Opacity optimization of waterborne paints

Pedro Miguel Alua

July 2012

Abstract

A paint usually comprises in its formulation: extenders, pigments,binder, solvents (in waterborne
paints, the water) and additives.
Part of the wide variety of methods which characterizes waterborne paints, are those related to the
optical properties.
The objective of this work consists on the study of one of the optical properties: the opacity.
Therefore a standard formulation was used in which the parameter to be changed was the extender or
the pigment content in order to evaluate their contribution to hiding power.
The standard routine tests as well as the more specific ones were applied, and some conclusions
were obtained about the efficiency of the components tested.
The most relevant results about opacity were obtained with titanium pigments (with na average opaciy
of 97,9% for a thickness of 25 m) and extenders of the type sulphides and silicates; otherwise
extenders of sulfates and slica should not be recommend due to low values they import.

Key-Words: waterborne paint, pigments, extenders, optical properties, opacity, hiding power

1. Waterborne Paints.
1.1) Paint components
[1]
By definition a paint could be described as a liquid, paste or solid which when applied in thin layer on
a suitable surface state that is provided in or after dilution, dispersion or melt volatiles, is converted
after some time into a solid film, colored and opaque.

[2]
A paint comprises extenders, pigments, binder, additives and solvents. The first three components
provide the dry extract of the paint while the solvents correspond to the vehicle volatile. In the dry
extract, the pigments and extenders correspond to the solid constituents which are intended the paint
to fix on the substrate. These two components can be easily distinguished, because of their different
optical and physical properties. For example pigments have smaller particle dimension than
extenders, and a much higher refractive index (usually this index is higher than 1.7 for pigments and
less than this value for extenders).
The other constituent of the dry extract is the binder. The binder has the function of ensuring cohesion
of the paint and the connection between the pigments. It can be formed by the polymerization process,
and the polymers that constitute the vehicle can be classified as homopolymers or copolymers,
according to the type of monomer they comprise.
The solvents, constituents of the vehicle volatile, have the purpose of dissolving the binder, allowing to
obtain the proper viscosity of the paint and giving a clear and homogeneous solution.
Other components that a paint comprises, but in a much lower quantity are the additives. They are
used in paints In order to facilitate the manufacture, application, to improve the stability and minimize
defects of the paints.
It is subject of this work to study the influence of pigments and extenders in the opacity of waterborne
paints.
The opacity of a paint film corresponds to the property of preventing the passage of light, obscuring
the substrate. This property results from light scattering and is also influenced by the refractive index.
From the referred components of a paint, the only ones that contribute to the opacity are the pigments
and the extenders. Pigments give greater contribution to the opacity than the extenders, by having
higher refractive indices and smaller particle sizes. On the other hand, binders do not absorb or
scatter light and therefore dont contribute to this property.
In paint production, pigments are used in order to impart color, opacity or other special characteristics
used in order to modify the optical properties of a paint product or incorporated therein. Their
properties result of the combination of two effects: the light absorption (which determines the color and
is influenced by the chemical structure of the pigment) and the diffraction of visible light with which
they interact (which determines the opacity).

[2]
The most relevant properties in pigments are :
i) Their color: Results of the selective absorption and subsequent reflection of specific
wavelengths of visible light spectrum. This result is due to the subtractive behavior of
paints.
ii) Hiding Power: Corresponds to the capacity to obliterate the color or different colors of a
substrate.
iii) Dye strength: Corresponds to the measure of the ability of the pigment to impart color
and provide information about how many parts of white pigment is needed to achieve a
given intensity.
iv) Ease of dispersion: An efficient dispersion of pigments in the binder of the paint is
essential to ensure that they obtain a maximum yield of pigment.

[3]
The dispersion process involves several steps . In a first step (milling-desintegration), the
agglomerates of primary particles of pigment break, then occurs the separation of primary particles
and smaller aggregates which would remain bonded (milling-dispersion).
Since the clusters contains within a certain amount of air, when it is released through means that each
particle be wrapped by the vehicle (wetting). The final step of the process is the stabilization of the
dispersion. This step is very important because without it pigments could sediment easily or flocculate
Other constituent of the referred dry extract of paint are the extenders.
[1]
Extenders could be defined as substances that are employed as a constituent of paints, with the
purpose of changing some of their properties, as well as acting as reducing element of the price of raw
materials.They can exist in the form of more or less fine particles, and are characterized for having low
hiding power and being insoluble in vehicles.
A high variety of extenders can be applied in paints, having each type different specific characteristics.
[3], [4]
The most common groups of extenders are :
Calcium carbonate (also known as Calcite)
Barium Sulfate ( exists in the form of Barites or Blanc Fixe)
Talc (hydrated magnesium aluminum silicate)
Kaolin (also known as China Clay, is an aluminum silicate)
Silica (products with the chemical formula SiO2)
Mica ( hydrous aluminum potassium silicates)
[2]
1.2) Types of Paints

Paints can be classified into several types according to the requirements of its application, content and
structure. The most relevant ones are: interior matt, semi-gloss, exterior, elastomeric paints, enamels,
varnishes and primers.

Generally a paint with a high volume of binder correspond to a low PVC paint, in other words a paint of
high quality. PVC is a property of the paint defined as pigment volume concentration (equation 1)

( ) (1)

In Equation 1, PVC is defined as a percentage by volume, because the performance of the paint
depends on the volume applied on the subtract. PVC can also be used as division criteria for paints.

[2]
It is expected that a paint presents a number of characteristics :
[5]
Applicability: The applicability of a paint can be characterized as good (G), fair (F) or poor
(P),being considered a good result when the classification lies between the first two. In terms
of the aspect of application, sometimes can occur some effects such as cracks, drips, micro-
foam, air bubbles or brush marks, effects that intended to be as minimum as possible.
Formation of a perfect film at a temperature above 5 C
No cracks (mud cracking): The presence of fissures or discontinuities may be evaluated
using the Mud-Cracking test. This test provides evidence for a given coating applied to a metal
[5]
block in a range of thicknesses of between 0 and 2 mm .The rating scale go from 0 (best) to
5 (very bad):
0-film without cracks visible under the microscope; 1-microcracks only visible with a
magnifying glass 8x; 2-Many microcracks only visible with a magnifying glass 8x; 3-Variable
cracks to the naked eye; 4-Many cracks to the naked eye ; 5-Film completely cracked
[5]
Storage stability: The stability of a paint can be evaluated by storing the sample in an oven
at 50 C for a period of 28 days. The product is considered stable if there is no change in
viscosity over 28% compared to initial values.
Optical properties Involves Color, brightness and Hiding Power.
These last characteristics will be detailed in the next chapter.
 [4], [6]
2) Optical Properties of Paints

As it was said in the previous chapter, the three most relevant optical properties in paints are color,
brightness and hiding power.
With regard to the color shown by the paint, this will result of three aspects: the amount reflected /
absorbed / transmitted from the paint, the illuminant and the response of the observers eye. The color
of the paint can be analyzed by measuring the light that is reflected (or transmitted) of an object by
using a spectrophotometer, more specifically determining the space coordinates CIELab
L*: This parameter, measures the luminosity of the paint (varies from 100 for perfect white to 0 for a
perfect black);
a *: A positive value of this parameter, shows a reddish color, whereas if the value is negative, it is of
greenish;
b *: A positive b * value corresponds to a more yellow paint, while a negative value means the
property that bluer hue.
In terms of the brightness of the paint, is associated with the mirror image and hence the sharpness of
the image, can be determined by using a gloss meter, for different angles of incidence. In order to
increase the proportion of reflected light in matt surfaces, is used the higher angle of incidence, 85 .
For semi-gloss paints, which have an average brightness, measurement is made at 60 , while for a
high gloss enamel the measurement is for 20 . Finally another optical property of extreme importance
as already indicated is the hiding power. The hiding power corresponds to a property of the paint
(rather than their film coating) which is associated with the ability to occlude the color or color
differences of the substrate. It can be expressed by the percentage for which the opacity of the film is
sufficient to completely cover the paperboard chart (providing a contrast ratio of 98%).

(2)

[4]
Some factors that could affect the hiding power of white pigments :

Particle size: As the particle size of the pigment low, the greater becomes the number of
those particles and surfaces to contribute to reflection and refraction. That way the ability to
disperse light from a given amount of pigment will tend to be enhanced.
If the particle size is too small in relation to the wavelength of light, the wavefront passes
around and through it. Thus no light scattering occurs and the dispersion is transparent.
Pigment dispersion: In order to obtain a satisfactory dispersion involves wetting the pigment
in a dispersion medium to displace air, then breaking larger particles by milling. After the
dispersion is usually followed by a stabilization step.
Concentration on the paint film: With high concentrations of pigment, crystal particles
become more compact and close to the optical condition of a large particle, resulting in loss of
efficiency of dispersion and hiding power.
Porosity of the film: Porosity contributes positively to increase the hiding power.

3) Experimental procedure
3.1) Objective and experience planning
It was subject of the present work to verify the influence of different extenders and pigments on the
opacity of waterborne paints. In that way and based on previous works, a formulation was chosen for
the constitution of a common paint for this study. The paint would present the constitution shown in
Table 1, where the only component that would change would be the extender or pigment.

Table1- Formulation proposed for the study of the opacity of waterborne paints

Component Weight (g)

Water 200,00
Thickener 1,00
Dispersant 0,40
Anti-foam 0,30
Ammonia,25% 0,20
Pigment/Extender (in volume) 40,00
Standard dispersion (binder) 15,45
In order to distinguish the different group of extenders and pigments, the following
nomenclature was used:

A-Carbonates;B-Silicates;C-titanium dioxides;D-Sulphates;E-Sulphides;F-Silica;G-Opacitante
pigment; H-Talc; I-Chlorite-mica-quartz; J-slurry Cop.Styrene / Acrylic
[2],[3]
3.2) Paint production

In a first step of the paint production, the necessary quantity of water, thickener and ammonia (pH

adjuster) was charged into a homogenizer, with the purpose of assuring the dispersion of the mixture,
and that it would not present any sign of lumps. When the mixture is complete and transparent, it is
then added to the above, the exact amount of dispersant and anti-foam, proceeding with the
homogenization. The mixture is then set aside for future use with the various extenders/ pigment to be
tested.
The mass of extender or pigment to be tested is weighed on an analytical balance, and added to the

mixture on a disperser. In order to ensure efficient grinding, the dispersion occurs at about 1500 rmp,
and the necessary time was controled until a Hegman 6-7 was obtained.
Once the dispersion is completed, the anti-foam is added and finally the binder. After completing the
paint, it is advisable to let it stand 24 hours in a controlled temperature and humidity room before being

able to analyze it.

[2],[5]
3.3) Experimental determination of Hiding Power

Once the paint is produced, a wide variety of tests could be taken. In the routine tests it is usual to
determine the guiding properties of the formulation which includes: solid content, viscosities
(according to the ICI Cone & Plate, Brookfield and Stormer, viscometers), densities, pH and PVC.
These tests are common to all types of paints.
Since it was objective of this work to evaluate the effect of extenders and pigments on the opacity, an
Hiding Power test was carried out.
Hiding Power determination:

i)Material/Equipment:

Paperboard chart BYK Gardner ref. 2854 (dim 10,5cm x 14,8 cm)
Applicator-thickness 100 m
Spectrophotometer BYK Gardner
Thickness gauge

ii) Procedure:
ii.1) Preparation of sample
On a Paperboard chart, initially it is measured the thickness of the chat, and identified in it, the date
and the name of the paint in study. A coating film with 100 m wet thickness is then applied, using an
automatic applicator. The film is then placed in a temperature and humidity controlled room for 24
hours before the parameters can be determined

ii.2) Determination of the paint Hiding Power:

24h after application of the film on the substrate, the test begins by measuring the dry film thickness.
The difference between the film and the chart thickness is given by equation 3:

= dry film thickness- wet film thickness (3)

The determination of the paints hiding power is obtained using the spectrophotometer, performing
three readings in the black area of the chart, and three reading in the white area. The determination
of the parameter is made by mean of the readings made above.

3.4) Results

According to the mentioned test, the following results were obtained for every paint with specific
extender or pigment.
[4],[5],[6],[8],[9],[11],[12]
Table 2 -Main results of the opacity of various fillers and pigments

Ave.partic
Compone Identificati Descriptio Refraction Opacity
Function le (m)
nt on n Index size(m) (%)

Omyacarb A1 Calcium
Extender 1,65 3,0 70,05 29
2 Extra (Standard) carbonate

Omyacarb A2 Calcium
Extender 1,65 6,0 64,92 30
5 Extra (Standard) carbonate

Dolomite
Extender A3 Dolomite 1,50 0,1-40 73,88 17
DRB 3

Microdol 1 Extender A4 Dolomite 1,50 7,40 61,2 25

Calcium
Mikhart 10 Extender A5 1,65 140 67,13 26
carbonate

Calcium
Mikhart 15 Extender A6 1,65 10,0 50,8 34
carbonate

Omya Calcium
Extender A7 1,65 17,0 74,66 30
viollet carbonate
Omyacarb Calcium
Extender A8 1,65 2,5 82,73 31
1 Extra carbonate

Calcitex Calcium
Extender A9 1,65 1,6 79,98 18
902 carbonate

Omyacarb Calcium
Extender A10 1,65 1,5-13 57,57 41
40 L carbonate

Crystalline
Carbocal
Extender A11 calcium 1,65 22,0 76,06 21
MEB 1
carbonate

Omyacarb Calcium
Extender A12 1,65 1,5-13 89,24 36
Extra CL carbonate

Precipitate
Socal P2 Extender A13 d calcium 1,65 0,9 86,01 27
carbonate

Ca and Mg
Ultracarb 5 Extender A14 1,65 0,28 90,54 39
Carbonate

Hydrocarb Calcium
Extender A15 1,50 0,1-40 81,77 34
90 carbonate

Hydrocarb
Calcium
90 Extra Extender A16 ----- 1,5-13 75,71 28
carbonate
OU
Precipitate
d
Alusil ET Extender B1 1,54 4,0 98,21 39
aluminum
silicate
Caolino
Extender B2 Kaolin 1,57 0,5-3,5 92,81 34
Vianalight

China Clay
Extender B3 Kaolin 1,57 5-40 86,12 40
B

Micromica
Extender B4 Muscovite ----- ----- 94,93 43
W1

Polestar
Extender B5 Kaolin 1,57 0,5-3,5 86,82 24
200P

Polygloss
Extender B6 Kaolin 1,57 0,6 80,58 32
90

Silicato de
Aluminum
alumnio Extender B7 ----- 0,02 86,85 48
silicate
P820

Speswhite Extender B8 Kaolin 1,57 0,7 87,71 28

Supreme Extender B9 Kaolin 1,57 0,5-3,5 87,43 34

Ti-Pure R C1 Titanium
Pigment 2,6-2,7 0,36 98,04 25
706 (padro) Dioxide

Kemira C2 Titanium
Pigment 2,6-2,7 0,22 97,71 24
660 (Padro) Dioxide

Kronos Titanium
Pigment C3 2,6-2,7 0,35 97,69 30
2190 Dioxide

Kronos Titanium
Pigment C4 2,6-2,7 0,34 97,21 19
2310 Dioxide

Kronos CR Titanium
Pigment C5 2,6-2,7 0,36-0,50 98,88 28
813 Dioxide
Ti O2 CR- Titanium
Pigment C6 2,6-2,7 0,36-0,50 97,18 26
826 Dioxide

TiO2
Titanium
Shatleben Pigment C7 2,6-2,7 0,36-0,50 97,63 25
Dioxide
RD3

Tiona RCL Titanium

Pigment C8 2,6-2,7 0,36-0,50 97,19 20
535 Dioxide

Finnititan Titanium
Pigment C9 2,6-2,7 0,36-0,50 96,95 22
RDI-S Dioxide

Ti-Pure R Titanium
Pigment C10 2,6-2,7 0,51 98,75 24
931 Dioxide

Tronox CR Titanium
Pigment C11 2,6-2,7 0,36-0,50 99,32 28
813 Dioxide

Barium
Barita
Extender D1 Sulfate 1,64 2-30 72,81 30
diamelia
(Barite)
Barium
Barita
Extender D2 Sulfate 1,64 2-30 70,22 31
EWO
(Barite)
Barium
Branco
Extender D3 Sulfate 1,64 0,5-1,0 67,22 32
Fixo
(Blanc fixe)

Litopone
Extender E1 Zinc sulfide 2,40 0,7 92,23 31
30%

Litopone
Extender E2 Zinc sulfide 2,40 0,7 92,58 27
30R

Litopone D Extender E3 Zinc sulfide 2,40 0,7 91,78 28

Farisil 200 Extender F1 Slica 1,54 5-40 --- ---

Sykron M
Extender F2 Silica 1,54 14,0 57,02 50
3000

FP
opacifying
Pigment Pigment G ---- 1,1 96,33 36
pigment
FP 460

Microtalc Magnesite
Extender H1 ---- 5,0 88,48 38
AT 1 and talc

Magnesiu
Indutalc 20 Extender H2 m silicate 1,58 5,0-40,0 70,83 26
(talc)
Magnesiu
Mistron
Extender H3 m silicate 1,58 2-15 87,51 39
Monomix
(talc)

Magnesiu
Talco M 30 Extender H4 ----- 2-15 50,96 24
m silicate

Hydrous
Talco OXO Extender H5 magnesiu ----- 2-15 70,17 30
m silicate

Talco SE Magnesiu
Extender H6 ----- 2-15 81,27 37
Micro m silicate

Mica-
Plastorit
Extender I chlorite- ----- 13,0 79,04 36
000
quartz
(Slurry
Ropaque CoP.Sthyr
Extender J ----- 0,4 72,04 19
Ultra E ene/Acrlic
o)
It is important to refer that the carbonates Omyacarb 2 Extra and Omyacarb 5 Extra were considered
the extenders of reference, because they are widely used in waterborne formulations, and because of
their well-known properties and behavior, which makes it easier to draw conclusions of the present
study. For the same reason Ti-Pure R 706 and Kemira 660 were considered the pigments of
reference.

3.5) Results analysis and conclusions

According to the results shown in table 2, there is a huge difference in the opacity of paints that used
extenders in their compositions and the ones with pigments. The higher opacity results were obtained
with pigments of titanium dioxide (C) and FP 460 pigment (G). Paints with titanium dioxide show
values of opacity between 97.18 and 99.32%, for thickness variations from 19 to 30 m. These values
are considerably high, and can be explained due to the high values of refractive index, and small
average size, these particles present. As it was referred previously, particles with substantial

refractive index, have the ability to scatter light more significantly and contribute more to opacity.
On the other hand smaller particles may allow more compaction and fill, contributing to increased
absorption or scattering of light and consequently to the hiding power. Comparing the titanium

pigments with each other and with the ones of reference, it was clear that the results were very
similar. The titanium with the highest opacity was the one with Tronox CR813 (99,32%) , while the
lowest result were with Kronos 2310 (97,18%). Opacity of the paint using FP 460 pigment was also
high (96,33%), but even so, a little bellow of the average of the titanium. Relatively to the extenders,
the highest values were obtained with fillers of sulphides and silicates and the poorest results with
silicas and sulfates.Considering the paints with carbonate extenders, the results proved to be not
very high (with an average opacity of 73, 89% for a thickness of 29 m), being also inferior to the
ones with pigments mentioned. Comparing the carbonates studied with the ones considered as
references (A1 and A2), it was clear a great variation. Some fillers like A7 and A11 had values lower
than the references (due to higher size particles) while some like A9,A13,A14,A15 and A16 had
bigger values (particles with size inferior to A1 and A2).
Relatively to the silicates studied, the values obtained were intermediate when compared to titanium
and carbonates, having an average opacity of 89% for a thickness of 41 m. It was expected since
refractive indices of silicates B1 and B3 were included in the range of carbonates and titanium
pigments, and the sizes of these two fillers are less than or equal to the carbonates. The other
studied silicates shown hiding power values higher than carbonates (similar refractive indices but
smaller particles), but inferior to titanium (have the smallest size particles of all studied). Considering
the sulfates properties in table 2, it is clear that there are 2 particular groups. Ones with particle size
2-30 m, and others with particles of 0,5-1 m. In both cases the sizes is much higher than titanium
pigments and the majority of silicates, being on the other hand similar to carbonates fillers. Taking
this in consideration as well as the order of refraction indices (titanium>sulfates carbonates>
silicates), the results prove to be consistent. The paints that comprise extenders of sulphide, were
the ones that shown higher opacity levels. The results are consistent with the properties in table 2. In
fact the opacity follows the same order as the refractive indice, and in terms of particle size it was
expected that sulphide paints would give opacities higher than the one with carbonates, than sulfates
with size 2-30 m and silicates with size 4 or 5-40 m. According to the same table it should be of the
same order of magnitude of the one with silicates with 0,5-3,5 m and sulfates with 0,5-1m and
inferior to titanium pigments and silicates with 0,6 and 0,22 m. All of that proved to be true. Paints
with silica fillers were indeed the ones who gave lower opacity levels, which was expect since they are
the particles with lower refractive indice and have particle sizes in the magnitude of carbonates and
majority of silicates. Relatively to the talcs used in this study, it was concluded that they confer
reasonable opacities (an average of 74,87% for a thickness of 32 m). According to the properties of
table 2, there can be found two particular groups of talcs. One with particle size between 2-15 m, and
another with particles of 5-40 m.
The first group are particles with the same size as some of the carbonates and silicates. In addition to
that fact talcs have refractive indices similar to carbonates, silicates and silicas. So it was expected the
first group of talcs to present an opacity of the magnitude of the silicates and carbonates of the same
dimension. The results prove to be consistent with that fact. In other way talcs of the second group
show lower opacities because they have larger particle size then the first group, and as it was said
before, the larger the average particle size less opaque are the paints incorporating these extenders.
In addition to the groups of extenders mentioned, two other were tested, the Plastorit 000 and
Ropaque ultra E. None of them shown significantly high values of opacity,being the resuls on the
magnitude of the talcs,carbonates and sulfates studied.
4. References
[1]- http://gabrielafernandes.com/blog/wp-content/uploads/2010/02/NP-41-1982.pdf (NP41)
[2]- Tintas Plsticas para construo Civil, Resiqumica, 2001;
[3] -Noes Bsicas de Tintas e Vernizes, Resiqumica
[4]-Paints and Coatings testing Manual, Joseph Y Koleske editor, Gardner, BYK 14th Edition;
[5]-Base dados produtos Resiquimica, acedido em Janeiro de 2012
[6]- Mattielo, Joseph J.; Protective and Decorative Coating, Volume II Raw Materials:
Pigments, metallic powders, and metallic soaps, John Wiley & Sons, Londres, 1947;
[7]-Stoye, Dieter; Freitag, Werner; Paints, Coatings and Solvents, 2 edio, Wiley-VCH, 1998;
[8]- Polymer Dispersions and Their Industrial Applications-Cap6: Extenders, Protective and
decorative coating, Wiley-VCH Verlag GmbH & Co. KGaA, 2002
[9]- Hare, Clive; Extenders, Coating System Design Inc., Canada, 2001;
[11]- www.chemindustry.com
[12]- www.european-coatings.com