Industrial Chemistry of Oxides for Emerging Applications

Valuable insights into the extraction, production, and properties of a large number of natural and synthetic oxides utilized in applications worldwide from ceramics, electronic components, and coatings

This handbook describes each of the major oxides chronologically—starting from the processes of extraction of ores containing oxides, their purification and transformations into pure alloyed powders, and their appropriate characterization up to the processes of formation of 2D films by such methods as PVD, CVD, and coatings by thermal spraying or complicated 3D objects by sintering and rapid prototyping. The selection of oxides has been guided by the current context of industrial applications. An important point that is considered in the book concerns the strategic aspects of oxides. Some oxides (e.g. rare earth ones) become more expensive due to the growing demand for them, others, because of the strategic importance of countries producing raw materials and the countries that are using them.

Industrial Chemistry of Oxides for Emerging Applications provides readers with everything they need to know in 7 chapters that cover: technical and economical importance of oxides in present and future; fundamentals of oxides manufacturing; extraction, properties, and applications of Al₂O₃; extraction, properties, and applications of ZrO₂; synthesis, properties, and applications of YBaCu₂O_7x; extraction, properties, and applications of TiO₂; and synthesis, properties, and application of hydroxyapatite. 

• Presents the extraction, production, and properties of a large fraction of oxides applications worldwide, both natural as well as synthetic multi‐oxides
• Covers a very important segment of many industrial processes, such as refractories and piezoelectric oxides—both applications constituting very large market segments
• Developed from a lecture course given by the authors for over a decade

Industrial Chemistry of Oxides for Emerging Applications is an excellent text for university professors and teachers, and graduate and postgraduate students with a solid background in physics and chemistry.

LECH PAWŁOWSKI, PhD, is a Professor at The University of Limoges in France. He was awarded the honorific title of Dr.- Ing. E.h. by Technical University of Chemnitz in 2013 (Germany) and inducted into the Thermal Spray Hall of Fame in 2015.

PHILIPPE BLANCHART, PhD, is Emeritus Professor at Limoges University in France. He is also consultant in science and technology of mineral materials for technological survey, consulting and project management in industries, and technological training.

Preface xiii

Acknowledgments xvii

Abbreviations and Symbols xix

1 Technical and Economic Importance of Oxides 1
Lech Pawowski

1.1 Industrial Sectors in Development 1

1.1.1 Mechanical Applications of Oxides 1

1.1.1.1 Al2O3 3

1.1.1.2 ZrO2 3

1.1.2 Application of Oxides in Electrical and Electronic Engineering 4

1.1.3 Oxides for High-temperature Applications 7

1.1.4 Biomedical applications of oxides 9

1.2 Reserves, Availability and Economic Aspects of Oxides and their Ores 10

1.2.1 Al2O3 10

1.2.2 ZrO2 11

1.2.3 TiO2 12

1.2.4 Rare earth oxides: Y2O3 and CeO2 13

1.2.5 BaO 17

1.2.6 Cu2O 17

1.2.7 CaO 18

1.2.8 P2O5 19

References 20

2 Fundamentals of Oxide Manufacturing 25
Lech Paw³owski

2.1 Introduction 25

2.1.1 Principal Manufacturing Processes 25

2.1.2 Oxide Powders 27

2.1.3 Major Phenomena in Manufacturing 27

2.2 Fundamentals of Selected Processes related to Oxide Manufacturing 28

2.2.1 Introduction 28

2.2.2 Fundamentals of Reactions in Gaseous Phase 28

2.2.2.1 Types of Reaction 28

2.2.2.2 Thermodynamic Calculations 29

2.2.2.3 Gas in Motion 30

2.2.2.4 Thermodynamics of Condensation 34

2.2.3 Fundamental Phenomena in Solutions 36

2.2.3.1 Introduction 36

2.2.3.2 Diffusion 36

2.2.3.3 Brownian Motion and Stokes’ Law 37

2.2.4 Fundamental Phenomena in Suspensions 38

2.2.4.1 Introduction 38

2.2.4.2 Forces and Energies in Suspension 39

2.2.4.3 Characterization of Suspensions 43

2.2.4.4 Gelation 47

2.2.5 Characterization of Powders 48

2.2.5.1 Size and Shape 48

2.2.5.2 Chemical and Phase Composition 49

2.2.5.3 External and InternalMorphology 53

2.2.5.4 Apparent Density and Flowability 53

2.3 Selected Oxide Powder Production Methods 54

2.3.1 Introduction 54

2.3.2 Granulation of Powders 55

2.3.2.1 Direct Granulation 55

2.3.2.2 Spray Drying 56

2.3.3 High-temperature Synthesis of Powders 60

2.3.3.1 Sintering and Melting 60

2.3.3.2 Self-propagating High-temperature Synthesis 61

2.3.3.3 Mechanofusion 63

2.3.4 Synthesis of Powders from Solutions 63

2.3.4.1 Sol–Gel 64

2.3.4.2 Synthesis by Reaction of Liquids (Wet Precipitation) 64

2.3.5 Powder Synthesis by CVD 64

2.4 Manufacturing Objects in 2D: Films and Coatings 70

2.4.1 Introduction 70

2.4.2 Chemical Methods of Thin Film Deposition 71

2.4.2.1 Sol–Gel 71

2.4.2.2 Electrolytic anodization 74

2.4.3 Physical Methods of Thin Film Deposition 76

2.4.3.1 CVD Methods 76

2.4.3.2 PVD Methods 79

2.4.4 Methods of Coating Deposition 86

2.4.4.1 Thermal Spraying 86

2.4.4.2 Bulk Coatings Methods 96

2.5 Manufacturing Objects in 3D 102

2.5.1 Introduction 102

2.5.2 Forming 103

2.5.3 Sintering 106

2.5.4 Rapid Prototyping 114

3 Extraction, Properties and Applications of Alumina 125
Lech Paw³owski

3.1 Introduction 125

3.2 Reserves of Bauxite and Mining 125

3.3 Methods of Obtaining Alumina 127

3.3.1 Bayer Process 127

3.3.1.1 Chemical Backgrounds 128

3.3.1.2 Technology of the Bayer Process 128

3.3.1.3 Waste Management 130

3.3.2 Pure Alumina Powder Synthesis 131

3.3.3 Alumina Recovery from Coal Ashes 132

3.3.3.1 Sintering Process 134

3.3.3.2 Leaching Process 135

3.4 Properties of Alumina 135

3.4.1 Thermodynamical and Chemical Properties of Monocristalline Alumina 137

3.4.2 Properties of Alumina 137

3.4.2.1 Thermophysical Properties of Alumina 138

3.4.2.2 Self-diffusion Data of Alumina 139

3.4.2.3 Electrical Properties of Alumina 139

3.4.2.4 Dielectric Properties of Alumina 140

3.4.2.5 Mechanical Properties of Alumina 142

3.5 Methods of Alumina Functionalizing 145

3.5.1 Introduction 145

3.5.2 Alumina in 2D: Films and Coatings 145

3.5.2.1 Chemical Methods of Alumina Film Deposition 145

3.5.2.2 Atomistic Methods of Alumina Films Deposition 146

3.5.2.3 Granular Methods of Alumina Coating Deposition 147

3.5.3 Alumina in 3D 147

3.5.3.1 Forming 147

3.5.3.2 Sintering 147

3.5.3.3 Laser Machining 149

3.6 Applications of Alumina in Different Industries 150

3.6.1 Mechanical Engineering 150

3.6.1.1 Thread Guides in Textile Industries 150

3.6.1.2 Armor 151

3.6.1.3 Cutting Tools 151

3.6.2 Electronic and Electrical Applications 152

3.6.2.1 Substrates for Microelectronics 153

3.6.2.2 Corona Rolls 153

3.6.3 Biomedical 154

3.6.3.1 Hip Prosthesis 154

3.6.3.2 Dental Prostheses 155

3.6.3.3 Other Biomedical Applications 155

3.6.4 Chemical and Thermal Industries 155

3.6.4.1 Catalyst Supports 156

3.6.4.2 Heat Exchanger 156

3.6.5 Emerging Applications 156

Questions 157

References 158

4 Extraction, Properties and Applications of Zirconia 165
Philippe Blanchart

4.1 Introduction 165

4.2 World Reserves of Ores and Mining Industry 165

4.3 Metallurgy of Zirconia 167

4.3.1 Chlorination andThermal Decomposition 167

4.3.2 Alkaline Oxide Decomposition 168

4.3.3 Lime Fusion 168

4.3.4 Thermal Decomposition of Zircon in a Plasma 168

4.4 Properties of Zirconia 169

4.4.1 Monocrystal 169

4.4.2 Partially and Fully Stabilized Zirconia Powders 170

4.4.3 Binary System ZrO2–MgO 171

4.4.4 Binary System ZrO2–CaO 172

4.4.5 Binary System ZrO2–Y2O3 173

4.4.6 Binary system ZrO2–CeO2 174

4.5 Physical Properties of Zirconia 175

4.5.1 Dilatation Coefficient with Temperature 175

4.5.2 Ionic Conductivity 176

4.5.3 Mechanical Properties and Toughness 177

4.5.4 Corrosion Resistance inWater Environment 179

4.5.5 Zirconia Composite Ceramics 181

4.6 Ceramic Sintering 182

4.6.1 Zirconia Sintering 182

4.6.2 Sintering of Alumina–Zirconia Composite Ceramics: 186

4.7 Industrial Applications of Zirconia 189

4.7.1 Biomedical 189

4.7.2 Solid Electrolyte 194

4.7.3 Zirconia Sensor 197

4.7.4 Thermal Barrier Coatings 199

4.8 Future Trends of Zirconia Materials 204

Questions 206

References 206

5 Synthesis, Properties and Applications of YBa2Cu3O7−x 211
Lech Paw³owski

5.1 Introduction 211

5.2 Phase Diagram 212

5.3 Methods of YBa2Cu3O7−x Powder Manufacturing 213

5.3.1 Reactive Sintering 214

5.3.2 Synthesis of Powder from Solutions 215

5.3.2.1 Sol–gel 215

5.3.2.2 Wet PrecipitationMethods 215

5.3.2.3 Freeze-dryingMethod 216

5.4 Superconductivity of YBa2Cu3O7−x 216

5.4.1 Fundamentals of Superconductivity 217

5.4.2 High-temperature Superconductors 220

5.5 Properties of YBCO 221

5.6 Methods of YBa2Cu3O7−x Functionalizing 221

5.6.1 Introduction 221

5.6.2 YBCO in 2D: Films and Coatings 221

5.6.2.1 Thin Films 222

5.6.2.2 Thick Coatings byThermal Spraying 229

5.6.3 YBCO in 3D 232

5.6.3.1 Manufacturing ofWires 235

5.6.3.2 Manufacturing of Discs, Rings and Parallelepipeds 235

5.7 Industrial Applications of YBa2Cu3O7−X 239

5.7.1 Superconducting Cables 239

5.7.2 Fault Current Limiter 242

5.7.3 Magnetic Levitation Devices 243

5.7.4 High-power Superconducting Synchronous Generators 244

5.7.5 Magnetic Energy Storage Systems 245

5.7.6 Superconducting Transformers 246

5.7.7 YBCO Superconductors for Magnets in Tokamak Devices 246

5.7.8 Other Applications 247

References 247

6 Extraction, Properties and Applications of Titania 255
Philippe Blanchart

6.1 Introduction 255

6.2 World Reserves and Mining Industry 255

6.3 Structural Characteristics of Titania 259

6.3.1 Anatase 259

6.3.2 Rutile 259

6.3.3 Brookite 260

6.3.4 TiOx phases 261

6.3.5 Structural Transformation of Anatase to Rutile 261

6.3.6 Synthesis of TiO2 263

6.4 Properties of Titanium Dioxide 265

6.4.1 General Physical Properties 265

6.4.2 General Chemical Properties 265

6.4.3 Structural Properties 266

6.4.4 Defect Chemistry of TiO2 268

6.4.5 Dielectric Properties of TiO2 Phases 269

6.4.6 Dielectric Properties vs. Microstructure of Ceramics 272

6.4.7 Dielectric Properties of TiO2 Films 274

6.4.8 TiO2 Sintering 276

6.4.9 TiO2 Coating Processing Methods 279

6.4.10 Optical Properties ofThin Films 282

6.4.11 Catalytic Properties 284

6.5 Industrial Applications of Titania 289

6.5.1 Titania Pigment 289

6.5.2 Industrial Uses of TiO2 Pigments 291

6.5.2.1 Vitreous Enamels on Steel and Aluminum 291

6.5.2.2 Paints 293

6.5.2.3 Paper 294

6.5.2.4 Textiles 295

6.5.3 Photocatalysts 296

6.6 Future Perspectives 300

6.6.1 Pigments 300

6.6.2 Photocatalysis 301

6.6.3 Solar Energy 302

6.6.4 TiO2 Nanotubes 302

Questions 303

References 303

7 Synthesis, Properties and Applications of Hydroxyapatite 311
Lech Paw³owski

7.1 Introduction 311

7.2 Phase Diagram 311

7.3 Methods of Ca10(PO4)6(OH)2 Powder Manufacturing 313

7.3.1 Solid-state Synthesis 315

7.3.2 Wet-route Methods 316

7.3.2.1 Wet PrecipitationMethod 317

7.3.2.2 Sol–Gel Method 317

7.3.2.3 HA Synthesis by Atomization 318

7.3.3 Powder Synthesis using Natural Precursors 320

7.3.4 Synthesis of Nanopowders 321

7.3.5 Composite Powder Synthesis 322

7.4 Properties of Ca10(PO4)6(OH)2 324

7.4.1 Thermodynamic and Thermophysical Properties of HA 324

7.4.2 Mechanical Properties of HA 325

7.4.2.1 Single Crystals 326

7.4.2.2 Coatings 326

7.4.2.3 3D Objects 326

7.4.2.4 Electric Properties 328

7.4.3 Biochemical Properties 328

7.5 Methods of Ca10(PO4)6(OH)2 Functionalizing 330

7.5.1 Introduction 330

7.5.2 HA in 2D: Films and Coatings 330

7.5.2.1 Physical Methods of Film and Coatings Deposition 330

7.5.2.2 Chemical Methods of Film and Coating Deposition 336

7.5.3 HA in 3D 337

7.5.3.1 Conventional Sintering 337

7.5.3.2 Activated Sintering 338

7.6 Practical Applications of HA 340

7.6.1 Medical Applications 340

7.6.1.1 Hip Prostheses 340

7.6.1.2 Knee Prostheses 342

7.6.1.3 Dental Prostheses 343

7.6.1.4 Possible Future Applications 344

7.6.2 Catalysis 345

7.6.3 Biosensors 345

7.6.4 Other Possible Applications 345

Questions 345

References 346

Answers to Questions 353

Index 367

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