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Glass Ceramic Technology, 2nd Edition

ISBN: 978-0-470-48787-7
440 pages
July 2012
Glass Ceramic Technology, 2nd Edition (0470487879) cover image
Glass-ceramic materials share many properties with both glass and more traditional crystalline ceramics. This new edition examines the various types of glass-ceramic materials, the methods of their development, and their countless applications. With expanded sections on biomaterials and highly bioactive products (i.e., Bioglass and related glass ceramics), as well as the newest mechanisms for the development of dental ceramics and theories on the development of nano-scaled glass-ceramics, here is a must-have guide for ceramic and materials engineers, managers, and designers in the ceramic and glass industry.
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INTRODUCTION TO THE SECOND EDITION XI

INTRODUCTION TO THE FIRST EDITION XIII

HISTORY XVII

CHAPTER 1 PRINCIPLES OF DESIGNING GLASS-CERAMIC FORMATION 1

1.1 Advantages of Glass-Ceramic Formation 1

1.1.1 Processing Properties 2

1.1.2 Thermal Properties 3

1.1.3 Optical Properties 3

1.1.4 Chemical Properties 3

1.1.5 Biological Properties 3

1.1.6 Mechanical Properties 3

1.1.7 Electrical and Magnetic Properties 4

1.2 Factors of Design 4

1.3 Crystal Structures and Mineral Properties 5

1.3.1 Crystalline Silicates 5

1.3.1.1 Nesosilicates 6

1.3.1.2 Sorosilicates 7

1.3.1.3 Cyclosilicates 7

1.3.1.4 Inosilicates 7

1.3.1.5 Phyllosilicates 8

1.3.1.6 Tectosilicates 8

1.3.2 Phosphates 32

1.3.2.1 Apatite 32

1.3.2.2 Orthophosphates and Diphosphates 34

1.3.2.3 Metaphosphates 36

1.3.3 Oxides 37

1.3.3.1 TiO2 37

1.3.3.2 ZrO2 38

1.3.3.3 MgAl2O4 (Spinel) 39

1.4 Nucleation 39

1.4.1 Homogeneous Nucleation 42

1.4.2 Heterogeneous Nucleation 43

1.4.3 Kinetics of Homogeneous and Heterogeneous Nucleation 45

1.4.4 Examples for Applying the Nucleation Theory in the Development of Glass-Ceramics 48

1.4.4.1 Volume Nucleation 49

1.4.4.2 Surface Nucleation 54

1.4.4.3 Time–Temperature–Transformation Diagrams 57

1.5 Crystal Growth 59

1.5.1 Primary Growth 60

1.5.2 Anisotropic Growth 62

1.5.3 Surface Growth 68

1.5.4 Dendritic and Spherulitic Crystallization 70

1.5.4.1 Phenomenology 70

1.5.4.2 Dendritic and Spherulitic Crystallization Application 72

1.5.5 Secondary Grain Growth 72

CHAPTER 2 COMPOSITION SYSTEMS FOR GLASS-CERAMICS 75

2.1 Alkaline and Alkaline Earth Silicates 75

2.1.1 SiO2–Li2O (Lithium Disilicate) 75

2.1.1.1 Stoichiometric Composition 75

2.1.1.2 Nonstoichiometric Multicomponent Compositions 77

2.1.2 SiO2–BaO (Sanbornite) 88

2.1.2.1 Stoichiometric Barium-Disilicate 88

2.1.2.2 Multicomponent Glass-Ceramics 89

2.2 Aluminosilicates 90

2.2.1 SiO2–Al2O3 (Mullite) 90

2.2.2 SiO2–Al2O3–Li2O (β-Quartz Solid Solution, β-Spodumene Solid Solution) 92

2.2.2.1 β-Quartz Solid Solution Glass-Ceramics 93

2.2.2.2 β-Spodumene Solid-Solution Glass-Ceramics 97

2.2.3 SiO2–Al2O2–Na2O (Nepheline) 99

2.2.4 SiO2–Al2O3–Cs2O (Pollucite) 102

2.2.5 SiO2–Al2O3–MgO (Cordierite, Enstatite, Forsterite) 105

2.2.5.1 Cordierite Glass-Ceramics 105

2.2.5.2 Enstatite Glass-Ceramics 110

2.2.5.3 Forsterite Glass-Ceramics 112

2.2.6 SiO2–Al2O3–CaO (Wollastonite) 114

2.2.7 SiO2–Al2O3–ZnO (Zn-Stuffed β-Quartz, Willemite-Zincite) 116

2.2.7.1 Zinc-Stuffed β-Quartz Glass-Ceramics 116

2.2.7.2 Willemite and Zincite Glass-Ceramics 119

2.2.8 SiO2–Al2O3–ZnO–MgO (Spinel, Gahnite) 120

2.2.8.1 Spinel Glass-Ceramic Without β-Quartz 120

2.2.8.2 β-Quartz-Spinel Glass-Ceramics 122

2.2.9 SiO2–Al2O3–CaO (Slag Sital) 123

2.2.10 SiO2–Al2O3–K2O (Leucite) 126

2.2.11 SiO2–Ga2O3–Al2O3–Li2O–Na2O–K2O (Li–Al–Gallate Spinel) 130

2.2.12 SiO2–Al2O3–SrO–BaO (Sr–Feldspar–Celsian) 131

2.3 Fluorosilicates 135

2.3.1 SiO2–(R3+)2O3–MgO–(R2+)O–(R+)2O–F (Mica) 135

2.3.1.1 Alkaline Phlogopite Glass-Ceramics 135

2.3.1.2 Alkali-Free Phlogopite Glass-Ceramics 141

2.3.1.3 Tetrasilicic Mica Glass-Ceramic 142

2.3.2 SiO2–Al2O3–MgO–CaO–ZrO2–F (Mica, Zirconia) 143

2.3.3 SiO2–CaO–R2O–F (Canasite) 145

2.3.4 SiO2–MgO–CaO–(R+)2O–F (Amphibole) 151

2.4 Silicophosphates 155

2.4.1 SiO2–CaO–Na2O–P2O5 (Apatite) 155

2.4.2 SiO2–MgO–CaO–P2O5–F (Apatite, Wollastonite) 157

2.4.3 SiO2–MgO–Na2O–K2O–CaO–P2O5 (Apatite) 157

2.4.4 SiO2–Al2O3–MgO–CaO–Na2O–K2O–P2O5–F (Mica, Apatite) 159

2.4.5 SiO2–MgO–CaO–TiO2–P2O5 (Apatite, Magnesium Titanate) 164

2.4.6 SiO2–Al2O3–CaO–Na2O–K2O–P2O5–F (Needlelike Apatite) 165

2.4.6.1 Formation of Needlelike Apatite as a Parallel Reaction to Rhenanite 169

2.4.6.2 Formation of Needlelike Apatite from Disordered Spherical Fluoroapatite 173

2.4.7 SiO2–Al2O3–CaO–Na2O–K2O–P2O5–F/Y2O3, B2O3 (Apatite and Leucite) 173

2.4.7.1 Fluoroapatite and Leucite 175

2.4.7.2 Oxyapatite and Leucite 177

2.4.8 SiO2–CaO–Na2O–P2O5–F (Rhenanite) 179

2.5 Iron Silicates 182

2.5.1 SiO2–Fe2O3–CaO 182

2.5.2 SiO2–Al2O3–FeO–Fe2O3–K2O (Mica, Ferrite) 182

2.5.3 SiO2–Al2O3–Fe2O3–(R+)2O–(R2+)O (Basalt) 185

2.6 Phosphates 187

2.6.1 P2O5–CaO (Metaphosphates) 187

2.6.2 P2O5–CaO–TiO2 191

2.6.3 P2O5–Na2O–BaO and P2O5–TiO2–WO3 191

2.6.3.1 P2O5–Na2O–BaO System 191

2.6.3.2 P2O5–TiO2–WO3 System 192

2.6.4 P2O5–Al2O3–CaO (Apatite) 192

2.6.5 P2O5–B2O3–SiO2 194

2.6.6 P2O5–SiO2–Li2O–ZrO2 196

2.6.6.1 Glass-Ceramics Containing 16 wt% ZrO2 197

2.6.6.2 Glass-Ceramics Containing 20 wt% ZrO2 197

2.7 Other Systems 199

2.7.1 Perovskite-Type Glass-Ceramics 199

2.7.1.1 SiO2–Nb2O5–Na2O–(BaO) 199

2.7.1.2 SiO2–Al2O3–TiO2–PbO 201

2.7.1.3 SiO2–Al2O3–K2O–Ta2O5–Nb2O5 203

2.7.2 Ilmenite-Type (SiO2–Al2O3–Li2O–Ta2O5) Glass-Ceramics 204

2.7.3 B2O3–BaFe12O19 (Barium Hexaferrite) or (BaFe10O15) Barium Ferrite 204

2.7.4 SiO2–Al2O3–BaO–TiO2 (Barium Titanate) 205

2.7.5 Bi2O3–SrO–CaO–CuO 206

CHAPTER 3 MICROSTRUCTURE CONTROL 207

3.1 Solid-State Reactions 207

3.1.1 Isochemical Phase Transformation 207

3.1.2 Reactions between Phases 208

3.1.3 Exsolution 208

3.1.4 Use of Phase Diagrams to Predict Glass-Ceramic Assemblages 209

3.2 Microstructure Design 209

3.2.1 Nanocrystalline Microstructures 210

3.2.2 Cellular Membrane Microstructures 211

3.2.3 Coast-and-Island Microstructure 214

3.2.4 Dendritic Microstructures 216

3.2.5 Relict Microstructures 218

3.2.6 House-of-Cards Microstructures 219

3.2.6.1 Nucleation Reactions 221

3.2.6.2 Primary Crystal Formation and Mica Precipitation 221

3.2.7 Cabbage-Head Microstructures 222

3.2.8 Acicular Interlocking Microstructures 228

3.2.9 Lamellar Twinned Microstructures 231

3.2.10 Preferred Crystal Orientation 232

3.2.11 Crystal Network Microstructures 235

3.2.12 Nature as an Example 236

3.2.13 Nanocrystals 237

3.3 Control of Key Properties 239

3.4 Methods and Measurements 240

3.4.1 Chemical System and Crystalline Phases 240

3.4.2 Determination of Crystal Phases 240

3.4.3 Kinetic Process of Crystal Formation 242

3.4.4 Determination of Microstructure 246

3.4.5 Mechanical, Optical, Electrical, Chemical, and Biological Properties 247

3.4.5.1 Optical Properties and Chemical Composition of Glass-Ceramics 248

3.4.5.2 Mechanical Properties and Microstructures of Glass-Ceramics 249

3.4.5.3 Electrical Properties 249

3.4.5.4 Chemical Properties 250

3.4.5.5 Biological Properties 250

CHAPTER 4 APPLICATIONS OF GLASS-CERAMICS 252

4.1 Technical Applications 252

4.1.1 Radomes 252

4.1.2 Photosensitive and Etched Patterned Materials 252

4.1.2.1 Fotoform and Fotoceram 253

4.1.2.2 Foturan 254

4.1.2.3 Additional Products 259

4.1.3 Machinable Glass-Ceramics 260

4.1.3.1 MACOR and DICOR 260

4.1.3.2 Vitronit™ 264

4.1.3.3 Photoveel™ 264

4.1.4 Magnetic Memory Disk Substrates 265

4.1.5 Liquid Crystal Displays 269

4.2 Consumer Applications 269

4.2.1 β-Spodumene Solid-Solution Glass-Ceramic 269

4.2.2 β-Quartz Solid-Solution Glass-Ceramic 271

4.3 Optical Applications 277

4.3.1 Telescope Mirrors 277

4.3.1.1 Requirements for Their Development 277

4.3.1.2 Zerodur Glass-Ceramics 277

4.3.2 Integrated Lens Arrays 279

4.3.3 Applications for Luminescent Glass-Ceramics 281

4.3.3.1 Cr-Doped Mullite for Solar Concentrators 281

4.3.3.2 Cr-Doped Gahnite Spinel for Tunable Lasers and Optical Memory Media 285

4.3.3.3 Rare-Earth Doped Oxyfluorides for Amplification, Upconversion, and Quantum Cutting 288

4.3.3.4 Chromium (Cr4+)-Doped Forsterite, β-Willemite, and Other Orthosilicates for Broad Wavelength Amplification 293

4.3.3.5 Ni2+-Doped Gallate Spinel for Amplification and Broadband Infrared Sources 297

4.3.3.6 YAG Glass-Ceramic Phosphor for White LED 301

4.3.4 Optical Components 301

4.3.4.1 Glass-Ceramics for Fiber Bragg Grating Athermalization 301

4.3.4.2 Laser-Induced Crystallization for Optical Gratings and Waveguides 309

4.3.4.3 Glass-Ceramic Ferrule for Optical Connectors 310

4.3.4.4 Applications for Transparent ZnO Glass-Ceramics with Controlled Infrared Absorbance and Microwave Susceptibility 310

4.4 Medical and Dental Glass-Ceramics 311

4.4.1 Glass-Ceramics for Medical Applications 312

4.4.1.1 CERABONE 312

4.4.1.2 CERAVITAL 314

4.4.1.3 BIOVERIT 314

4.4.2 Glass-Ceramics for Dental Restoration 315

4.4.2.1 Moldable Glass-Ceramics for Metal-Free Restorations 317

4.4.2.2 Machinable Glass-Ceramics for Metal-Free Restorations 327

4.4.2.3 Glass-Ceramics on Metal Frameworks 330

4.4.2.4 Glass-Ceramic Veneering Materials on High Toughness Polycrystalline Ceramics 335

4.5 Electrical and Electronic Applications 342

4.5.1 Insulators 342

4.5.2 Electronic Packaging 344

4.5.2.1 Requirements for Their Development 344

4.5.2.2 Properties and Processing 344

4.5.2.3 Applications 346

4.6 Architectural Applications 346

4.7 Coatings and Solders 350

4.8 Glass-Ceramics for Energy Applications 351

4.8.1 Components for Lithium Batteries 351

4.8.1.1 Cathodes 351

4.8.1.2 Electrolytes 351

4.8.2 Joining Materials for Solid Oxide Fuel Cell Components 352

EPILOGUE: FUTURE DIRECTIONS 354

APPENDIX: TWENTY-ONE FIGURES OF 23 CRYSTAL STRUCTURES 355

REFERENCES 378

INDEX 407

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WOLFRAM HÖLAND, PhD, is the Head of the Department of Research and Development, Inorganic Chemistry Technical Fundamentals, at Ivoclar Vivadent AG, Liechtenstein. He is also a Lecturer in the Department of Inorganic Chemistry, Eidgenössische Technische Hochschule (ETH Zurich) in Switzerland. Dr. Höland is the recipient of several awards, including the Wöhler Prize of the German Chemical Society and the Turner Award of the International Commission on Glass.

GEORGE H. BEALL, PhD, received his PhD in geology from MIT in 1962 and was a Research Fellow in the Science and Technology Division of Corning Incorporated, Corning, New York. Until 1995, Dr. Beall was a Courtesy Professor in the Department of Materials Science and Engineering at Cornell University, and has authored or coauthored approximately eighty technical papers and one book, and holds more than 100 U.S. patents.

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