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Spacing for better effects
Influence of fine particle size extenders and entrapped air on
utilisation of TiO2 in emulsion paints. A number of
interactions can occur between titanium dioxide and mineral
extenders, which can effect a range of paint properties, such
as rheology, durability, opacity and scrub resistance, some
of which are not fully appreciated. This paper looks at one of
these interactions, TiO2 spacing by extenders, and the effect
it has on the optical properties and scrub resistance of
emulsion paints. Evaluation of the possible TiO2 savings
suggest that, while small reductions (ca. 5%) in TiO2
loadings could be made with flash calcined extenders in
certain paint systems, implementing greater savings, as
suggested by the manufacturers, led to detrimental effects
on several other important paint properties.
Paul Frederick Dietz.
TiO2 pigments provide opacity and whiteness to paints and
influence a wide range of other properties. However, the
manufacturing processes of TiO2 are relatively expensive,
hence it is often one of the most expensive raw materials
used in emulsion paints. Many techniques and additives
have been developed to help improve the utilisation of TiO2
and thus reduce the amount used whilst maintaining the
performance properties of the paint. Extender manufacturers
have been promoting their products as potential ways of
saving TiO2, often proposing savings as high as 30 vol.%.
Fine particle size extenders save TiO2
It is true to say that over a period of 30 or so years paint
formulators have made use of smaller particle size
extenders in their paints and significantly reduced their TiO2
content. For example, a typical high quality matt paint of the
1970's would often contain in excess of 18 vol.% TiO2.
Through use of small size calcined clay extenders, and to
some degree opaque polymers, this level has now been
reduced to typically between 10 and 14 vol%.
It is difficult to see, however, how modern paints could
continue to benefit from extender manufacturers' continuing
claims of potential savings of 20 to 30% TiO2 by using their
fine particle size extenders.
Thus, this study looked at several current fine particle size
extenders and some "new" flash calcined extenders to see
how the manufacturers' claims hold up when the extenders
are used in a relatively modern paint formulation.
Improving TiO2 use through spacing
In decorative emulsion paints it has long been known that
TiO2 is often poorly dispersed and crowded by the extender
and emulsion particles [1]. Indeed the higher the pigment
and extender volume concentration the worse the crowding
can become. It is well understood that by reducing the size
of the extender particles used, the spacing of the TiO2 can
be significantly improved (Figure 1).
Replacing a 6m extender/filler with a 2m calcined clay
would, and did, lead to improved TiO2 spacing, better
opacity and to the possibility of reducing TiO2 levels.
However, to further improve the spacing to levels leading to
significant improvements in scattering and opacity would
ideally require the extender particle size to be an order of
magnitude smaller at least. Figure 2, shows the theoretical
effect on the TiO2 nearest neighbour distance when
extender particle size varies from 0.01 to 1.0m. This
modelling program, developed by Temperley et al. [2],
assumes that there is random packing between TiO2 and
extender particles.
Clearly, further spacing of the TiO2 only begins to have a
significant effect on opacity when the particle size of the
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extender reaches a size less than 0.5m. The optimum TiO2
spacing and maximum increase in scatter occurs with a
particle size between 0.1 and 0.2m.
The majority of extenders which still claim to offer potential
savings of 20 to 30% through TiO2 spacing are well in
excess of this particle size and therefore are unlikely to be
able to have such an impact on opacity using this
mechanism, unless some other property which could affect
film porosity or scrub resistance, such as air entrapment,
comes into play.
pvc ladder with varying extender volume concentration
A number of leading extender manufacturers were asked to
provide fine particle size extenders which they would
recommend for improving TiO2 utilisation. Table 1 lists the
ones used in the evaluation with the chemical type and
particles sizes quoted by the manufacturers. Extender A
was selected as the standard and represents a well known,
and much used, calcined clay extender which is known to
have improved the utilisation of the TiO2 when substituting a
larger filler type product.
To evaluate the extender performance it was felt necessary
to produce a pvc ladder with constant TiO2 vc and varying
extender vc. This evaluation allowed to determine the critical
pigment volume concentration (cpvc) for each type of
extender in this paint system. It would not, however, easily
allow multiple extender paints to be tested and one therefore
accepted that the evaluation would be limited and that one
may lose any synergistic effects (good or bad) by using
extenders in combination.
Several paint properties were tested including opacity
(contrast ratio dry and wet) measured using black and white
charts and a number 6 K-Bar wire-wound applicator, colour
(CIELab), resistance to Gilsonite oil-based stain and glycol
opacity (reflectance after the application of a propylene
glycol film). The glycol film removes the effects of increased
porosity (dry hiding) and helps confirm the position of the
cpvc for each extender.
The performance was plotted against the extender vc and
compared to that of the standard Extender A.
Figures 3a and b show how three of the extenders
performed in terms of dry opacity and glycol opacity.
Extender flocculating performs worse
Considering the relationship of the curves and the cpvc
levels, shown in Figure 4, one can draw certain conclusions
from their shape and direction. For example, both Extender
A and Extender I in Figure 4 show a downward trend with
increasing extender volume, which suggests the degree of
crowding is also increasing. The decrease is steeper for
Extender I - it is crowding the pigment more, producing a
more rapid fall-off in opacity. Given the particle size of
Extender I is 3.2m this is as would be expected, since
Extender A has a slightly smaller particle size and tighter
distribution. We would thus consider Extender I to have a
worse performance and not to offer any potential savings
over Extender A.
Extender H has a much smaller particle size of 0.18m and,
given the modelling data, should produce a much better
opacity than Extender A. Figure 4 shows, however, that this
is not the case. In fact the performance below the cpvc is
worse than Extender I. The reason for the unexpected result
is that the extender is badly flocculated, leading to a much
larger effective particle size. It is therefore not surprising that
the opacity is well down and that this extender is performing
worse than Extender A.
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Extender with air voids improves opacity
It is thus important to note that the measured particle size of
the extender may not truly reflect the particle size in
application. It can not be stressed enough that in order to
obtain the best TiO2 utilisation both the extender and the TiO
2 must be well dispersed and stable.
Extender F is of the "new" flash calcined family. The
manufacturing process produces an extender particle
containing air voids (both interconnected and discrete),
which are claimed to help scatter light, thus improving the
opacity of the paint film. The particle size is very similar to
Extender A and so one would not expect to gain any
advantage through a reduction in pigment crowding. Figure
4 shows that there is an improvement over and above the
opacity generated using Extender A. This is most likely
produced by the entrapped air which is off-setting the
crowding effect.
Ranking of extenders
It is not possible to review all of the results obtained in this
study. However, each property was carefully considered and
compared to Extender A and the results used to rank the
extenders in order of performance. Table 2 shows the
results.
Four extenders appeared to give an improved, and therefore
potentially TiO2 saving performance - Extenders C, D, E,
and F, the latter two being flash calcined china clays.
Examination of the four curves in Figure 5 shows that C and
D are both gaining most of their advantage by reducing the
cpvc of the paint, although small increases in opacity below
the cpvc are also evident.
The brightness of these two extenders is very high and their
shape and size may make them reflect rather than scatter
light, as is the case with some platelet type extenders. E and
F, although reducing the cpvc slightly, still show an overall
increase in opacity across the pvc ladder. Considering
Extender E, the increase in opacity below the cpvc is quite
substantial (at pvc 30%, Delta Contrast Ratio DCR = 1.5)
and should allow for a reasonable reduction in TiO2 loading.
TiO2 reductions of 20% are possible
To determine how much TiO2 could potentially be saved and
to determine what, if any, detrimental effects this would have
on the other paint properties, a series of paints were made
with incremental reductions in TiO2. A pvc of 30%, below the
cpvc, was chosen to avoid complications of dry hiding. This
pvc also showed a substantial improvement in opacity over
Extender A. As Figure 6a shows, a reduction in TiO2 vc of
20% is possible if a match in opacity is required. If, however,
one consider the reflectance over black (Figure 6b), the
equivalent reflectance is at a slightly lower saving of
between 10 and 15% TiO2 vc. This also suggests that some
of the opacity advantage exhibited by Extender E (and F) is
coming from absorption rather than scattering.
Only the smallest level of TiO2 reduction could be made
without a significant decrease in wet opacity (Figure 7a).
This confirms that TiO2 is not spaced sufficiently well and
also suggests that the voids within the flash calcined
extender are not discrete and only begin to scatter light
when the paint dries.
Replacing TiO2 gives poor scrub resistance
A greater porosity in the paint with Extender E was
confirmed by Mercury porosimetry. Whilst not completely
ideal for assessing the total porosity of paint films, this
method does appear to work well in systems where any
voids are likely to be interconnected rather than discrete.
The porosity of the paint made with Extender E is
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approximately 5% greater than that for Extender A. Also,
most of this additional porosity appears to come in the size
range between 0.1 and 1.0m, the exact size range given
for the voids within the flash calcined clays. This also covers
the ideal range of void sizes for the scattering of light,
although much of the additional porosity indicated is above
0.5m in size.
Given that a greater porosity was identified in the Extender
E paint film the level of scrub resistance was examined to
see if there were any adverse effects in reducing the TiO2
level. Figure 7b shows that simply exchanging Extender A
for Extender E has led to a slight decrease in scrub
resistance. On reducing the level of TiO2 and replacing it
with Extender E, the scrub resistance continues to fall and
fails the requirements of <5mg/cm loss when more than 5%
TiO2 vc is replaced. This again falls well short of the claimed
30% saving in TiO2.
Entrapped air effects on TiO2 utilisation
Flash calcined extenders with their air void structures can
improve the opacity of emulsion paints through some
additional scattering although it has been shown that the
majority of the voids are not of a suitable size to
preferentially scatter light. This suggests that there is
another component in the equation that is adding to the
opacity of the paint and is imparted by the extender.
In comparison to a solvent-borne alkyd paint the TiO2
pigment in an emulsion paint is usually flocculated and
under-utilised and yet in many cases for an equal loading of
TiO2 the opacity of the emulsion paint can be equal to, or
surpass that, of the alkyd. This apparent contradiction can
be explained by the differences in refractive index of the two
systems.
Alkyd resins have a typical refractive index of ca. 1.51, an
acrylic emulsion will be slightly lower at ca. 1.48. Modelling
the scattering power of TiO2 as a function of resin refractive
index (RI) shows that this small difference is sufficient to
produce an uplift of 0.5 units contrast ratio. Also, a level of
5% air, entrapped within the paint film, will approximately
account for a similar reduction in refractive index and thus
increase opacity.
Opacity increases if more air is entrapped
From earlier Mercury porosimetry work, it is believed that a
typical emulsion paint contains between 5 and 15% of
entrapped air mainly due to incomplete film coalescence.
This quantity of air would account for an additional 1.5 units
of contrast ratio and would be sufficient to offset the opacity
loss due to flocculation when compared to the solvent borne
alkyd paint. Table 3 indicates the relative increases in
opacity that can be achieved by reducing the refractive
index of the resin system used.
If, upon addition of certain extenders, more air is entrapped,
then this would reduce the perceived refractive index of the
paint medium and thus increase the opacity. This effect is
contributing to the opacity advantage seen when using
Extender E.
Further work is now being done to determine better the
levels of air entrapped in emulsion paints, the "particle size"
of the air voids, how these interact with the paint film and
how, if at all, it is possible to control the inclusion of air in the
paint.
Acknowledgements
The Author would like to express his thanks to Dr Les
Simpson, John Temperley, Kathryn Fullerton and Frank
Holden for their help in preparing this paper and carrying out
the necessary laboratory work. He would also like to thank
Mahomed Maiter, Group Marketing Director and Brian
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Thomas, Group HR & Communications Director, for their

support.

References
[1] L Cutrone, D Becherel, Huntsman Tioxide, Technical
Report D9202GC "Interaction Between Fine Particle
Extenders and Titanium Dioxide in Paints"
[2] J. Temperley, M. J. Westwood,M. R. Hornby, L. A.
Simpson, "Use of a Mathematical Model to Predict the
Effects of Extenders on Pigment Dispersion in Paint Film",
Journal of Coatings Technology, Vol.64 (1992) No.809, p
33-40

Result at a glance
A range of fine particle size extenders have been evaluated
and there are some small improvements in TiO2 utilisation.
The claims of 20 to 30% saving in TiO2 could not be fully
substantiated. Current extenders with a particle size in
excess of 0.5m have been shown not to improve the
spacing of TiO2. Extenders with particle sizes of less the
0.5m were not easily dispersed down to their primary size
and tended to homo-flocculate creating large multi-particle
extenders causing increased crowding and lower opacities.
Flash calcined china clays did appear to offer better TiO2
utilisation.
The incorporation of air voids within the paint film by these
extenders have a positive effect on opacity. The inclusion of
air voids is thought to reduce the apparent refractive index
of the medium and this reduction is contributing to the
increase in scattering of the TiO2 pigment.
This paper was presented at the European Coatings Show,
7th Nrnberg Congress, 7 and 8 April 2003,
Nuremberg/Germany.

The author:
->Paul Frederick Dietz, Huntsman Tioxide, joined the
company in 1986. He graduated in Chemistry atthe
University of Teesside, since 1998 he has worked in
Technical Service Department where, in his current role as
Decorative Applications Manager, he has technical
responsibility for UK, Nordic and French customer service
and provides a supporting role in North America.

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Figure 1: Effect of decreasing extender particle size on spacing of TiO2 pigment .

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Figure 2: Theoretical effect of reducing extender particle size on the TiO2 nearest
neighbour distance and scattering .

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Figure 3: Opacity curves for 4 extenders over a pvc range: a) without application of
glycol film, b) with application of glycol film.

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Figure 4: Opacity curves showing crowding effect.

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Figure 5: Extenders giving improved performance.

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Figure 6: Reducing TiO 2 content using extender E: a) effect on contrast ratio, b) effect
on equivalent reflectance..

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Figure 7: TiO2 savings with extender E: a) effect on wet opacity, b) effect on scrub
resistance..

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Figure 8: Mercury porosity with 30% pvc.

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