Pigment TiO 2 TiO 2 End-Use Markets Quality-of-life product, no - - PowerPoint PPT Presentation

Pigment – TiO2

Paints & Coatings 59% Paper & Specialties 16% Plastics 25%

TiO2 End-Use Markets

Quality-of-life product, no effective substitutes Unsurpassed opacifying & whitening properties

• Paints & coatings, plastics, paper, consumer products & specialties
• Semi-specialty, differentiated & frequently customized

TiO2 Demand By End-Use Market Total Market Size: 5.5 MM MT

Titanium Dioxide TiO2

Technology

4

Why Use TiO2?

• Achieve opacity
• Obtain a given color
• Provide UV protection

Titanium Dioxide

Rutile Anatase

Crystal Phase Tetragonal Tetragonal Refractive Index 2.71 2.55 Density (g/cm3) 4.2 4.0 Hardness (Moh’s Scale) 6-7 5.5-6

Reflectivity

Refractive Index Relative Reflectivity Rutile 2.71 100 Anatase 2.55 80 Zinc oxide 2.01 25 Kaolin 1.56 0.5

In organic binder with R.I. of 1.5

 − −

Natural Rutile , Synthetic Rutile, Slag, Ilmenite Coke Chlorine

Chlorination

TiCl4

Purification

Byproduct

Oxidation TiO2 Rutile or Anatase

Oxygen

Chlorine Recycle

Ilmenite , Slag, Sulfuric Acid

Digestion Reduction

Scrap Iron

Clarification Crystallization

TiOSO

4

Solution Byproduct

Hydrolysis

Nuclei

Filtration Calcination Milling Surface Treatment

Drying and Grinding

Packaging

Finished TiO2 Pigment

TiO2 Rutile

Chloride Process Sulfate Process Finishing

TiO2 is produced using titanium containing ores such as Ilmenite and rutile  Ilmenite: More plentiful than rutile but has a lower TiO2 content (approximately 50% versus approximately 94% for rutile). Ilmenite is usually upgraded to a higher TiO2 content  Rutile: Natural occurring titanium ore found in ancient mineral sand deposits containing high concentrations of titanium There are two major processes used to produce TiO2:  Chloride process: A high-temperature process that produces TiO2 by reacting titanium ores with chlorine gas  Sulfate process: A wet chemical process that produces TiO2 by reacting titanium ores with concentrated sulfuric acid

TiO2 Production Process

TiO2 Production Process

10

Sulfate process advantages

 Batch process: capacity additions can be made in small increments  Feedstocks with lower purity can be tolerated; however, waste disposal concerns are an issue  Preferred for producing pigment in specialty applications such as food, catalysts, and inks  Easier process to operate

Chloride process advantages

Tronox is well positioned as an industry leader with 100% chloride technology in all three regions

Source: (1) Internal estimates

 Produces a superior intermediate product, which is purer and has a tighter range of particle size providing an excellent base pigment suitable for a wide range of properties  Less labor and energy intensive  Historically cash costs for the chloride process are approximately 15% lower than those for the sulfate process (1)  The chloride process is believed to be more environmentally friendly compared to the sulfate process due to higher purity feed stocks and lower energy requirements

2013 production process mix (1)

12% 60% 24% 88% 100% 88% 40% 76% 100% 12%

0% 20% 40% 60% 80% 100%

DuPont Cristal Huntsman Kronos Tronox Other Sulfate Chloride

Base Pigment

• Sulfate Process

–Originally developed in 1920’s –Produce anatase or rutile –Less expensive feedstocks

• Chloride Process

–Developed in the 1950’s –Produce rutile only –Lower contaminants –Higher brightness

Chloride Process

• Chlorination of Raw or Synthetic Rutile
• Purification of TiCl4
• Oxidation of TiCl4
• Wet Milling/Surface Treatment
• Filtration/Washing/Drying
• Micronization

TRONOX Confidential Information

Manufacturing Process of TiO2

TiO TiO2

2 Chloride Process

Chloride Process

ORE STORAGE SURFACE TREATMENT CHLORINE CAR PACKER WAREHOUSE T0 ATMOSPHERE SLURRY PRODUCTION SOLIDS SEPARATION FILTRATION WASTE SOLIDS el1499 CHLORINATOR COKE O2 N2 RECYCLE CHLORINE PURE TiCl4 STORAGE CONDENSATION PURIFICATION STILL GAS PURIFICATION BURNER OXYGEN MILLING DRYING RECYCLE CHLORINE PIGMENT & GAS SEPARATION SLURRY TANK TiO2 WATER WET MILLING RAW PIGMENT CRUDE TiCl4 STORAGE

TRONOX Confidential Information

Manufacturing Process of TiO2

TiO TiO2

2 Chloride Process

Chloride Process

ORE STORAGE SURFACE TREATMENT CHLORINE CAR PACKER WAREHOUSE T0 ATMOSPHERE SLURRY PRODUCTION SOLIDS SEPARATION FILTRATION WASTE SOLIDS el1499 CHLORINATOR COKE O2 N2 RECYCLE CHLORINE PURE TiCl4 STORAGE CONDENSATION PURIFICATION STILL GAS PURIFICATION BURNER OXYGEN MILLING DRYING RECYCLE CHLORINE PIGMENT & GAS SEPARATION SLURRY TANK TiO2 WATER WET MILLING RAW PIGMENT CRUDE TiCl4 STORAGE

Surface Finishing

Wet Milling / Sandmilling

• Raw TiO2 dispersed in water
• Sand milled to breakdown agglomerates
• Classified to remove remaining oversized particles

TRONOX Confidential Information

Sandmilling

• Objective: To narrow the

particle size distribution and reduce the mean particle diameter in order to optimize both optical and physical properties.

0.1 1 10 5 10 15 20 25

Weight Percent Microns

After milling Before milling Particle Size Distribution

TRONOX Confidential Information

Sandmilling - A Key First Step

Agglomerated raw pigment Sandmilling NO Sandmilling Treatment, filtration & drying Treatment, filtration & drying Micronization Micronization Exposed TiO2 surfaces

Finishing

DRYER FILTRATION PACKAGING TREATMENT CLASSIFICATION MILLING MILLING RAW PIGMENT FINISHED PIGMENT DISTRIBUTION TREATMENT CHEMICALS

Surface Treatment

• Consists of the Application of hydrous oxides of:

–Silica –Titania –Zirconia –Alumina

• TiO2 particles are treated on the surface to obtain the

maximum possible value from the pigment for the customer.

• This value is expressed in terms of:

–Dispersion –Hiding Power –Tinting Strength –Gloss –Durability

Why is Surface Treatment Necessary?

TRONOX Confidential Information

Surface Treatment

• Basic Chemistry:

2NaAlO2 + H2SO4 + 2H2O

2Al(OH)3 + Na2SO4

Na2SiO3 + H2SO4 + H2O Si(OH)4 + Na2SO4 Zr(SO4)2 + 4NaOH Zr(OH)4 + 2Na2SO4

Precipitate onto the surface of the TiO2

Silica Treatment

• Most frequently used to promote:

–Durability –Dry Hiding

• Effect depends on deposition conditions

–Slow addition at basic pH = durability –Quick addition at neutral or acid pH = dry hide

• Reduces gloss

Silica Treatment

Dense Silica

Silica Treatment & Durability

• When added slowly under alkaline conditions, the

silica coating:

–Forms dense impervious shell around the TiO2 particles –Minimizes direct contact between TiO2 surface and vehicle –Inhibits photocatalytic degradation of paint vehicle

TRONOX Confidential Information

Value of coating the pigment

Durability

uv light

Free radicals escape to react with resin or polymer

UNTREATED TiO2

uv light

TREATED TiO2

Free radicals trapped beneath pigment coating Coating of Dense SiO2 & Al2O3

Resin

.OH + .O2H

Or free radical re- absorbed by coating

• f ZrO2

Silica Treatment and Dry Hiding

• When added rapidly under neutral or acidic

conditions, the silica coating:

–Forms silica gel which only loosely coats the pigment and maximizes air entrapment which in turn promotes high dry-hiding

Fluffy Silica

Zirconia Treatment

• Although acknowledged for several decades for

its unique properties, it is only in last few years that zirconia has attained the level of usage on TiO2

• Applied principally for durability
• Mechanism electron-hole trap

Alumina Treatment

• Applied almost universally
• Improves dispersibility and gloss
• Helps to maximize hiding power by promoting

inter-particle spacing

• Can promote durability (co-burned)
• External boehmite (AlOOH) coating provides large

number of hydroxyl sites for rapid adsorption of

• rganic milling aids and resins

Organic Treatment

• Purpose

–Improve compatibility & dispersion –Reduce water absorption –Reduce agglomeration during storage

• Organic treatments used include

–Polyhydroxy compounds –Amines , amine salts & amine soaps –Silicones & silanes

• Not all pigments have organic treatment

Final Milling / Micronization

• Typically fluid energy mill
• Reduces agglomeration from treatment and

drying resulting to optimizing dispersibility and

• ptical properties of finished pigment
• Intensity depends on

–Treatment –End use

• High for very good gloss
• Low for dry hide grades

–Previous milling

TRONOX Confidential Information

The Effect of Particle Size on Opacity

2 4 6 8 10 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Particle Diameter (µm) Relative Opacity

Effect of Particle Size on Gloss

Frequency

0.5 1.0 1.5 2.0 2.5 3.0

Particle diameter [µm]

3.5

Schematic particle size distributions of 4 pigments and their gloss 67 73 78 81 20° gloss in solvent paint

TRONOX Confidential Information

Particle Size vs. Hiding Power, Gloss & Dispersion

Titanium Dioxide Particle

HO

TiO2 Core

Inner Coating

• f Titania, Silica,
• r Zirconia

Outer Coating

• f Alumina

Organic Moieties

Hydroxyl Groups

Summary

Interior Gloss Grade Alumina Interior Flat Grade Fluffy Silica, Alumina Universal Grade Zirconia, Dense Silica, Alumina Durable Grade Dense Silica, Alumina

Titanium Dioxide

Tronox Presentation Title 39

Ilmenite Ore TRONOX TiO2

TRONOX Titanium Dioxide Operation

Tronox Presentation Title 40

TRONOX Titanium Dioxide Operation

Tronox Presentation Title 41

TRONOX TiO2 for Coatings Quality Control Tests

42

Standard QC Tests on Finished TiO2 for Coatings

• Brightness CIE L*
• Color CIE b*
• Waterborne Tint Strength, %
• Waterborne Tint Tone, b
• Waterborne Gloss @60
• Alkyd Dispersion/ Cleanliness, micron/ nib count
• Residue @325 mesh
• pH
• Specific Resistance, kohms.cm
• Oil Absorption, grams oil / 100 g pigment
• Chemical Analysis

EI = CI x IS

• Tronox’s quality performance measurement for pigment

and basis for STAR quality metric –Highest weighted metric for Operations (50%).

• Two part metric

–Consistency Index: how close performance is to target relative to the spec range –% In-specification: percent of product within acceptable range

Plant Quality Metrics Quality Excellence Index

Tronox TiO2 Grades for Coatings

45

TRONOX Grades for Coatings

Application Surface Treatment % TiO2 CR-800E Electro coat, high resistivity, high gloss, blue tint tone Alumina 96 CR-813/ CR-813S Flat/ High P.V.C. Alumina & Silica (gel) 86 CR-828 Universal, highest gloss blue tint tone, med. durability Alumina, & zirconia 95 CR-826/ CR-826S Universal, high gloss yellow t.tone, high durability Alumina & dense silica 93 CR-880 Ultra-high durability Yellow tint tone Alumina & dense silica 91

Typical Properties of Tronox Grades

*pH *Specific Resistance kohms.cm *Oil Absorption g / 100g Particle Size, µ (TEM) CR-800E 7.7 33 15 0.19 CR-813 8.1 7 36 0.21 CR-826 8.7 11 18 0.20 CR-828 7.5 10 18 0.19 CR-880 7.9 7 19 0.23

*Based on QC 2011Average

Optical Properties - Tronox Grades

Brightness (CIE L*) Color (CIE b*) *W/B Tint Strength (%) *W/B Tint Tone (b) *W/B Gloss @60 CR-800E 95.52 0.42 104

• 5.1

71 CR-826 95.28 0.78 107

• 4.8

64 CR-828 95.46 0.50 107

• 5.0

67 CR-880 95.11 0.78 107

• 4.7

58

*Based on QC 2011 Average

Gloss of TRONOX Grades in Latex Paints

10 20 30 40 50 60 70 80 QC W/B Gloss* (60°) Semi-Gloss (60°) Eggshell (60°) Flat (85°) CR-826 CR-828 CR-880 CR-813

Tronox Presentation Title 49

Gloss

Gloss of TRONOX Grades in Solvent Based Paints

10 20 30 40 50 60 70 80 90 QC W/B Gloss*

• Ext. Alkyd

Paint, 20°

• Ext. Alkyd

Paint (aged), 20° NC Lacquer, 60° NC Lacquer, 20° CR-826 CR-828 CR-880 CR-813

Tronox Presentation Title 50

Gloss @60°

Brightness of TRONOX Grades in Latex Paints

94 94.5 95 95.5 96 96.5 97 97.5 98 98.5 99 99.5 QC Dry Pellet* Semi-Gloss Eggshell Flat CR-826 CR-828 CR-880 CR-813

Tronox Presentation Title 51

Brightness, L*

Color/ Masstone of TRONOX Grades in Latex Paints

0.00 0.50 1.00 1.50 2.00 2.50 QC Dry Pellet Semi-Gloss Eggshell Flat CR-826 CR-828 CR-880 CR-813

Tronox Presentation Title 52

Color / Masstone b*

Tint Strength of TRONOX Grades in Architectural Paints

70 75 80 85 90 95 100 105 110 115 120

QC W/B Gloss* S/G Latex Satin Latex Flat Latex Ext. Alkyd Gloss

CR-826 CR-828 CR-880 CR-813

Tronox Presentation Title 53

Tint Strength, %K/S

Tint Tone of TRONOX Grades in Latex Paints

• 6
• 4
• 2

2 4 QC W/B Tint Tone Semi-Gloss Eggshell Flat CR-813 CR-880 CR-828 CR-826

Tronox Presentation Title 54

Tint Tone, b

55

Tint Strength Advantage of CR-813 over Universal Grade

CR-813 vs. CR-826 in Flat Latex Paint

56

Tronox TiO2 Grades And Competition in Coatings

57

Properties pH Specific Resistance kohms.cm Oil Absorption g/100g Acrylic Brightness, L* Acrylic Color, b* Latex Tint Strength, % Alkyd Tint Tone, b CR-828 7.5 10 18 95.6 0.4 105

• 4.08

Comp A 8.1 11 19 95.8 0.6 103

• 3.86

Comp B 7.3 13 18 95.6 0.7 104

• 3.98

20 25 30 35 40 45 50 55 60 65 70

Acrylic Gloss Latex Gloss Gloss @ 60° CR-828 Comp A Comp B

Interior High Gloss Grades

CR-826

2011 Avg

• Comp. A
• Comp. B
• Comp. C
• Comp. D

TiO2 (min.), % 93 93* 95* 93* 93.5* Surface Treatment alumina silica alumina silica alumina zirconia alumina silica zirconia Alumina silica zirconia pH 8.7 8.2* 7.5* 8.0 8.0 S.Resistance kohms.cm 11 10* 12 13 20 Oil Absorption g/100g 18 18 17 18 17* Acrylic Brightness, L* 95.3 95.6 95.6 95.6 95.7 W/B Tint Tone, b

• 4.8
• 4.9
• 4.9
• 4.9
• 4.8

Universal Grades – Interior/ Exterior

*Data from TDS

60 70 80 90 100 110 120

54% PVC PVA Flat (1 lb TiO2/ gal) 39% PVC Acrylic Satin (3 lb TiO2/gal) 22% PVC W/B Gloss (2.6 lb TiO2/gal) 36% PVC Vinyl Acrylic S/G (1.5 lb TiO2/gal) QC W/B Gloss

Tint Strength, %

Tint Strength in Various Latex Formulas

CR-826 Comp A Comp B Comp C Comp D

Universal Grades – Interior/ Exterior

TRONOX CONFIDENTIAL Information contained herein is to be considered of a proprietary and confidential nature, and may not be used other than for the benefit of TRONOX and its affiliates nor disclosed to any

• ther person without prior authorization.
• 10

10 20 30 40 50 60 70 80

22% PVC W/B Gloss (2.6 lb TiO2/gal) 36% PVC Vinyl Acrylic S/G (1.5 lb TiO2/gal) QC W/B Gloss

Gloss

Gloss @ 60° in Various Formulas

CR-826 Comp A Comp B Comp C Comp D

Universal Grades – Interior/ Exterior

0.5 1 1.5 2 2.5 3 880 1760 2640 3520 4400

ΔE Exposure Time, hours

22% PVC Acrylic Gloss- Fading, ΔE

CR-826 Comp A Comp B Comp C Comp D

Universal Grades – Interior/ Exterior Xenon Arc Weathering

10 20 30 40 50 60 70 80 90 880 1760 2640 3520 4400

% Gloss Loss @ 60° Exposure Time, hours

22% PVC Acrylic Gloss, % Gloss Loss @ 60°

CR-826 Comp A Comp B Comp C Comp D

Universal Grades – Interior/ Exterior Xenon Arc Weathering

1 2 3 4 5 6 7 8 880 1760 2640 3520 4400

ΔE Exposure Time, hours

39% PVC Acrylic Satin- Fading, ΔE

CR-826 Comp A Comp B Comp C Comp D

Universal Grades – Interior/ Exterior Xenon Arc Weathering

0.0 2.0 4.0 6.0 8.0 10.0 12.0 3080 3520 3968

Chalk, ASTM Rating Exposure Time, hours

36% PVC Vinyl Acrylic S/G- Chalk, ASTM Rating

CR-826 Comp A Comp B Comp C Comp D

0.0 2.0 4.0 6.0 8.0 10.0 12.0 3968 4400 4840

Chalk, ASTM Rating Exposure Time, hours

22% PVC Acrylic Gloss- Chalk, ASTM Rating

CR-826 Comp A Comp B Comp C Comp D

0.0 2.0 4.0 6.0 8.0 10.0 12.0 3968 4400 4840

Chalk, ASTM Rating Exposure Time, hours

39% PVC Acrylic Satin- Chalk, ASTM Rating

CR-826 Comp A Comp B Comp C Comp D

Universal Grades – Interior/ Exterior Xenon Arc Weathering

South Florida Exposure High Gloss Latex Chalk, Y

3 6 9 12 6 12 18 24 Months Comp C Comp A CR-828 CR-826

Tint Strength in Latex Paint Formulations

Tronox Presentation Title 68

88 90 92 94 96 98 100 102 104 106 36 54 22 39 Tint Strength, % % PVC CR-826 Competitor A Competitor B Competitor C Competitor D g TiO2/ L 180 120 312

Acrylic PVA

TRONOX CONFIDENTIAL Information contained herein is to be considered of a proprietary and confidential nature, and may not be used other than for the benefit of TRONOX and its affiliates nor disclosed to any other person without prior authorization.

1 2 3 4 5 6 7 8 12 24 36 48 Chalk, Y Exposure Time, Months

Acrylic Semi-Gloss Latex- Chalk, Y Reflectance

CR-826 Competitor A1 Competitor A2 Competitor A3

B E T T E R

45º South Florida Exposure

TRONOX CONFIDENTIAL Information contained herein is to be considered of a proprietary and confidential nature, and may not be used other than for the benefit of TRONOX and its affiliates nor disclosed to any other person without prior authorization.

0.0 1.0 2.0 3.0 4.0 5.0 6.0 12 24 36 48 Chalk, Y Exposure Time, Months

Exterior Latex with ZnO- Chalk, Y Reflectance

CR-826 Comp A1 Comp A2 Comp A3

45° South Florida Exposure

B E T T E R

TRONOX CONFIDENTIAL Information contained herein is to be considered of a proprietary and confidential nature, and may not be used other than for the benefit of TRONOX and its affiliates nor disclosed to any

• ther person without prior authorization.

0.0 1.0 2.0 3.0 4.0 5.0 6.0 48 Months Chalk, Y Acrylic Semi-Gloss Latex- Chalk CR-826 Comp A1 Comp A2 Comp A3

45° South Florida Exposure

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 48 Months Chalk, Y Exterior Latex with ZnO- Chalk CR-826 Comp A1 Comp A2 Comp A3

Coil System

Grade/ Competitor L* a* b* Tint Strength (%) Gloss @ 60° CR-880 92.1

• 1.44
• 0.91

100 21 A1 92.2

• 1.49
• 0.89

99 18 A2 92.4

• 1.51
• 1.07

97 20 B 92.6

• 1.53
• 1.06

101 27

Two Component Acrylic Urethane

Grade/ Competitor L* a* b* Tint Strength (%) Gloss @ 60° CR-880 75.7

• 15.40
• 25.56

100 92 Comp A1 75.0

• 15.63
• 26.06

94 92 Comp A2 76.3

• 15.25
• 25.25

106 92 Comp B2 74.8

• 15.82
• 26.34

92 91

Super Durable Grades – Exterior

TRONOX CONFIDENTIAL Information contained herein is to be considered of a proprietary and confidential nature, and may not be used other than for the benefit of TRONOX and its affiliates nor disclosed to any other person without prior authorization.

10 20 30 40 50 60 70 5 min 10 min 15 min 20 min

Hegman Reading, µm Dispersion Time

Medium Alkyd System

CR-880 Comp A1 Comp A2 Comp B

Super Durable Grades – Exterior Dispersibility

45 South Florida Exposure Acrylic 2K Urethane, 20° Gloss Retention

20° Gloss Retention for Super Durable Grades- Washed Panels

0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 12 18 24 30

Exposure (months) Gloss Retention (%)

CR-880

• Comp. A
• Comp. B
• Comp. D
• Comp. A1

TR-O-060-37

TRONOX CONFIDENTIAL Information contained herein is to be considered of a proprietary and confidential nature, and may not be used other than for the benefit of TRONOX and its affiliates nor disclosed to any other person without prior authorization.

45 South Florida Exposure Acrylic 2K Urethane, 60° Gloss Retention

60° Gloss Retention for Super Durable Grades- Washed Panels

40% 50% 60% 70% 80% 90% 100% 12 18 24 30

Exposure (months) Gloss Retention (%)

CR-880

• Comp. A
• Comp. B
• Comp. D
• Comp. A1

TR-O-060-37

45 South Florida Exposure Acrylic 2K Urethane, Total Color Change (ΔE)

Total Color Change (ΔE) for Super Durable Grades- Washed Panels

1 1 2 2 3 3 12 18 24 30

Exposure (months) Total Color Change (ΔE)

CR-880

• Comp. A
• Comp. B
• Comp. D
• Comp. A1

TR-O-060-37

Outdoor Durability @ 45° South Florida

2 4 6 8 10 12

Coil Coating after 36

• mos. Exposure

2K Acrylic Urethane after 36 mos. Exposure Primid Coating after 48

• mos. Exposure

Chalk, ASTM Rating

ASTM Chalk Rating Comparison in Various Formulations

CR-880 Comp A1 Comp A2 Comp B

Comp A/ A1 Comp A2 Comp B Comp C Comp D CR-826 R-706 RCL-595 K 2310 TR-93 CR-828 R-900 RCL- 9 CR-880 R-960 TS 6200 RCL-696

APPENDIX

Thank You For Your Continued Support and Business.