Sulfate and Chloride Process TiO2

Blind Evaluation in Flat and Gloss PaintsCRGI Project 201624

Rich CsumittaTechnical Manager – Product Development

Keeping our members competitiveSince 1956

Coatings Research Group

Screen various Chloride and Sulfate process dry TiO2s in a flat and gloss paint formula (provided by Guild CPO Members) for the following properties:

• Tint Strength• Contrast Ratio• Color• Gloss and Sheen• Viscosity• Particle Size

Control TiO2’s highlighted in yellow(C) = Chloride Process (S) = Sulfate Process

Objective

Description Quantity Units Gal % Weight

Water 220 Lb 26.41 18.75

Attagel 50 5 Lb 0.25 0.43

Tamol 1124 Dispersant 7 Lb 0.70 0.60

Tergitol 15-S-9 2 Lb 0.24 0.17

DEE FO 1015 2 Lb 0.28 0.17

Dry Titanium Dioxide 150 Lb 4.51 12.78

Minex 10 100 Lb 4.61 8.52

Optiwhite MX 75 Lb 4.07 6.39

Omyacarb 10 150 Lb 6.65 12.78

Celite 499 25 Lb 1.30 2.13

RUN HIGH SPEED 1510 rpm 25.673 HZ 10 mins.

Ammonium Hydroxide, 28% 6.4 Lb 0.85 0.55

Water 25 Lb 3 2.13

Sub-Total 767.4 Lb 65.39

Rovace 10 210 Lb 23.6 17.89

Kathon LX 1.5% In-Can Biocide 1 Lb 0.12 0.09

Water 100 Lb 12 8.52

Add grind to letdown

Optifilm Enhancer 400 (5% on Latex solids) 6 Lb 0.74 0.51

Premix

Acrysol DR-6600 10 Lb 1.12 0.85

Acrysol DR-180 7.5 Lb 0.85 0.64

Water 67.4 Lb 8.09 5.74

then add

DEE FO 1015 3 Lb 0.42 0.26

Ammonium Hydroxide, 28% 1.3 Lb 0.17 0.11

Total 1173.6 Lb 100 100

Zero VOC 63.6 PVC Flat Formula 36.2 VS

Description Quantity Units Gal % Weight

Water 80 Lb 9.6 7.75

Tamol 2011 Dispersant 8 Lb 0.88 0.77

Ammonium Hydroxide, 28% 0.7 Lb 0.09 0.07

Byk-022 Defoamer VOC Silicone-containing 1 Lb 0.12 0.1

Kathon LX 1.5% In-Can Biocide 1.5 Lb 0.18 0.15

Triton CF-10 1 Lb 0.11 0.1

Dry Titanium Dioxide 220 Lb 6.62 21.31

Water 7.5 Lb 0.9 0.73

RUN HIGH SPEED 1510 rpm 25.673 HZ 10 mins.

Add grind to letdown

Rhoplex HG-706 584.1 Lb 66.2 56.58

Texanol 7.9 Lb 1 0.77

Water 68.72 Lb 8.25 6.66

Acrysol RM-5000 23 Lb 2.64 2.23

Premix

Water 10 Lb 1.2 0.97

Triton X-100 Surfactant, Nonionic 4.4 Lb 0.5 0.43

Propylene Glycol 6 Lb 0.7 0.58

Add the Following

Acrysol SCT-275 Thickener, Nonionic 5.5 Lb 0.64 0.53

Byk-024 Defoamer, VOC-free silicone-containing 3 Lb 0.36 0.29

Total 1032.32 Lb 100 100

48 VOC 19.3 PVC Gloss Formula 36.4VS

Sulfate Process Chloride Process

uses lower grade, cheaper ores needs high grade ore

batch process continuous process

large amounts of waste materialssmall amounts of waste formed with

toxicity problems: Cl2 and TiCl4

pollution control expensiverecovery and recycling of chlorine

possible

produces anatase and rutile pigments

only produces rutile pigments

Sulfate vs. Chloride Process

Dry TiO2 - Blind TestedHuntsman (Chloride Process) (C)

TR93 (as a control)

TR90

TR81

Billions (Chloride Process) (C)

BLR895

BLR-896

Billions (Sulfate Process) (S)

BLR-698

BLR-699

Others (Sulfate Process) (S)

Dawn Grade R-2195

Lomon R996

Tioxitron L10-707

Sachtleben RKB6

Others (Chloride Process) (C)

DuPont R-706

Sample Lot D10 D50 D90 D99SACHTLEBEN RKB6 (S) 441008894 0.210 0.386 0.672 0.97

BILLIONS BLR699 (S) B16012006-11101 0.288 0.434 0.681 0.92

DUPONT 706 (C) 2509740136 0.349 0.483 0.696 0.90

BILLIONS BLR698 (S) B16050609 0.349 0.484 0.697 0.91

BILLIONS BLR895 (C) B1511223111513 0.349 0.484 0.697 0.91

LOMON R996 (S) 201506135019 0.350 0.486 0.702 0.91

TIOXIDE TR81 (C) H501801/01 0.353 0.490 0.703 0.90

TIOXIDE TR93 (C) Q525A2 0.354 0.491 0.705 0.91

TIOXITRON L10-707 (S) BATCH 1 0.358 0.504 0.736 0.96

TIOXIDE TR90 (C) Q4272 B1 SP49 0.366 0.515 0.738 0.93

DAWN R-2195 (S) 1512090604 0.375 0.553 0.852 1.16

Particle Size Distribution

Analysis courtesy of Diamond Vogel Paints

All samples tested exhibited less than 10% deviation in mean particle size and distribution to control except BLR699, DAWN R2195, and RKB6. DAWN R2195 and RKB6 had large differences (10-20% for D50 and 10-30% for Distribution)

Flat Formula Results

85.00

90.00

95.00

100.00

105.00

110.00

DAWN R2195(S)

LOMON R996(S)

BLR895 (C) BLR896 (C) R706 (C) TR81 (C) TIOXITRON (S) TR93 (C) BLR699 (S) BLR698 (S) TR90 (C) RKB6 (S)

95.27 95.82 96.1497.69 98.27 98.66 99.43 100.00

101.47

103.81 103.91

109.74

4 mil Air Dry Tint StrengthFlat Formula

100.02 +/- 4.18

WEAKERSTRONGER

Tioxitron is effectively equal to control (< 1% strength)

85.00

87.00

89.00

91.00

93.00

95.00

97.00

99.00

TR90 (C) RKB6 (S) TR93 (C) BLR896 (C) TR81 (C) BLR699 (S) TIOXITRON (S) BLR698 (S) R706 (C) BLR895 (C) DAWN R2195 (S) LOMON R996 (S)

95.22 95.43 95.46 95.63 95.77 95.83 95.86 95.88 95.89 96.15 96.22 96.48

2.5 mil Contrast RatioFlat Formula

95.82 +/- .36

RKB6, BLR896, TR90, and TR81 are effectively equal in contrast ratio to control at 2.5 mils wet film thickness

85.00

87.00

89.00

91.00

93.00

95.00

97.00

99.00

TR90 (C) TR93 (C) TR81 (C) BLR896 (C) RKB6 (S) R706 (C) TIOXITRON (S) BLR699 (S) BLR895 (C) BLR698 (S) LOMON R996(S)

DAWN R2195(S)

97.79 97.93 97.93 97.96 98.04 98.12 98.24 98.25 98.27 98.28 98.41 98.43

4 mil Contrast RatioFlat Formula

98.14 +/- .21

All samples tested are effectively equal in contrast ratio to control at 4 mils wet film thickness

Color ReadingsFlat Formula

Dry TiO2 Type L* a* b* X Y ZR706 (C) 96.29 -0.80 2.29 85.57 90.71 93.92

BLR895 (C) 96.28 -0.75 2.18 85.58 90.68 94.06

BLR896 (C) 96.26 -0.75 2.31 85.53 90.63 93.81

TR93 (C) 96.25 -0.81 2.32 85.49 90.62 93.79

TR90 (C) 96.18 -0.79 2.25 85.32 90.43 93.69

TR81 (C) 96.16 -0.79 2.29 85.29 90.40 93.59

DAWN R2195 (S) 95.93 -0.73 2.70 84.80 89.84 92.41

BLR699 (S) 95.90 -0.76 2.53 84.71 89.77 92.58

TIOXITRON (S) 95.86 -0.75 2.65 84.63 89.68 92.32

BLR698 (S) 95.86 -0.74 2.49 84.61 89.66 92.53

LOMON R996 (S) 95.80 -0.66 2.79 84.53 89.53 91.95

RKB6 (S) 95.74 -0.71 2.70 84.37 89.38 91.93

R706, BLR896, TR81, TR90, and BLR895 are effectively equal in color to control (< 0.2 DE*)

Gloss MeasurementsFlat Formula

All samples tested are effectively equal in 60 and 85 degree gloss to control

Dry TiO2 Type 20◦ 60◦ 85◦

TR93 (C) 0.6 1.4 1.6TR81 (C) 0.6 1.4 1.6

R706 (C) 0.7 1.4 1.7

TR90 (C) 0.6 1.4 1.7

BLR698 (S) 0.7 1.4 1.7

BLR896 (C) 0.7 1.4 1.8

BLR699 (S) 0.7 1.4 1.8

TIOXITRON (S) 0.7 1.4 1.8

RKB6 (S) 0.6 1.4 1.8

BLR895 (C) 0.7 1.4 1.9

DAWN R2195 (S) 0.7 1.4 1.9

LOMON R996 (S) 0.7 1.4 1.9

108

109

111

112 112

113 113

114 114

116

117

118

1.171.15

1.13

1.221.23 1.20

1.23 1.22

1.16

1.24

1.28

1.26

1.10

1.12

1.14

1.16

1.18

1.20

1.22

1.24

1.26

1.28

1.30

106

108

110

112

114

116

118

120

BLR698 (S) TR93 (C) TR81 (C) BLR895 (C) LOMON R996 (S) DAWN R2195 (S) BLR896 (C) TIOXITRON (S) R706 (C) BLR699 (S) RKB6 (S) TR90 (C)

ViscosityFlat Formula

KU ICI

All samples tested exhibited less than 10% viscosity difference to control for both KU and ICI except RKB6 @11.2% for ICI

Gloss Formula Results

85.00

90.00

95.00

100.00

105.00

R706 (C) BLR699 (S) TR81 (C) BLR698 (S) TR90 (C) DAWN R2195(S)

TR93 (C) TIOXITRON (S) BLR896 (C) BLR895 (C) LOMON R996(S)

RKB6 (S)

97.68 97.79 98.2999.39 99.83 99.98 100.00 100.27

101.95 102.13 102.75 103.57

4 mil Air Dry Tint StrengthGloss Formula

100.30 +/- 1.94

STRONGER WEAKER

TR90, Tioxitron, BLR698, and DAWN R2195 effectively equal in Tint Strength to control (< 1%)

85

87

89

91

93

95

97

99

BLR896 (C) TR81 (C) RKB6 (S) TR93 (C) TIOXITRON (S) DAWN R2195 (S) R706 (C) BLR699 (S) BLR698 (S) LOMON R996 (S) TR90 (C) BLR895 (C)

96.55 96.59 96.78 96.82 96.90 96.92 96.93 96.95 96.98 96.99 97.03 97.08

2.5 mil Contrast RatioGloss Formula

96.88 +/- .16

All products tested effectively equal for contrast ratio to control at 2.5 mils wet film thickness (<0.2%)

85

87

89

91

93

95

97

99

BLR896 (C) RKB6 (S) BLR895 (C) TR81 (C) LOMON R996(S)

TIOXITRON (S) TR93 (C) DAWN R2195(S)

BLR699 (S) R706 (C) BLR698 (S) TR90 (C)

98.45 98.48 98.53 98.55 98.56 98.57 98.59 98.62 98.64 98.68 98.69 98.77

4 mil Contrast RatioGloss Formula

98.59 +/- .09

All products tested effectively equal for contrast ratio to control at 4 mils wet film thickness

Color ReadingsGloss Formula

Dry TiO2 Type L* a* b* X Y ZR706 (C) 98.04 -1.04 1.67 89.51 95.01 99.37

TR90 (C) 97.97 -1.03 1.56 89.35 94.84 99.36

TR93 (C) 97.93 -1.03 1.57 89.25 94.73 99.24

BLR895 (C) 97.91 -1.01 1.54 89.23 94.69 99.24

TR81 (C) 97.87 -1.00 1.62 89.15 94.60 99.03

BLR896 (C) 97.77 -0.98 1.59 88.92 94.35 98.80

BLR698 (S) 97.50 -0.95 1.87 88.29 93.66 97.64

BLR699 (S) 97.46 -0.97 1.84 88.19 93.58 97.60

RKB6 (S) 97.46 -0.98 2.06 88.18 93.56 97.25

LOMON R996 (S) 97.42 -0.92 2.23 88.14 93.49 96.92

TIOXITRON (S) 97.42 -0.98 2.03 88.10 93.48 97.22

DAWN R2195 (S) 97.38 -0.93 2.07 88.02 93.37 97.04

TR81, TR90, R706, BLR895 and BLR896 effectively equal in color to control (< 0.20 DE*)

Gloss MeasurementsGloss Formula

Dry TiO2 Type 20◦ 60◦ 85◦

R706 (C) 61.8 84.5 97.0

TR81 (C) 60.8 84.2 96.9

TIOXITRON (S) 57.9 83.4 97.0

TR90 (C) 57.1 83.1 96.9

TR93 (C) 58.3 83.0 96.2

BLR699 (S) 56.1 83.0 96.4

RKB6 (S) 53.5 81.6 96.3

BLR698 (S) 52.8 80.8 96.6

BLR896 (C) 46.9 77.8 96.2

BLR895 (C) 45.7 76.8 95.5

LOMON R996 (S) 42.0 74.8 93.9

DAWN R2195 (S) 38.0 71.9 93.6

TR81, TR90, Tioxitron, BLR698, BLR699, BLR 896, RKB6, and R706 are effectively equal in gloss to control (< 5% difference to control for 60 angle which is imperceptible at high gloss levels)

All samples tested exhibited less than 10% viscosity difference to control for both KU and ICI

ViscosityGloss Formula

102

103 103 103 103

104

106 106

107

108 108

109 109

110

1.246

1.267

1.204

1.242 1.225

1.2921.308

1.279

1.3211.337

1.433

1.358

1.329

1.383

1.05

1.1

1.15

1.2

1.25

1.3

1.35

1.4

1.45

1.5

98

100

102

104

106

108

110

112

R706 TR25 TR23 TIOXITRON BLR896 LOMON R996 TR93 BLR699 BLR895 TR90 DAWN R2195 TR81 BLR698 RKB6

KU ICI

Summary and ObservationsProducts were force ranked from 1 – 11 for each test result and Guild CPO Member weighting applied

Resultant weightings were summed and sorted in rank order.

An overall rank of 1 would be an exact match to the TR93 control for all tests, and an overall rank of 11 would be the worst match

Guild CPO Member Technical DirectorsAttribute Weighting

Testing Characteristic TD 1 TD 2 TD 3 TD 4 TD 5 TD 6 TD 7 TD 8 Average % Weight

Tint Strength1 2 1 1 1 2 1 3 1.5 30%

Contrast Ratio2 3 3 2 3 1 2 1 2.1 26%

Color Readings3 4 2 3 2 3 3 2 2.8 21%

Gloss4 1 4 4 4 4 4 4 3.6 15%

Viscosity5 5 5 6 4 6 5 5 5.1 6%

Particle Size6 6 6 5

65 6 6 5.8 2%

Flat Formula ResultsWeighted by Guild CPO Technical Directors

Dry TiO2 TypeTint

StrengthContrast

Ratio Color Gloss Viscosity Particle Size Sum Rank

TR93 (C) 0 0 0 0 0 0 0

TR81 (C) 0.60 1.02 0.64 0.16 0.12 0.02 2.56

BLR896 (C) 1.49 0.51 0.43 0.47 0.40 0.18 3.48

R706 (C) 1.19 2.05 0.21 0.31 0.23 0.08 4.07

BLR699 (S) 0.89 1.28 1.29 0.47 0.52 0.13 4.58

TIOXITRON (S) 0.30 1.54 1.93 0.47 0.46 0.10 4.80

TR90 (C) 2.38 0.77 0.86 0.31 0.64 0.12 5.08

BLR698 (S) 1.79 1.79 1.50 0.31 0.06 0.07 5.52

BLR895 (C) 2.08 2.31 1.07 0.63 0.17 0.05 6.31

RKB6 (S) 3.27 0.26 2.15 0.47 0.58 0.17 6.90

DAWN R2195 (S) 2.98 2.56 1.72 0.63 0.29 0.15 8.33

LOMON R996 (S) 2.68 2.82 2.36 0.63 0.35 0.03 8.87

Gloss Formula ResultsWeighted by Guild CPO Technical Directors

Dry TiO2 TypeTint Strength

Contrast Ratio Color Gloss Viscosity Particle Size Sum Rank

TR93 (C) 0 0 0 0 0 0 0

TR81 (C) 1.49 1.28 0.64 0.63 0.12 0.02 4.18

DAWN R2195 (S) 0.30 0.26 2.15 1.57 0.29 0.15 4.72

TIOXITRON (S) 0.89 0.51 1.93 0.94 0.46 0.10 4.83

BLR698 (S) 1.19 2.05 1.29 0.47 0.06 0.07 5.13

TR90 (C) 0.60 2.82 0.43 0.79 0.64 0.12 5.40

BLR895 (C) 2.08 1.54 0.21 1.41 0.17 0.05 5.46

BLR699 (S) 2.38 1.02 1.50 0.16 0.52 0.13 5.71

R706 (C) 2.68 1.79 0.86 1.10 0.23 0.08 6.74

BLR896 (C) 1.79 2.56 1.07 1.26 0.40 0.18 7.26

LOMON R996 (S) 2.98 0.77 2.36 1.73 0.35 0.03 8.22

RKB6 (S) 3.27 2.31 1.72 0.31 0.58 0.17 8.36

Overall RankingAll Attribute Scores Included

All products were force ranked from 1-11 for each

test and Guild CPO Member weightings

applied. All tests were included regardless of

whether or not the results were significant

differences to control or not.

Flat paint results were weighted at 50% and

Gloss paint results weighted at 50% to obtain final ranking

percentages.

Dry TiO2 Type Rank %

TR93 (C) 100%

TR81 (C) 66%

TIOXITRON (S) 52%

BLR699 (S) 49%

TR90 (C) 48%

BLR698 (S) 47%

BLR896 (C) 46%

R706 (C) 46%

BLR895 (C) 41%

DAWN R2195 (S) 35%

RKB6 (S) 24%

LOMON R996 (S) 15%

Overall RankingAttributes Excluded where Equal to TR93 Control

Dry TiO2 Type Rank %

TR93 (C) 100%

TR81 (C) 90%

TR90 (C) 88%

BLR896 (C) 84%

TIOXITRON (S) 81%

R706 (C) 81%

BLR698 (S) 77%

BLR699 (S) 69%

BLR895 (C) 61%

RKB6 (S) 46%

DAWN R2195 (S) 44%

LOMON R996 (S) 25%

Tests where results were effectively equal to

control (TR93) were set to 0% difference from control and ranking percentages were

recalculated.

Flat paint results were weighted at 50% and

Gloss paint results weighted at 50% to obtain final ranking

percentages.

Criteria:• < 1% strength• < 0.6 contrast ratio• < 0.2 DE*• < 5% gloss difference• < 10% difference KU & ICI• < 10% D50 & Distribution

All products tested effectively equal for viscosity and particle size to control

-5.00

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00

Tint Strength(F)

Tint Strength(G)

Contrast Ratio(F)

Contrast Ratio(G)

Color (F) Color (G) Gloss (F) Gloss (G)

Top 5 OffsetsActual Test Results

(Not Weighted)

TR81 (C) TR90 (C) BLR896 (C) TIOXITRON (S) R706 (C)

Conclusions and Observations

1. Based upon these lots of TiO2 tested in a model flat and gloss formula, several products performed similar to the controls

2. Several Sulfate grades tested similar to Chloride grades3. All Sulfate grades tested lower for brightness/reflectance than Chloride grades4. No single product was a pure offset for the control5. The top performing products in the Flat formula were not the same as in the

Gloss formula6. Companies should determine which attributes are most important to them and

test in their own formulas

CRGI does not recommend, approve, nor endorse any product or vendor. The results of this study should not be interpreted as a recommendation by CRGI to use any product. CRGI makes no claims with regard to

performance of any product used in this study with the exception of the performance in the model formulas used in the study, and only of the attributes tested. Accelerated weathering and outdoor test fence weathering

was not a part of this study.