Professional Documents
Culture Documents
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
0 SOLVENT 11
EXTENDERS 12
0 ADDITIVES 12
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
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
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
MILLBASE STABILISATION 33
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
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
....................................................................................................
2 SOLVENT
~ ~
-.
13
F: Formulative; R: Remedial; S: Speculative
- 7 - - - _ _ --. - - - -- ._i __
--
-__ _ 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)
FG=0.44
~~
-
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
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
-. __ - .. -
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,
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.
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
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