60 Part I - Paint formulation

3 Paint formulation

Any coating material to be developed has to meet specific requirements, i.e., it must fulfil
the demands of the customer (properties of the coating, substrate, application), the environ-
ment and so on. The skilled paint chemist has to accommodate all these different demands,
choose the appropriate raw materials from the vast number available and, finally, develop a
paint formulation. This is mostly done in paint laboratories.
One objective of this textbook is to prepare students for working in industry. Therefore, it
is vital to understand the workflows that occur in an industrial paint laboratory [1]. Figure
I-3.1 tries to show these workflows in simplified form. All paint development starts with the
statement of the problem. The paint formulation is then devised, and a sample is made in
the lab. The sample is applied to the substrate concerned and the coating is dried or cured.
This coating then has to be tested.
The test results have to be compared against the specifications of the problem. Usually, they
are not perfect. So, in practice, the paint formulation has to be optimized. Therefore, the
cycle shown in Figure I-3.1 has to be repeated many times. The optimization steps become
smaller from cycle to cycle. The input into this cycle of paint development is the statement
of the problem while the output is the optimized paint formulation [1].
A calculation recipe contains all the information about the components of the paint; it is for-
mulated to yield 100 parts by weight. The calculation recipe usually lists the raw materials
in the following order: binders, pigments and fillers, additives, solvents. A production recipe
is formulated for each quantity, along with additional information about the production pro-
cess. The production recipe lists the raw materials in the order in which they are added. It
is common industrial practice to provide additional information about the properties of the
paint or coating, the test methods and permissible variations.

Figure I-3.1: Cycle of paint development

Bodo Mller, Ulrich Poth: Coatings Formulation

Copyright 2011 by Vincentz Network, Hanover, Germany
ISBN: 978-3-86630-872-5
 Ratio of binder to solid particles 61

When the paint is being formulated, allowance is made for some fundamental physical
parameters that greatly influence the technological properties of a coating:
Pigment/binder ratio and pigment volume concentration
Particle size and packing of pigments or fillers
Of course, the types of binders and pigments or fillers (chemical composition) are also very
important. Finally, the physicochemical interactions of the binders with the surfaces of pig-
ments and fillers (i.e., the quality of the composite coating) are important.

3.1 Ratio of binder to solid particles

3.1.1 Pigment/binder ratio and pigment volume concentration
Only the non-volatile content (solids) of a paint remains after the coating has solidified.
Important formulation parameters, such as pigment/binder ratio (P/B), pigment volume con-
centration (PVC 1) and the ratio of binders, always refer to the non-volatile content (solids).
The pigment/binder ratio is the weight ratio of the sum of the pigments and fillers to the
binder (solids): P/B.
The pigment volume concentration (PVC) is the ratio of the pigment volume to the total volume of
the solid coating [vol.%]. The pigment volume is the sum of the pigment and filler volumes.
VP + VF
PVC = 100%
VP + VF + VB
V P: Volume of the pigments
V F: Volume of the fillers (extenders)
VB: Volumes of the dried film of all binders (sum of film-forming agents, resins,
plasticizers and additional resins)
The volumes (V) are calculated as the quotient of mass (m) and density ():
m
V=

The densities of pigments and
fillers are listed in the manu- Table I-3.1: Average densities of dried binder films
facturers data sheets. Average
binder (paint resin) average density
densities of dried films of sev- [g/cm3]
eral binders are shown in Table
I-3.1 [2]. These average densities styrene-acrylates 1.1
of dried films are sufficiently SP, AK, EP, CAB, PF, AY, PUR, PVAC, CN 1.2
accurate to allow an approxi- UF, MF 1.5
mate calculation of the PVC.
RUC 1.6
It should be noted that most
commercial paint resins (binders) are supplied already dissolved in solvents; therefore, the
densities listed in the resin data sheets mostly refer to the resin solution and not to the density
of the dried or cured film.
For example, glossy topcoats have PVCs of 10 to 20%. Matt coatings of latex paints have PVCs
of 40 to 85%. Transparent varnishes may have PVCs below 10%.

1) Do not confuse with polyvinyl chloride

62 Part I - Paint formulation

Figure I-3.2: Properties of oxidatively cured coatings as a function of pigment/binder ratio

Critical pigment volume concentration

The critical pigment volume concentration (CPVC 1) is the PVC at which the binder con-
centration is just barely sufficient to completely wet pigments and fillers. Furthermore,
the spaces between the particles are filled with binder. The pigments and fillers are very
closely packed.
Table I-3.2: Simplified formulation for a stoving enamel Above the CPVC, the porosity of
the coating increases rapidly. The
parts by weight raw material solids
position of the CPVC depends heav-
51 SP, 60% solids 30.6 ily on the particle size, the particle
5.0 HMMM, about 100% solids 5.0 size distribution and the shape of
35.6 titanium dioxide rutile 35.6
the pigment and filler particles.
Latex paints have a CPVC of about
8.4 solvents + additives*
60%.
100 sum 71.2
The following example illustrates
* for simplification, in this first example solvents and additives are not
the influence of the PVC or pig-
presented individually because this is not necessary for the following
calculations. ment/binder ratio on the prop-
erties of a coating. Consider an
Examples for binders: Vialkyd AN 950 (SP) and Cymel 300
(HMMM = hexamethoxymethylmelamine)
oxidatively curing paint (long oil
alkyd resin) with iron oxide red :
barium sulphate (filler) = 1 : 1. The pigment/binder ratios are P/B = 1: 1 and 1 : 4. The
PVCs compute to 21% and 51%. The properties of these two coatings are summarized in
Figure I-3.2. As the pigment/binder ratio rises, the flexibility and, especially, the gloss
decrease dramatically, whereas the hardness is barely affected at all.
The following sample calculation shows how the pigment/binder ratio and the PVC is used
in practice (more calculations like this will be presented later in the book). A simplified
formulation for a stoving enamel is listed in Table I-3.2. This kind of paint formulation with

1) Do not confuse with polyvinyl chloride

 Ratio of binder to solid particles 63

a sum of 100 parts by weight is also called the calculation recipe. Usually, all numbers in
paint formulations are specified to one decimal place. It is not usual to list parts by weight
(solids) in starting formulations and so these have to be calculated.
Calculation of the pigment/binder ratio
(Sum) of pigments (+ fillers): 35.6
Sum of binders (solids): 30.6 + 5.0 = 35.6
Pigment/binder ratio P/B = 35.6 : 35.6 = 1 : 1
Calculation of the PVC (density of titanium dioxide rutile 4.1 g/cm3; see Table I-3.1 for densi-
ties of the dried binder films)

35.6 / 4.1
PVC = 100% = 23%
35.6 / 4.1 + 30.6 / 1.2 + 5 / 1.5

This PVC calculation is an approximation because the real density of the crosslinked
binders has not been measured. But this simple type of calculation is sufficient for many
applications.

3.1.2 Oil adsorption value

The oil adsorption value (OA) is determined with linseed oil (of specified quality, acid
number about 2.8 mg KOH/g). The linseed oil is slowly worked with a spatula into a given
amount of pigment on a glass plate. When just enough linseed oil has been added, a coherent
pigment paste is formed; oil adsorption value: g linseed oil/100g pigment.
The oil adsorption value is not transferable to other binders (even when different densities are
allowed for) since the specific wetting action of those binders needs to be taken into account.
Empirically determined oil adsorption values can vary significantly (by up to 50%).
Table I-3.3 clearly shows that the oil adsorption value increases with increase in specific
surface area (BET) but not to the same extent.

Table I-3.3: Pigment and filler data

pigment for filler mean BET surface oil adsorption density (P) CPVC
particle [m2/g] value [g/cm3] (linseed oil)
diameter [g linseed [vol.%]
[nm] oil/100 g]
gas black 13 460 620 1.8 8
furnace black 95 20 280 1.8 16
phthalocyanine blue 1 50 72 50 1.6 54
phthalocyanine blue 2 100 36 45 1.6 56
precipitated calcium 80 20 40 2.8 45
carbonate

grinded marble (CaCO3 ) 2500 3.4 19 2.7 65

transparent iron oxide red 20 100 40 4.5 34
opaque iron oxide red 300 6 24 5.0 44
64 Part I - Paint formulation

Possible explanations are:

T he oil adsorption value char-
acterizes not only the phase
boundary between the pig-
ments and the linseed oil but
also the volume between the
pigment particles at maximum
packing density. Furthermore,
there is a relationship between
the oil adsorption value and the
critical pigment volume con-
centration (CPVC; see below).
Presumably, the linseed oil can
only be adsorbed on a smaller
part of the total surface area
relative to nitrogen especial-
ly in the case of fine pigments.
Unlike the much larger linseed
oil molecule, the small nitro-
gen molecule is believed to
penetrate into very small pores
of the pigment agglomerates;
Figure I-3.3: Simplified diagram of the space-filling models
comparison of the sizes of both
of linseed oil (glycerol ester of oleic, linolic and linolenic
molecules makes this assump-
acid) and nitrogen
tion plausible (Figure I-3.3).
Adsorption of the linseed oil in contrast to that of non-specific nitrogen adsorption can
also be influenced by the polarity (oleophilicity) of the pigment surface.
To sum up so far, the specific surface area (BET) of pigments and fillers is only an approxi-
mate value of the area of the phase boundaries in paints. For coatings technology, the oil
adsorption value is more important because this value characterizes the binder demand of
pigments and fillers.
The CPVC (for linseed oil) can be calculated from the oil adsorption value (OA; see
Table I-3.3).
P OA
CPVC = 100 /(1 + )
L 100

P : Density of the pigment

L : Density of linseed oil (0.93 g/cm3)
Sample calculation of the CPVC of opaque iron oxide red (P = 5.0 g/cm3):

5 24
CPVC = 100 /(1 + ) = 43.7 44 [vol.-%]
0.93 100

Sometimes, it is assumed that the oil adsorption value characterizes only the free volume
between the pigment particles (maximum packing density). If this is true, then the calcu-
lated CPVC could be transferred to other binders. However, this assumption is untenable as
the specific interaction of different binders with the very large pigment surface areas is an
important factor controlling paint and coating properties [3].
 Influence of pigments on the properties of coatings 65

3.2 Influence of pigments on the properties

of coatings
The influence of particle size of pigments on properties of coatings is discussed briefly
below. Table I-3.4 shows that coarse pigments opacify (hide) whereas fine pigments are
transparent. The smallest possible particle size is a single molecule; it forms a molecularly
disperse solution and is thus a soluble dye (Figure I-3.4).
The particle sizes of pigments have other consequences, as shown in Figure I-3.4.
Light fastness is only a problem for organic pigments and dyes; inorganic pigments are
unaffected by light (i.e. are photostable; Figure I-3.4). As soluble dyes are not photostable,
they cannot used for exterior coatings.
Carbon blacks absorb radiation
across the complete spectrum of Table I-3.4: Opaque and transparent pigment types
visible light and, at higher levels pigment type mean primary particle dia-
of addition, exhibit adequate hid- meter [nm]
ing power. Fine carbon blacks are phthalocyanine blue 1
transparent at low addition levels
transparent 50
and can be used in transparent
coatings. Moreover, carbon blacks iron oxide red
are photostable, absorb ultraviolet transparent 20
light and, therefore, improve the
opaque 300
weathering resistance of coatings.
Thus, carbon blacks are excep- iron oxide yellow
tions among pigments. transparent 20

Pigment particles of different size opaque 1500 100*

(polydisperse) have a greater pack- titanium dioxide (rutile)
ing density than particles of the
transparent 10 to 20
same size (monodisperse). Figure
I-3.5 shows that, in the case of opaque 250 to 300
polydisperse particle packing, the * needle-shaped

Figure I-3.4: Comparison of opacifying, transparent pigments and dyes