Clays, Calcined Clays, Talc, and Carbonates: Their role in Coatings: An Overview

For EICL November 2009

Introduction
One question that is often asked of me when I work as a Paint Technology Consultant is why Paint Formulators in one country or region or Company use certain types of Fillers/Extenders and other formulators making very similar paints use a completely different set of Fillers/Extenders to achieve what in the end must be a very similar set of properties The aim of this presentation is to try and answer this question which is both simple and complex at the same time

Introduction 2
But before we try to answer the question we need to provide some back ground for the following concepts: Opacity Theory CPVC Crowding/spacing Theory Packing Theory

Opacity Theory 1
The opacity of a thin film is determined by the action of two phenomena simultaneously or not : Light scattering and/or Light absorption

Opacity Theory 2

Opaque film

Substrate

Opacity Theory 3
Two conditions have to be met simultaneously for light scattering to occur in a paint film : 1) The system must be heterogeneous the different phases must be insoluble in each other. eg a dispersion of solid particles in a continuous phase. 2) The dispersed and continuous phases must have different refractive indices.

Opacity Theory 3

Dispersed phase (nd)

Continuous phase (nc)

nc= nd

nc= nd

Opacity Theory 5
Refractive Index (n) Pigments - TiO2 (rutile) - ZnO Extenders Binders Water Air

2.7
2.0 1.5 to 1.6 1.5 to 1.6 1.33

1.0

Light scattering becomes significant when the refractive index difference between the dispersed and continuous phases is greater than 0,2. The dispersed phase is then said to have pigmentary properties.

Opacity Theory 6

Coating No pigment No colorant Light Reflected at surface Transmitted to substrate White reflects Black absorbs Appearance No hiding No color

Opacity Theory 7

Coating TiO2 pigment No colorant

Light
Reflected at surface Scattered by TiO2 White reflects Black absorbs Appearance Good hiding White color

Opacity Theory 8

Coating No white pigment Phthalo blue colorant Light Reflected at surface Red and yellow absorb White reflects Black absorbs Appearance No hiding Black chart is black White chart is blue

Opacity Theory 9
Coating TiO2 pigment Phthalo blue colorant Light Reflected at surface Scattered by TiO2 Red and yellow absorbed Less absorbance Appearance Best hiding Light blue color

CVPC Theory
With Opaque Polymer

Property

Hiding

Scrub Resistance

CPVC

Pigment PVC Air

<CPVC

= CPVC

>CPVC

Spacing Theory 1
Opacity Opaque Polymer TiO2
From approx. 10%PVC TiO2 , the interparticle distance is small and the diffraction volumes overlap, reducing TiO2-pigment efficiency (crowding effect)

10% TiO2

PVC (TiO2)

Below 10%PVC TiO2 the pigment particles are sufficiently far apart that the diffraction volumes do not overlap.

Effective scattering sphere (or sphere of influence)

Spacing Theory 2: Effect of TiO2 Spacing on Film Opacity

0.2

TiO2 has a particle size of about half the wavelength of visible light Due to its wave form, the light beam can impinge upon a TiO2 particle without being directly in the centre of the beams path. The effective scattering diameter is therefore greater than the physical diameter

Spacing Theory 3: Effect of Extenders (at constant TiO2 PVC)

Opacity

fine extender Coarse extender TiO2 coarse extender Fine extender PVC

Fine particle extenders are able to space the pigment particles thus avoiding loss in TiO2 efficiency.

Packing Theory 1
The Term Packing density/ratio expresses how compactly the pigment and extender particles fit/lie together in the dry film or basically how large the hollow spaces filled with binder are between them, i.e. the more spaces the worse the packing

Packing Theory 2
Following from this you can see that a dry paint film with only coarse particles will have big gaps and thus these gaps could act as weak links for things like water or stains to penetrate the film and attack the substrate (water/salts in metal primers) or remain in the film (stains in Water based sheens or matt) it would be much better if these gaps were filled with smaller particles of Pigment/Extender

Packing Theory 3
In theory it should be possible to calculate the packing density if you know the PVC and the specific area of the pigments/extenders are known but in practice we normally determine a good packing density/ratios by testing for the required film properties

Kaolin/China Clay 1
A good water washed China Clay has an Average Particle size of less 1 micron with an Oil Absorption of circa 35-40 There it should be good for sheen control and TiO2 spacing Clays are also slightly Thixotropic, Pseudo Plastic so they also tend to impart good anti-settling and anti-sag properties

Kaolin/China Clay 2
In fact China Clay was the first TiO2 spacer to be utilized and it was widely used in Gloss (SB) and Sheen paints (WB) in this role However as finer (1/2 Micron) grades of CaCO3 were developed in the 1970/80s there was a gradual move away from China Clay in WB as the finer CaCO3 grades tended to be cheaper and have less effect on water resistance and were whiter/bluer and had less effect on tinted hue than Clays

Kaolin/China Clay 3
However in some Markets Clays are still preferred for Sheen paints and some Ultra fine grades (e.g. Polygloss 90) are again being used to get the most out of Tio2 Also specialized Ultra fine Clays are still widely used in ED coatings in order to help with film build etc In Medium-High PVC coating Clays are still widely used in combination with CaCO3S of different sizes to give the best packing ratio, TiO2 utilization with out depressing the CPVC too much

Kaolin/China Clay 4
In certain Paint markets where local good Quality Clay deposits are mined you find that in Medium-High PVC coating Clays are still widely used in combination with CaCO3S of different sizes to give the best packing ratio, TiO2 utilization with out depressing the CPVC too much, thus maintaining good washability /Durability

Pyrofillite/Kaolanite
In certain Markets e.g. RSA Pyrofillites which have some of the properties of both Kaolin and Talc have become very popular for Medium to high PVC products as they more cost effective than Clays and impart similar properties However for certain end uses (Pigment Dispersions) Pyrofillites are not fine enough and Clays may have to be used

Calcined Clays 1
The Calcination process takes place at Temperatures between 800-1100 Deg C and drives off water, changes the crystal structure, Mohs hardness (from 2-3 to 6-7) and the refractive index (increases), Sintering, fusing of the hot particles can also cause irregular shapes which increase the Oil absorption dramatically

Calcined Clays 2
In view of these properties Calcined Clays can be used as a TiO2 Spacer, a CPVC depressor (to improve dry hiding) and its higher Mohs hardness allow us to reduce latex levels slightly with out adversely effecting scrubs-this again boosts dry opacity, which turn may allow for a further TiO2 reduction

Calcined Clays 3
Obviously a paint formulator has to know how to reformulate with Calcined Clays to reap the benefits outlined above but from cost point of view the pain is worth the gain E.g. we have seen paints where the PVC has been increased from 55-60 to 65-70% and TiO2 levels reduced from 200-225 to circa 150-160g/l without any Customer perceived changes in properties

Calcined Clays 4
In the last few years their has been a shift away from normal Calcined Clays to the more effective but more costly, structured Calcined Clays which again requires reformulation/re balancing but again does reap property and cost benefits

Talc
Are Laminar Magnesium Silicates Soft mineral Mohs hardness=1 Laminar platelets and hydrophobic nature help to improve water resistance and topcoat hold out Softness improves sanding

Talc 2
Traditional uses in primers, undercoats and roof paints Now firmly established in products where high stain resistance is required-mostly Sheens But we are also now seeing the use of Talc in Medium to higher PVC products where its water resistance and Laminar nature help impart better scrubs, give better packing, increase CPVC all of which means that the PVC can be increased, the latex level raised, which gives high dry hiding and may be to a slight reduction in the required TiO2 level

Talc 3
Originally these uses were seen in the traditional Talc markets like Northern/Central Europe but we are now seeing it in Africa/Far East We are also now seeing a tendency to combine Talc with Calcined clays to get the best compromise from a cost/performance point of view especially for tint bases where the use of Talc helps to Negate the yellow hue imparted by Calcined Clays

Talc 4
One thing that has to be watched for when using Talc alone or in Combination with other fillers is its tendency to cause Synersis/settling in systems, especially water based- which to be combated by the use of anti-settling additives such as Bentonite (SB) and Atapugalite (WB) Clays

Conclusions
It can be seen from the above that different fillers can be used to get the required Paint properties in the most cost effective manner each resolve and give rise to problems Over the last few years we have begun to see combinations rather than the traditional Filler types being used as people strive for even better and more cost effective formulations