Contents
1 Introduction 1
1.1 General Aspects 1
1.1.1 History, Classification, Standards 1
1.1.1.1 Definition 1
1.1.1.2 History 7
1.1.1.3 Classification 8
1.1.2 Economic Aspects and Uses 8
1.1.2.1 Economic Aspects 8
1.1.2.2 Uses 9
1.1.3 New Developments 10
1.2 General Chemical and Physical Properties 11
1.2.1 Fundamental Aspects 11
1.2.1.1 Chemical Composition 11
1.2.1.2 Analysis 12
1.2.1.3 Crystallography and Spectra 14
1.2.1.4 Particle Size 14
1.2.2 Methods of Determination 17
1.2.2.1 General Methods 17
1.2.2.2 Matter Volatile and Loss on Ignition 18
1.2.2.3 Aqueous Extracts 18
1.2.2.4 Particle Size Distribution 19
1.2.2.5 Pigment Density 21
1.2.2.6 Hardness and Abrasiveness 21
1.3 Color Properties 22
1.3.1 Fundamental Aspects 22
1.3.1.1 Colorimetry 22
1.3.1.2 Kubelka–Munk Theory 27
1.3.1.3 Multiple Scattering 27
1.3.1.4 Mie’s Theory 28
1.3.2 Color Measurement 31
1.3.2.1 General 31
1.3.2.2 Methods of Determination 32
1.3.3 Tinting Strength, Lightening Power, and Scattering Power 34
1.3.3.1 Tinting Strength 35
1.3.3.2 Lightening Power 35
1.3.3.3 Relative Scattering Power 36
1.3.4 Hiding Power and Transparency 36
1.3.4.1 Hiding Power 37
1.3.4.2 Transparency 38
1.4 Stability Towards Light, Weather, Heat, and Chemicals 38
1.4.1 Fundamental Aspects 38
1.4.2 Test Methods 40
1.4.2.1 Light Stability 40
1.4.2.2 Weather Resistance 41
1.4.2.3 Heat Stability 42
1.4.2.4 Fastness to Chemicals 42
1.5 Behavior of Pigments in Binders 43
1.5.1 Fundamental Aspects 43
1.5.2 Test Methods 44
1.5.2.1 Pigment–Binder Interaction 44
1.5.2.2 Dispersing Behavior in Paint Systems 45
1.5.2.3 Miscellaneous Pigment–Binder Systems 47
References 48
2 White Pigments 51
2.1 Titanium Dioxide 51
2.1.1 Properties 51
2.1.1.1 Physical Properties 51
2.1.1.2 Chemical Properties 53
2.1.1.3 Surface Properties of TiO2 Pigments 53
2.1.2 Raw Materials 53
2.1.2.1 Natural Raw Materials 53
2.1.2.2 Synthetic Raw Materials 57
2.1.3 Production 59
2.1.3.1 Sulfate Method 59
2.1.3.2 The Chloride Process 64
2.1.3.3 Pigment Quality 66
2.1.3.4 Aftertreatment 67
2.1.3.5 Waste Management 69
2.1.4 Economic Aspects 73
2.1.5 Pigment Properties 74
2.1.5.1 Scattering Power 76
2.1.5.2 Mass-Tone (or Color) 76
2.1.5.3 Dispersion 76
2.1.5.4 Lightfastness and Weather Resistance 76
2.1.6 Analysis 77
2.1.7 Uses of Pigmentary TiO2 78
2.1.7.1 Paints and Coatings 78
2.1.7.2 Printing Inks 79
2.1.7.3 Plastics 79
2.1.7.4 Fibers 79
2.1.7.5 Paper 79
2.1.7.6 Other Areas of Application 79
2.1.8 Uses of Nonpigmentary TiO2 80
2.1.8.1 Electroceramics 80
2.1.8.2 Catalysts 80
2.1.8.3 Mixed Metal Oxide Pigments 81
2.1.8.4 UV Absorption 81
2.1.9 Toxicology 81
2.2 Zinc Sulfide Pigments 81
2.2.1 Properties 82
2.2.2 Production 83
2.2.2.1 Raw Materials 83
2.2.2.2 Lithopone 83
2.2.2.3 Sachtolith 85
2.2.2.4 Hydrothermal Process 85
2.2.2.5 Environmental Protection 86
2.2.3 Commercial Products 86
2.2.4 Uses 87
2.2.4.1 Lithopone 87
2.2.4.2 Sachtolith 87
2.2.5 Economic Aspects 88
2.2.6 Toxicology 88
2.3 Zinc Oxide (Zinc White) 88
2.3.1 Introduction 88
2.3.2 Properties 89
2.3.2.1 Physical Properties 89
2.3.2.2 Chemical Properties 90
2.3.3 Production 90
2.3.3.1 Raw Materials 90
2.3.3.2 Direct or American Process 90
2.3.3.3 Indirect or French Process 91
2.3.3.4 Wet Process 92
2.3.3.5 Aftertreatment 92
2.3.4 Quality Specifications 92
2.3.5 Uses 93
2.3.6 Economic Aspects 94
2.3.7 Toxicology and Occupational Health 94
2.3.8 Ecological Aspects 94
3 Colored Pigments 99
3.1 Oxides and Hydroxides 99
3.1.1 Iron Oxide Pigments 99
3.1.1.1 Natural Iron Oxide Pigments 100
3.1.1.2 Synthetic Iron Oxide Pigments 101
3.1.1.3 Toxicology and Environmental Aspects 108
3.1.1.4 Quality 108
3.1.1.5 Uses 110
3.1.1.6 Economic Aspects 110
3.1.2 Chromium Oxide Pigments 111
3.1.2.1 Properties 111
3.1.2.2 Production 112
3.1.2.3 Quality Specifications and Analysis 114
3.1.2.4 Storage and Transportation 114
3.1.2.5 Uses 115
3.1.2.6 Economic Aspects 115
3.1.2.7 Toxicology and Occupational Health 116
3.1.3 Mixed Metal Oxide Pigments 116
3.1.3.1 Manufacturing 117
3.1.3.2 Quality Aspects 118
3.1.3.3 Properties 119
3.1.3.4 Economic Aspects 120
3.2 Cadmium Pigments 121
3.2.1 Properties 122
3.2.2 Manufacture 122
3.3 Bismuth Pigments 123
3.3.1 Historical and Economic Aspects 123
3.3.2 Properties 124
3.3.3 Production 125
3.3.4 Uses 126
3.3.5 Toxicology 128
3.4 Chromate Pigments 128
3.4.1 Chrome Yellow 128
3.4.1.1 Production 129
3.4.1.2 Uses 130
3.4.2 Molybdate Red and Molybdate Orange 130
3.4.2.1 Production 131
3.4.2.2 Uses 132
3.4.3 Chrome Orange 132
3.4.4 Chrome Green and Fast Chrome Green 132
3.4.4.1 Production 132
3.4.4.2 Uses 133
3.4.5 Toxicology and Occupational Health 133
3.4.5.1 Occupational Health 133
3.4.5.2 Environmental Aspects 134
3.4.5.3 Classification and Labeling 134
3.5 Ultramarine Pigments 136
3.5.1 Chemical Structure 136
3.5.2 Properties 139
3.5.3 Production 140
3.5.3.1 Clay Activation 140
3.5.3.2 Blending and Heating Raw Materials 140
3.5.3.3 Oxidation 141
3.5.3.4 Purification and Refinement 141
3.5.4 Uses 142
3.5.4.1 Plastics 142
3.5.4.2 Paints 143
3.5.4.3 Printing Inks 143
3.5.4.4 Paper and Paper Coatings 143
3.5.4.5 Detergents 143
3.5.4.6 Cosmetics and Soaps 143
3.5.4.7 Artists’ Colors 143
3.5.4.8 Toys and other Articles/Materials for Children’s Use 144
3.5.5 Toxicology and Environmental Aspects 144
3.5.6 Economic Aspects 144
3.6 Iron Blue Pigments 145
3.6.1 Structure 145
3.6.2 Production 146
3.6.3 Properties 147
3.6.4 Uses 147
3.6.4.1 Printing Ink Industry 148
3.6.4.2 Agriculture 153
3.6.4.3 Paints and Coatings 154
3.6.4.4 Paper 154
3.6.4.5 Pigment Industry 154
3.6.4.6 Medical Applications 155
3.6.5 Toxicology and Environmental Aspects 155
References 157
4 Black Pigments 163
4.1 Physical Properties 164
4.1.1 Morphology 164
4.1.2 Specific Surface Area 166
4.1.3 Adsorption Properties 166
4.1.4 Density 166
4.1.5 Electrical Conductivity 166
4.1.6 Light Absorption 167
4.2 Chemical Properties 167
4.3 Raw Materials 168
4.4 Production Processes 169
4.4.1 Furnace Black Process 170
4.4.2 Gas Black and Channel Black Processes 173
4.4.3 Lamp Black Process 175
4.4.4 Thermal Black Process 175
4.4.5 Acetylene Black Process 176
4.4.6 Other Production Processes 176
4.4.7 Oxidative Aftertreatment of Carbon Black 177
4.5 Testing and Analysis 178
4.5.1 Density 179
4.5.2 Electrical Conductivity 180
4.6 Transportation and Storage 180
4.7 Uses 181
4.7.1 Rubber Blacks 181
4.7.1.1 Active Blacks 181
4.7.1.2 Semi-Active Blacks 182
4.7.1.3 Inactive Blacks 182
4.7.2 Pigment Blacks 183
4.7.2.1 Pigment Properties 183
4.7.2.2 Pigment Blacks for Printing Inks 184
4.7.2.3 Pigment Blacks for Paints 187
4.7.2.4 Pigment Blacks for Plastics 188
4.8 Toxicology and Health Aspects 190
4.8.1 Carbon Black, Soot, and Black Carbon 190
4.8.2 Safety: Fire and Explosion 191
4.8.3 Storage and Handling 191
4.8.4 Confined Space Entry 192
4.8.5 First Aid 192
4.8.6 Health 192
4.8.7 Environmental Disposal 192
References 194
5 Specialty Pigments 195
5.1 Magnetic Pigments 195
5.1.1 Iron Oxide Pigments 195
5.1.1.1 Production 195
5.1.1.2 Properties 196
5.1.2 Cobalt-Containing Iron Oxide Pigments 197
5.1.2.1 Production 197
5.1.2.2 Properties 198
5.1.3 Chromium Dioxide 199
5.1.3.1 Physical Properties 199
5.1.3.2 Production and Chemical Properties 199
5.1.3.3 Uses and Economic Aspects 199
5.1.4 Metallic Iron Pigments 200
5.1.4.1 Production 200
5.1.4.2 Properties 200
5.1.4.3 Economic Aspects 200
5.1.5 Barium Ferrite Pigments 201
5.1.5.1 Properties 201
5.1.5.2 Production 203
5.1.5.3 Magnetic Recording Properties 203
5.1.6 Toner Pigments 204
5.1.6.1 Production 205
5.1.6.2 Iron Oxide Properties 206
5.2 Anticorrosive Pigments 207
5.2.1 Introduction 207
5.2.2 Corrosion Mechanism 207
5.2.3 Classification of Anticorrosive Pigments 209
5.2.4 Traditional Lead and Chromate Pigments 211
5.2.4.1 Lead Pigments 211
5.2.4.2 Chromate Pigments 212
5.2.5 Phosphate Pigments 214
5.2.5.1 Zinc Phosphate 214
5.2.5.2 Modified Orthophosphates 215
5.2.5.3 Modified Polyphosphates 217
5.2.5.4 Other Phosphates 219
5.2.6 Other Phosphorus-Containing Pigments 219
5.2.6.1 Zinc Hydroxyphosphite 219
5.2.6.2 Iron Phosphide 219
5.2.7 Borate Pigments 219
5.2.7.1 Calcium Borate Silicates 220
5.2.7.2 Barium Metaborates 220
5.2.8 Molybdate Pigments 220
5.2.9 Ion-Exchange Pigments 221
5.2.10 Titanium Dioxide-Based Pigments 222
5.2.11 Inorganic Organic Hybrid Pigments 223
5.2.12 Zinc Cyanamide Pigments 224
5.2.13 Micaceous Iron Oxide Pigments 224
5.2.14 Zinc Pigments 226
5.2.15 Corrosion Control of Metals by Protective Coatings 227
5.2.16 Toxicology and Occupational Health 227
5.2.16.1 Occupational Health 228
5.2.16.2 Environmental Aspects 228
5.2.16.3 Classification and Labeling 229
5.3 Effect Pigments 230
5.3.1 Special Effect Pigments 230
5.3.1.1 Introduction 230
5.3.1.2 Optical Principles of Pearl Luster and Interference Pigments 232
5.3.1.3 Substrate-Free Pearl Luster Pigments 235
5.3.1.4 Pigments Formed by Coating of Substrates 237
5.3.2 Metal Effect Pigments 252
5.3.2.1 Definition 252
5.3.2.2 History and Technology 252
5.3.2.3 Characterization 253
5.3.2.4 Optical Principles 255
5.3.2.5 Measurements 258
5.3.2.6 Applications 258
5.4 Transparent Pigments 261
5.4.1 Transparent Iron Oxide Pigments 262
5.4.1.1 Manufacture 263
5.4.1.2 Properties and Application 264
5.4.2 Transparent Cobalt Blue 266
5.4.3 Transparent Functional Pigments 267
5.4.3.1 Transparent Titanium Dioxide 267
5.4.3.2 Transparent Zinc Oxide 268
5.5 Luminescent pigments 269
5.5.1 Introduction 269
5.5.2 Historical Overview 269
5.5.3 Luminescence Mechanisms 271
5.5.3.1 Center Luminescence 272
5.5.3.2 Charge Transfer Luminescence 275
5.5.3.3 Donor–Acceptor Pair Luminescence 276
5.5.3.4 Long-Afterglow Phosphors 276
5.5.4 Excitation Mechanism 277
5.5.4.1 Optical Excitation of Luminescence and Energy Transfer 277
5.5.4.2 Electroluminescence 278
5.5.4.3 Excitation with High Energy Particles 279
5.5.5 Application of Luminescent Materials 280
5.5.5.1 Application Areas and Phosphors Used 280
5.5.5.2 Energy Efficiency Considerations of Important Luminescent
Devices 284
5.5.6 Preparation of Luminescent Materials 284
5.5.7 Outlook 286
5.5.7.1 Cascade Phosphors 286
5.5.7.2 Quantum Dots 288
References 289
Index 297