HOW TITANIUM DIOXIDE SELECTION

CAN IMPROVE COLOR MATCHING

PERFORMANCE AND
FORMULATION CAPABILITY
Joseph M. Bidwell Jr.
Philipp M. Niedenzu

ABSTRACT
Titanium dioxide pigments offer the plastics industry attractive physical and optical
performance characteristics. Tinting strength and undertone are quantifiable
measurements of optical properties of titanium dioxide and pigment performance
characteristics. These parameters provide opacification and brightness data to
downstream consumers of titanium dioxide to allow them to appropriately develop
formulations in combination with colored pigments to achieve a target specification in
the color space. This paper describes the relationship between titanium dioxide optical
properties of tinting strength and undertone and the resulting effect on chroma, hue and
saturation within the color space. This relationship is crucial to understanding the impact
of titanium dioxide grade differences and optical space analysis for color formulation and
resulting product color performance.
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

Introduction

Tinting strength and undertone are two performance parameters that provide details of titanium dioxide
grades and their end use optical performance characteristics. Tinting strength and undertone of the
chosen grade of titanium dioxide contribute to the final color of the product.

The ability of titanium dioxide to selectively scatter certain wavelengths Tinting strength requirements of titanium dioxide are application-
of light is a function of the pigment particle size diameter and dependent. A high tinting strength titanium dioxide is advantageous in
distribution. The relationship of particle diameter to light scattering fully opaque, bright white applications; for example, thin films where
efficiency was first described by Rayleigh (Lilienfeld, 2004) and further the scattering of light must occur in a thin cross-section prior to light
refined by Mie (Mie, 1908), Horvath (Horvath, 2009), and Van de Hulst passing through the product, minimizing visibility of the substrate. In
(Van de Hulst, 1981). The relationship between particle diameter and exterior color applications, a lower tinting strength pigment can be
light scattering defines the maximum scattering efficiency of a particle advantageous to minimize the amount of colorant required to overcome
as a function of the ratio between the particle diameter to wavelengths the whiteness of titanium dioxide and reach the targeted product color
of light. Light scattering is most efficient when the particle is half the while still providing appropriate levels of durability and UV stability
diameter of the wavelength of light it scatters. (Davis, Niedenzu, & performance. (Feng & Birmingham, 2003)
Reid, 2010)
The undertone of titanium dioxide pigments range
Tinting strength is controlled by the particle size distribution of titanium
dioxide. A narrower distribution provides higher tinting strength as from “cream” to “blue” and is a function of the mean
more particles will be appropriately sized, as described by Mie theory, particle size of the titanium dioxide grade.
for optimal scattering of light in the visible spectrum (Davis, Niedenzu,
& Reid, 2010). The reflectance/scattering of titanium dioxide in a tinted The undertone of titanium dioxide pigments range from “cream” to “blue”
system can be measured by mixing with black pigment to create a gray and is a function of the mean particle size of the titanium dioxide grade.
tinted system in polyvinylchloride. Monitoring the scattering intensity The average particle size of pigmentary titanium dioxide determines
of the green wavelength in the gray plastic allows for determination of the scattering affinity of light across the visible spectrum. Mie theory
a tinting strength effect when compared to a standard to quantify the explains that the optimum particle size for light scattering occurs when
opacifying strength of the pigment. the particle is half the diameter of the wavelength of light it scatters.

2
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

Therefore, larger particles scatter yellow02

Figure light more efficiently (longer Therefore, larger particles scatter yellow light
wavelength in the visible spectrum) and provide a cream undertone,
whereas smaller particles provide better scattering efficiency of blue more efficiently (longer wavelength in the visible
light (shorter wavelength in the visible spectrum). spectrum) and provide a cream undertone,
Consistent undertone of titanium dioxide is particularly important to whereas smaller particles provide better scattering
colored products since variation in titanium dioxide undertone can have efficiency of blue light (shorter wavelength in the
a large impact on the final product color.
visible spectrum).

Figure 1. Tinting strength and undertone values in experimental grid Figure 2. Effect of tinting strength and pigment loading on the whiteness index of samples

Optical Color Space 80

120
70

Whiteness Index (dimensionless)

Tinting Strength (dimensionless)

110 60

50
100
40
90
30

80 20

10
70
0
60 0 5 10 15 20
-0.05 -0.03 -0.01 0.01 0.03 0.05
Pigment Mass (g)
Undertone (dimensionless)
Ti02 B-1 Ti02 B-5 Ti02 B-7
Ti02 B Ti02 A

3
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

Experimental
Figure 03
The purpose of this work was to evaluate the impact of titanium degree of pigment opacification power. Epsom salt does not create
dioxide grades having different tinting strengths on the color of a a color center, but serves to dilute the hiding power of the titanium
tinted product with consistent undertone, as well as a difference in dioxide in the overall pigment blend.
titanium dioxide undertone while evaluating similar tinting strength
Two grades of titanium dioxide, with differing median particle size,
performance. This was completed by analyzing laboratory-prepared
were chosen for this experiment: one grade with a blue (positive)
blends of titanium dioxide pigments with different concentrations of
undertone (TiO2 A) and one with a cream (negative) undertone (TiO2 B).
Epsom salt (MgSO4.7H2O, refractive index 1.43) to achieve a varying

Table 1. Experimental grid of titanium dioxide/salt blends Figure 3. Figure 3. Effect of tinting strength and pigment loading on the chroma of samples
(as measured by the difference between the sample and standard as described in a polar
coordinate system)
Pigment Sample ID Pigment Mass (g) Epsom Salt (g)

TiO2 A TiO2 A-1 100 0

1.4
TiO2 A TiO2 A-2 99 1
1.2
TiO2 A TiO2 A-3 98 2

Chroma (dimensionless)
TiO2 A TiO2 A-4 96 4 1
TiO2 A TiO2 A-5 92 8
0.8
TiO2 A TiO2 A-6 88 12

TiO2 A TiO2 A-7 84 16 0.6

TiO2 B TiO2 B-1 100 0

0.4
TiO2 B TiO2 B-2 99 1

TiO2 B TiO2 B-3 98 2

0.2

TiO2 B TiO2 B-4 96 4

0
TiO2 B TiO2 B-5 92 8 0 5 10 15 20
TiO2 B TiO2 B-6 88 12
Pigment Mass (g)
TiO2 B TiO2 B-7 84 16
Ti02 B-1 Ti02 B-5 Ti02 B-7

4
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

By preparing samples with different concentrations of Epsom salt, Pigment blends were prepared in the laboratory by mixing the
evaluations were conducted comparing pigment blends with the same desired grade of titanium dioxide with varying concentrations of
undertone but different tinting strengths, and pigment blends with Epsom salt using a V-cone blender. The pigment blends were first
similar tinting strengths but different undertones. This evaluation analyzed for tinting strength and undertone values. Then, various
served to summarize the relationship between these two optical sample sizes of select pigment blends were combined with one pellet
property measurements and the resulting effect on product color. The of a 40% black masterbatch in polyethylene and a 1.9MI, 0.92 g/
tinting strength and undertone of the pigment blends tested in these cc low density polyethylene resin on a two-roll mill and pressed to
experiments are summarized in Figure 1 (p. 3). produce rigid plaques for additional optical evaluation and analysis.
Blend concentration data are summarized in Table 1 (p. 4) and black
masterbatch data are summarized in Table 2 (below).
Table 2. Pigment blends with black masterbatch: sample preparation

Black Masterbatch Black Masterbatch

Pigment Pigment Mass (g) Mass Polymer (g) Pigment Pigment Mass (g) Mass Polymer (g)
mass (g) mass (g)
TiO2 0 0 190 0.0266 TiO2 B-1 1 189 0.0246

TiO2 A-1 1 189 0.0260 TiO2 B-1 2 188 0.0239

TiO2 A-1 2 188 0.0266 TiO2 B-1 4 186 0.0245

TiO2 A-1 4 186 0.0274 TiO2 B-1 8 182 0.0243

TiO2 A-1 8 182 0.0260 TiO2 B-1 16 174 0.0242

TiO2 A-1 16 174 0.0261 TiO2 B-5 1 189 0.0263

TiO2 A-5 1 189 0.0263 TiO2 B-5 2 188 0.0269

TiO2 A-5 2 188 0.0269 TiO2 B-5 4 186 0.0278

TiO2 A-5 4 186 0.0278 TiO2 B-5 8 182 0.0265

TiO2 A-5 8 182 0.0265 TiO2 B-5 16 174 0.0277

TiO2 A-5 16 174 0.0277 TiO2 B-7 1 189 0.0262

TiO2 A-7 1 189 0.0262 TiO2 B-7 2 188 0.0261

TiO2 A-7 2 188 0.0261 TiO2 B-7 4 186 0.0264

TiO2 A-7 4 186 0.0264 TiO2 B-7 8 182 0.0267

TiO2 A-7 8 182 0.0267 TiO2 B-7 16 174 0.0268

TiO2 A-7 16 174 0.0268

Continued at right...

5
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

Results and Conclusion

The results of this experiment showed the different optical Analysis of samples with similar undertone and different tinting
performance characteristics of the pigment blends by studying strengths showed similar hue, chroma and yellow values as the
pigments with the same undertone but different tinting strengths, as pigment blend concentration was increased in the polyethylene/carbon
well as similar tinting strengths but different undertones. The tinting black compound. However, the whiteness (saturation) of the samples
strength and undertone values of the pigment blends used in this increased with increasing levels of titanium dioxide in the pigment
experiment are summarized in Table 3 (below). blend. Increasing the tinting strength of the pigment blend provided an
increase of 25.2% in whiteness at 2.1% pigment in the compound.
The effect of tinting strength on optical properties of the sample are
displayed graphically in Figures 2, 3, 4 and 5 (pp. 3, 4, and 7).

Table 3. Tinting strength and undertone values of starting pigment blends

Pigment Pigment
Sample ID Tinting Strength Undertone Sample ID Tinting Strength Undertone
Concentration (%) Concentration (%)

TiO2 A-1 100 113 0.027 TiO2 B-1 100 100 -0.048

TiO2 A-2 99 109 0.028 TiO2 B-2 99 98 -0.047

TiO2 A-3 98 111 0.028 TiO2 B-3 98 95 -0.048

TiO2 A-4 96 105 0.029 TiO2 B-4 96 90 -0.048

TiO2 A-5 92 103 0.030 TiO2 B-5* 92 80 -0.048

TiO2 A-6 88 97 0.030 TiO2 B-6* 88 70 -0.048

TiO2 A-7 84 91 0.032 TiO2 B-7* 84 60 -0.048

Continued at right...

*Please note that due to samples sticking to rollers, blends B-5 through B-7 tinting strength and 6
undertone were extrapolated from data collected on other pigment blends in the sample set.
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

The analysis of pigments with similar tinting strengths and different pigments with similar tinting strengths are summarized in Figures 6,
undertone values was also performed. The hue and yellowness values 7, 8 and 9 (pp. 8 and 9). These results reinforce the critical nature of
of the pigment blends showed significant
Figure 05differences as increased choosing a titanium dioxide pigment that is designed for use in each
levels of pigment were used in the sample preparation. Chroma was application.
substantially different at low pigment loading levels, but merged as
additional pigment was added to the sample. The whiteness values Increased tinting strength, resulting in higher hiding
(as measured by whiteness index) were offset due to slightly different
tinting strength values, but showed similar results for pigments with
power, is advantageous in applications where high
different undertones. The results of the different undertone value opacification requirements are desired, such as
opaque film production.

Figure 4. Effect of tinting strength and pigment loading on the hue of samples (as measured by the Figure 5. Effect of tinting strength and pigment loading on the yellowness index of samples
difference in angle between the sample and standard as described in a polar coordinate system)
4
0.04

Yellowness Index (dimensionless)

2
0.02
0
0
Hue (dimensionless)

-2
-0.02
-4
-0.04
-6
-0.06
-8
-0.08
-10
-0.1
0 5 10 15 20
0 5 10 15 20
Pigment Mass (g)
Pigment Mass (g)
Ti02 B-1 Ti02 B-5 Ti02 B-7
Ti02 B-1 Ti02 B-5 Ti02 B-7

7
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

Figure
Increased tinting strength, resulting 07
in higher hiding power, is Tinting strength and undertone are quantifiable measurements of
advantageous in applications where high opacification requirements optical properties of titanium dioxide and pigment performance
are desired, such as opaque film production. Lower tinting strength characteristics within the overall color space. This work detailed
can be preferred in exterior color applications where ultraviolet light changes in color space resulting from differences in tinting strength
stability requirements are necessary, as a lower concentration of and undertone of titanium dioxide pigments. The relationship of tinting
colorants can be required to overcome the whiteness provided by strength and undertone of titanium dioxide pigments and grade
titanium dioxide. selection are crucial to establish consistent product color performance.

Figure 6. Effect of undertone and pigment concentration on the whiteness index of samples Figure 7. Effect of undertone and pigment concentration on the chroma of samples (as measured
by the difference between the sample and standard as described in a polar coordinate system).

80
3
70
Whiteness Index (dimensionless)

2.5
60

Chroma (dimensionless)
50 2

40
1.5
30
1
20

10 0.5

0
0
0 5 10 15 20
0 5 10 15 20
Pigment Mass (g)
Pigment Mass (g)
Ti02 A-5 Ti02 B-1
Ti02 A-5 Ti02 B-1

8
 Figure 09

How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

Figure 8. Effect of undertone and pigment concentration on the hue of samples (as measured by Figure 9. Effect of undertone and pigment concentration on the yellowness index of samples
the difference in angle between the sample and standard as described in a polar
coordinate system)
4

0.04

Yellowness Index (dimensionless)

2

0.02 0

0
Hue (dimensionless)

-2

-0.02 -4

-0.04 -6

-0.06 -8

-0.08 -10
0 5 10 15 20
-0.1
0 5 10 15 20 Pigment Mass (g)

Pigment Mass (g) Ti02 A-5 Ti02 B-1

Ti02 A-5 Ti02 B-1

9
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

Acknowledgements

The authors wish to thank the Chemours Company and many colleagues for their support in the preparation of this paper.

REFERENCES
Davis, S. P., Niedenzu, P. M., & Reid, A. H. (2010). Lilienfeld, P. (2004).
The Optical Impact of Low-Index Inorganic Fillers on the Performance A Blue Sky History. Optics and Photonics News, 32-39.
of Plastic Articles Pigmented with Titanium Dioxide. Orlando, FL:
Mie, G. (1908).
ANTEC.
Beiträge zur Optik trüber Medien, speziell kolloidaler Metallösungen.
Feng, A. A., & Birmingham, J. N. (2003). Annalen der Physik, 377-445.
Use of Titanium Dioxide in Exterior PVC Applications.
Van de Hulst, H. (1981).
Wilmington, DE.
Light Scattering by Small Particles. New York: Dover Publications.
Horvath, H. (2009).
Gustav Mie and the scattering and absorption of light by particles:
Historic developments and basics. Quantitative Spectroscopy &
Radiative Transfer, 787-799.

10
How Titanium Dioxide Selection Can Improve Color Matching Performance and Formulation Capability

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