USE OF OPTICAL DENSITY AND TIO2 LIGHT SCATTERING TO IDENTIFY

OPTIMIZATION POTENTIAL IN ARCHITECTURAL COATINGS

Abrahao. R.T., Umemura. R., Chemours do Brasil S.A., Brazil
Diebold, M. P., Chemours, USA

ABSTRACT

Optical density is a technique that evaluates the amount of light scattered by particles in a
suspended paint sample. After developing an improvement in it, it is now possible to
understand the titanium dioxide (TiO2) light scattering efficiency without knowing the complete
paint formulation. Spreading rate analyses take into consideration the TiO2 amount to define
this material scattering coefficient in the dry paint film.

With these analyses it was possible to identify how well the TiO2 was dispersed in the liquid
paint and how evenly distributed in the dry paint film it was (reflecting dispersion/flocculation
problems or crowding effect during drying process), which we called the TiO2 dispersion
efficiency and formulation efficiency. Some paints presented an opportunity to improve the
TiO2 dispersion by almost 20% and the formulation (extenders/fillers, resin, etc.) by 55%.
After defining the TiO2 usage efficiency it was possible to compare paints from different
countries in Latin America.

KEYWORDS

Properties optimization; architectural coatings; titanium dioxide; artificial neural networks

INTRODUCTION

Titanium dioxide (TiO2) is the most important white pigment in several industries due to its
ability to facilitate light scattering and white color (1-4). However, to achieve adequate
performance, coatings that use TiO2 pigments must have good dispersion of individual
particles (5).

In this study, a direct measurement of TiO2 dispersion in dry film was studied using electron
microscopy. The image was broken into sub-images, and then the sub-images were compared
to one another (6). Spatial point statistics methodologies were used, such as those developed
by Clark-Evans and Ripley, as well as the neighborhood distribution function (7).

Not all paint producers have access to equipment like electron microscopes, so the purpose
of this work was to understand the final coatings’ formula TiO2 dispersion – how well the TiO2
stays dispersed in dry film and how this directly affects its final properties – using a
combination of theoretical and empirical methodologies.

TIO2 DISPERSION IN DRY FILM

The light scattering provided by TiO2 is strongly influenced by several factors, including particle
size, crystal phase, refractive index of the binder or surrounding medium, and degree of
isolation from other TiO2 particles. This degree of isolation is also referred to as the degree of
dispersion or lack of crowding (8-11).

To achieve the best possible performance, TiO2 particles must be separated with a particle to
particle distance of at least 400 nm (8). For instance, agglomerated pairs of particles exhibit a
20% decrease in the scattering parameter associated with the hiding power of a paint film
relative to a single particle.

Another way of looking at this is demonstrated in Figure 1, which depicts the impact of particle-
to-particle spacing on the efficiency of a paint’s hiding power. The Figure shows electron
micrographs of three different paints with different particle dispersions. It can be seen that
good particle spacing increases the hiding power performance of the paint in this case by 30%.

Agglomerated Random Spaced

Relative Hiding Power:

100.0 121.5 130.0

PVC = 20% for all three paints

Figure 1 – Impact of particle-to-particle distance on the paint’s hiding power.

To achieve the condition in which the particles are separated or isolated from each other, the
dispersion process and stability of the suspension must be carried out such that when the
coating film is drying or curing, the particles remain dispersed and isolated from each other.

A proper TiO2 dispersion in the dry film can be achieved by combining a good dispersion of
the TiO2 with a proper formula for keeping the TiO2 apart after the film is formed (12). On the
one hand, previous studies have shown that the de-agglomeration process is influenced by
the wetting ability of the pigmentary TiO2 (13-14) and the mechanical forces applied by the
equipment design (15). On the other hand, Diebold (16) demonstrated that TiO2 spacing is
effective for scattering light and that its crowding is influenced by other coatings of raw
materials.

There are several theories for explaining the interaction of a light beam with a particle (see,
for example, the work of Mie, Rayleigh, and Fraunhofer - 17). Mie developed a basic theory
for spherical particles that is useful when particles with more complex shapes are under
evaluation. Rayleigh’s scattering theory applies when particles are smaller than the
wavelength of the incident beam, and Fraunhofer’s theory can be applied when the particles
are larger than the wavelength of the incident beam.

In the case of pigmentary TiO2, optimal scattering is seen for particles that are about half the
size of the visible light wavelengths (400 nm to 750 nm). Therefore, the particles range
between 200 nm and 350 nm. Bigger particles are sometimes found due to the particular
requirements of the application. Therefore, Rayleigh’s and Mie’s solutions for Maxwell’s
equation were used in this study to calculate the particle size based on light scattering.

According to Rayleigh’s and Mie’s theories, the scattering pattern (I) is independent of the
particle’s shape, but it takes into account the distance from each particle to the detector (r),
the incident light intensity (I0), and the wavelength () as shown in Equation 1:

Equation 1
,
where  is the light polarization or the parameter of the equation that contains the relative
refractive index (m) and the volume of the particle (V) as presented in Equation 2:
Equation 2

.
OPTICAL DENSITY

Optical density originated from the Lambert-Beer law, which was derived from the first-order
Taylor expansion of Maxwell’s equations and is depicted by Equation 3 (18).
𝐼(𝑡)
𝑂𝐷 = −𝑙𝑜𝑔 ( ), Equation 3
𝐼0

where I(t) is the light transmitted through the media of interest and I0 is the incident light; e.g.,
the optical density is the attenuation of light when passing through the media under
investigation. Since the main function of TiO2 is to scatter light, measuring attenuation is
equivalent to measuring the light scattering efficiency of this TiO 2. Measuring particle size
could be an alternative option, but the different refractive index of each particle makes it harder
to understand and interpret the output data.

The problem of optical density is to define a reference of the optimized dispersion. By dividing
the sample into two and sonicating one of these halves, we can create the reference that we
are looking for. Sonication might break some extenders and resins down into smaller particles,
but the TiO2 particles will remain intact - only any particle agglomerates that remain from the
poor dispersion process are broken down, rather than the individual particles themselves. The
ratio of the sonicated and nonsonicated samples gives us the dispersion efficiency of that
sample of TiO2 (𝜖𝐷𝑖𝑠𝑝 ).

SPREADING RATE

The weighed hiding test method is a form of ASTM D2805-11, Hiding Power of Paints by
Reflectometry. The ISO equivalent is the ISO 6504-1:1983. The Kubelka-Munk hiding power
method can be applied to white and light-colored paints. Both test methods include a means
to perform the calculations presented by the Kubelka-Munk theory (Equation 4 to Equation
11).

1  Rg (a  b ctgh bSX ) and

R  f ( SX , Rg , R )  Equation 4
a  Rg  b ctgh bSX
1 1  aRo ,
SX  f ( Ro , R )  Ar ctgh Equation 5
b bRo
where
1 Ro  R  Rg  ,
a R   Equation 6
2  Ro Rg 
b  (a 2  1)
1
2 , Equation 7
R  a  b , Equation 8

, and Equation 9
K
1 R  ,2

 Equation 10
S R

where R is the reflectance of film applied to the substrate, Rg is the substrate reflectance, R
is the reflectance of a film so thick that increasing its thickness has no effect on R, Ro is the
reflectance of the film applied to an ideal black substrate (Rg = 0), X is the thickness of the
film, S is the scattering coefficient of the film, and K is the absorption coefficient of the film.
Basically, in the ASTM test method the dry film thickness is measured whereas the and wet
film thickness is back-calculated using an additional measurement (i.e., nonvolatile content).
The ISO test method and the ASTM test methods are similar in this regard.

Using the scattering coefficient of the film and the TiO2 amount, it is possible to calculate the
scattering coefficient of TiO2 (STiO2). The TiO2 concentration determines the average refractive
index of the coating film, since resin, fillers, and extenders all have about the same refractive
index (1.56 to 1.6). The average refractive index will determine the TiO2 scattering efficiency
in dry film.

If a single particle of TiO2 (refractive index 2.73) is surrounded by resin (with a refractive index
of 1.5), the refractive index ratio would be of 1.82. This is the highest value that this ratio can
reach for a TiO2 resin mix – adding moreTiO2 to the resin increases the average refractive
index rises and reduces the TiO2 scattering efficiency. If arbitrary values are given to the
scattering value, then the curve of light scattering as a function of TiO2 concentration would
be described as in Figure 2.

Figure 2 – Scattering efficiency of TiO2 as a function of the

average refractive index of dry film coatings.

The curve in Figure 2 assumes that the TiO2 is fully dispersed into the resin or dry film,
meaning that this would be the maximum value possible for achieving each TiO2
concentration. It is possible to compare the opacities of paints with different TiO2
concentrations by simply comparing their overall scattering values. However, it is better to
compare them by using the theoretical curve as a reference point. For example, in Figure 3
the TiO2 efficiency of Paint 1 is 85%, while it is 90% for Paint 2. We see that the better
scattering value for Paint 1 is due to its lower average refractive index and that the pigment in
this paint is actually more poorly dispersed than the pigment in Paint 2.
 Figure 3 – Comparison of paints with different TiO2
concentrations.

As previously mentioned, poor TiO2 dispersion efficiency in paints may be a result of

dispersion or formulation, and the STiO2 efficiency is an intensive property that basically ignores
formulas differences, looking to the TiO2 scattering efficiency alone. To calculate the
formulation efficiency of a paint (𝜖𝐹𝑜𝑟𝑚 ), the dispersion efficiency (𝜖𝐷𝑖𝑠𝑝 ) must be excluded from
the overall efficiency and calculated from the STiO2 (𝜖𝑆𝑇𝑖𝑂2 ), as shown in Equation 11.

𝜖𝐹𝑜𝑟𝑚 = 1 − (𝜖𝐷𝑖𝑠𝑝 − 𝜖𝑆𝑇𝑖𝑂2 ). Equation 11

SAMPLES

For this study, 208 paint samples from different Latin American countries were collected.
Colombia, Argentina, Brazil, Chile, Ecuador, Peru, Venezuela, and Mexico were the most
dominant countries. The samples were collected from producers that controlled at least 50%
of their markets to assure that they are representative. As many of these countries do not have
regulations regarding paint quality, this was determined according to the perception of our
representatives in these countries.

RESULTS AND DISCUSSIONS

An average dispersion efficiency boxplot for each of the paints from the different countries is
presented Figure 4. It can be seen that most of the countries have a dispersion efficiency
above 90%, meaning that the dispersion is primarily efficient. Since. there was no way to
increase dispersion before these paints are used, these dispersion efficiencies directly affect
the paint quality.
 100.00%

Average of Dispersion efficienc

90.00%

80.00%

70.00%

60.00%

50.00%
at at at at at at in in in in at at at at at in a t i n at in a t in at i n at a t i n at at at
F l Fl Fl F l Fl Fl at at at at Fl Fl F l Fl Fl at F l at F l at Fl a t F l at F l F l at F l F l Fl
w id p w id p S S S S w id p w id S p S w S id S p S w id S w id p
Lo M To l Lo l M l To To p Lo w Mid To p Lo M T o Lo r M Mi d r To Top Lo Low M Mi d To Top Lo M Top Lo M To
a a a i i i a ia ia r o o o u u a la la
in in in z az az il le le le bi b b o do or do or ic o ic o ic o er er ru el e e
nt nt nt Br a Br Br r az C hi C hi Chi o m o m om ua d ua a d u a ad éx x ic éx éx ic éx éx ic P P Pe ez u ezu ezu
ge r ge r ge B l l l q q u q u M é M M M M n n n
Ar A A Co Co Co E E E q E Eq M Ve Ve V e

Figure 4 – Average dispersion efficiency of paints from

different countries.

In Figure 4, it is also possible to see which paints have poor dispersion, such as the low-quality
paints from Mexico whose dispersion efficiency is about 60%. Our investigation showed that
this poor dispersion was a mix of poor TiO2 quality and direct use of the pigment without pre-
dispersing it.

Figure 5 shows paint efficiency for each country. This efficiency is primarily determined by
the mix of resin and extenders, since these particles push the TiO2 into a crowding state,
reducing the TiO2 efficiency in the dry paint film. If the TiO2 particles were more evenly
separated from each other, the paint would have better opacity.

100.00%
Average of Fromula Efficiency

90.00%

80.00%

70.00%

60.00%

50.00%

40.00%
at at at at at at in in in in at at at at at in a t i n at in a t in at i n at a t i n at at at
F l Fl Fl F l Fl Fl at at at at Fl Fl F l Fl Fl at F l at F l at Fl a t F l at F l F l at F l F l Fl
w id p w id p S S S S w id p w id S p S w S id S p S w id S w id p
Lo M To l Lo l M l To To p Lo w Mid To p Lo M T o Lo r M Mi d r To Top Lo Low M Mi d To Top Lo M Top Lo M To
a a a i i i a ia ia r o o o u u a la la
in in in z az az il le le le bi b b o do or do or ic o ic o ic o er er ru el e e
nt nt nt Br a Br Br r az C hi C hi Chi o m o m om ua d ua a d u a ad éx x ic éx éx ic éx éx ic P P Pe ez u ezu ezu
r ge r ge r ge B ol ol o l Eq E q qu Eq q u M é M M M M
M e n en en
A A A C C C E E V V V

Figure 5 – Average formula efficiency of paints from

different countries.

The reason that the Mexican low-quality paint appears as one of the top performers is that the
crowding effect due to a lack of dispersion of the pigment does not allow the TiO2 particles to
be pushed to the available space between the other particles. This means that it does not
matter what extenders and resins are used, the TiO2 dispersion cannot be improved (or in
other words, a bad initial dispersion cannot be worsened by a bad choice of extenders and
resins).
A different way of looking at the same data above is the graph in Figure 6, which combines
the dispersion and formulation efficiencies with TiO2 content (i.e., bubble size). A different
perspective is then presented, showing that the Latin American region’s average dispersion
efficiency is 93% and that its average formulation efficiency is about 70%.

When looking to specific cases (in Figure 6), the Brazilian Coating 18 shows good
performance regarding formulation of the paint - the proper fillers and extenders are used -
and the success of this paint maker to disperse the TiO2 .

Bubble Plot of Average of Dispersion ef vs Average of Fromula Effic

Bubble siz e: Average of TiO2 %(Paint w/w)
70. 00%
100. 00%
BRA 18
B RA 7
Average of Dispersion efficienc

CO L 1CBORLA34 B RA 5 BRA 12 BRA 15

BRA 11
95. 00% BRA 17
B RA 2
B RA 8
ECBURA1 19
CO LB2RA 10 B RA 6
B RA 1 BRAAR3G5
ARG 3 VC
EN
HI 11 BRA 13
BRAACR9H
GI 12 BRA 20 91
90. 00% ARG 2 VEN 2
ARG 4 MEX 4 ECU 3
P ER 2 BRA 14
BRA 16
A rgent i na
85. 00% Br az i l MEX 2 ECU 2
Chi l e
Col ombi a
Equador MEX 1
80. 00% Méxi co
Peru MEX 3
CHI 1
Venez uel a P ER 1

55. 00% 60. 00% 65. 00% 70. 00% 75. 00% 80. 00% 85. 00% 90. 00%
Average of Fromula Effic iency

Figure 6 – Formula and dispersion efficiency combined with TiO2 amount (i.e.,
bubble size).

When looking at the individual qualities, like the high-end coatings (Figure 7), it is clear that
Brazilian coatings have lower TiO2 amounts (i.e., smaller bubble sizes), but most of them are
well dispersed (with dispersion efficiency of more than 90%). The range of formulation
efficiency spreads throughout all the existing ranges, meaning that good dispersion is
achieved, but not used well by the combination of ingredients, like in Brazilian Paints 2 and 3.
On the other hand, the Mexican coatings have an impressive formulation efficiency but lack
dispersion efficiency. At this point, one can only assume that this is probably caused by
Mexico’s habit of not pre-dispersing the TiO2.
 Top paints of Latin America Region
Bubble siz e: g TiO2 / L
100. 00% PCEO
R2 B RA 7
P ERL21 CO L P1EBRR2 A 5 B RA 7 BBRRAA
B1R1A 4
B1BRH
RAIA
I 252 6 RR
ECU 1 COCL H3I CC H 15BA AG6 1 ACROGL 12BRAB6RAARG 4 1 B RA 8
CHIB2RA 2 BRA 3
VEN 1 ARG 2
B RA 8 B RA 7 B RA 8
ARG 2 BRA 3
90. 00% CO L 2
ARG 2
Dispersion effic ienc y

ECU 2
Co u n t r y ( Flat/Satin )
80. 00% Argen tin a Flat
Argen tin a Satin P ER 1 P ER 1
Braz il Flat MEX 2 MEX 3
Braz il Satin
Ch ile Flat MEX 3
70. 00% Ch ile Satin MEX 3
Colombia Flat
Colombia Satin
Equ ador Flat
Equ ador Satin CHI 1
60. 00% México Flat
México Satin MEX 1
P eru Flat MEX 1 MEX 2
MEX 1
P eru Satin
MEX 2
Ven ez u ela Flat
50. 00%
0. 5 0. 6 0. 7 0. 8 0. 9 1. 0
Fromula Efficienc y

Figure 7 – Top-quality coatings’ dispersion and formula

efficiency.

Figure 8 adopts the perspective of a single paint maker to determine if he is facing batch-to-
batch variations and to allow the targeting of specific paint lines and grades. For example, this
customer has selected a particular paint as being top quality (Top 1); it uses a good amount
of TiO2, but lacks dispersion. This coating’s dispersion average is below the other coatings
average from this same customer (that ranges about 96%). It is also possible to see variations
in the same paint lines, such as Top 3, where a difference of almost 20% is found between
two samples, or in the Mid paint, where no sample is close to any of the others (which is the
same for the Top 2 paint), suggesting formula and process variations.

Figure 8 – Customer-specific perspective.

CONCLUSIONS

Through the analyses described in this paper, it was possible to identify how well TiO2 is
dispersed in the liquid paint and if it is evenly distributed in the dry paint film (i.e., if there are
dispersion/flocculation problems or a crowding effect during the drying process, which are
referred to as TiO2 dispersion efficiency and formulation efficiency in this study). Almost 20%
of the paints showed a need to improve the TiO2 dispersion, and 55% of the paints
demonstrated a need for improved formulation (extenders/fillers, resin, etc.). When combined,
the optical density and the scattering efficiency of the dry film can also guide improvement
projects where the most benefit can be extracted from the TiO2 particles.

It is also possible to use the same basis to compare TiO2 use and performance in paints
produced by different companies, even those from different countries.

ACKNOWLEDGMENTS

The authors extend their gratitude to Chemours for the opportunity to work on this project.
Thanks is also given to Dr. Paulinia’s laboratory team for the work they performed and to Pablo
Aragon for his continuous support during this study.

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