6

Applications of fillers

This chapter is intended for people who use mineral fillers in coating system formulations. The examples provide an idea of formulation parameters where fillers exert a direct influence, along with their significance and hints on interpretation. Users will also learn how to select the optimum fillers for imparting desired prop-erties in a given application. Numerous worked examples and practical illustrations round out the discussion on filler applications.

6.1

Importance of fillers in paints and coatings

Fillers were once commonly perceived as nothing more than cheap material for bulking up profits, their sole purpose being to reduce the manufacturing cost of coatings. How times have changed. Users of fillers have since discovered additional, technical functionality in these unprepossessing materials, not least because filler development activity has made progress despite the nay-sayers. There is indeed a great deal of ongoing research and development in the filler field, directed at imparting extra functionality or enhancing established features see also Chapter 7. Yet existing, tried and true fillers have a major part to play in paint and coating formulations. Fillers can be pivotal to a variety of key technical properties: _ Increased solids content and filling capacity _ Reduced level of volatile organic compounds _ Enhanced optical properties _ Regulation of coating reflectivity _ Enhanced mechanical properties, e.g. strength _ Reinforcement of coating materials _ Rheology control Depending on the application and the property requirements profile, selecting the right filler is not always easy. Frequently, that means resorting to tried and true formulas. It is unfortunate that fillers are not always tested and evaluated with the same diligence applied to other classes of raw materials. An oft-heard argument here is that fillers, after water, are the cheapest formula ingredients and therefore do not merit thoroughgoing tests. Accordingly, binders, pigments and additives tend to attract higher priority this despite the fact that fillers comprise the dominant class of raw material in formulations for interior emulsion paint, faade paints, renders, plasters and other thick film systems, marking paints, primers, and many

more besides, see also Chapter 1.2. Such products frequently contain 30 to 40% filler, rising as high as 80% in certain applications. It follows that fillers can also play a governing role in the overall property requirements profile of a coating ma-terial, and this should not be underestimated.
Meanwhile, natural fillers have attained levels of quality where users may easily forget that these are, in fact, products of nature. It is well known that natural products are subject to variations in their composition, and these subsequently affect the properties of the coating materials into which they are made. Producers of fill-ers are aware of this, and use selective mining techniques to minimise such varia-tions. But to eliminate them altogether would be unrealistic, so at this juncture it needs to be pointed out once and for all: natural fillers are variable products.

6.2

Important formulation parameters

Special formulation parameters exist, which are important for characterising coat-ing materials that use filler ingredients. Formulation parameters make it possible to classify coating materials, as well as predict the property profile of a given formula. 6.2.1 Non-volatile matter

Solids, solids content (SC) or stoving residue are frequent terms for describing nonvolatile matter (NVM). ISO 4618 defines what is considered non-volatile matter in coating materials, binders and other raw material ingredients, while ISO 3252 covers the quantitative determination aspects. Non-volatile matter is de-termined analytically as a means to deducing the composition of an unknown mate-rial. Manufactured materials are subjected to similar analysis for quality control purposes. The temperature and drying time used are major factors in the stated result: one popular determination method for non-volatile matter involves exposure to a temperature of 105C for 2 hours. The initial weight of the material under test is divided by the output weight after drying and multiplied by 100, see Equation 6.1.

Equation 6.1: Calculation of non-volatile matter from empirically determined values

For material of known composition like a laboratory test formulation, it is also possible to determine non-volatile matter by arithmetic means alone, without prior measurement. The arithmetic method requires knowledge of the NVM in each raw material ingredient of the formulation. Figure 6.1 shows a worked ex-ample based on a simplified formulation for demonstration purposes. Starting with the NVM in each individual ingredient used and the ingredients percentage by weight of the overall formulation, it is then possible to calculate the NVM of each

Function Binder Pigment Fillers

Substance Styrene-acrylic emulsion Titanium dioxide Calcium carbonate Talcum Precipitated aluminium silicate

NVM in substance [%] 50 100 100 100 100 33

Weight [kg] 160.0 80.0 300.0 80.0 30.0 18.0

NVM in formula [%] 8.0 8.0 30.0 8.0 3.0 0.6

Additives

Thickener, defoamer, wetting and dispersing agents, preservatives, etc. Water

Solvent Total

332.0 1,000.0

0.0 57.6

Figure 6.1: Worked example of calculating non-volatile matter in a simplified emulsion paint formulation

formulation ingredient, and from that, the cumulative NVM. Our sample formula-tion contains 57.6% NVM of which over two thirds, 41% to be exact, is attribut-able to the filler content. It is fillers that give coating materials their body, so it is logical that they are major contributors of non-volatile matter. It is possible to reduce the amount of volatile matter present by substituting fillers that have higher oil absorption by others which are less absorbent, with low binder consumption. The result is higher filler and solids content, yet viscosity holds steady. Although very high levels of non-volatile matter are desirable from an environmental viewpoint, there are prac-tical upper limits, due by the requisites of the production process and the way the product is designed to behave when applied to a substrate. 6.2.2 Spreading rate

Spreading rate according to ISO 4618 part 1 is understood to mean the average substrate area that can be covered by a given volume or mass of coating material. Practically speaking, the method of application needs to be capable of producing a single layer in one pass. The resultant spreading rate is stated either in m/l, or m/kg. Spreading rate is often considered in tandem with coating material opacity. EN 13300, for example, describes classification of coating materials by their opti-cal and mechanical properties. The practical method for determining opacity meas-ures the contrast ratio between films of differing thickness; they are dried and subsequently weighed to determine their mass per unit area. The result is convert-ible to spreading rate by factoring-in non-volatile matter and the coating material density. A plot of spreading rate vs. contrast ratio allows interpolation and com-parison of contrast ratios for various paints that have a [1] similar nominal spreading rate: 7.5m/l in the example shown in Figure 6.2 .

100 Class 1 99 rati Contrast o [%]

Class 2

98 97 96
Class 3

Coating material 1 Coating material 2 Coating material 3

95
Class 4

94 0

10

12

Spreading rate [m/l]

Figure 6.2: Graphic example of correlation between spreading rate and contrast ratio

Filler content can exert a marked influence on spreading rate in pigmented coating materials. As the filler content increases, so does the solids content and, as a rule, spreading rate as well. These observations only apply where the pigment content is comparable in each case: if the pigment level changes, the spreading rate will change too. Fillers of differing density produce a similar effect, likewise changing the spreading rate expressed in terms of area per unit volume. High-density fillers reduce the volume spreading rate more than lightweight fillers, so coating consump-tion increases as a result. 6.2.3 Pigment volume concentration
Pigment volume concentration (PVC) is a key parameter of paints and coatings. Along with a few other parameters, PVC makes it possible to predict numerous interrelationships between a coating systems composition, and the resulting properties. PVC makes an equally effective tool for characterising and classifying paints and coatings. ISO 4618 part 1 defines PVC as the ratio of pigment and filler volume in a coating film to the aggregate volume of non-volatile matter. This further implies that the binder is considered in its final, solid form, rather than as supplied. Equation 6.2 shows the mathematical definition of PVC.

Equation 6.2: Definition of pigment volume concentration (PVC)

To illustrate the theory, the following is a PVC calculation example based on the numbers in Figure 6.1. Calculating PVC requires details of the individual raw material ingredients and the masses used, their non-volatile matter and density. Mass is divided by the materials density to convert the mass of raw material to its corresponding volume, see Equation 6.3.

kg l

vV [ l ] =

Equation 6.3: Conversion of raw material mass to volume

For each of the raw material ingredients involved in the worked example, Figure 6.3 lists NVM, mass as supplied and the NVM component of that mass, plus density. The last column shows the calculated volume of each raw material ingredient.
Substance NVM in substance [%] 50 100 100 100 100 33 Weight [kg] 160.0 80.0 300.0 80.0 30.0 18.0 NVM in weight [kg] 80.0 80.0 300.0 80.0 30.0 6.0 Density [kg/l] 1.05 4.00 2.70 2.75 2.10 neglected Volume [l] 76.2 20.0 111.1 29.1 14.3

Styrene-acrylic emulsion Titanium dioxide Calcium carbonate Talcum Precipitated aluminium silicate Thickener, defoamer, wetting and dispersing agents, preservative, etc. Water Total

332.0 1,000.0

0.0 57.6

1.00

0.0 250.7

Figure 6.3: Worked example of calculating the volume of individual raw material ingredients in a simplified demonstration emulsion paint formulation

Once the respective raw material ingredient volumes have been calculated, the PVC can be derived as shown in Equation 6.4. The volumes used in the example result in a PVC of 69.6%.

Equation 6.4: PVC calculation for a simplified demonstration emulsion paint formulation based on the data provided in Figure 6.3

As mentioned previously, PVC by itself is already a highly significant parameter. Yet something more is required for a really meaningful interpretation: the critical [2] pigment volume concentration (CPVC) . The relation of PVC to CPVC allows

qualitative statements about coating materials and their properties, see also Chap-ters 6.2.4 through 6.2.6. Equation 6.2 and the worked example reveal just how strongly PVC is affected by the type and amount of filler used. With coating materials, switching from one mineral filler to another without accounting for their density difference can have drastic results, see Chapter 6.4.1. 6.2.4 Critical pigment volume concentration

ISO 4618 part 1 covers not just pigment volume concentration, but critical pigment volume concentration (CPVC) as well. CPVC is defined as the PVC at which binder just fills the voids between adjacent solid particles of pigment, filler, etc. in a coating film. Above this point, a number of properties experience significant change, see Figure 6.4. Various properties are predictable based on a coating ma-terials CPVC and PVC, see also Chapter 6.2.5.
When the PVC lies below the CPVC. The excess binder present (plus wetting agents and dispersants) completely envelopes the pigment surfaces and fills the voids between particles. In this case, the excess binder can produce a glossy

high

Porosity Corrosion Density

Development of property

med.

Gloss Wet scrub resistance 0 20 40 PVC [%] 60 80 100

low

Figure 6.4: Changes in coating properties vs. PVC around the CPVC region