Robert B. Heimann Classic and Advanced Ceramics From Fundamentals to Applications Robert B. Heimann Classic and Advanced Ceramics Related Titles Aldinger, F., Weberruss, V. A. Volume 4: Applications Advanced Ceramics and 2012 Future Materials Hardcover ISBN: 978-3-527-31158-3 An Introduction to Structures, Properties and Technologies Öchsner, A., Ahmed, W. (eds.) 2010 Hardcover Biomechanics of Hard Tissues ISBN: 978-3-527-32157-5 Modeling, Testing, and Materials 2010 Riedel, R., Chen, I-W. (eds.) Hardcover Ceramics Science and ISBN: 978-3-527-32431-6 Technology 4 Volume Set Krenkel, W. (ed.) Hardcover Ceramic Matrix Composites ISBN: 978-3-527-31149-1 Fiber Reinforced Ceramics and their Applications Volume 1: Structures 2008 Hardcover 2008 ISBN: 978-3-527-31361-7 Hardcover ISBN: 978-3-527-31155-2 Öchsner, A., Murch, G. E., de Lemos, M. J. S. (eds.) Volume 2: Properties Cellular and Porous Materials 2010 Hardcover Thermal Properties Simulation and Prediction ISBN: 978-3-527-31156-9 2008 Hardcover ISBN: 978-3-527-31938-1 Volume 3: Synthesis and Processing 2010 Hardcover ISBN: 978-3-527-31157-6 Robert B. Heimann Classic and Advanced Ceramics From Fundamentals to Applications The Author All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and Prof. Dr. Robert B. Heimann publisher do not warrant the information Am Stadtpark 2A contained in these books, including this book, to 02826 Görlitz be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografi e; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfi lm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifi cally marked as such, are not to be considered unprotected by law. Cover Design Formgeber, Eppelheim Typesetting Toppan Best-set Premedia Limited Printing and Binding Betz-Druck GmbH, Darmstadt Printed in the Federal Republic of Germany Printed on acid-free paper ISBN: 978-3-527-32517-7 V To Gabriele whose love, support, and patience were indispensable for creating this text. Classic and Advanced Ceramics: From Fundamentals to Applications. Robert B. Heimann © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32517-7 VII Contents Preface XV 1 Introduction to Classic Ceramics 1 1.1 Ceramics through the Ages, and Technological Progress 1 1.2 Classifi cation of Ceramics 6 References 9 2 Mineralogy, Structure, and Green Processing of Clay Minerals 11 2.1 Natural Clay Minerals 12 2.1.1 Formation of Clay Minerals 13 2.1.2 Structure of Important Clay Minerals 16 2.1.2.1 Kaolinite 18 2.1.2.2 Illite 19 2.1.2.3 Montmorillonite: Structure and Application 22 2.1.3 Nomenclature of Clays 26 2.2 Synthetic Raw Materials 27 2.3 Processing and Forming of Clay Powders 30 2.3.1 Dry Forming Methods 31 2.3.2 Wet Forming Methods 31 2.4 Rheology of Clay Particle Suspensions 32 2.4.1 Modeling of Rheological Behavior 32 2.4.1.1 Linear Two-Element Models 34 2.4.1.2 Linear Three-Element Models 36 2.4.1.3 Nonlinear Models 37 2.4.2 Colloidal Processing of Clay 37 2.4.2.1 Structural Viscosity 37 2.4.2.2 Hofmeister Series 40 2.4.2.3 Effect of pH on Clay–Water Suspensions 41 2.4.2.4 Zeta (Electrokinetic) Potential 42 2.4.2.5 Thixotropy and Rheopexy 46 2.5 Drying of Green Clay Bodies 47 References 50 Classic and Advanced Ceramics: From Fundamentals to Applications. Robert B. Heimann © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32517-7 VIII Contents 3 Important Ceramic Phase Systems 55 3.1 Fundamentals of Phase Diagrams 55 3.1.1 Gibbs’ Phase Rule 55 3.1.2 One-Component Phase Diagrams 57 3.1.3 Two-Component (Binary) Phase Diagrams 59 3.1.3.1 Simple Binary Phase Diagram without Intermediate Compound or Solid Solution 59 3.1.3.2 Complete Solid Solution of Two Components 61 3.1.4 Three-Component (Ternary) Phase Diagrams 62 3.1.4.1 Composition of a Ternary Compound 62 3.1.4.2 Phase Boundary Lines, Eutectic Points, and Degrees of Freedom 63 3.1.4.3 Compatibility Joins (Conodes) and Compatibility Triangles 64 3.1.4.4 The Complete (3-D) Ternary Phase Diagram 65 3.1.5 Four-Component (Quaternary) Phase Diagrams 68 3.1.5.1 Conclusion 70 3.2 Phase Systems with Ceramic Relevance 71 3.2.1 One-Component Systems 71 3.2.1.1 Silica 71 3.2.2 Two-Component Systems 81 3.2.2.1 Al2O3–SiO2 81 3.2.2.2 MgO–SiO2 84 3.2.2.3 CaO–SiO2 86 3.2.3 Three-Component Systems 88 3.2.3.1 CaO–Al2O3–SiO2 88 3.2.3.2 K2O–Al2O3–SiO2 89 References 94 4 Mineralogy and Chemistry of the Ceramic Firing Process 99 4.1 Introduction 99 4.2 Crystallography of the Thermal Transformation of Kaolinite 100 4.3 Thermal Transformations in Illitic Clays 104 4.4 Thermal Transformations and Phase Formation in the System MgO–CaO–Al2O3–SiO2 109 4.5 Thermal Transformations and Phase Formation in the System MgO–(Fe2O3)–Al2O3–SiO2 113 References 117 5 Mineralogy and Chemistry of Cements 119 5.1 Historical Development 119 5.2 Portland Cement 120 5.2.1 Introduction 120 5.2.2 Typical Composition and Materials Properties 121 5.2.3 Phase Composition 124 5.2.4 Hydration of Clinker Minerals 128 5.2.4.1 Calcium Silicates 128 Contents IX 5.2.4.2 Calcium Aluminate 129 5.2.4.3 Ferrite (Brownmillerite) 131 5.2.4.4 Kinetics of Hydration 132 5.2.5 Models of Hydration 133 5.2.5.1 Delayed Nucleation Model 133 5.2.5.2 Protective Layer Model 134 5.2.6 Setting and Hardening of Cement 136 5.3 High-Performance Concretes (HPC) 138 5.3.1 Mineral and Chemical Admixtures 138 5.3.1.1 Mineral Admixtures 138 5.3.1.2 Chemical Admixtures 139 5.3.2 DSP Cement 142 5.3.3 Macro-Defect-Free (MDF) Cement 143 5.3.4 Gas Concrete (Autoclaved Aerated Concrete; AAC) 144 5.4 Environmental Impact and Concrete Recycling 145 5.4.1 CO2 Emissions 146 5.4.2 NOx Emissions 146 5.4.3 Particulate Emissions and Visual Pollution 147 5.4.4 Water Pollution 147 5.4.5 Environmental Benefi ts 148 5.5 Future Developments and Outlook 150 5.5.1 Reduction of the Emission of Greenhouse Gases 150 5.5.2 Recycling of Concrete 151 References 153 6 Introduction to Advanced Ceramics 157 6.1 General Properties of Advanced Ceramics 157 6.2 The Current World Market Situation 163 6.2.1 Advanced Structural Ceramics 164 6.2.2 Advanced Electronic Ceramics 164 6.2.3 Advanced Ceramic Coatings 166 6.2.4 Chemical Processing and Environment-Related Ceramics 167 6.2.5 Bioceramics, Bioactive Glasses, and Coatings 168 6.3 Recent US and Global Forecasts 168 6.3.1 Advanced Ceramic Powders 170 6.3.2 Carbon Nanotubes 171 6.3.3 Ceramic Superconductors 171 References 172 7 Oxide Ceramics: Structure, Technology, and Applications 175 7.1 Alumina 175 7.1.1 General Properties and Application 175 7.1.2 Processing of Alumina 176 7.1.2.1 Extraction 176 7.1.2.2 Precipitation 177 X Contents 7.1.2.3 Calcination 178 7.1.3 Structure of Alumina Polymorphs 178 7.1.3.1 Stable Alumina Polymorphs 178 7.1.3.2 Transitional Alumina Polymorphs 182 7.1.4 Specifi c Properties and Applications 185 7.1.4.1 Duplex Al2O3–ZrO2 Ceramics 185 7.1.4.2 Stuffed Alumina Ceramics 185 7.1.4.3 Selected Applications of Alumina Ceramics 186 7.2 Zirconia 196 7.2.1 Introduction 196 7.2.2 Processing of Zirconia 197 7.2.3 Structure of Zirconia 199 7.2.4 Transformation Toughening of Zirconia Ceramics 201 7.2.5 Binary Phase Systems 208 7.2.5.1 System ZrO2–MgO 208 7.2.5.2 System ZrO2–CaO 208 7.2.5.3 System ZrO2–Y2O3 208 7.2.5.4 System ZrO2–CeO2 211 7.2.5.5 System ZrO2–Sc2O3 213 7.2.6 Selected Applications of Zirconia 215 7.2.6.1 Structural Applications 215 7.2.6.2 Functional Applications 219 7.3 Titania 235 7.3.1 General Properties and Applications 235 7.3.2 Processing of Titania 235 7.3.3 Structure of Titania 237 7.3.4 Selected Applications 238 7.3.4.1 Pigments 238 7.3.4.2 Semiconductor Gas Sensors 239 7.3.4.3 Photocatalysis 240 7.3.4.4 Antimicrobial Coatings 243 7.3.4.5 Photovoltaic Applications 243 References 245 8 Electroceramic Materials 253 8.1 Introduction 253 8.1.1 Defi nition and Properties of Ferroic, Smart, and Intelligent Materials 254 8.1.2 Historical Development of Dielectric Ceramics 256 8.2 Physics of Dielectric Materials 258 8.2.1 Dielectric Effects 258 8.2.2 Electric Polarization in Dielectric Materials 259 8.2.3 Characteristic Dielectric Parameters 267 8.3 Ferroelectric Ceramics 269 8.3.1 Barium Titanate (BT) 273 Contents XI 8.3.2 Lead Zirconate/Lead Titanate (PZT) 275 8.3.3 Ferroelectric Relaxor Ceramics 277 8.4 Microwave Ceramics 281 8.4.1 Grain Boundary Engineering 281 8.4.2 Design of Microwave Ceramics 283 8.5 Pyroelectric and Piezoelectric Ceramics 288 8.5.1 Pyroelectric Ceramics 289 8.5.2 Semiquantitative Model of Piezoelectricity 291 8.5.3 Novel Piezoelectric Single Crystals with CGG Structure 294 8.5.3.1 Structure of CGG Compounds 295 8.5.3.2 Czochralski Growth of Single Crystals 296 8.5.3.3 Selected Properties of Single Crystals with CGG Structure 297 8.6 Electro-Optic Ceramics 301 8.6.1 Linear Electro-Optic (Pockels) Effect 301