Ceramics Science and Technology
Applications
Ceramics Science and Technology (VCH) Series

Although ceramics have been known to mankind literally for millennia, research has never ceased. Apart from the classic uses as a bulk material in pottery, construction, and decoration, the latter half of the twentieth century saw an explosive growth of application fields, such as electrical and thermal insulators, wear–resistant bearings, surface coatings, lightweight armour, or aerospace materials. In addition to plain, hard solids, modern ceramics come in many new guises such as fabrics, ultrathin films, microstructures and hybrid composites. Built on the solid foundations laid down by the 20–volume series Materials Science and Technology, Ceramics Science and Technology picks out this exciting material class and illuminates it from all sides. Materials scientists, engineers, chemists, biochemists, physicists and medical researchers alike will find this work a treasure trove for a wide range of ceramics knowledge from theory and fundamentals to practical approaches and problem solutions.

Preface XV List of Contributors XVII Part One Structural Applications 1 1 Oxidation and Corrosion of Ceramics 3 Elizabeth J. Opila and Nathan S. Jacobson 1.1 Introduction 3 1.2 Silica–Forming Ceramics 4 1.2.1 Ideal Oxidation Behavior of Silica–Forming Ceramics 4 1.2.1.1 Structure of Silica and Transport of Oxygen in Silica 4 1.2.1.2 Oxidation of Silicon in Dry Oxygen 5 1.2.1.3 Oxidation of Silicon Carbide in Dry Oxygen 7 1.2.1.4 Oxidation of Silicon Nitride in Dry Oxygen 9 1.2.2 SiC Oxidation: Deviations from Norton Permeation 11 1.2.2.1 Crystallization of the Silica Scale: Effect on SiC Oxidation 11 1.2.2.2 Ionic Exchange with the Silica Network: Effect on SiC Oxidation 12 1.2.2.3 Effects of Low–Level Impurities on SiC Oxidation 12 1.2.3 Oxidation of Silica–Formers in the Presence of Low–Level Impurities 13 1.2.3.1 Effect of Alkali–Metal Impurities on the Oxidation of Silica–Formers 13 1.2.3.2 Effect of Aluminum Impurities on Silica–Formers 14 1.2.4 Additive Effects on the Oxidation of Silica–Formers 14 1.2.4.1 Al and B Additions to SiC: Effect on Oxidation Rates 15 1.2.4.2 Effect of Sintering Additives on the Oxidation of Silicon Nitride 15 1.2.5 Deposit–Induced Corrosion of Silicon–Based Ceramics 16 1.2.6 Temperature Cycling 24 1.2.7 Oxidation of Silica–Formers in Other Oxidants 25 1.2.7.1 Oxidation of Silica–Formers in Other Oxidants: H2O 26 1.2.7.2 Oxidation of Silica Formers in Other Oxidants: Carbon Dioxide (CO2) 36 1.2.7.3 Oxidation of Silica Formers in Other Oxidants: Dissociated Oxygen 37 1.2.8 Active Oxidation of Silica Formers 38 1.2.9 Upper Temperature Limit for Silica–Forming Materials 45 1.2.10 Oxidation of Polymer–Derived Si–Based Ceramics 46 1.2.11 Oxidation of SiC–Based Composites 48 1.2.11.1 Oxidation of Carbon 48 1.2.11.2 Oxidation of Boron Nitride 49 1.2.11.3 Oxidation of SiC/C/SiC and C/C/SiC Composites 49 1.2.11.4 Oxidation of SiC/BN/SiC Composites 51 1.2.11.5 Improved Oxidation–Resistant SiC Composites 53 1.2.11.6 Oxidation–Resistant Coatings and Additives for SiC–Based Composites 55 1.2.12 Environmental Barrier Coatings for Silicon–Based Ceramics and Composites 55 1.3 Alumina–Forming Ceramics 57 1.3.1 Oxidation of AlN 58 1.3.1.1 Onset of AlN Oxidation 58 1.3.1.2 Early Stages of AlN Oxidation 58 1.3.1.3 Oxidation Kinetics of AlN 59 1.3.1.4 Oxidation of AlN in Water Vapor 61 1.3.1.5 Effect of Oxygen and Nitrogen Partial Pressure on Oxidation of AlN 62 1.3.1.6 Effect of Sintering Additives on the Oxidation of AlN 62 1.3.2 Oxidation of Al4C3 63 1.4 Ultrahigh–Temperature Ceramics 64 1.4.1 Oxidation of Zirconium and Hafnium 65 1.4.2 Oxidation of ZrB2 and HfB2 65 1.4.2.1 Effect of Additives on ZrB2 and HfB2 Oxidation Rates 67 1.4.3 Oxidation of ZrC and HfC 74 1.4.4 Oxidation of ZrN and HfN 77 1.4.5 Oxidation of TaC and Ta2C 78 1.4.6 Oxidation of UHTC Composite Materials 79 1.5 Oxide Ceramic Degradation Mechanisms 80 1.5.1 Oxide Ceramic Degradation in Water Vapor 80 1.5.2 Oxide Corrosion 81 1.6 Concluding Remarks 83 References 83 2 Thermal Barrier Coatings 95 Robert Vaß,en 2.1 Introduction 95 2.2 Manufacturing Routes 97 2.2.1 Electron Beam–Physical Vapor Deposition (EB–PVD) 97 2.2.2 Atmospheric Plasma Spraying (APS) 98 2.2.2.1 General Remarks 98 2.2.2.2 Thermally Sprayed MCrAlYs (M————Ni, Co) Bond Coatings 99 2.2.3 Atmospheric Plasma–Sprayed (APS) Yttria–Stabilized Zirconia (YSZ) Topcoats 101 2.2.4 New Thermal Spray Processes 103 2.2.4.1 Liquid Feedstock/Suspension Plasma Spraying 103 2.3 YSZ–Based TBCS 105 2.3.1 Some Basic Properties of YSZ (Bulk Material) 105 2.3.2 Properties of APS YSZ Thermal Barrier Coatings 106 2.3.3 Property Changes During Heat Treatment 107 2.3.4 Failure of YSZ–Based TBC Systems 109 2.4 New TBC Systems 110 2.5 Summary 112 Acknowledgments 112 References 112 3 Ceramic Filters and Membranes 117 Ingolf Voigt, J&euro,org Adler, Marcus Weyd, and Ralf Kriegel 3.1 Ceramics in Hot Gas Filtration 117 3.1.1 Introduction 117 3.1.2 Hot Gas Cleaning in Advanced Coal–Fired Electrical Power Systems 118 3.1.2.1 Advanced Coal–Fired Electrical Power Systems 118 3.1.2.2 Ash Filtration From Hot Gases 119 3.1.2.3 Filter Materials 119 3.1.2.4 Rigid Candle Filter 121 3.1.2.5 Candle Filter Failings and Failsafe Devices 123 3.1.2.6 Experience with Candle Filters in PFBC Applications 124 3.1.2.7 Experience with Candle Filters in IGCC Applications 124 3.1.2.8 Combination of Filtration and Catalytic Treatment 124 3.1.2.9 Summary of Hot Gas Cleaning in Advanced Coal–Fired Electrical Power Systems 125 3.1.3 Particulate Filtration of Diesel Exhaust Gases 125 3.1.3.1 Pollutants in Diesel Exhaust 126 3.1.3.2 Limits of Pollutants by Legislation 126 3.1.3.3 Principles and Function of the Diesel Particulate Filter 126 3.1.3.4 Architecture of a DPF and its Manufacture 127 3.1.3.5 Ceramic Materials for DPF 130 3.1.3.6 DPF Summary and Outlook 132 3.2 Ceramic Membranes for Liquid Filtration 132 3.2.1 Introduction 132 3.2.2 Microfiltration Membranes 135 3.2.2.1 Preparation of Ceramic Microfiltration Membranes 135 3.2.2.2 Application of Ceramic Microfiltration Membranes 136 3.2.3 Ultrafiltration Membranes 137 3.2.3.1 Preparation of Ceramic Ultrafiltration Membranes 137 3.2.3.2 Application of Ceramic Ultrafiltration Membranes 138 3.2.4 Nanofiltration Membranes 139 3.2.4.1 Preparation of Ceramic Nanofiltration Membranes 139 3.2.4.2 Application of Ceramic Nanofiltration Membranes 139 3.3 Ceramic Membranes for Pervaporation/Vapor Permeation 142 3.3.1 Introduction 142 3.3.2 Membranes for Pervaporation/Vapor Permeation 144 3.3.3 Dehydration of Isopropanol 148 3.3.4 Dehydration of Ethanol 149 3.4 Ceramic Membranes for Gas Separation 151 3.4.1 Introduction 151 3.4.2 Mixed Ionic Electronic Conducting Membranes 152 3.4.3 Oxygen Separation from Air 155 References 162 4 High–Temperature Engineering Ceramics 169 Ronald J. Kerans and Allan P. Katz 4.1 Introduction 169 4.2 Engineering Ceramic Systems 170 4.3 Turbine Engine Applications 172 4.4 Applications for Rocket Propulsion and Hypersonic Vehicles 179 4.5 Friction Materials 184 4.6 Concluding Remarks: Barriers to Application 186 References 188 5 Advanced Ceramic Glow Plugs 191 Takeshi Mitsuoka 5.1 Introduction 191 5.2 Glow Plugs 191 5.3 Metal–Type Glow Plugs 193 5.4 Ceramic Glow Plugs 194 5.5 Fabrication Procedure of Heater Elements for Ceramic Glow Plugs 197 5.6 Material Design of the Ceramic Heater Element 200 5.7 Silicon Nitride Ceramics 201 5.8 Conclusions 206 References 206 6 Nanosized and Nanostructured Hard and Superhard Materials and Coatings 207 Stan Vep9rek, Maritza G.J. Vep9rek–Heijman, and Pavel Holub—a9r 6.1 Introduction: Small is Strong 207 6.2 Different Mechanisms of Hardness Enhancement in Coatings 213 6.3 Mechanisms of Decomposition of Solid Solution and Formation of Nanostructure 220 6.3.1 Mechanical Properties and the Issue of the Reproducibility of High Hardness in nc–TiN/a–Si3N4 and nc–TiN/a–Si3N4/TiSi2 Coatings 224 6.4 Industrial Applications of Nanocomposite and Nanostructured Coatings on Tools 232 6.5 Conclusions and Future Challenges 238 Acknowledgments 240 References 240 7 Polymer–Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics 245 Paolo Colombo, Gabriela Mera, Ralf Riedel, and Gian Domenico Sorar—u 7.1 Introduction to Polymer–Derived Ceramics (PDCs) 246 7.2 Preceramic Polymer Synthesis 248 7.2.1 Poly(organosilanes) 250 7.2.2 Poly(organocarbosilanes) 251 7.2.3 Poly(organosiloxanes) 252 7.2.4 Poly(organocarbosilanes) 253 7.2.5 Poly(organosilylcarbodiimides) 254 7.3 Processing of Preceramic Polymers 255 7.3.1 Shaping and Cross–Linking 255 7.3.2 Addition of Fillers 258 7.3.3 Polymer–to–Ceramic Conversion 261 7.3.4 Processing Parameters Influencing the Fabrication of PDCs 264 7.4 Microstructure of PDCs 265 7.4.1 Raman Spectroscopy 267 7.4.2 Multinuclear MAS&ndash,NMR 269 7.4.3 X–Ray Diffractometry (XRD) 270 7.4.4 TEM 271 7.4.5 EELS 273 7.4.6 Electron Diffraction Technique 273 7.4.7 SAXS 273 7.4.8 Theoretical Modeling 275 7.5 Properties of PDCs 277 7.5.1 Electrical Properties 277 7.5.2 Magnetic Properties 280 7.5.3 Optical Properties 281 7.5.4 Chemical Properties 283 7.5.4.1 Oxidation Resistance 283 7.5.4.2 Chemical Durability 284 7.5.5 Mechanical Properties 284 7.5.5.1 Fibers 284 7.5.5.2 Bulk Samples 285 7.6 Applications of PDCs 290 7.6.1 Fibers 290 7.6.2 Ceramic–Matrix Composites 291 7.6.3 Highly Porous Components 293 7.6.4 Coatings 293 7.6.5 Microcomponents 294 7.6.6 Other Applications 294 7.7 Conclusions and Outlook 295 Acknowledgments 297 References 298 Part Two Functional Applications 321 8 Microwave Ceramics 323 Bo9stjan Jan9car and Danilo Suvorov 8.1 Introduction 323 8.2 Microwave Dielectric Properties 324 8.2.1 Dielectric Constant (er) 324 8.2.2 Temperature Coefficient of Resonant Frequency (tf) 325 8.2.3 Quality Factor (Q) 326 8.3 Overview of Microwave Dielectric Materials 327 8.4 Crystal Chemistry of Perovskite and Tungsten–Bronze–Type Microwave Ceramics 330 8.5 Microstructural Features in High–Q Perovskites 333 8.6 Glass–Free Low–Temperature Co–Fired Ceramic LTCC Microwave Materials 337 8.6.1 Sillenite Compounds Bi12MO20–d (M ¼, Si, Ge, Ti, Pb, Mn) 340 8.6.2 Bi2O3&ndash,Nb2O5 340 8.6.3 KxBa1&ndash,xGa2&ndash,xGe2þ,xO8 and MWO4 (M ¼, Ca, Sr, Ba) 341 References 343 9 Ceramic Fuel Cells: Principles, Materials, and Applications 345 Peter Holtappels and Bhaskar Reddy Sudireddy 9.1 Introduction 345 9.2 Fuel Cell Systems Efficiency and the Role of Ceramic Fuel Cells 345 9.3 Ceramic Fuel Cell Systems and Applications to Date 346 9.4 Efficiency and Principles of Ceramic Fuel Cells 348 9.5 Historical Overview of Ceramic Fuel Cells 351 9.6 SOFC Materials and Properties 354 9.6.1 Electrolytes 354 9.6.2 Electrodes 356 9.6.2.1 Anode 356 9.6.2.2 Cathodes 360 9.6.3 Interconnect 364 9.6.4 Sealing 364 9.7 New Approaches for Ceramic Fuel Cells 365 9.7.1 Proton–Conducting Fuel Cells 365 9.7.2 m–SOFC 366 9.7.3 Direct Carbon Cells 367 9.8 Concluding Remarks 368 References 368 10 Nitridosilicates and Oxonitridosilicates: From Ceramic Materials to Structural and Functional Diversity 373 Martin Zeuner, Sandro Pagano, and Wolfgang Schnick 10.1 Introduction 373 10.2 Synthetic Approaches 375 10.2.1 High–Temperature Reactions 375 10.2.2 Flux Methods and Precursor Routes 377 10.3 1D Nitridosilicates 378 10.4 2D Nitridosilicates 379 10.5 3D Nitridosilicates 382 10.5.1 Tectosilicates 382 10.5.2 SiAlNs 390 10.5.3 SiAlONs 392 10.5.4 Zeolite–Like Structures 394 10.6 Chemical Bonding in Nitridosilicates 397 10.6.1 Bond Lengths and Degree of Condensation 397 10.6.2 Lattice–Energy Calculations According to the MAPLE Concept 398 10.7 Material Properties 399 10.7.1 Nitride Ceramics 400 10.7.2 Thermal Conductivity 400 10.7.3 Lithium Ion Conductivity 401 10.7.4 Nonlinear Optical (NLO) Materials 402 10.7.5 Luminescence 403 10.8 Outlook 407 References 408 11 Ceramic Lighting 415 Rong–Jun Xie, Mamoru Mitomo, and Naoto Hirosaki 11.1 Introduction 415 11.2 Solid–State Lighting and White Light–Emitting Diodes 416 11.2.1 Introduction 416 11.2.2 Phosphor Requirements 418 11.2.3 Classification of Phosphors 419 11.3 Ceramic Phosphors 419 11.3.1 Garnet Phosphors 419 11.3.2 Silicate Phosphors 421 11.3.2.1 Sr2SiO4:Eu2þ, 421 11.3.2.2 Sr3SiO5:Eu2þ, 423 11.3.3 Oxynitride Phosphors 425 11.3.3.1 a–sialon:Eu2þ, 425 11.3.3.2 b–sialon:Eu2þ, 428 11.3.3.3 MSi2O2N2:Eu2þ, (M ¼, Ca, Sr, Ba) 430 11.3.3.4 Other Oxynitride Phosphors 431 11.3.4 Nitride Phosphors 432 11.3.4.1 AlN:Eu2þ, 432 11.3.4.2 Sr2Si5N8:Eu2þ, 434 11.3.4.3 CaAlSiN3:Eu2þ, 435 11.3.4.4 Other Nitride Ceramic Phosphors 436 11.4 White Light–Emitting Diodes Using Ceramic Phosphors 437 11.4.1 One–Phosphor–Converted White LEDs 437 11.4.1.1 YAG:Ce3þ, 437 11.4.1.2 a–sialon:Eu2+ 438 11.4.2 Multiphosphor–Converted White LEDs 439 11.4.2.1 Green + Red Phosphors 439 11.4.2.2 Green + Yellow + Red Phosphors 440 11.4.3 White LEDs Using Transparent Ceramics 441 11.5 Outlook 443 References 443 12 Ceramic Gas Sensors 447 Aleksander Gurlo 12.1 Introduction: Definitions and Classifications 447 12.2 Metal–Oxide–Based Gas Sensors: Operational Principles and Sensing Materials 451 12.3 Performance Characteristics 454 12.4 Nano–Micro Integration 456 12.5 Mechanism of Gas Detection 459 12.5.1 Ionosorption Model 459 12.5.2 Oxygen–Vacancy Model (Reduction&ndash,Reoxidation Mechanism) 462 12.6 Characterization Methodology 463 12.7 Conclusions and Outlook 466 References 467 13 Oxides for Li Intercalation, Li–ion Batteries 471 Natalia N. Bramnik and Helmut Ehrenberg 13.1 Introduction 471 13.2 Why Oxides are Attractive as Insertion Materials 473 13.3 Titanium 474 13.4 Vanadium 476 13.5 Chromium 478 13.6 Manganese 478 13.7 Iron 482 13.8 Cobalt– and Nickel–Based Oxides 485 13.9 Copper 488 13.10 Conclusion 488 References 489 14 Magnetic Ceramics 495 Lambert Alff 14.1 Background 495 14.2 Introduction 496 14.3 Magnetite 497 14.4 Doped Manganites 501 14.5 Ferrimagnetic Double Perovskites 506 14.6 Iron Nitrides and Summary 508 References 509 Index 511

Prof. Riedel has been Professor at the Institute of Materials Science at the Darmstadt University of Technology in Darmstadt since 1993. He received a Diploma degree in chemistry in 1984 and he finished his dissertation in Inorganic Chemistry in 1986 at the University of Stuttgart. After postdoctoral research at the Max-Planck-Institute for Metals Research and the Institute of Inorganic Chemistry at the University of Stuttgart he completed his habilitation in the field of Inorganic Chemistry in 1992. Prof. Riedel is Fellow of the American Ceramic Society and was awarded with the Dionyz Stur Gold Medal for merits in natural sciences. He is a member of the World Academy of Ceramics and Guest Professor at the Jiangsu University in Zhenjiang, China. In 2006 he received an honorary doctorate from the Slovak Academy of Sciences, Bratislava, Slovakia. In 2009 he was awarded with an honorary professorship at the Tianjin University in China. He published more than 300 papers and patents and he is widely known for his research in the field of polymer derived ceramics and on ultra high pressure synthesis of new materials.

I-Wei Chen is currently Skirkanich Professor of Materials Innovation at the University of Pennsylvania since 1997, where he also gained his master's degree in 1975. He received his bachelor's degree in physics from Tsinghua University, Taiwan, in 1972, and earned his doctorate in metallurgy from the Massachusetts Institute of Technology in 1980. He taught at the University of Michigan (Materials) during 1986-1997 and MIT (Nuclear Engineering; Materials) during 1980-1986. He began ceramic research studying martensitic transformations in zirconia nano crystals, which led to work on transformation plasticity, superplasticity, fatigue, grain growth and sintering in various oxides and nitrides. He is currently interested in nanotechnology of ferroelectrics, thin film memory devices, and nano particles for biomedical applications. A Fellow of American Ce