
use of fast-set polyurethane linings. Judi-
ciously selected and qualified high-perfor-
28 day adhesion @ 65C CSA Z245.20-06 #2 ratings
28 day adhesion @ 80C Clause 12.14 #1 ratings mance polyurethanes and hybrids are well
suited to year-round rehabilitation of steel
1.5 J impact resistance @ -30C, -10C, 0C, CSA Z245.20-06 No holidays pipelines.19 It should be noted, however, that
23C, 65C and 75C Clause 12.12 the service temperature for suitable
1.5 flexibility @ 0C No cracks or
polyurethanes is invariably rated up to 65C,
1.5 flexibility @ -30C CSA Z245.20-06 stretch marks i.e., less than the temperature of alternative
2.5 flexibility @ 0C Clause 12.11 Cracking and qualified epoxy coatings with high glass tran-
2.5 flexibility @ 0C disbondment sition temperatures.
Considering accelerated laboratory testing,
Hardness (-30C, -10C, 0C and 23C) Shore D 80 to 85 the authors have stressed, in previous work,
the importance of not relying heavily on cer-
ASTM D2240
tain tests and understanding the relevance of
Hardness (65C and 80C) Shore D 57 to 68
said tests.20 For transmission pipeline coat-
Gouge Test NACE Draft 54.1% ings, caution must be exercised in not placing
too much credence in any individual pre-quali-
Electrochemical Impedance Spectroscopy ISO 16773 Log Z > 10 fication test. Therefore, testing programs for
(10.7 to 10.8)
epoxies, polyurethanes, and polyurethane hy-
brids typically consist of a regime that in-
cludes electrochemical impedance, cathodic disbondment resistance, wet adhesion, impact
resistance, flexibility, hardness, and gouge-resistance assessments.
Table 3 shows the pre-qualification test results for a thick film, solvent-free polyurethane hybrid
developed for use on a major oil companys transmission pipelines.21 The coatings wet adhesion
characteristics and its impact resistance were excellent, and it displayed good flexibility at the 1.5
degrees per pipe diameter bend, but displayed poor flexibility at a 2.5 degree bend. Gouge resist-
ance was rated at 54.1% (average gouge depth of total film thickness). The coating showed excel-
lent electrochemical impedance characteristics, with the log Z impedance remaining constant
during 28 days of exposure to the test conditions.
In the final analysis, all the test results were excellent, except for one anomalous result in the CD
test in accordance with CSA Z254-20-02. Outstanding cathodic disbondment resistance was exhib-
ited by the polyurethane lining at elevated temperatures. At 80C for 28 days, the average disbond-
ment radius was 0.6 mm; at 65C for 28 days, the average disbondment radius was 1.8 mm.
However, at 23C for 28 days, the average disbondment radius was 35.9 mm. At first glance, this re-
sult would disqualify the coating until the coating chemistry and the relevance of the test methodol-
ogy were considered in addition to other physical tests. The coating has a much higher tensile
strength (6,000 psi) and elasticity at ambient temperature when compared to its tensile adhesion
(3,500 psi). Therefore, in the CD test at 23 C, this polyurethane coating had a very high molecular
strength, but the coating would peel when pried off in the CSA test, thereby erroneously giving the
impression of poor adhesion. Elevating the test temperature to 65 C and 80 C progressively lowers
the tensile strength, and the coating subsequently becomes more difficult to pry from the substrate.
Hence, caution should be exercised in the disqualification criteria for a polyurethane (or polyurea
lowed by one coat of polyurea.26 The asset can be rapidly returned to service because of the rapid
curing characteristics of the polyurea.
An innovative bonded geomembrane system for the application of certain polyurethane hybrids
to concrete surfaces has gained acceptance and is schematically depicted in Fig. 8. The geomem-
brane basically consists of pre-cut, heat-set, non-woven 100% polypropylene geotextile fabric pan-
els that are embedded between two layers of polyurethane hybrid.8 The panels are pressed onto a
still-fluid basecoat (or the concrete) and are held in place with Hilti-studs. Then, the panels are top-
coated. The system is especially suited to vertical, new, or old poured-in-place concrete surfaces
(walls). The polyurethane hybrid is reported to bridge bugholes and other voids in concrete as well
as eliminate pinholes produced by the normal outgassing of concrete. Hence, the fabric filters and
dissipates air or water vapor throughout itself. Therefore, there is said to be no way for outgassed
air to blow holes through the coating when it is being applied as a topcoat onto the geotextile fabric.
Once applied, (a) the embedded fabric can dissipate hydrostatic pressure and (b) remain unaf-
fected by normal surface shrinkage cracks, most dynamic cracks and the designed movement of
expansion joints in concrete.
Conclusions
Solvent-free polyurethanes, polyureas, and polyurethane/polyurea hybrid technologies have shown
promise for immersion service in various market segments.
A wide array of solvent-free technologies of this type can be formulated to have a plethora of
chemical physical properties by carefully selecting the amines, polyols, or a combination thereof.
This is particularly true for the polyurethanes and polyurethane hybrids.
Solvent-free polyurethanes, polyureas, and polyurethane/polyurea hybrid technologies can be
used in either a pure form or when slightly modified to customize required performance properties.
Acknowledgements
The authors are indebted to Dan Schneider of Polibrid, Jeff and Mark Buratto of Lifelast Inc., and
Mark Dromgool of KTA-Tator Australia for their valuable insight with respect to polyurethane,
polyurea, and polyurethane hybrid linings.
References
1. H. Hower, PolyureasWhats in a Name? JPCL (December 2003), pp. 3133.
2. C.H. Hare, Polyurethanes. In Protective Coatings, Fundamentals of Chemistry and Composition,
1994.
3. T. Kenworthy, 100% Solids Polyurethane and Polyurea: A Comparison of Properties and Uses,
JPCL (May 2003), pp. 5863.
4. R. Alliston and J. Dzatko, Recent Advances in Epoxy Coatings for Automated External
Rehabilitation of Pipelines, NACE Northern Area Western Region Conference, Anchorage, AK,
2001.
5. D.J. Primeaux II, Polyurea Elastomer Technology: History, Chemistry and Basic Formulating
Techniques, 2004.
6. D.J. Primeaux II, Two Component Polyurea Coatings/Linings. In Selecting Coatings for Industrial
and Marine Structures, SSPC: The Society for Protective Coatings, Pittsburgh, PA, 2008,
pp. 107123.
7. D.J. Primeaux II, The Protective Coatings Specialist and Polyurea: The Sequence of Events, JPCL
(September 2012), pp. 5057.
8. D. Schneider, Polibrid Coatings Inc., personal communication, August 2012.
9. M. Winter, Discussion on Polyurea Linings for Oilfield Applications, International Paint LLC, April
2011.
10. Introduction to Thick-Film Polyurethanes, Polyureas and Blends, T-6A-67 Technical Committee
Report No. 6A198, NACE International, Houston, TX, 1998, pp. 18.
11. M. Broekaert, Polyurea Spray Coatings: The Technology and Latest Developments, European
Coatings Conference, pp. 3755.
12. Polyurea Elastomeric Coating/Lining Systems, Polyurea Development Association General
Guidelines, Kansas City, MO, 2003.
13. G. Oertel, Polyurethane Handbook, Second Edition, Hanser Publishers, 1994.
14. M. Buratto, Lifelast Inc., personal communication, August 2012.
15. S. Guan, High Solids and 100 Percent Solids Aliphatic Polyurethanes for Exterior Applications: A
Survey of Approaches, JPCL (July 1997), pp. 4452.
16. D.J. Primeaux II, Spray Application of 100% Solids Plural-Component Aliphatic Polyurea
Elastomer Systems, JPCL (March 2001), pp. 2632.
17. R.D. Stutsman, Innovations in Penstock Lining, Hydro Review, May 1993.
18. Study on Hull Corrosion and Coatings, B.H. Levelton & Associates Ltd., October 1988.
19. R. Garret, HDIM, personal communication, November 2012.
20. M. ODonoghue, V.J. Datta, M. Winter, and C. Reed, Hubble, Bubble, Tests, and Trouble: The
Dark Side of Misreading the Relevance of Coating Testing, JPCL (May 2010), pp. 3045.
21. J. Buratto, Lifelast Inc., personal communication, October 2012.
22. M. ODonoghue, V.J.Datta , and R. Spotten, Angels and Demons in the Realm of Protective
Coatings: The Underworld of VOCs, JPCL (April 2011), pp. 1429.
23. F.M. Fowkes, The Role of Adhesion in Corrosion Protection by Organic Coatings, JOCCA
(October 1985), p. 229.
24. C. Reed, International Paint LLC, personal communication, October 2012. 25.
25. Madison Chemical, http://www.madisonchemical.com.
26. J. Wynne Darden, D. Zabinski, and S. Smith, Spray Polyurea Coatings for Protecting Concrete
Structures, pp. 178184.
27. L. Hanson, Hanson Group, personal communication, November 2012.
28. K. Nollsch, International Paint LLC, personal communication, November 2012. JPCL
JPCL
A s with other topics in this special section, coatings developments have been covered in
JPCL regularly since 1985. The last main review was in the 25th Anniversary issue (Au-
gust 2009), where Michael Donkin summed up the changes in coating formulation for the
heavy-duty protective market since JPCL started. He discussed the drivers for change over that time
and how they had led to the introduction of new technologies. The present article will summarize
Donkins findings and then look at key developments for the protective and marine coatings since
2009. This article is not claimed to be comprehensive, but is instead a guide to some of the main con-
tinuing trends and innovations.
Waterborne Coatings
The introduction of waterborne coatings has
been limited essentially to two market areas:
coatings for internal use or very low and now
moderate corrosivity areas, and sealants and
coatings for concrete.
As metal coatings, low-VOC, two-component
waterborne polyurethanes have been developed
as primers and direct-to-metal systems for com-
ponents for light industrial projects. For concrete
and masonry applications, acrylic systems are
popular as topcoat/sealers to give good weather
and chemical resistance.
Waterborne epoxies have also been devel-
oped as concrete coatings, particularly for coat-
ing moisture-sensitive concrete (flooring).
istockphoto.com/leofrancini Systems have been developed as sealers and primers that can also be applied over green concrete
and that have good adhesion without the need for a profile. Waterborne epoxy floor topcoats are also
available, including antistatic versions.
High-Solids Coatings
Conventional solvent-borne coatings have volume solids contents of around 5060%. High-solids
coatings can be divided into solvent-free systems (100% solids) and those solvent-borne systems
with higher solids than the traditional coatings. In this summary, high-solids coatings are defined as
those with volume solids greater than 70%.
Higher-Solids Coatings
The higher-solids protective coatings are generally based on polysiloxane resins and polyureas. High-
gloss topcoats for steel, with good durability and corrosion protection as well as fast cure have been
developed based on modified polysiloxanes. An even more environmentally friendly type of system, an
isocyanate-free single-component acrylic-siloxane, features good abrasion and a low VOC.
Aliphatic polyurea and polyaspartic resin systems also feature fast cure and high gloss for concrete
floors and for medium corrosivity steelwork protection.
High-solids epoxies with a range of curing agents, including phenalkamines, are used for immersion
and atmospheric protection of steelwork and concrete floors.
Conventional Coatings
Although the trend is for higher-solids (or waterborne) coatings to meet the VOC regulations,
there have also been developments in the traditional solvent-borne coatings, although volume
Specialty Coatings
Intumescent Coatings
istockphoto.com/GBlakeley
Fire protection has become an important subject for many raw material suppliers, as observed at the
European coatings shows in 2011 and 2013, and for paint companies. For cellulosic fires, 120 minutes
of protection are being provided by one-component, solvent-borne, acrylic intumescent coatings, with
some systems that can be applied under shop conditions or onsite.
Marine Coatings
As with protective coatings, there have been changes in marine coating over the past 30 years. The
25-year review identified the key developments that had occurred up until 2009. These mainly in-
volved hull coatings, resulting in two alternative high-performance antifouling technologies: tin-free
polishing coatings (copper-containing), and low-energy, foul-release coatings (silicon and fluo-
ropolymers).
Since 2009, very little has occurred, but various paint manufacturers have been making incre-
mental changes to their products to establish differentiation among them and have been partnering
with third-parties in an attempt to develop a methodology for measuring and validating claims about
potential fuel savings.
However, a copper-free, high-performance antifouling has become available that is based on self-
polishing binder technology and is aimed specially at keeping underwater hulls clean from fouling
while vessels are stationary in seawater.
The other major concern in the shipbuilding industry has been the corrosion of seawater ballast
tanks and the establishment of the IMOs Performance Standard for Ballast tank coatings. The IMO
requirements were essentially copied for a regulation describing a performance standard for cargo
oil tanks. This regulation has provoked some concern about the testing of (new) coatings to meet
the standard.
Polysiloxanes, which are showing increased usage in the protective coatings sector, are also
starting to appear in marine coatings, with durable, aesthetic topcoats that are easy to clean and
maintain, thus saving on costs
The Future
What does the future hold for protective and marine coatings? Health & safety and environmental
regulations will still drive coatings development. It is most likely that the VOC restrictions will get
even more restrictive. We do not know what technologies will become more dominant: waterborne
or high-solids. Various industry forecasts predict strong growth in waterborne systems, and going
by the products exhibited this year at the European Coatings show, the resin suppliers are all active
in this area. However, when I talk to the formulating chemists in the protective coating manufactur-
ers, they all agree that for the next 10 to 20 years, 80% of the heavy-duty and marine coatings will
be solvent-borne, albeit with higher volume solids than currently.
The use of other toxic or hazardous raw materials will be banned and more environmentally sus-
tainable raw materials will become available.
With a great deal of research being carried out in nanotechnology for coatings, it is expected that
we will see new smart or functional coatings coming to the market. Already, we have had demon-
strations of what this technology can deliver, and market acceptance should follow once new formu-
lations have been demonstrated in the field and production methods have been scaled-up.
Brian Goldie, technical editor for JPCL, has worked with protective coatings for many years,
including in the oil industry.
JPCL
Bayer MaterialScience AG
Olson
L iquid polyurethane (PU) coating systems are of growing importance in the field of external
coatings for oil and gas pipelines. Coating systems based on aromatic polyisocyanates
and pre-polymers are used for new pipeline construction and for maintenance work.
Major drivers for the use of polyurethane coatings in pipe applications are their favorable cure char-
acteristics combined with superior mechanical properties especially under harsh conditions. Solvent-
free, two-component polyurethane systems have been approved as suitable protective coatings
systems within the pipeline industry and have been used for new tubes (steel and ductile iron) and for
field joints.
Furthermore polyurethanes are of growing importance for the renovation of oil and gas pipelines in
the field due to their ability to cure at low temperatures and their exceptional mechanical properties.
Application Properties
Solvent-free two-component PU coatings have
the ability to create an inherent thickener effect
during application. This effect avoids sagging on
vertical surfaces and allows the formation of high
film thicknesses applied in one coating layer.
Therefore PU systems can fulfill the postulated
requirements with dry film thicknesses of about a
minimum of 500 m up to 5,000 m and higher.
Mechanical Properties
Fig. 2: High versatility for adjusting mechanical properties elongation and Shore hardness Most relevant technical parameters for oil and
gas pipeline coatings are related to mechanical
properties such as film hardness and flexibility along with adhesion, and resistance to chemicals
and solvents. Liquid polyurethane pipe coatings typically provide increased impact resistance at
higher Shore hardness than standard pipe-coating epoxy systems. High-impact resistance is bene-
ficial because the transport of coated pipes to the site and the laying procedure in the soil can dam-
age the coating. Flexibility is important because PU-coated tubes in the field must endure bending
and must withstand frost during winter in colder regions. High abrasion resistance of the coating is
advantageous for withstanding soil stress.
The physical strength of polyurethane systems allows them to withstand mechanical forces longer,
such as creep. These mechanical properties can be customized by varying the ratio of hard and soft
segments, molecular weight and the crosslinking density of the cured film. Therefore it is possible to
create different PU coatings with physical properties that can range from soft, plastic across elastic up
to hard, rigid and even brittle.
Figure 2 displays the potential versatility in adjustment of mechanical properties of polyurethane
coatings. It compares different polyurethane formulations in terms of flexibility measured as elonga-
Laboratory Testing
Cathodic Disbonding Test
Various test procedures exist within the pipeline industry and have different requirements for voltage,
temperature, salt solution and test period. The most regularly-used test methods follow standards
ASTM G8, Standard Test Methods for Cathodic Disbonding of Pipeline Coatings, and ASTM G42,
Standard Test Method for Cathodic Disbonding of Pipeline Coatings Subjected to Elevated Tempera-
tures.
Polyurethane pipe coatings which provide higher crosslinking densities in the cured film usually pass
the cathodic disbonding tests up to 65 C. The prepared surface, specifically the roughness profile after
blasting, has an important influence on adhesion and cathodic-disbonding-test results. The minimum
surface quality should be Sa 2.5 with a roughness minimum of 5070 m, and a recommended rough-
ness of 80100 m.
Pipe coatings must fulfill certain cathodic-disbonding properties. Figure 3 illustrates a schematic de-
sign of a cathodic disbonding (CD) test. CD tests are used to evaluate the damaged coating's delami-
nation behavior using conditions that model the service environment including cathodic
protection, elevated service temperature, and salt solution (representing ground water).
Steel panels with different surface profiles (roughness) were tested at various tempera-
tures. Coated steel panels were sent to an independent test institute for investigation of
cathodic disbonding characteristics according to T/SP/CW/6 Part 1. The tests were car-
ried out for 15 days at 80 C and for 15 days at 95 C. The electrolyte was maintained at
30 C in both tests. The results of these tests were approximately 3 mm disbondment
after 15 days at 80 C and approximately 5 mm disbondment after 15 days at 95 C.
Figure 4 depicts the result of the cathodic disbonding test after 14 days at 80 C. The
result in terms of adhesion and disbondment is very good at surface roughness of ap-
proximately 30m. The requirement is normally 80120m. In this case it was not possi-
ble to lift the coating with a knife at the end of the test.
Blasting
After shot blasting the surface with garnet, the profile measured Sa 2.5 and the average
roughness was approximately 70 m.
Adhesion ++ ++ ++ ++
crosslinked yielding exceptional cathodic-disbonding proper-
Conclusion
Polyurethane pipe coatings are a versatile product class that can be tailored to meet a wide range of
end-use applications. Varying the catalyst, crosslinker and polyol allows the coating formulator to de-
velop a range of properties from elastomeric to rigid. A new class of rigid polyurethane pipe coating raw
materials were developed to meet higher cathodic disbondment requirements and their performance
under harsh, real-world conditions looks promising.
Dr. Matthias Wintermantel holds a Ph.D. in macromolecular chemistry from the University of Bayreuth,
Germany. Since October of 2012 Dr. Wintermantel has been responsible for product development for
protective coatings, construction coatings and pipe coatings within the EMEA region and Latin America
for Bayer MaterialScience AG.
Todd Williams earned a Ph.D. from the University of Southern Mississippi in 2005 where he wrote his
thesis on alkyd-modified latexes. After a two-year post-doctoral position studying polyurethane coatings
and two years with startup Segetis focusing on renewable polymers, Williams joined Bayer Materi-
alScience developing UV-curable coating formulations. In 2012 he became manager of the companys
corrosion protection group.
Ahren Olson is the marketing manager for corrosion protection with Bayer MaterialScience LLC in
Pittsburgh, Pa. He has been with Bayer for 10 years, with experience in automotive, construction and
corrosion-protection coatings. He holds a Bachelor of Arts degree with a major in chemistry from The
College of Wooster. Mr. Olson currently provides market development support in Bayers efforts to un-
derstand and prevent corrosion for the heavy and light-duty industrial-maintenance markets.
JPCL
A t the end of March 2011, the worlds paint raw material suppliers met at the European
Coatings Show in Nuremberg, Germany.
The bienniel show, which is the largest coatings event in Europe, had a record 26,000
trade visitors this year. Some 890 suppliers to the paint industry from 45 countries displayed their new
and traditional products. At the parallel European Coatings Congress, 650 participants from 40 coun-
tries heard some 150 papers of outstanding interest in the topical issues of this highly innovative sec-
tor.
This review of the exhibition and conference discusses what the developments in new products
and technologies mean to users of protective coatings and what users can expect in new paints or im-
proved performance. The properties described in the review are based on comments and data sheets
from suppliers and have not been independently verified.
Photo courtesy of NuernbergMesse and Thomas Geiger 2011-2015 Technology Publishing Co.
31
Additives
Green again was the word when it came to new additives, but, as stressed by Byk Chemie, no
global standard precisely defines green in the context of the surface coating industry. Every-one has
a perception of its meaning, and the demand for green products keeps growing, hence the number
of new developments. Green is also a synonym for environmentally friendly, but what does that
phrase mean? According to Byk, the VOC content of products and raw materials is one important in-
dicator of their impact on the environment; however, the deciding factors are often the various eco-
labeling systems in existence and the percentage of renewable materials in a product. Formulators
often have to balance the use and type of green materials against performance requirements. With
this in mind, Byk has developed products and technologies that meet current environmental stan-
dards without sacrificing the quality of the products being replaced.
New products on show included Byk-1740, a green defoamer based on eco-friendly and sustain-
able raw materialsvegetable oil derivatives. It is VOC-free and completely sustainable while pro-
viding the same performance as the standard mineral oil-based defoamers. Especially suitable for
waterborne emulsion paints, the new defoamer has no negative influence on color or odor.
Other new Byk products exhibited for waterborne systems included silicone-free defoamers, de-
foamers free of mineral oil as well as silicone, and wetting and dispersing agents.
According to Clariant, it was one of the first companies to offer a 100% APEO-free alternative for
manufacturing binder emulsion polymers. In addition to its low VOC levels, Emulsogen EPA 073 is
now one of few anionic emulsifiers with FDA approval. When combined with nonionic emulsifiers like
Emulsogen LCN 287 or Emulsogen LCN 407, these APEO-free emulsifiers offer increased latex sta-
bility and better shelf life. They increase the availability of more environmentally acceptable alterna-
tives to solvent-borne paints and coatings in contact with foodstuffs.
Rhodia is also moving toward more sustainable coatings with its portfolio of breakthrough per-
formance additives created to meet formulators demands for specific solutions for creating the next
generation of eco-friendly coatings. The company highlighted its new eco-friendly evaluation ap-
proach to designing sustainable coatings by spotlighting its growing line of zero-VOC, APEO-free
performance additives and solvents for waterborne coating. Rhodoline OTE is a novel zero-VOC,
APEO-free range of additives for extended open time (workability) in waterborne coating formula-
tions. It provides a two- to four-fold increase in open time without the addition of solvents, thus giv-
ing painters longer to work overlays seamlessly or to touch up paint to correct imperfections such as
drips and brush marks.
Air Products launched a new range of defoamers and de-aerators based on organic, silicone, and
molecular chemistry that will allow manufacturers to produce high-performance coatings that are
more durable, efficient, and environmentally friendly. The defoamers and de-aerators are particularly
useful for waterborne systems and can be used in floor coatings in combination with the companys
epoxy curing agent technology.
BASF also featured Dehydran SE 2, a high-performance silicone polymer emulsion defoamer for
premium waterborne paints and clear coats. It offers good foam suppression and long-term persis-
tency, is highly compatible and easy to handle, and minimizes gloss reduction. Because Dehydran
SE 2 is VOC-free and has an ultra-low semi-volatile organic compound (SVOC) content, it also helps
manufacturers formulate paints and clear coats that meet the requirements of environmental stan-
dards and safety certifications, such as the German TV, Green Seal GS-11, the EU Ecolabel, and
the Blue Angel.
In the range of rheology modifiers, BASF introduced DSX 3801, a VOC-free, mid-shear rheology
modifier with excellent ICI thickening. The ICI build of the thickener clearly exceeds that of benchmark
waterborne products, even at lower dosages. Due to the high efficiency and improved performance
of DSX 3801, a smaller amount of it is needed in formulationsa do more with less approach that
delivers sustainability benefits.
Dow Coating Materials announced the launch of its new EVOQUE Pre-Composite Polymer Tech-
nologya revolutionary development for paints and coatings that promises to change the way for-
mulators think about hiding and the use of titanium dioxide (TiO2). The acrylic-based technology im-
proves the particle distribution and light scattering efficiency of TiO2, facilitating improvements in
hiding efficiency and allowing for up to 20 percent less TiO2 used in the formulation. Additional ben-
efits include improved barrier properties such as stain and corrosion resistance.
Depending on their formulation goals, paint manufacturers can choose to reduce TiO2 content or
improve hiding while they improve paint performance. The Pre-Composite Polymer Technology may
also help formulators reduce the carbon footprint of their end products by reducing the energy foot-
print that comes from mining, processing, and transporting TiO2 to their formulation plants. Dow Coat-
ing Materials is conducting a life cycle analysis, which will be verified by a third party, to quantify the
full spectrum of sustainability advantages that may result from using its new technology.
Pigments
The trend for green products also extended into the new pigments offered from the various suppli-
ers. The developments were predominately in color pigments, although some new environmentally
friendly anti-corrosion pigments were on show from companies such as Halox, Nubiola, SNCZ,
Sachtleben, and Pigmentan.
Smart Coatings
One class of smart coatings are the self-healing systems that incorporate Bayer MaterialScience
products. The systems are functionalized anti-corrosion coatings or topcoats that can heal dam-
age autonomously, similar to the self-healing mechanism of the human skin.
Other products for smart coatings were for graffiti resistance.
New perspectives for smart coatings are being found in marine coatings with the use of carbon
nanotubes, again from Bayer MaterialScience. The nanotubes allow another approach to provid-
ing different properties and additional functions, and their use as coating additives could open up
even more intriguing perspectives. The high mechanical strength and electrical conductivity of
the particles, in particular, promise novel possibilities for formulating coatings and for improving
the strength of structural components while keeping their weight extremely low. Novel epoxy-gel
coatings with nanotubes are already significantly improving the scratch-resistance of coatings for
ship hulls.
Nanotechnology is also being used to give floor coatings with improved properties. The COL.9
nano-based binder from BASF, which has been used to produce self-cleaning wall coatings, can
also be used to coat substrates such as concrete, stone, or tiles. This means that, for example, tire
marks or oil stains on garage floors can be a thing of the past. The functional principle is the same
for both facade and floor applications. The binder combines the benefits of synthetic resin disper-
sions with those of silicates. (COL.9 is a dispersion of organic polymer particles in which nanoscale
particles of silica are incorporated.)
The organic part of the binder, i.e., the acrylic resin, ensures sufficient elasticity while the mineral
part lends the colored coating the required rigidity. This makes coatings particularly resilient as well
as resistant to dirt and chemicals.
Congress
The themes at the show were also prominent at the parallel. In fact, the plenary lecture by Professor
Matthias Beller, University of Rostock, Germany, was Sustainable chemistry: A key technology for the
21st century, which addressed the improvement of industrial chemicals production. Approximately
Dr. Matthias Beller addressed sustainable
150 papers were presented in 25 sessions covering a range of technologies and end uses, with specific
chemistry in his keynote speech.
sessions on sustainability and bio-based coatings, smart coatings, and nano-technology. The majority
of new products on show were also the subject of detailed technical presentations.
Summary
The emphasis of the products being exhibited and technologies presented was on their environmen-
tally friendliness, with materials for waterborne systems predominating. Companies were also keen
to explain their desire to use renewable ingredients as their raw material sources and their efforts in
reducing the carbon footprint of their production facilities.
Brian Goldie, technical editor for JPCL, has worked with protective coatings for many years,
including in the oil industry.
JPCL