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This publication describes the use of titanium dioxide pigments T I T A N I U MD I O X I D E

in solvent based decorative paints. The information contained herein PIGMENTS IN


is the distillation of the knowledge and expertise of numerous Tioxide
personnel gained over a period of more than fifty years. The Solvent based
contributions of those many workers are gratefully acknowledged. decorative paints
by

BRIAN GREGORY

& P A U LH O D G S O N
T I T A N I U MD I O X I D E
C O N T E N T S
PIGMENTS IN
PAGE

1 COMPOSITION OF SOLVENT BASED


DECORATIVE PAINTS Solvent based
0 BINDER 6
decorative paints
I . . a

1.1 CHEMICAL NATURE 6


1.2 O I L S AND FATTY A C I D S 7
1.3 E F F E C T OF OIL PROPORTION OF ALKYD RESINS 8
1.4 MODIFIED ALKYD RESINS 9
1.4.1 Styrenated and vinyltoluenated alkyds 9
1.4.2 Urethane alkyds 9
1.4.3 Polyamide modification (thixotropic alkyds) 9
1.4.4 Siliconealkyds 10
1.5 OTHER RESIN SYSTEMS 10
1.5.1 NAD/alkyd systems 10
1.5.2 Chlorinated rubber and related resins 11

0 SOLVENT 11

EXTENDERS 12

0 ADDITIVES 12

2 TITANIUM DIOXIDE PIGMENTS IN


SOLVENT BASED DECORATIVE PAINTS
....
0 DISPERSION O F TITANIUM DIOXIDE 14 This publication is a g w a l guide to the
technology of titanium dioxide pi’gments.
1.1 STAGES O F DISPERSION 14
Further technical information is available
MECHANISM OF INTERACTION 15
from Technical Semjice personnel within
W I T H A L K Y DR E S I N M E D I A
the Tioxide Group.
FLOCCULATION 16 Although all information is given in good

OPACITY 18 faith, we do not guarantee the completeness


of the information, nor that it will be
4.1 PIGMENT CONCENTRATION 18
4.2 FILM THICKNESS 19 suitable for yourparticularpuvose.
You should ensure that any process you
GLOSS 19
use or product you make using Tioxide
0 COLOUR AND COLOUR RETENTION 20 pigment does not infringe any patent.

61 COLOUR ASSESSMENT 20
6.2 PIGMENT PURITY 20
63 PARTICLE SIZE 20 Tioxide Group Limited
64 A N A T A S E VERSUS RUTILE 20
&&&red Office:
6.5 R E S I N CONSIDERATIONS AND YELLOWING 21
Tioxide House, 137-143Hammersmith Road
0 WEATHERING RESISTANCE 22
London W140QL, England

Registered in England No: 249759


DRYINGA N D DRYING RETENTION 25
Tioxide Group Limited is a member of the
8.1 INFLUENCE OF DRIER METAL TYPE 25 IC1Group of companies
8.2 R O L E O F T H E P I G M E N T AND E X T E R N A L FACTORS26 Tioxide is a registered trade mark
---

It is Fi.o&policy to update this information


regularly You are t k e f w e advised to check
that this publication is the most up-to-date.

0Tioxide Group Limited 1992

MARCH 1992
CONTINUED
C O N T E N T S

PAGE

STORAGE STABILITY 26

91 INFLUENCE OF T H E RESIN 26
9.2 S E T T L E M E N TA N D S Y N E R E S I S 27

APPLICATION 27
... ,
10.1 BRUSHABILITY 27
10.2 FLOW A N D SAGGING 28

3 FORMULATION AND MANUFACTURE


OF SOLVENT BASED DECORATIVE PAINTS

0 MILLBASE FORMULATION 29

11 FLOWPOINT METHOD 29
s
1 2 INFLUENCE O F TITANIUM PIGMENT 30
1 3 INFLUENCE O F RESIN 31
1 4 INFLUENCE O F SOLVENT 31
1 5 APPLICATION O F F L O W P O I N T DATA 32

2.1 GOOD D I S P E R S I N G SYSTEMS 32


22 A D E Q U A T E DISPERSING SYSTEMS 32
2.3 POOR D I S P E R S I N G SYSTEMS 32

MILLBASE STABILISATION 33

4 DEFECTS AND THEIR CAUSES, 34


REMEDIAL SUGGESTIONS AND PREVENTION

REFERENCES 41
Titanium dioxide first became commerciallyavailable in surface coating applications. Those readers who require
1918,in the anatase crystal form. Anatase was found to have more detailed information are referred to the Tioxide
significantdeficiencies,both with regard to its opacifying publication: Manufacture and GeneralProperties of
power in comparison with the rutile crystal form, and the TitaniumDioxide Pigments.
photocatalytically active nature of its surface. The latter is Solvent based decorative paints may be described as that
responsible for increasing the rate at which a binder is broken class of finish which produces a cured film by a process of
down during weathering. It was therefore only after World solvent evaporation followed by oxidation. The cured film
War 11,when production of rutile titanium dioxide may be highly glossy, semigloss(eggshell)or matt,
commenced in significant quantities, that anon toxic depending on the compositionof the coating, as will be
replacement for the lead and zinc based prime white discussed later. Most solvent based decorative paints
pigments previously used, became available. nowadays are based on synthetic ‘alkyd’resins derived from
Initially, production of titanium dioxide was only by the natural oils. This type of coating has been a major application
‘Sulphate’process. This method essentially involves the area for titanium pigments for almost half a century.
dissolution of ilmenite, FeTiO, (or beneficiated forms of this Although the performance of both titanium pigments
material arising from the iron and steelmaking processes), in and alkyd resins has been progressively improved, the basic
concentrated sulphuric acid. After separation and technology underlying these systems has remained virtually
purification of the resultant titanyl sulphate liquor from unchanged. In essence they comprise: a titanium dioxide
insoluble contaminants, titanium dioxide precipitation is pigment, a soluble resin (or binder) which is capable of being
effected by the addition of suitable nuclei. These crystals are cured by oxidation, a solvent (or blend of solvents) and small
then calcined to promote their growth to optimum size for quantities of suitable transition metal soaps to accelerate the
pigmentary application. In subsequent stages inorganic rate of oxidative cure.
coatings, such as alumina, silica and zirconia and an organic The environmental impact of solvent emission and the
addition are usually applied. effect of the long, or even short term, exposure of human
The newer, ‘Chloride’process requires the use of purer beings to the vapours of such solvents is causing much
titanium bearing ores. The feedstock is firstly chlorinated in concern. This has led to solvent based coatings becoming the
the presence of carbon. The resultant titanium tetrachloride, object of intense environmental and toxicologicalscrutiny in
a volatile liquid, is purified by distillation. Oxidation of the the USA and several Western European countries. It remains
tetrachloride regenerates titanium dioxide, which, under the to be seen whether the transition to higher solids coatings by
correct reactor conditions, is already of pigmentary the use of increased non volatile, low viscosity binders will be
dimensions. Application of inorganic coatings by wet sufficient to prevent its ultimate demise. Developments of
treatment and of organic additions at final milling, is carried water based (emulsion polymer) and/or water dispersible
out in the same way as for sulphate route titanium dioxide alkyd technologies, while currently viewed in some quarters
pigments. as environmentally preferable to solvent based alkyd paints,
Coatinghas a twofold purpose: firstly, to enhance are not without their own shortcomings. Many are, in fact, far
durability by reducing the photocatalytic activity of the from ‘solvent free’, and may necessitate the use of small
pigment surface and secondly, to influence dispersibility quantities of unpleasant and possibly toxic chemical
characteristics. The application of an organic addition usually additives. The shortcomings of current solvent and water
takes place during the final, dry refining (fluid energy milling) based decorative paint technologiesrepresent opportunities
stage. These additions frequently contain hydroxyl and/or to future generations of paint formulators and the suppliers of
amino groupings, whose purpose is to facilitate the dry their raw materials.
milling process by acting as a lubricant, and to enhance the
ease ofwetting of the final pigment.
Inorganic coatings and organic additions vary for
different grades of titanium pigment. Titanium dioxide
rapidly became established as the prime white pigment by
virtue of its high refractive index, good optical stability and
chemical inertness. It is now used in a very wide range of
There are five components which determine the application, The backbone of the alkyd resin is a complex polyester
optical, mechanical, durability and chemical resistance which may be branched. Fatty acid residues or additional
properties of a solvent based decorative paint. They are: polybasic acid residues are attached at intervals to the
binder (resin), solvent, extender, additives and titanium remaining free -OH groups of the polyhydric alcohol. All
dioxide. The influence of the first four components will now alkyd resins contain some uncombined -COOH and -OH
be examined in greater detail. Titanium dioxide will be groups. The residual acidity is reflected by the acid value and
discussed in Section 2. free -OH groups by the hydroxyl number. Most commercial
long oil alkyd resins have acid values in the range 5- 10.
Gel permeation chromatography,112 infra-red
spectroscopy studies and other techniques have revealed
that a typical ‘nonyellowing’pentaerythritol alkyd contains
The binder is responsible for containing the components of
nonpolar material, polar material and phthalic half esters.
the formulation in a continuous film and ensuring adhesion
There is also a large proportion of polymeric material of a
onto the article to be coated, ie: the substrate. To alarge
wide molecular weight range.
extent, it is the physical and chemical properties of the
The average molecular weight and molecular weight
binder which determine the physical and chemical resistance
distribution of this polymeric material largely determines the
of the coating and, hence, its useful lifespan. This can,
properties of the alkyd resin. Two alkyds of similar mean
however, be influenced to a greater or lesser extent by the
molecular weight, but widely differing molecular weight
composition of the pigmentary component and the relative
distribution, may show significantdifferences in their
proportions of binder and pigment(s), as will be discussed
physical properties such as solubility and dilution behaviour.
later.
An alkyd with a broad distribution may contain a significant
amount of high molecular weight material, which will be less
1.1 CHEMICAL NATURE soluble and less compatible than other components of the
same resin of lower molecular weight. This incompatibility
The complexity of binder systems has evolved with Man’s may be exhibited through a slow seeding out of the less
understanding of and control over chemical processes. The soluble high molecular weight material. Application
early binders were naturally occurring materials such as properties may also be affected, as the precipitation of any
bone marrow and egg white. Cave drawings from the proportion of low solubility, high molecular weight species
Palaeolithicera used these materials to ‘fix’naturally during the early stages of solvent evaporation can have a
occurring oxide pigments. These coatings were normally profound effect on rheology. An alkyd resin of narrow
applied by finger or crude animal fur brushes. The Egyptians, molecular weight distribution is preferable for these, and
and subsequently the Greeks and Romans, further developed other, reasons. These are discussed later, in Section 2.2.
the use of coatings basedon natural gums pigmented with Alkyd resins are normally based on dibasic (usually
metal oxides and carbonates-or occasionallysuch materials aromatic) acids (such as o-phthalic acid or its anhydride) and
dispersed in molten waxes. These waxes, along with stand polyols (eg: glycerol),modified with a proportion of vegetable
oils and oil varnishes (usually based on linseed oil) were the or animal derived oils, or monobasic fatty acids derived from
primary media for paint for many centuries. these sources. A proportion of the polybasic acid component
In the last fifty years these materials have been almost may be replaced by, for example, iso, terephthalic or maleic
totally superseded by alkyd resins. These offer notable acids, to enhance the hardness, chemical resistance and
advantages in terms of initial colour, colour retention durability of the resin. Another example is the use of azelaic
:resistance to yellowing), faster drying and enhanced acid to plasticise the alkyd and improve flexibility. The use of
durability. Oleoresinousbinders are now largely restricted to the two alternative phthalic acid isomers and their
specialised applications such as, for example, artist’s colours. derivatives is restricted by their comparatively low
The alkyd resin is now the predominant binder system for solubility, and hence reactivity, in the alkyd reactant mix.
solventbased decorative paints. The term ‘alkyd’is a This effectivelylimits their employment as structural or
:orruption of ‘alcohol’plus ‘acid’,these materials mechanical property modifiers.
6 somprisingthe major proportion of such resins. Similarly, part or all of the glycerol may be replaced by an
alternative polyol such as pentaerythritol, which confers a typical long oil alkyd inevitably determine its properties.
better drying and flow characteristics on the resultant alkyd The effect of each constituent will now be examined in
resin, Three alkyds produced from identical molar reactant greater depth.
ratios of, for example, glycerol, trimethylolethane and
trimethylolpropane will show a gradation in properties. The
increase in molecular weight from glycerol to trimethylol- 1.2 OILS AND FATTY ACIDS

propane effectively ‘dilutes’the aromatic(phtha1ic acid or


anhydride) component and thereby increases the flexibility A representative structure of naturally occurring oils is
and reduces the hardness and chemical resistance of the shown in Figure 3. These oils are composed of fatty acid
resultant resin. Some typical raw materials for the synthesis residues with varying degrees of unsaturation, some of which
of long oil alkyd resins are given in Table 1,chemical ‘ are shown in Table 2. The degree of unsaturation controls
structures for some of the polyol and polybasic acid the ability of the oil to confer airdrying performance on resins.
components, respectively, being &own inFigures 1and 2. Double bonding and conjugation improve drying properties,
The nature and proportions of the various constituents of although the latter is at the expense of initial colour and
colour retention properties. Saturated oils are non drying.
The compositions of some of the more important oils
used in the manufacture of surface coatings are given in
Table 3. These oils are categorised in Table 4 as ‘drying’,
‘semidrying’and ‘nondrying’and their compositions in
terms of their constituent fatty acids are indicated. Drying
properties are usually determined by the oil’suptake of
iodine, expressed in grammes per 100grammes of solid resin,
as the ‘IodineValue’. Oils with an Iodine Value of less than
100are described as ‘nondrying’,between 100and 140 as
‘semidrying’and above 140 as ‘dryingoils’.This is shown by
*Lineolicrich
Le values quoted for this parameter inTable 4. The usual
ethodfor measuring Iodine Values,the Wijs method*, is
)metimesinaccurate where conjugatedsystems are
tvolved, therefore the values obtained must be interpreted
,ith some caution. Further informationon the composition
Coils may be obtained from the saponificationvalue. This
ives an indication of the fatty acid chain length, assuming
-tatthe original oil was intact and composedentirely of
riglycerides.

E F F E C T OF O I L P R O P O R T I O N O F
1.3 ALKYD RESINS
Principally ricinoleic, not oleic
ConjugatedY, 11-linoleic
Conjugatcdandisomerisedlinoleic, and9,11,13-
elaeostcaric:proportionsdependent on source ncreasingthe proportion of oil in an alkyd resin, described a:
Approximate Yh weight specified acid he ‘oillength’ in the case of glycerol alkyds has the following
:ffectson the performance of the resultant alkyd resin:
.......................................................
Increased ..................................................................
Reduced
Application
. . . . . . . . . .ease ...................................................
. . . . . . . . . . . . . . .Viscosity
...
Flexibility
...... Hardness
............................................................................................

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Suitability
. .Nonaromatic . . . . . . . . . . . . .for
. . . stoving
. . . . . . . finishes . .
, , ,, , , , ,

Yellowness
. . . . . . . . .
Whiteness
.............................................
Dryingspeed by oxidation Durability
....................................................................................................

The foregoing assumes that the oil under consideration is


of the drying or semi drying variety. Properties are
summarised inTable 5.

’ Method according to BS 684 (Part 2.13)


Short oil alkyds based on drying oils, for example,
linseed, can be used for airdrying or short schedule stoving 1.4.2 Urethane alkyds
finishes. Those based on semidrying oils, for example,
dehydrated castor, are usually used in amino resin appliance Urethane alkyds are produced by the reaction of suitable
finishes. Those based on non drying oils do not form films and di-isocyanates, for example, toluene di-isocyanate (TDI),
commonly find application as plasticisers for amino resin with conventional alkyd resin components such that the
stoving finishes and nitrocellulose lacquers. alkyd component is always in a large excess over the highly
The most versatile alkyds are the medium oil variety, toxic di-isocyanate. This ensures that the di-isocyanate is
which can, depending on the modifying oil, be used for completely reacted with the alkyd excess to yield the
airdrying or stoving finishes. Hardness reaches a maximum required urethane modification.
at medium oil length, so these alkyds generally offer a good The presence of urethane linkages reduces oil length,
balance between gloss retention and flexibility.Long oil thereby improving film hardness and shortening drying
alkyds are generally used for exterior applications where time, this being at the expense of a deterioration in colour.
high film flexibility is of paramount importance. Their
predominant use is in decorative gloss finishingcoats. 1.4.3 Polyamide modification
Typical compositionsof short, medium, long and very long oil (thixotropic alkyds)
alkyds are given in Table 6.
-- - - 7
.- -
In order to confer thixotropy, an alkyd resin is normally
Table 6
_ _ --
Typical alkyd compositions
.
% Oil
__ v
% Phthalic anhydride
reacted with a linear polyamide. The rheologicalproperties
- 7
-_ - of such polyamide modified alkyds are delicately balanced. In
Short o
m v
d 33-45 35 particular, the rheological profile of the resin (its gel strength,
Llcdium oil aihyd 46 55 30-35 gel recovery rate and general application properties) when
Longoilalk~d 56-io 20 c30 incorporated into a paint, are highly dependent on the
_ long oil alkvd
_ leis > 70 < 20 following:
. -

(i) the processing history and composition of the alkyd;


(ii) the proportion of polyamide (usually no more than 55%
1.4 MODIFIED ALKYD RESINS
on total resin yield); and
(iii) most importantly, the solvent polarity.
Alkyd resins containing proportions of other modifying
The lower the polarity of the solvent, the higher the
components are also in common use in decorative paints.
resultant degree of thixotropy. Conversely, highly polar
Typical modifiers are: styrene, vinyltoluene, urethanes,
solvents, such as lower alcohol homologues and aromatics,
polyamides and silicones.
are likely severely to impair or to destroy any thixotropic
effects.
1.4.1 Styrenated and vinyltoluenated alkyds Thixotropic polyamide modified alkyd resins are in a
gelled state at ambient temperature, and must be heated to
Polystyrene is I tormally incompatible with alkyd resins. It around 50 to 55OC to return them to a liquid state. In the past,
can, however, be made to react with alkyds via double bonds polyamide modified alkyds often exhibited poorer flow, gloss
in the presence of a peroxide catalyst. This is normally and colour than their liquid counterparts and also tended to
achieved by slowly adding styrene to the part reacted alkyd induce TiO, flocculationto a greater extent. These
over a protracted period as polymerisation proceeds. disadvantages have been reduced considerably in recent
Styrenation reduces the oil length of the alkyd, resulting years due to general improvements in both the flocculation
in faster drying, better colour, better water and alkali resistance of titanium dioxide and in the wetting and
resistance and increased hardness. There are corresponding suspension properties of thixotropic alkyd resins. The
disadvantages which include a requirement for ‘stronger’ recommended procedure for pigmentation of thixotropic
solvents, poorer application properties and recoatability and paints with titanium dioxide is to carry out the dispersion and
poor exterior durability. The solvent strength requirements stabilisation stages in a combination of liquid and thixotropic
and recoatability deficienciesof vinyltoluenated alkyds are alkyd resins. The heated bulk of the thixotropic alkyd resin is
generally less pronounced than those of styrenated alkyds, then added at let down with driers, anti-skinning agent, any
otherwise they are very similar. additional white spirit and other minor components. In this
way any problems caused by either insufficientwetting or
flocculation on let down are minimised. 1.5 OTHER RESIN SYSTEMS

A second class of thixotropic alkyd resins is available,


which, in contrast to conventional polyamide modified There are other systems worthy of note at this stage. Perhaps
variants, are not in gelled form at ambient temperatures. the most interesting of these is the combination of acrylic non
This type of thixotropic alkyd is miscible in all proportions aqueous dispersions (NADs) with alkyd resin^.^,^
with liquid alkyd resins, and the extent ofgelation is actually
enhanced by the presence of polar components such as 1.5.1 NAD/alkyd systems
glycols and their ethers or glycol ether acetates.
The specialised NAD acrylic dispersions consist of a suitably
1.4.4 Siliconealkyds stabilised low Tg polymer such as polyethyl acrylate,
modified to appropriate polarity by incorporation of suitable
This class of modified alkyd is synthesised by the reaction of carboxyl or hydroxyl containing monomers and dispersed in
an alkyd with a silicone intermediate, carrying alkoxy a low polarity hydrocarbon diluent. The acrylic NADs are
(usually methoxy) groups. This is achieved at an elevated usually stabilised by a species having a polar ‘anchor’group,
temperature in the presence of small quantities (ca 0.1%)ofa for example, methyl methacrylate, modified with an
strong acid catalyst such as para-toluenesulphonic acid oleophilic, diluent soluble component, for example, vinyl
(PTSA): terminated poly-1,2-hydroxystearic acid. The methacrylate
provides a high polarity backbone, while the polar
-Si-O-CH, + HO-R PTSA > -Si-0-R + CH,OH hydrocarbon solvent confers a steric barrier to coalescence of
225OC
the polymer microgels.
Silicone Alkyd Silicone
resin alkyd Also essential to adequate performance is the presence of
a suitable difunctional crosslinker such as diallyl phthalate,
Siliconemodification results in improved weathering which gives the required degree of crosslinkingconsistent
properties, that is, excellent gloss and colour retention, and with the formation of a microgel dispersion, but without
enhanced heat resistance. Balanced against these inducing an unacceptable degree of microgel polymer
advantages is the high cost of the siliconeprecursors, since flocculation.
the degree of performance enhancement is in direct The modification of acrylicNADs with a proportion (up to
proportion to the extent of silicone modification.The effects 25 % w/w) of an alkyd resin is claimed to produce an ideal
on film properties of the various alkyd modifiers are combination of the properties of acrylic and alkyd resins. In
summarised in Table 7. addition to the fast drying, long term flexibility, durability
and colour retention of acrylics, these also apply well at low
temperatures and have good general application and flow
properties of alkyds.
Significant claims have been made for these systems in
relation to their enhanced adhesion and lower cracking
performince and hence, exterior dnra.bi1ity cf conventional
alkyd resins. This is mainly through:
(1) the significantreduction in these systems in the rate and
ultimate extent of embrittlement on ageing;
(2) the alteration of the nature of the resultant cracking/
adhesion failure from macro to micro scale.
Microcrackingis claimed to enable the relief of coating stresses
arising from substrate dimensional changes without resulting
in the gross adhesion failures which characterise an age
embrittled alkyd resin. The main current deficiency of these
systems appears to be in their gloss retention properties,
which are markedly inferior in the early stages to those of
10 conventional and new generation ‘flexible’alkyd types.
configuration and then maximises the ‘swept volume’ of the
1.5.2 Chlorinated rubber and related resins polymer molecules. This in turn maximises the viscosity of
the polymer solution at any given concentration. In the case
Since they are sometimes used for decorative, architectural of poor solvation (use of anon solvent) the converse is true,
finishes, chlorinated rubber resins and their derivatives with the resin adopting a compact, closed molecular
should also be mentioned. configuration and, thus, exhibiting a lower viscosity.
Chlorinated rubber resins are produced by the The extent to which a resin dissolves in a solvent
chlorination of either natural or styreneibutadiene rubber depends on the degree of interaction between solvent and
(SBR).They do not, in fact, have ‘rubbery’properties and resin molecules. The interactions between alkyd resins and
must be plasticised by suitable chloroparaffin compounds. the hydrocarbon solvents currently used in solvent based
They are largely restricted to applications such as roadline decorative paints are suggested to be weak and non ~ p e c i f i c . ~
paints, high build architectural, transport and marine Hydrocarbon solvents are considered to be of low solvency
anticorrosion coatings. and form only weak hydrogen bonds, this mechanism is
Related resins, which are copolymers of styrene/ therefore not considered to play a significant part in these
butadiene, vinyltolueneibutadiene or styrene/acrylate interactions. This topic will also be further discussed in the
polymers, and which are soluble in aromatic hydrocarbons, section dealing with titanium dioxide in solvent based
are also available. These types of resin offer good exterior decorative paints.
durability and high resistance to a broad spectrum of Generally, the more strongly solvating and hydrogen
chemicals. They are, however, only soluble in aromatic bonded a solvent, the higher the resin solids content
solvents and exhibit poorer application and dry film optical permitted in the liquid paint at a given level of viscosity. This
properties than, for example, alkyd resins. As a has implications for the appearance and durability of the
consequence, these systems are predominantly used for dried film. The rate of solvent evaporation affects many
masonry finishes, road marking paints (as distinct from application related properties, such as: brushability, flow
thermoplastic roadline compositions) and durable flooring and levelling, sagging, wet edge time andgloss. This rate is,
finishes. itself, affected by solvent composition, temperature,
-_ - ..... .
.-. ............. ......
I

2 SOLVENT
~ ~
-.

The essential function of the solvent in a decorative paint is to


provide a means by which a uniform, homogeneous film of
the binder and the pigment can be applied to the substrate.
Once this has taken place, an ideal solvent should diffuse
from the curing film and evaporate, playing no significant
part in the subsequent life of the coating. As has already been
noted, the use of the predominantly hydrocarbon based
solvents which volatilise to atmosphere during drying of the
coat,ing,is hecoming increasingly environmenhlly
unacceptable. For this reason it is anticipated that water will
humidity and film thickness, but largely unaffected by
play a more dominant role as a diluent for any
pigment content or type or, initially, resin concentration.
‘environmentally friendly’ developments of the alkyd type
The evaporation process proceeds in two distinct stages:
finish.
initially the rate of solvent evaporation is determined
Currently, however, the two prime requirements of the
predominantly by the solvent vapour pressure, the dissolved
solvent blend are that it:
polymer having little influence. Next, during the polymer
(a) dissolvesthe binder resin; and film formation stage, solvent is trapped within the film and its
(b) evaporates at such a rate as to provide the least escape proceeds by a diffusion controlled, slow process.
disruption to the film, together with the desired Evaporation of solvent therefore takes place at a progressively
rheology. decreasing rate, the coating being ‘dry’for practical purposes
A solvent which efficiently solvates the molecular chains when it can be recoated. Table 8 gives representative solvent
of a dissolved polymer, leads to an open molecular contents and viscosity information for a long oil alkyd gloss
mutagenic materials such as paint solvents, to the extent that
professsional painters in some European countries are legally
restrained from using conventional solvent based paints
occupationally.
Exposure of individuals to solvent laden atmospheres is
regulated by the imposition of ‘threshholdlimit value’ (TLV)
and ‘occupationalexposure limit’ (OEL) maxima. Employers
paint containing white spirit. failingto ensure that these values are not exceeded in
The solvents currently used in predominance for confined spaces, where their employees are habitually
airdrying decorative paints are almost invariably paraffinic present, risk prosecution. It is likely that there will, in the
mixtures. The three available types are detailed in Table 9. future, also be increasing pressure on employers through
Small quantities of higher boiling solvents, such as dipentene legislationto curb further, and possibly even eventually
or pine oil, are sometimes added to improve brushability , discontinue, the venting to atmosphere of solvent vapours.
maintain wet edge or control flow.
In ageneral review it is not appropriate to discuss in
detail the body of theory which has been amassed in
attempting to provide a framework to characterise
The term extender, or filler, refers to a range of inert, finely
solventhesin interactions through so called ‘solubility
divided inorganic compounds, originallyused in paint as a
parameter’ concepts. Suffice it to say that all of the recent
cheap replacement for expensive pigment. They are not true
treatments of these phenomena have attempted to relate the
pigments and contribute little to opacity. Typical examples of
interactions between solvent blend and binder in terms of the
extenders used in decorative paints are calcium carbonates,
relative propensities of the solvent and binder to interact
clays, talcs, silicates and a wide range of other minerals. All
through dispersion, polar, and hydrogen bonding forces.
are typified by low refractive indices and are available in a
This leads to the use of a three dimensional Cartesian
wide particle size range. In water based paints extenders are
coordinate treatment of solubility parameters, and to the
used extensively, particularly at high pigment volume
concept of ‘volumeof solubility’.6
concentrations, where opacity is obtained by dry hiding.
For certain polar solvents, Hansen7has estimated the J,
However, in solvent based decorative paints the replacement
extent of the contributions of polar and hydrogen bonding
of titanium dioxide by extenders normally results in a lower
interactions by comparing the energy of volatilisation of the
opacity and a lower gloss.
solvent with that of a hydrocarbon of roughly similar size and
In the UK the majority of sol4ent based decorative paints
shape (the ‘homomorph’concept). The difference between
that contain extenders are semi gloss finishes and
solvent and hydrocarbon volatilisation values is ascribed to
undercoats. Gloss finishes are normally only pigmented with
the effects of polar and hydrogen bonding interactions.
titanium dioxide. On the Continent, particularly France and
An alternative approach suggested by Nelson et a18uses
Scandinavia, extenders are more prominent in gloss paints. If
the original solubility parameter, delta, first proposed by
a reasonable opacity can be obtained, then the lower
Hildebrand, but also recognises the potential influence of
resultant gloss is simply a matter of personal taste.
polar and hydrogen bonding contributions through
‘fractionalpolarity’ and ‘hydrogenbonding index’ terms.
This is normally expressed in the form of two dimensional, so
called ‘solubilitymaps’. The interested reader is referred to
Lambourne et al.9 Additives are components which are incorporated into a
The final considerations in this review of solvents relate formulation at low concentrations. They generally fall into
to them being inherent hazards both from a combustibility one of three categories: formulative, remedial or speculative.
viewpoint and their toxicological character. Concern about The inclusion of formulative additives is essential for the
the transport of potentially hazardous substances has led to achievement of the balance of fundamental properties
the imposition of stringent controls on the carriage and expected of the final paint composition. Driers and
labellingof typical paint solvents, although a product does antiskinning agents exempllfy this type of reagent.
not fall into the ‘highlyflammable’ category in the UK unless Remedial additives offer an alternative method for
its flashpoint is below 32 O C . Similar concerns have been modifying the performance characteristics of a given
12 expressed about the occupational exposure to potentially combination of raw materials, only otherwise achievable by
a substantial variation in composition. Pigment wetting and Experience within the Tioxide Group over many years
dispersing agents, flow control and anti-flooding,anti-flotation suggests that the use of additives, or combinations of
agents, and anti-settling aids would be examples of this class. additives, in a given formulation can frequently be counter
The final class, that of speculative additives, has productive. These materials are often surface active, and
expanded dramatically in recent years and continues to therefore are likely to modify the interactions between
expand. Invariably these materials are offered on the basis pigment and resin, not always in the manner intended, nor
that they increase cost effectiveness. The use of very small indeed necessarily to the formulator’s benefit. It would
quantities of a usually very expensive additive being claimed always be our recommendation that the formulator should
to confer a disproportionate improvement in the seek to incorporate as many desirable properties as possible
performance of a somewhat cheaper, but cost determining, into the formulation through the correct choice of pigment(s),
formulation component. Opacity boosters, optical resin and solvent(s), including the least possible number and
brighteners and, for those solvent based decorative finishes quantity of further additives. Advances in pigment and resin
pigmented with durable titanium pigments, UV absorbers technology over many years have made this eminently
would be representative of this category. Use of such feasible. Table 10is anon exhaustive list of some of the
materials often fails to deliver the claimed benefits and may additives which are likely to be encountered in solvent based
actually induce other, unwanted side effects. decorative paints.

13
F: Formulative; R: Remedial; S: Speculative
- 7 - - - _ _ --. - - - -- ._i __
--

2- TITANIUM DIOXIDE PIGMENTS IN SOLVENT BASE;


- -
DQCORATIVE PAINTS
--
Titanium dioxide in the rutile form is the principal white separation as to maximise the scattering efficiencyfor visible
opacifyingpigment used in solvent based decorative paints. electromagnetic radiation. This state is, unfortunately, never
This is by virtue of its unique combination of opacity and tint achieved in practice, the presence of oversize particles
reducing power, whiteness, toxicologicalinertness and, in reducing the optical effectiveness of practical systems below
the suitably treated versions of the rutile form, high that theoretically achievable. Grades of titanium dioxide
durability. As such, it is therefore frequently the single commonly used in solvent based decorative paints are finely
largest raw material purchase of any organisation involved in divided solids with surface areas of the order of 12-15 m2/g.
the manufacture of solvent based decorative paints. In As supplied, the pigment consists of particles which may be
consequence, increasing demands have and will conbinue to single crystals, aggregates or agglomerates.
be placed on the manufacturers of titanium dioxide by their Aggregates are sintered groups of particles, occurring
customers to increase the extent, ease and cost effectiveness during the reaction stage of the titanium dioxide making
with which the full performance potential of these products processes and joined at their faces or edges. These particles
can be exploited. Such requirements must not, however, be are extremely difficultto break down.
at the expense of social and environmental considerations. Agglomerationoccurs between particles or individual
As indicated earlier in this publication, there are currently crystals through a ‘cementing’effect during surface
two commerciallyviable routes for the production of titanium treatment and subsequent drying. The pigment producer
dioxide pigments, the sulphate and chloride processes. seeks to minimise the incidence of both aggregation and
Having formed the titanium dioxide as particles of agglomeration through efficient milling processes during
pigmentary dimensions by one of the two above processes, it manufacture. This is particularly important in the case of
is the subsequent coating and milling stages which are the aggregates, since these are unlikely to be broken down to
main determinants of the performance characteristics of the their constituent primary particles by the type of equipment
pigment. Titanium pigments are used in such a wide range of used in normal paint making operations.
applications that it is unlikely that a truly universal grade will The dimensions of typical titanium pigment particles are
ever be produced. However, the advances made by the such that they are subject to the mutual attractive forces that
industry since its inception have now made it possible to act on all dispersions of colloidalmagnitude. Hence, in the
produce titanium dioxide pigments with such wide absence of the dispersive effects of mechanical milling forces
applicabilitythat they are worthy of this description. or other stabilising influences, the particles will begin to
flocculate(see later under ‘Flocculation’).The product
.
- -_ ..- -
DISPERSION OF received by the customer consists of a mass of pigment-air-
1 TITANIUM DIOXIDE pigment flocculates(or agglomerates)loosely held together
-. ___ ._ - --
by Van der Waal’sforces. Each volume of pigment is
The process of dispersion of titanium dioxide is the initial, associated with approximately three volumes of entrained air
and perhaps single most important, lostage in determining its and, in the case of general purpose titanium dioxide
influence on the manufacture and subsequent properties of pigments, up to 1% of moisture may be adsorbed.
solvent based decorative paints, since this stage must The purpose of the dispersion process is to replace the
inevitably precede all other manufacturing operations. If the pigment-air interfaces in these initial agglomerates with
dispersion process is inadequate, for whatever reason, then pigment-medium interfaces, to disrupt and wet completely
it is certain that the performance of the resultant paint will in the primary particles composingthese agglomerates, and
turn exhibit deficiencies in one or more aspects, the nature of subsequently to preserve the dispersed state of the resultant
which will be discussed later in this publication. This is also primary particles and to prevent their reflocculation.
reviewed in greater detail in Tioxide publication: Dispersion
of TitaniumDioxidepigments:General Principles.
The ideal state of dispersion of a titanium dioxide
1.1 STAGES OF DISPERSION

pigment would be one in which the crystal and particle size


distributions of the pigment are identical. That is to say, all of The process of dispersion of titanium dioxide in a medium
the particles present are discrete, single crystals, completely such as a long oil alkyd resin solution may be resolved into
14 wetted by the medium, and exhibiting such an interparticle three stages: wetting, disruption and dispersion stabilisation.
Wetting involvesthe displacement of air, and possibly water,
from the pigment surface by resin and solvent. Disruption
entails the mechanicalbreakdown of agglomeratesinto
smaller particles. This process involves little, if any,
disruption of aggregateswhen the type of equipment
commonly used in the manufacture of decorative paints is
employed. The proportion of these , in any case, is normally
extremely low in titanium dioxide designed for decorative
paint applications. The efficiency of the final stage,
dispersion stabilisation, is influenced by a number of factors.
These include: the compositionof the millbase and the
equipment used to process it, the millbase dilution
procedure, the solubility and compatibilityof the resin
component(s)and the nature of the drying process for the
wet paint. In essence, the dispersion stabilisation process
seeks to maintain a separation between primary particles
sufficient to prevent their mutual attractive forces from
operating and promoting reflocculation.

-__ _ I -

-- - -- -_ -
MECHANISM OF INTERACTION
WITH ALKYD RESIN MEDIA species involved in the adsorption process which determine
its outcome. The steric mechanism actually arises from the
Titanium dioxidepigments for solvent based decorative paint osmotic pressure of solvent diffusing into a region where
applications can be coated with combinationsof alumina, close approach of polymer chains separately adsorbed onto
silica and zirconia, the reasons for which have already been different pigment particles causes a localised increase in
indicated earlier in this publication. The nature of the polymer concentration. 14
pigment surface plays a predominant role in determining the Size of the adsorbed species is not necessarily the prime
type of interaction which takes place with a solution of an consideration. Thinner, but strongly adsorbed layers can be
alkyd resin. We may characterise the pigment surface as more effective than thicker, more weakly adsorbed ones. It
relatively acidic or basic, accordingto whether its surface is might be anticipated that the larger the adsorbed species, the
predominantly silica or alumina respectively in chemical greater the increase in free energy resulting from the
nature. The radically different ways in which titanium desorption of the solvent released solvating that portion of
dioxide pigments with these two surface treatment types the resin molecule surface interacting with the pigment
interact with an alkyd resin solution have been investigated particle. In fact, lower molecular weight, polar species, such
by Goldsbrough,Peacock et all19l2and are illustrated in as phthalic half esters, have been shown to be extremely
Figure 4. efficient in interacting with the basic surface of titanium
Pigmentswhich have a relatively basic, predominantly pigments.l 6
alumina surface interact strongly with the very limited
number of free carboxylgroups on the alkyd molecule.This
leads to firm attachment of the alkyd at very few anchor
points. The alkyd resin moleculetherefore remains in an
extended, well solvated configuration, protruding into the
surroundingresin solution environment. This can also be
conceived as providingan excellent ‘barrierto flocculation’
for the titanium dioxide particle to which it is attached.
This view of the mode of action of the adsorbed resin
species as obstacles to pigment-pigment dispersion force
interactions and hence, flocculation, is now consideredto be
an overly simplistic one. l3It is now recognised that it is
predominantlychanges in free energy undergone by the
Figure 6a Airdrying alkyd paint based on alumina Figure 6b Airdrying alkyd paint based on silica
treatedgrade(FG: 0.2) treated grade (FG: 0.55)

In the case of the relatively acidic, silica type surface, it is


the basic hydroxyl and ester groups interspersed along the
backbone ofthe alkyd resin which interact with the acidic
titanium pigment surface. This leads to a very compact Flocculation is the loose association of primary particles
configuration for the resin molecules. The tightly coiled which can arise through the attractive forces acting on
structure provides a poor steric barrier to flocculationand particles of colloidaldimensions. These forces arise through
also excludes a large proportion of the solvent which would the ability of polar molecules to exert electrostatic forces on
otherwise be associated with the alkyd molecule and would other polar molecules, to induce dipoles in polar materials
contribute to its stability in solution in its normal, more open and, in the case of non polar materials, through the short
configuration. The end result of this type of interaction is lived dipoles arising from transient fluctuations in charge
poor flocculationresistance. This can be confirmed density of the molecular orbitals of these molecules.l6>l79l8
experimentally in studies on alkyd paints, made to the same These latter forces reach their greatest magnitudes at
formulation, incorporating titanium dioxide pigments with separations of lOnm (0.Olpm)or less, but are still significant
the two types of surface treatment, as shown in Figure 5. over much larger distances. They can be overcome by
The concept of Flocculation Gradient will be reviewed in mechanical means, but their existence promotes a return to
more depth in the next section. The predominantly alumina the flocculatedstate.
surfacetreated pigment exhibits a lower flocculationgradient Flocculation can vary significantlyin both its degree and
;han its predominantly silica treated analogue, consistent its effects on coating properties, through its detrimental
with it having a lower degree of flocculation. This is influence on pigment distribution. A high degree of
sonfirmed in electron micrographs of the two dry paint films flocculation in a decorative white alkyd gloss paint is
Ln Figures 6a and 6b. immediately identifiable. The dry film of this paint will be
The work of Goldsbroughet a1suggests that the found to be deficient in opacity, gloss and weather resistance
ilternative possible mode of interaction, that of electrostatic properties. Colour and other properties may also be
"epulsion,plays little part in the mechanism of dispersion adversely affected.
jtabilisationof titanium dioxide pigments in solutions of The two perhaps most immediately obvious defects
ilkyd resins. which can be encountered with tinted systems are flooding
and flotation. These are frequently the outcome of the
16 pronounced tendency toward homoflocculationof fine
particle organic pigments. Different charge mobilitiesresult evolved within the Tioxide Group. Clear correlation can be
between titanium dioxide and organic pigment particles. observed in Figure 8 between the increasing flocculation
Inhomogeneity in the distribution of the pigments can thus gradient values obtained from measurements on dry films of
occur in a drying film, surface tension effects trapping the paints and the increasing extent of titanium pigment
particles of the lighter, more mobile pigment in the ‘skin’at flocculation.
the film surface, while the heavier, less mobile particles tend
to concentrate at the edges of the convection cells formed Figure 8 Scanning electron micrographs and flocculation
gradient values for alkyd gloss paints
during drying. In cases where the disparity in mobility is only
moderate, localised separation of the two types of pigment
particle occurs, resulting in the effect known as ‘flotation’or
‘floating’,where amottled appearance emerges as the film
dries. When the disparity is larger, the separation becomes
more extreme. The film appears homogeneous unless or until
it is disturbed when almost dry. In this situation, the particles
of the more mobile pigment, which have congregated near
the film surface are removed, revealing a different shade
beneath the surface. This effect is known as ‘flooding’and
schematic diagrams of pigment distributions for a binary
system are shown in Figure 7 for each of the two cases. For a
more comprehensive review of this topic the reader is
referred to S ~ h n a 1 l . l ~
FG = 0.27

FG=0.44

In all practical pigmented paint systems there is some


degree of flocculation, a perfectly dispersed state remains a
desirable, but as yet unachieved, goal. If, however, the
extent of the plgment flocculation is only slight, the
deterioration in performance relative to a deflocculatedpaint
will be virtually undetectable. In addition, a slight degree of
flocculation is useful in avoiding hard settlement, which is
the main adverse effect of attaining the highest possible level
of dispersion.
An instrumental method for quantifying flocculationof FG=0.76
titanium dioxide in some paint systems, called the
‘FlocculationGradient Technique’ 20121,22,23has been
-
Because of the diversity of paint formulations there can
be no specific recommendations for the control of 4.1 PIGMENT CONCENTRATION

flocculation.General guidelines can, however, be offered:


It is found that the light scattering efficiencyof small particles
(1) Establish millbase formulations, stabilisingand letdown is maximised when they are sufficientlywell spaced so that
techniques, consistent with the availablepaint making
their scattering volumes do not overlap. Reducing the
equipment and raw materials.
interparticle separation below this threshold of two particle
(2) Particular attention should be paid to the medium. diameters results in a progressive reduction in scattering
Resins of nominally similar compositioncan vary widely efficiency.The work of Tunstall and Hird 26y27 suggests that,
in their dispersing power. They may have similar film in a long oil alkyd medium, the visible light scattering
formation capabilities, but widely differingeffects on efficiency per unit of titanium pigment reaches its peak at a
pigment flocculation. pigment volume concentration of just under 10% .
Thereafter, scattering efficiency per unit volume
(3) The use of surfactants or pigment dispersants should be
progressively decreases. Table 1128shows the relationship
avoided, ifpossible. If persistent flocculation forces a
between surface to surface spacing and pigment volume
formulation change, it is usually preferable to use a
concentration calculated for a pigment distribution which
different resin or pigment, rather than attempt to
has been approximated to an array of hexagonally close
remedy the deficiencies of the existing formulation with
packed spheres. This also suggests that the p.v.c.(d) value at
an additive. The potential adverse effects of such actions
which surface to surface separation, s, is equal to the particle
frequently outweigh the advantages.

The status of titanium dioxide as the prime white opacifying


pigment arises from its unique combination of very high
refractive index, minimal absorption of radiation in the
visible region of the electromagnetic spectrum and chemical
inertness. In white solvent based decorative paints, aside
from the degree of flocculationalready discussed, the main
determinants of the opacity of a dry paint film are the volume
concentration of the pigment and the film thickness, that is,
the number of scattering centres per unit volume of film. This
is because, when considering the scattering and refraction of
electromagnetic radiation by a finely divided particular
material, such as titanium dioxide pigment, the distribution
of the pigment particles behaves, to a reasonable degree of diameter, d (hence centre tocentre separation, c=2d), is just
approximation, like an array of spherical scattering centres. less than 10% , supporting the theoretical calculations of
Each centre may be regarded as having an effective Tunstall and Hird.
scattering diameter roughly twice that of its actual The observed relationship between opacity and titanium
diameter.24i25In consequence, the individual particles dioxide volume concentration is depicted in Figure 9. This is
interact most effectively, that is, have the highest scattering representative of a dry film of an alkyd paint containing a well
efficiency,for radiation whose wavelength is roughly twice dispersed Type R2 titanium dioxide pigment. The shape of
that of the pigment particle’s diameter. It is for this reason this curve is thus readily rationalised in terms of the variation
that titanium dioxide pigments generally have mean crystal in the visible light scattering efficiencyof titanium pigment
sizes of the order of a quarter of a micron. with increasing pigment volume concentration. In the region
ofp.v.c.(d)beyond the first opacitymaximum, the pigment
particles have become so closely crowded that they interfere
with the scattering of light by their neighbours to such an
extent that there is a reduction in opacity at p.v.c.(d) values
18 above about 30%.
4.2 FILM THICKNESS

The second controlling factor with regard to opacity is film


thickness. This is influenced by the solids content and
rheological properties of the paint, and these in turn are
largely determined by the viscosity characteristics of the
resin solution. The conventional approach has been to
apply two, or more, coats of a liquid alkyd paint of near
Newtonian rheology. High solids, low viscosity media applied
at typical spreading rates will dry to give a thick film. This
leads to high opacity in the absence of factors such as
flocculation,which can compromise the advantages of a
thicker film. However, if the paint is not formulated with
some degree of thixotropy, the risk of sagging is increased.
The self undercoating, one coat finish achieves high
Examination of Figure 9 indicates that there is a region of opacity by exactly this route, high solids content combined
medium to high pigment volume concentration in which very with a degree of thixotropy. These two characteristics result
high opacity coatings may be formulated. This opacity boost in restriction of the natural spreading rates of these products,
occurs because the individual pigment particles are leading to high opacity. This is, however at the expense of
becoming less adequately bound as the volume ratio of flow, levellingand gloss, relative to the conventional liquid
pigment to binder increases. Air is being progressively alkyd paint with more Newtonian rheology.
introduced into the dry film of the coating, reducing the As has already been observed, flocculationtends to
average refractive index of the binder. Because scattering lower opacity by reducing the number of effective scattering
efficiency depends on the magnitude of the difference in centres per unit volume, and should be minimised. The
refractive index between the pigment and the surrounding opacity differences which arise between titanium dioxide
binder, this enhances scattering efficiency of the pigmentary pigments are often the result of differences in the extent to
component. The penalty which is paid for this enhanced which dispersion is developed and maintained. Differences
scattering efficiency is a deterioration in film integrity. This between levels of ultimate opacity achieved by different
may manifest itself in a number of ways, including reduced grades of titanium dioxide are nowadays quite small.
gloss, high porosity, poor washability and stain resistance,
and a drastic deterioration in outdoor weathering
performance.
Although the pigment loading which confers the most
efficient use of titanium dioxide pigment is approximately The gloss of a resin film is a function of its refractive index and
10%p.v.c.(d),most white liquidalkydgloss paints areformul- surface roughness. The refractive indices of alkyd resins are
ated in the range 14 to 20 % . Those at the higher end of this always lower than those for harder resins, such as copal
range are designed to confer higher opacity and better colour. varnish. The gloss of a predominantly alkyd system can,
Solvent based decorative coatings are not, of course, therefore, be enhanced by the inclusion of some hard resin,
always formulated for the highest opacity and gloss. In the such as a condensed cyclohexanone, up to a maximum of
case of, for example, an undercoat formulation, it is desirable 10%w/w of total binder solids, where exterior durability is
to sacrificeopacity and gloss in favour of a combination of cost important. Other, poorer colour, resins, for example, maleics
effective partial substrate obliteration, flexibility and a may also be considered where their use is appropriate.
sufficient level of porosity to provide adequate adhesion of At all practical levels of p.v.c.(d), the gloss of a solvent
the finishing coat without compromising its gloss based alkyd gloss paint is little affected by extended milling.
development. This balance of properties may clearly still be The reason for this is detailed in the Tioxide publication:
achievable in the pigment volume concentration region Measuring Gloss and is explained by the presence of a clear
beyond that where the pigmentary component is fully layer at the surface of the film. The gloss is little affected
bound, that is, above the critical pigment volume providing the recommendations outlined earlier in this
concentrationorc.p.v.c., as depictedinFigure 9. publication are observed. That is, to minimise flocculation,
and follow the relevant procedures listed in the defect chloride over sulphate process pigments. However, the
identificationand resolution guide at the end of this booklet. resultant extremely small colour difference is not significant
Gloss development can, however, be compromisedby many in many applications.
factors other than the paint itself, such as the substrate, the
method of application and the surroundings. 6.3 PARTICLE SIZE

~~

-
COLOUR A N D The mean particle size of a titanium dioxide pigment is
6
._ .. -
COLOUR RETENTION determined by its crystal size and distribution, and by the
amount of work done to achieve dispersion in agiven
Colour is a sensation produced in the eye and interpreted by
medium. It is the aim of the pigment manufacturer to make
the brain, when stimulated by light. It has been described by
these two distributions identical, that is, to produce the
the statement, ‘Colouris easy to appreciate, less easy to
pigment as all single crystals. This is not currently achievable
measure, and difficult to u n d e r ~ t a n d ’The
. ~ ~manufacturer of
in practice, although a close relationship normally exists
titanium dioxide pigment is generally concerned with white,
between the mean crystal and mean particle sizes. The
which as a neutral pigment should be capable of description
explanation of optical characteristics is frequently reviewed
by its brightness characteristics alone, as measured by the
in terms of crystal size.
amount of light reflected.
As the mean crystal size of the pigment is reduced from
the theoretical optimum of approximately 0.22pm, its peak
light scattering efficiency moves to shorter wavelengths,
6.1 COLOUR ASSESSMENT
from the greedneutral toward the bluehiolet region and
ultimately into the near ultraviolet. This confers an increas-
The colour of a paint film is the result of a combination of the
ingly blue tone in whites and an increasingly blue undertone
scattering and absorption characteristics of the components
in reduced shades, ultimately at the expense of opacity.
making up the film. When white light is incident on a typical
Pigments designed for low volume concentration
white paint film, with a dry thickness of 25 to 30pm, the
applications in very thick films, such as thermoplastics, are
overwhelming proportion of the incident light is eventually
frequently of fine crystal size, approximately 0.17pm. The
scattered back without change. Those wavelengths which
larger number of scattering centres generated per unit
are preferentially absorbed will determine the extent to
volume by the reduction in mean crystal (and hence particle)
which the film deviates from a pure white. This means if
size more than compensates for the loss in scattering
either light from the blue end of the spectrum is absorbed, or
efficiencyof the smaller individual particles. This is not
light from the yellow end of the spectrum is scattered, the
possible in hlghly crowded, thin film applications such as
film will appear yellowish in tone. Numerous colour
paints and printing inks, due to the effects on scattering
measurement systems now exist and are fully documented in
efficiencycaused by pigment crowding. Indeed, increasing
the l i t e r a t ~ r e . ~ ~
the mean crystal size in thin film applications, thereby
reducing the number of scattering centres per unit volume of
pigment, may enhance scattering efficiencyby reducing
6.2 PIGMENT PURITY
crowding effects, but at the expense of gloss development. A
larger crystal size pigment tends to exhibit a browner tone
The main determinants of the colour developed by a titanium
and undertone, for reasons converse to those applying to the
pigment in a given end application are its chemical purity and
optics of fine crystal variants.
its mean particle size. The former is affected by the ability of
the manufacturing process used to remove chromophoric
cationic contaminants, such as chromium, iron, nickel, 6.4 ANATASE VERSUS RUTILE

manganese, vanadium, etc prior to the formation of the


titanium dioxide crystal. The sulphate and chloride processes Both anatase and rutile titanium dioxide pigments reflect
enable the manufacture of high purity pigments. The strongly and virtually identically across the predominant
distillation stage employed for the purification of titanium proportion of the visible spectrum. Rutile, however, begins
tetrachloride in the chloride process permits a slightlyhigher to absorb radiation at a longer wavelength than anatase, as
degree of heavy metal removal than that achievable by the shown in Figure 10. In addition to the crystal size effects
20 sulphate route. This confers a slight brightness advantage for described earlier, it is the onset of this strong absorption by
RESIN CONSIDERATIONS
6.5 AND YELLOWING

The small colour differences between individual titanium


dioxide pigments are still further reduced when they are
incorporated into resin. Figures 1l a and 1l b compare the
colour of general purpose chloride and sulphate route
titanium pigments in both afull gloss paint based on a typical
long oil alkyd and an acrylic/melamine formaldehyde stoving
finish. Titanium dioxide pigments are colour stable, and do
not yellow on exposure to daylight or darkness. Any
discolourationoccurring in a solvent based decorative paint
pigmented solely with titanium dioxide cannot therefore be
ascribed to the pigment alone, and must be a function of the
rutile at the blue end of the visible spectrum which causes it whole coating system.
to appear more yellow than anatase. The preferential Since titanium dioxide pigment seldom comprises more
absorption by rutile also protects the organic species present than 20 % of the volume of a dry paint film, particularly in full
in binding media. The short wavelength radiation would gloss finishes, the binder also has a significant effect on the
otherwise be responsible for the breakdown of these organic colour of the dry film. The alkyd resins predominantly used to
species, which compose the nondurable binders commonly make solvent based decorative paints are based on drying or
used in solvent based decorative paints. semidrying oils, which are increasingly yellow in colour as
In addition to its adverse effects on durability, anatase is the proportion of oil in the resin increases. The type and
a less efficient light scatterer than rutile because of its lower quantities of additives present, such as driers, will also affect
refractive index. This markedly restricts the range of uses for the colour of the film. Ambient conditions also have a major
anatase pigments in solvent based decorative paints. They influence on film colour. It is well established, for example,
are occasionally used, in small proportions, in finishes based that alkyd resin media yellow in darkness and bleach in the
predominantly on rutile, in order to induce a degree of self light. The yellowing of oleoresinous systems has been
cleaning by controlled chalking. This merely makes use of the extensively studied.30 Little or no yellowing occurs when the
highly photoactive anatase surface to accelerate the rate of dry film of an airdrying alkyd is exposed to direct sunlight,
binder breakdown and thus the rate of chalking. Other moderate yellowing in normal interior lighting conditions,
applications make use of the reflectance characteristics of and severe yellowing in darkness. In addition, yellowing is
anatase in order, for example, to allow the incorporation of accelerated by heat and very high humidity, but inhibited
optical brighteners, whose fluorescence is almost completely when oxygen is absent. This suggests that yellowing is
quenched by rutile titanium dioxide. Such effects are, associated with oxidative breakdown afthe binder, the
however, not usually sought in decorative paint applications. breakdown products recombining to form
coloured species. The choice ofgrade of rutile titanium Two effective yellowing inhibitors have been
pigment has been found to have virtually no effect on the proposed,36 these are acetoacetic ester and 2,3-dihydroxy-
extent of yellowing observed, that is, exposure conditions propylazelaldehydate, which is formed from the ozonisation
and the choice of binder have been found to have a far greater of monoolein. Their structures are given in Figure 13.
influence.31 For example, intense illumination minimises Effective yellowing inhibitors have been found to contain
the extent of yellowing and an ammonia or a tobacco smoke highly reactive aldehyde functions adjacent to methylene
rich atmosphere, in the dark or very subdued illumination, groups. However, acetoacetic ester, which has two adjacent
tends to promote the greatest degree of discolouration. reactive carbonyl groups, has been found to be less efficient
With regard to the binder, the propensity to yellow than the ozonised monoolein derivative. Approximately 5 %
increases with the degree of unsaturation of the fatty acids by weight of acetoacetic ester is required to achieve the same
present in the binder. It has been found32that the degree of degree of yellowing resistance as that conferred by 0.5% by
yellowing is least for oleic acid and increases for linoleic, weight of ozonised monoolein.
elaeostearic and linolenic acids in that order. This may also
be explained by the tendency of the film to bleach in the light
increasing with the degree of saturation of the fatty acids
present in the alkyd. The two effects are believed to be
contributory. A dry film of a soyabean alkyd will not yellow
so much in the dark, and will bleach more in the light, than a
linseed oil alkyd exposed under the same conditions.
Various mechanisms and causal agents33*34,35 have been
proposed for the yellowing process. The prime suspects are,
in the first instance, surplus hydroperoxides from the drying
process, although some effects may be attributable to the
choice of drier combination. The most likely resultant It is clear that the prime requirements in formulating for
chromophores are probably unsaturated carbonyl whiteness and its retention are the choice of
compounds and nitrogen heterocycles, their proposed (a) a titanium dioxide grade of good whiteness;
formation mechanisms being outlined in Figure 12. From
these reactions it is clear that variations in the ambient (b) a resin of pale colour based on fatty acids containing the
conditions will markedly affect the relative rate of each mininimum degree of, preferably unconjugated,
reaction, supporting the comments made earlier about the unsaturation. This is consistent with acceptable
overriding importance of this ‘environmental’factor. oxidative drying performance, and consequently
exhibiting good colour retention on ageing;

(c) additives that will detract as little as possible from the


brightness and tone of the paint;

(d) minimum manufacturing induced contamination; and

(e) minimum toning, which, at the same time as modifying


the tone of the paint, also results in a reduction in
brightness.
~ .- -- -
7 WEATHERING RESISTANCE
__-__ _- -
-

Paint films break down primarily because of the degradation


of the binder matrix. There are two degradation
mechanism^^^>^^?^^ responsible for this breakdown,
photochemical and photocatalytic.
The photochemical mechanism involves the direct
breakdown of the interatomic bond(s) between the
22 constituent atoms of the binder molecules by absorption of
predominantly responsible for chalking.
The photocatalytic mechanism arises from the
photoactive nature of the surface of titanium dioxide. When
the surface of titanium dioxide is irradiated with light whose
wavelength is below a critical threshhold (405nm), electrons
are excited from the valence band into the conduction band,
leaving positive holes in the crystal lattice. These electrons
and their complementary positive holes are then both free to
migrate within the crystal lattice, where some will
recombine. Aproportion, however, will reach the surface of
the crystal, where they are then free (in the presence of
oxygen and moisture) to initiate radical catalysed depolymer-
isation reactions within the binder matrix which result in
degradation. The two breakdown mechanisms are
schematicallyillustrated in Figure 14. It must be stressed that
binder breakdown seldom takes place solely by one of the
above two mechanisms, in fact both are generally operative.
the short wavelength component of the radiation incident on What determines the character of particular binder
them. This is characterised, in a system pigmented with systems is the relative rates at which the two processes
titanium dioxide, by a gradual erosion of the binder, occur. Bindersmay thus be broadly classified into two
eventually leaving unbound pigment particles at the surface classes, durable and non durable. Durable binders are those
of the film. It is these unbound particles which are in which the rate of photochemicalbreakdown is negligible

23
under most natural weathering exposure conditions. lacquer, over a 2000 hour exposure period in a carbon arc
Polyurethanes and silicone modified polyester resins would artificial weathering apparatus.
be examples of this class of binder. The only way in which As might be expected from the foregoing discussion, for
significantbinder breakdown can normally be induced in nondurable binding media such as alkyd resins, the
these systems is therefore by the photocatalytic mechanism. protective effect of titanium dioxide increases with
In these durable systems, the rate of mass and gloss loss with increasing pigmentation level, as is shown in Figure 18.
time increases with the level oftitanium dioxide. This is due There is, however, apracticallimit ofaround 25% p.v.c.(d)at
to the pigment particles acting as centres for the initiation of which titanium pigments are normally used in solvent based
binder breakdown by the photocatalytic route, as illustrated decorative paints. This is dictated by cost effectiveness and
in Figures 15and 16. The rate of mass and gloss loss with time gloss retention considerations.
can be minimised by the selection of a speciallytreated, With regard to the selection of titanium dioxide pigments
superdurable grade of titanium pigment. The coatings of for optimum weathering resistance in solvent based
these pigments are designed to contain and promote decorative paints, it is apparent from the foregoing
recombination of the photocatalytically generated electrons discussionthat there is little justification for the use of a
and positive holes, minimising the extent to which they are superdurable pigment. The suppression of the photocatalytic
able to come into contact with the surrounding binder mechanism of binder breakdown in non durable systems
matrix. such as alkyd gloss paints makes little significant difference to
Nondurable binders are those where the rate at which the overall breakdown rate, which is effectively determined
photochemical breakdown occurs is much greater than that by the rate at which the photochemical mechanism proceeds.
at which photocatalytic breakdown takes place. In these The main factors influencingthe durability of a paint film
systems, pigmentation with titanium dioxide enhances the are the environment (weather and location) in which it is
durability of the system through its complete absorption of exposed, the type and amount of pigment, the type of binder
the highly destructive, very short wavelength radiation. In and the substrate to which the paint has been applied. It is
addition it scatters the longer wavelength, but still possible to observe wide variations in weathering resistance
potentially destructive, blue region visible component from samples of the same paint applied to nominally the same
incident radiation. The rate at which the overwhelmingly substrate, exposed at different weathering locations. These
predominant photochemical mechanism can occur is thereby weathering performance variations of the same coating
reduced. Photocatalytic breakdown will continue to occur, system exposed at different locationscan frequently be
initiated by the pigment, but at a rate much less significant correlated with variations in radiant intensity and incident
than that of the the photochemical mechanism. This latter wavelength frequency distribution, rainfall, humidity and
situation is illustrated in Figure 17.This compares the other local differences between weathering locations. In
relationship between mass loss and time, for a titanium many cases, however, the variations may be due more to the
dioxide pigmented alkyd paint and an unpigmented alkyd deficienciesin the quality of the most common, and most

24
dimensionally unstable, substrate to which decorative paints
are applied, namely wood. The significantdeterioration in 8.1 INFLUENCE OF DRIER METAL TYPE
-
recent years of the general quality and standard of surface
preparation of wood employed for durable joinery Drier metals may be grouped into two classes, active and
applications in the UK has led to a corresponding alarming auxiliary. Active driers are those metals which are
increase in the rate of massive coating failure and gross fungal multivalent, and capable of reducing hydroperoxides,
induced degradation. Since there has been no parallel decline assuming a higher valency state in the process. They are then
in the quality of UK decorative paints, it is clear that as much reduced back to their lower valency state by further reaction
attention should be paid to the preparation of the substrate as as shown in Figure 19, setting up a chain reaction which is
to the technology of the coating ~ystem.~OAs we enter an era propagated through the film even though only its surface is in
in which environmental concern and preservation assume direct contact with atmospheric oxygen. Cobalt and
paramount importance, these shortcomings in organic manganese are the primary examples of this class of drier
substrate quality will perhaps be more seriously addressed. metal. The mechanism and kinetics are modifiedwhen more
Choice of resin can have a profound effect on weathering than one drier metal is present, systems of this type currently
resistance for reasons already discussed above. Where the being the subject of intensive i n ~ e s t i g a t i o n . ~ ~
resins differ in chemical type, this is hardly surprising, since
their spectral absorption characteristics are also likely to
differ widely. Appreciable variation may also be observed,
however, within resins of the same type. These are usually
the result of defects of individual coating systems, for
example, through the incidence of substantial pigment
flocculation.
Further reading on the subject of durability can be found
in the Tioxide publication: Durability.

~. ___
DRYING AND
8 DRYING RETENTION
-. __ - .. -

Both internal and external factors influence the drying speed


of a solvent based decorative paint. The first stage in the
drying process is the evaporation of solvent, which
commences immediately the film is applied. The rate of
solvent evaporation is controlled by the resin system and is
virtually independent of the pigment used. The absorption of
atmospheric oxygen occurs simultaneously with the solvent
evaporation process. This absorption initiates the processes
which result in the hardening of the film through a
combination of oxidation and polymerisation. Driers increase
Cobalt is the most powerful active drier. It is capable of
the rate of autoxidative polymerisation and, hence the speed
reducing the energy of activation of oxygen uptake for an
with which the film hardens. Although driers and drier aids
alkyd resin, to one tenth of that in its absence.41 It can also
have been used for some considerable time, the exact way in
give rise to surface drying at a rate far in excess of its through
which they accelerate the oxidation rate is still a matter of
drying capabilities, which can lead to wrinkling in thick films.
conjecture. The followinghave all been suggested:
Cobalt is, therefore, only used alone in thin films. Like
(1) by increasing the rate of oxygen uptake; manganese, cobalt is strongly coloured, deep violet, but
highly effective, allowinglow levels of addition
(2) by counteracting the inhibitive effects of the natural
(approximately 0.05%w/w on binder solids).
antioxidants present in drying oils; and
Manganese is the second most powerful drier, but much
(3) by facilitatingthe decomposition of hydroperoxides and less efficient than cobalt. It confers both surface and through
thus increasing the crosslinking rate. drying, but its applicability is limited by its colour, light
brown manganous predominantly, turning to dark brown
ROLE OF THE PIGMENT
manganic. 8.2 AND EXTERNAL FACTORS
The second class, that of auxiliary, or through driers, is
characterised by metals which are not multivalent and are In a very small number of exceptional cases, with certain
thus unable to catalyse hydroperoxide decomposition. Lead, amine treated titanium pigments only, some loss of drying
zinc, calcium, zirconium, barium, and, less frequently, performance of solvent based alkyd paints has been observed
bismuth, cerium, vanadium and aluminium have all been under low temperature, very high humidity conditions and
applied to this role. They are used as through drying on prolonged storage. In general, however, the grade of
promoters, carrying the surface cure through the bulk of the titanium pigment has little or no effect on drying
underlying paint film. performance.
Lead was traditionally the most commonly used through The principal external factors which do strongly influence
drier and is still occasionallyused in combination with other the drying speed are the temperature and the humidity. Of
metals when toxicity considerations or the risk of dry film these, while lower temperatures do retard the drying
sulphide staining do not preclude its use. It is, however, process, relative humidity appears to exert a predominant
largely being replaced by zirconium on toxicologicalgrounds. effect. This probably arises from the combined effects of the
The gradual displacement of lead has probably generally inhibition of the evaporation process by retained solvent
resulted in a reduction of calcium driers. Calcium helps preventing polymer chains from approaching close enough to
prevent the precipitation of the lead on storage, in addition to facilitate cross linking reactions. The retention of an
enhancing low temperature drying performance and entrapped solvent vapour layer above the paint film surface
reducing blooming of the dry film. prevents access to the film surface by atmospheric oxygen.
Zirconium driers, which have a completely different - .- - ---
mode of action from that of lead, are nowadays frequently 9 STORAGE STABILITY
sold in combination with cobalt, facilitatingits replacement. ~-~ -__
Toxicologically,zirconium currently appears to be a low risk
The in can viscosity stability of a paint is a property which is
metal, in contrast to the other, alternative auxiliary drier
ofgreat interest to the formulator. Viscosity stability is in part
metals mentioned below.
dependent on the method of manufacture. Thorough milling
Zinc, added as the soap or the oxide pigment in drier allows resin adsorption to reach an equilibrium condition,
quantities, in terms of the metal, can be used to slow the
inefficientmilling leaving the paint unstable with regard to
surface dry and accelerate the rate of through dry, also the adsorption/desorption processes of resin molecules of
yielding enhanced film hardness. Barium has found use as a
varying molecular weight and, hence, with regard to
through drier, but is now under increasing toxicological
flocculation and viscosity stability.
scrutiny, while cerium and vanadium are generally
Such phenomena are generally less marked with
unsatisfactory on the grounds of poor retention of both colour
titanium dioxide than with finer particle size, larger surface
on ageing and drying performance on storage. Aluminium
area organic pigments. In general, the viscosity increases on
has frequently been proposed as an alternative, nontoxic
storage observed with titanium pigments are proportional to
through drier, although the resin must generally be purpose
the level of inorganic coating, and likely to be more
synthesised to extract the maximum advantages of this drier.
pronounced with predominantly silica t,hana1um.in.a coa.t.ed
The reported benefits are good colour, colour retention, good
grades, for the reasons detailed in a previous section devoted
through drying and hard films.
to ‘Flocculation’.An organic addition to the pigment surface
In general, the type and quantity of driers used in a paint
reduces the tendency toward viscosity instability, by
can have a marked effect on its drying rate. Care should,
partially satisfyingthe medium demand of the pigment
however, be exercised in the interpretation of the results
surface.
from different methods of measurement. Those generated by
a low load technique will lead to a misleadingly short
measured drying time in the presence of increased surface 9.1 INFLUENCE O F THE RESIN

drier, for example, cobalt, while testing by scratch hardness


would suggest that drying rate had been retarded. It is It has been established that in dispersions of titanium dioxide
primarily the resin type which determines the drier in high concentration alkyd resin solutions, preferential
requirement, and the manufacturer’srecommendations in adsorption of low molecular weight species, such as phthalic
26 this respect should be carefully observed. half esters, initially occurs on the pigment surface.l1?l2The
effective removal from the bulk of the solution of these low In general, any factor which facilitates pigment
molecular weight species may, in some systems, lead to an dispersion will help minimise settling and any factor which
increase in viscosity. An organic addition on the pigment promotes flocculationdetracts from storage stability and
surface will release much of this low molecular weight other properties. However, it must be stressed that a
material and is likely to reduce the tendency toward viscosity controlled amount of deliberately induced flocculationmay
instability. be preferable from a storage stability viewpoint to the highest
Strong solvents will also minimise the tendency for levels of dispersion. Hard settlement will be prevented and
viscosity instability, by maximising the chain extension and optical properties will not suffer to a measurable degree. The
opening the molecular configuration of the solvated resin difficulty arises in achieving this close control over the
molecules. This maximises the initial viscosity and reduces induced flocculation, since the degree required to reach this
not only the scope for increase with time, but also the risk of ideal state wiIl vary from system to system and at present can
seeding. This occasionally occurs with weak solvents, due to only be determined on an empirical basis.
the loss of the peptising effect of the low molecular weight Logically,a high viscosity will help prevent settlement,
material which has been adsorbed on the pigment. A potential but often to the detriment of application properties. The
then results for precipitation of the highest molecular weight, rheological properties of a paint can be modified by the use of
lowest solubility resin fraction. The risk of the latter is greater aproprietary thixotrope or antisettling agent, usually at
when isoparaffinic,low odour white spirit is used, and may some cost in increased pigment flocculation, since this is the
be reduced by the addition of some aromatic solvent. mode by which these reagents operate. Again the Casson
Within the Tioxide Group, a powerful, but relatively Brookfield technique45may be used to determine, at an early
inexpensive method, the Casson Brookfield technique,42is in stage, the degree of sedimentation and settling to be
use for studying the rheological properties of coatings. The expected. Applied to, for example, semiglosslatex paints, it
technique relies on Asbeck’srearrangement43of the Casson has been established that an unsheared yield value for a paint
equation44and provides a good deal of rheological of 10dynes.cm2or more, is advisable if sedimentation during
information employing an easy to use and inexpensive piece storage is to be minimised. The most cost effective level for
of equipment. The technique suggests that to achieve a stable any rheological agent can thus be determined experimentally.
viscosity, the difference in infinite shear viscosity between
an unsheared and sheared paint should be minimised. This
implies that the difference in the degree of flocculation
between the unsheared and sheared paint has been
minimised together with the likelihood of problems arising The talents and expertise of the paint formulator notwith-
from viscosity instability. standing, the application stage is frequently the most
important operation with regard to the performance level
attained by a coating. Ease of brushing, wet edge or lapping
9.2 S E T T L E M E N TA N D S Y N E R E S I S
time, levelling and resistance to sagging are probably the
application properties of greatest concern to the user. Some
Separation can occur between the titanium dioxide and the of these properties are difficultto assess by any other method
resin, and in tinted paints between titanium dioxide and than practical brushing trials, irrespective of the existence of
coloured pigment. In the case of pigment resin separation, mechanical methods which seek to quantify them.
this arises primarily because of the differences in density
between titanium dioxide and the resin. Grades oltitanium
dioxide have densities between 3.5 and 4.2g/cm3 and most 10.1 BRUSH ABILITY

resin media have densities around 1.0g/cm3.The extent and


rate of separation is strongly influenced by the state of Perhaps the most important internal factor which affects
pigment dispersion, flocculated pigment settling faster than brushability is the viscosity at high shear rate, typically
dispersed pigment and giving a soft sediment which is easily around lo4to lo5reciprocal seconds. A paint with a low, high
reincorporated. The more efficiently apigment is dispersed shear viscosity will normally be easy to apply. By the same
and stabilised the less will be its tendency to settle. Although token, however, the paint should not be too easily applied, or
when sedimentationdoes occur with a well dispersedpigment, overspreading and, hence, poor film build and opacity may
it is hard and may be difficult to reincorporate. However, this result. The degree of brush drag and the wet edge time are
usually only happens after long periods of storage. both strongly dependent on the rate of solvent evaporation
and the viscositykoncentration behaviour of the solution of with a Newtonian system. Thixotropic systems do not
the resin in the relevant solvents. Theoretical calculation^^^ necessarily provide a complete answer to this dilemma, rapid
have suggested that the viscosity of the paint immediately recovery of viscosity occurs soon after application and,
after application should not exceed that of the fresh paint on coupled with rapid solvent loss, poor levelling can result with
the brush by more than a factor of five times. these systems.
Titanium dioxide generally has a minimal effect on these
properties, which are much more residsolvent dependent.
10.2 FLOW AND SAGGING
Other, external factors such as the substrate and ambient
conditions can also profoundly affect application properties
As is often the case in paint technology, the factors which and careful substrate preparation, including the use of primer
lead to good brushability and flow, that is, good flow and and/or undercoat, is particularly important.
levelling, gradual viscosity increase with solvent loss, etc, are
also those which can promote sagging. The formulator must
therefore strike a compromise between these opposing
performance requirements. The conflict between the needs
for good flow, for example, to ensure the swift disappearance
of brushmarks and that for restriction of flow to prevent the
occurrence of sagging are probably impossibleto reconcile

In the preceding pages, numerous general statements have final milling stage. Virtually all the general purpose and high
been made about the constituent raw materials used in the performance grades of titanium dioxide currently available,
manufacture of solvent based decorative paints. It is now fall into the type R2 category.
appropriate to discuss the nature of the titanium dioxide in The final cat'egory, type R3, refers to heavily coated,
greater detail. refined rutile pigments designed primarily for use in medium
Titanium dioxide pigments used in solvent based to high p.v.c.(d) matt emulsionpaints. They are infrequently
decorative paints are almost exclusively rutile, for reasons used and of very limited relevance in solvent based
already discussed, and a number of systems have evolved for decorative paint applications. They will not, therefore, be
the categorisation of such pigments. These are categorised in discussed in detail here. Readers interested in the properties
IS0 591-1977(Specificationsfor titanium dioxide pigments of this type of titanium dioxide should refer to the Tioxide
for paints) as types R1, R2 and R3. publication: Titanium dioxide pigments in water-borne
Type R1 pigments are prepared from calciner or reactor decorativepaints. Table 12gives a synopsis of the three
discharge simply by dry grinding and selection of the desired types and an outline of their main areas of application.
particle size range. They are frequently described as
untreated or dry milled pigments within the titanium dioxide
industry, their use being limited to a small range of non
critical applications where lower cost is usually of more
significance than technical performance.
Type R2 pigments are prepared from R1 types by
successive coating and refining stages. The pigment base is
first dispersed in water and wet milled to remove oversize
particles. Between 1% and 10%ofotheroxides, usually
alumina, silica and zirconia are then precipitated on the
surface of the base pigment. The product is then filtered,
dried and, where necessary, size classified to obtain the
desired particle size distribution. These steps are frequently
28 followed by the application of an organic treatment at the
Paints are generally formulated to meet a particular product
requirement. These may already be in the form of a technical
specificationor may require conversion into such form by the
formulator, from the product description and cost constraints
describedby his customer. The formulator’s skill lies in fully
meeting this product specificationat the lowest practicable
cost. He must also take into consideration the raw materials
to hand, the anticipated inherent production demands and
the processingequipment most appropriate to carry out its
manufacture.Until relatively recently, the formulator’s skill
was based largely on intuitive feel coupled with the gradual
accumulationof experience over a period of many years.
While such knowledge and expertise is still invaluable, the
proliferation of raw materials and types of milling equipment
in recent years has resulted in the evolution of a more
systematicapproach.

1.1 F L O W P O I NM
TETHOD
flowpoint paste, including the solvent with the resin. This is
denotedbyp.v.c.(f),andisdefinedlater in the text. Atypical
A technique that has been found extremely useful in the flowpoint curve, which exhibits a maximum as a result of the
derivation of millbase compositionsis the Daniel flowpoint
method.47 This allows the formulator to make the most
effective use possible of the pigmentary components of the
formulation. It has been applied to specific types of
paintmakingequipment ,48949*50 and Dowling51has proposed
’ expression for p.v.c.(f), rather than aminimum, is illustrated
inFigure 21. Practical experience with titanium dioxide over
many years has enabled the clas~ification~~ of pigmenthesin
flowpoint curves into three categories, representing poor,

a scheme which seeks to establish which combinationsof


pigment type, resin type, and types of milling equipment
offer the most appropriate routes to particular end products.
The application of the Daniel flowpoint will now be
illustrated with particular reference to some of the media
used in the manufacture of solvent based decorative paints.
The flowpoint determination is a logical development of
the classical oil absorption test. Using the formulation
speclficpigments, resms and solvents,the formulator 1sable
to generate informationindicating the most efficient method
of processingthat formulation. In essence, the technique
involves the titration of pigment samples of fixed weight
against several concentrationsof the resin solution involved.
For each pigment/resin/solvent system, the volume of resin
solution required at each concentration to achieve an almost
fluid paste with the fixed amount of pigment, is plotted
against that weight percent resin concentration. Normally a
minimum occurs at a particular resin concentration, as
shown in Figure 20.
It has been found to be more convenient to express these
data in the terms of the pigment volume concentration of the 29
adequate and good dispersions, as shown in Figure 22. Each
of the three components,pigment, resin and solvent,
influences the shape, position and, hence the classification of
the flowpointcurve and will, therefore, be considered in turn.

1.2 INFLUENCE OF TITANIUM PIGMENT

Although the grade of titanium dioxide pigment has some


influence on the position of the flowpoint maximum, as may
be seen from Figure 23, it is normally the resin which has the
dominant effect. Since titanium dioxide is composed of highly
polar inorganic crystals: it is hardly surprising that it gives
flowpoint pastes falling into the good dispersion category,
with relatively polar media such as alkyd resins. In general,
the lower the polarity of the resin, the poorer the resultant
dispersion of the titanium dioxide.

30
dispersion category pigmenthesin solution combinations and
1.3 INFLUENCE OF RESIN the flowpointpaste is dilatant, indicative of a good
dispersion. In contrast, reduction of this alkyd with a 4: 1
?e overriding importance of the resin in determining the ixture of xy1ene:butanolappreciably depresses the
spersion class of the flowpointcurve is illustrated in Figure iwpoint maximump.v.c.(f),The paste at the flowpoint
2 , in which the flowpoint curves for an R2 type pigment in a ,aximum is now flocculent and the system best
inge of media typically used in the manufacture of solvent iaracterised in the adequate dispersion category. It is not
ased decorative finishes are shown. According to the ossible to generalise on the basis of the foregoing by
[assificationproposed by D ~ w l i n gall
, ~of~the curves fall into mcluding that all short oil alkyds are best reduced with
le good dispersion category, with the exception of the ylene. This is because examples exhibiting exactly the
nyltoluenated alkyd which is bordering on the adequate ?positebehaviour are frequently found. Such a system is
ispersion category. The implication of this is that it is more epicted in Figure 26.
ifficult to disperse titanium dioxide in a vinyltoluenated The influence of solvent on flowpointbehaviour is of
lkyd than, for example, alongoil linoleic rich alkyd, an reatest concern in industrial finishes. In solvent based
ssertion which is borne out in practice. However, it must be ecorative finishes white spirit is almost invariably the main
tressed that, even in this medium, titanium dioxide is olvent used and this aspect will therefore not be considered
elatively easy to disperse in comparisonwith certain other Lere. However, this topic, and the allied subject of millbase
igments, such as carbon black or toluidine red. ormulation, are more comprehensivelyreviewed in the
'ioxidepublication: Dispersion of Titanium Dioxide
'igments:General Principles. and the reader is referred to
his booklet ifgreater detail is required.

1.4 INFLUENCE O F SOLVENT

The choice of solvent blend can exert a profound effect on thc


rheological properties of a millbasecomposition.An examplt
illustrating this point is shown in Figure 25. The upper
flowpointcurve depicted, is that of a type R2 rutile titanium
dioxide, titrated against short oil alkyd resin solutions of
various concentrations in xylene. The flowpoint curve
maximum falls into the areaof p.v.c.(f)associated withgood
such systems may consequently be Newtonian, dilatant or
1.5 A P P L I C A T I O NO F F L O W P O I N T D A T A flocculent, although it is most frequently the latter, partic-
ularly as the flowpoint maximum approaches 30%p.v.c.(f).
The purpose of determining the pigmenthesin flowpoint Dispersing agents may be effective in specificsystems and
characteristics is to establish suitable milling equipment and usually at low resin concentrations, but they are by no means
millbase formulae for the efficient processing of this raw universally applicable. Their use should be given careful
material combination. This is done empirically with the consideration as this can yield unexpected results,
objective of obtaining systems in the good dispersion Three roll mills and ballmills can generally be used to
category. This is because of the generally faster processing process properly formulated millbases of the adequate
rates, arising from the higher pigmentation levels, viscosities dispersing category without difficulty.With care and
and dispersion rates, and greater formulation latitude attention to millbase formulation, they can also be processed
permissible with systems in the good dispersion category. in batch attrition mills, sand, and beadmills. Occasionally
- __ -. where thixotropic millbases lead to poor milling conditions
S E L E C T I O N OF M I L L I N G through inadequate shear transmission, beadmills have
2 EQUIPMENT
- generally been found more flexible than sandmills. Systems
containing type R2 pigments which exhibit adequate
2.1 GOOD DISPERSING SYSTEMS
dispersing characteristics may occasionallybe processed on
the kinetic dispersion mill. However, the high speed impeller
Most types of paintmaking equipment can be used
mill seldom gives satisfactory results with systems in this
successfullyto process pigmenthesin solution combinations
category. Productivity with adequate dispersions is reduced
falling into the good dispersions category, subject to the
relative to good dispersions due to lengthened milling
limitations imposed by the type of titanium dioxide used.
schedules and lower pigment loadings. Recommended
With R2 type pigments, good dispersions can usually be
millbase formulae for systems in this class processed on
rapidly processed on various commonly used types of
different types of milling equipment are given in Table 14.
equipment, as detailed in Table 13. Type R 1 titanium dioxide
pigments will not generally process satisfactorily on the high
speed impeller or kinetic dispersion mills and sometimes 2.3 POOR DISPERSING SYSTEMS

require sand milling or bead milling.


Systems falling into the poor dispersing category are
generally those which are most difficult to formulate. The
2.2 ADEQUATE DISPERSING SYSTEMS flowpoint titre is frequently extremely difficult to assess,
resulting in a poorly defined flowpoint curve. The flowpoint
Systems falling into the above category require rather more pastes are usually thixotropic, highly flocculent and
attention than those in the good dispersing category, in order substantially lacking in cohesion unless very high resin solids
to avoid unsatisfactory results. This is because millbases in are employed, which leads to detrimental effects on the rate
this category frequently lack cohesion, one of the primary of pigment wetting. Considerable care is thus needed to
requirements for obtaining good dispersion. The rheology of achieve a satisfactory level of pigment dispersion and to

32
prevent this dispersion level from deteriorating, due to the
strong tendency toward reflocculation in such systems. 3 MILLBASE STABILISATION
Few types of milling equipment are suitable for the -_
processing of poor dispersing systems, the most effective When the desired degree of pigment dispersion has been
being the triple roll mill, ballmill and attrition mill. These achieved in the millbase, it is often necessary to add more
three types are still subject to operational constraints. It is not resin solution as soon as possible in order to prevent the
advisable to use the triple roll mill with systems containing reagglomeration of pigment particles. Where this is
highly volatile solvents, long milling schedules must be accomplished by the addition of further solution of the resin
acceptable when using the ballmill and the processing of heat present in the millbase, this is called the stabilisation stage.
sensitive resins should be avoided with the attrition mill. Frequently, however, the further addition contains all the
Very occasionallykinetic dispersion, sandmill or beadmill raw materials not already present in the millbase, and should
may be used to process systems satisfactorily in this category, therefore be classified as a letdown addition. Letdown
depending on pigment quality and the degree of millbase without regard for the possible technical implications can
thixotropy. lead to detraction from the degree of dispersion already
The restrictions imposed by poor dispersing systems achieved. This could be in the form of gross flocculation
may often be avoided by dispersing and, where appropriate, leading to complete spoilage of the formulation under
stabilisingthe pigmentary component in the least possible processing.
quantity of a resin solution compatible with the main binder. The problems which occur during letdown procedures
This has the result of modlfyingthe millbase composition usually arise from compositionaldifferences between the
such that it falls into the good dispersing category and the millbase and the stabilisingaddition. A well designed
main binder may then be added at the letdown stage. A risk of stabilisation and letdown procedure results in a gradual
incompatibility inevitably arises in such circumstances, but transformation of the millbase from its initial pigment rich
this may be minimised by the addition of a small proportion of state to the final compositionof the paint. This may be
the main binder to the millbase, provided this does not achieved in one of two ways. Either the dispersed pigment
fundamentally disturb the good dispersion classification of must be stabilised immediately after the dispersive forces are
the millbase. This approach is no more than a variation on the removed, or the pigment must be dispersed from the start in a
one already used by many manufacturers when confronted comparatively concentrated resin solution. Both methods are
with the poor dispersing system problem, that is, recourse to used in practice, the choice depending generally on the type
the use of a dispersant. Other approaches may also be of milling equipment, but occasionallyalso on considerations
possible, a change of solvent may improve the dispersing of production expediency. It is, for example, sometimes
capabilities of the system, but seldom from poor to good difficult to stabilise a low resin content sand or bead mill base
dispersing. In other cases, where the resin is suitable, a hot reliably. Consequently, even though dispersion in low resin
melt pigment concentrate or chip may be produced on a two solids media is generally more efficient, with these
roll mill or heavy duty mixer. Frequently no alternative equipment types it is more usual to disperse in a higher resin
exists and millbase formulae such as those detailed in Table solids concentration millbase and thereby dispense with the
15must be used. need for a stabilisation stage. This also results in a reduced
throughput rate due to the higher resin solids employed.
Where stabilisation is necessary, this is best achieved
using resin of similar concentration to that in the millbase.
This is because letdown defects most frequently arise from
osmotic solvent transport between the solvent rich millbase
and the resin rich letdown c o m p o s i t i ~ nThis
. ~ ~ results in
insufficientliquid remaining to keep the pigment particles
separated. Pigment and resin therefore coagulate into hard
agglomerates which are almost impossible to redisperse and
very rapid settlement results. This phenomenon is variously
known as pigment shock, colloidalshock, solvent shock,
shock seeding, or vehicle shock.
Delayed shock may occur, agglomerationthen being
observed after the paint has been stored for several days or
even weeks. It is often difficult to distinguish between
chemical seeding, through the formation of lead phthalate
(where lead driers have been used) or zinc soaps, and the
precipitation from the resin solution of any low solubility,
high molecular weight resin fraction, as described earlier in
the section on binders under ‘Chemicalnature’. Table 16
offers some suggestions for stabilising millbases prepared in
commonly used paint mills in conjunction with the resin
types mentioned in Figure 24.

* Defined on page 40

On the subsequent pages, Table 17classifies some of the important to consider all the possibilitieslisted under a
more common defects encountered in producing solvent particular heading.
based decorative finishes. They are listed according to the For customers of Tioxide requiring additional
stage in the paint making process at which they become information on the topics covered here, and/or discussion of
apparent, that is, during manufacture and storage, during specific problems, the representatives and Technical Service
application, and in the dry film after exposure. Defects may personnel of Tioxide should be contacted and will be pleased
be the result of a combination of factors and it is therefore to assist in their resolution.

34
35
36
38
39
Definitions and abbreviations

p.v.c: pigment volume concentration

volume of pigment
p.v‘c’(d)%: volume of(pigment +n.v. binder) x 100
volume of pigment
p.v.c.(f)%:
volume of (pigment +binder + solvent) x 100

n.v: non-volatile

40 binder: ‘binder’used alone in the text stands for ‘non-volatilebinder’


1 Bartosiewicz, R: Journal ofpaint Technology, 1967,39, 26 Simpson, Dr L A, Tioxide TiINFO system technology brochure:
No 504, p28 Measuringopacity, pp3-18
2 Billmeyer, F W Jr: Journal ofpaint Technology, 1969,41, 27 Tunstall, D F & Hird, M J, JPaint Tech, 1974,46,No 588,p33
No 528, p3 28 A Doroszkowski in Lambourne, R (Ed), Paint andsurface
3 Funcke, WE: Journal of Coatings Technology, 1988,60, Coatings: Theory and Practice, (Ellis Horwood Limited,
No 767, p69 Chichester, 1987), p234
4 Bromley, C W A: Journal of Coatings Technology, 1989,61, 29 Tioxide TiINFO System technology brochure: Measurin,g
No 768, p39 colour, p3
5 Martens, C R(Ed): TechnologyofPaints, Varnishesand 30 Hall, J E, Tioxide technical report D9088: The yellowingof
Lacquers, (Rheinhold, New York, 1968), p285 oleoresinous airdryingf i l m : A Revim
6 Crowley, J D , Teague, GS&Lowe, JW: JournalofPaint 31 Simpson, DrLA, JOCCA, 64, No 12, p490(1981)
Technology, 1966,38,No496, p 269; 1967,39, No 504, p19 32 Bragdon, C R (Ed), Film Formation, Film Properties and Film
7 Hansen, C M: Journal of Paint Technology, 1967,39, No 505, Deterioration, (Interscience Publishers Inc, New York, 1958),
p104; 1967,39,No511, p505 p217
8 Nelson, R C, Hemwall, R W & Edwards, G D: Journal ofpaint 33 Elm, AC, Paintindia, 1961,10,p10
Technology, 1970,42,No 550, p636 34 Schieber, LackeundihreRohstoffe, 1926, Leipzig, p173
9 Lambourne, R (Ed), Paint and Surface Coatings: Theory and
35 O’Neill,LA, Rybicka, SM and Ropey, T L T , ChemInc, 1962,
Practice, (EllisHorwood, Chichester, 1987), pp194-211 No 1796
10 Quote from W Asbeck, 1977 Mattiello Lecture:
36 Rackoff, H, Kowlek, W F and Gast, LE, JCoatings Tech, 1978,
The degree of dispersion of the pigment in acoatings
50, No 637, p57
formulation influences all coating characteristics:
37 Balfour, J G, Tioxide technical report D9227: Durability and
manufacture; application;performance; appearance
titanium dioxide pigments
11 Franklin, M J B, Goldsbrough, K, Parfitt, G D & Peacock, J,
38 Simpson, Dr L A , Tioxide technical report D9160: Influenceof
Journal ofpaint Technology, 1970,42,No 551, p740
titanium dioxide pigment on durability of paintf i l m s
12 Goldsbrough, K & Peacock, J , Journal of the Oil & Colour
39 Moulton, D V , Tioxide technical report D9218: Therekxbility
ChemistsAssociation, 1971,54,p506
of durability testing
13 Napper, D H, Polgm&ncstabilisation ofcolloidal dispersions,
40 van Loon, J, Journal of the Oil and Colour Chemists’
Academic Press, 1983
Association, 1966,49,No 10, p865
14 A Doroszkowskiin Lambourne, R(Ed), Paint andsurface
41 Belletierre, S J , andMahoney, DM, JCoatings Tech, 1987,59,
Coatings: Theory and Practice, (Ellis Horwood Limited,
No752, p10
Chichester, 1987), p226
15 Walbridge, D J, Scott, E I & Young, C H, Vth Conferencein 42 Cutrone, L, JCoatings Tech, 1984,56, No 708, p59-63
Organic CoatingsScienceand Technology(Athens),1979, 43 Asbeck, W K, Fundamentals of the Rheology ofRgment
~~526-546 Dispersions, OfficialDigest, 1961,33,No432, p65
16 Keesom,WH,PhysZeit, 1921,21,p129 44 Casson, N, RheologyofDisperseSystems, 1959,(Pergamon
17 Debye, P, PhysZeit, 1920,22,p178 Press, New York), p84
18 London, F, PhysZeit, 1930,63,p245 45 Cutrone, L, Chabral, R, Charron, A, Hilton, F H, Philipp, H S
19 Schnall, M, J, Coatings Tech, 1989,61,No773, p23 andFlack, J,JCoatings Tech, 1984,56,No 709, p41-44
20 Balfour, J G, Tioxide technical report D8785: Thecost of 46 Beeferman, HL, andBergren, DA, JPaint Tech, 1966,38,
flocmrla,ti,on,,1 977 No 492, p9
21 Tioxide technical report D8786: The detection and 47 Daniel, F K, and Goldman, P, Industrial and Engineering
measurement offlocculation of titanium dioxide pigments in Chemistry(AnalyticalEdition),1946,18,No 1,p26
decorative alkyd glosspaints 48 Daniel, F K, National Paint, Varnish andLacquer
22 Rutherford, D J & Simpson, Dr L A, Tioxide technical report Association, Scienta&Section, October 1950, Circular 744
D9151: Designanduseof asampleflocculationgradient 49 Daniel, F K , JPaint Tech, 1966,38,No 500, p535
apparatus 50 Patton, T C ,Paint Flow and Pigment Lhspersion (Interscience
23 Rutherford, D J & Simpson, Dr L A, Tioxide technical report Publishers, New York, 1966), p284
D9186: Theuseof aflocculationgrdimt monitorfor 5 1 Tioxide publication BTP/14 1: Development of the Daniel
quantzlfyingpigment dispersion in dry and wet paintf i l m s flowpoint technique, and its application, in conjunction with
24 Simpson, Dr L A, Tioxide TiINFO System technology brochure: titanium oxide pigments,to the selection of appropriate
Measuringopacity, pp6,7 millingmachinery and mill baseformulaef o r the
25 Balfour, J G, Tioxide technical report D9226: Back to basics: manufactureof paints and printing inks
opacity and titanium dioxide pigments, p6 52 Daniel, FK, OfficialDigest, 1956, No 381, p837