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Electroceramics: Materials, Properties, Applications, Second شبکه آزمایشگاهی ایران مواد FESEM , SEM , TEM ,XRD XRF, SPS, TGA, DTA, DSC, FTIR, BET www.IMlabsnet.ir مرکز آموزش تخصصی ایران مواد Iran MavadEducation Professional Center آموزش های تخصصی و نرم افزاری مهندسی مواد و متالورژی www.IMpec.ir گروه فنی پژوهش ایران مواد ویراستاری، ترجمه تخصصی مقاﻻت و کتب مهندسی مواد مشاوره پژوهشی تا چاپ مقاله ISI www.IMpaper.ir www.iran-mavad.com اﯾﺮان ﻣﻮاد Electroceramics Second Edition Materials Á Properties Á Applications A. J. Moulson and J. M. Herbert www.iran-mavad.com اﯾﺮان ﻣﻮاد www.iran-mavad.com اﯾﺮان ﻣﻮاد Electroceramics Second Edition www.iran-mavad.com اﯾﺮان ﻣﻮاد www.iran-mavad.com اﯾﺮان ﻣﻮاد Electroceramics Second Edition Materials Á Properties Á Applications A. J. Moulson and J. M. Herbert www.iran-mavad.com اﯾﺮان ﻣﻮاد Copyright u 2003 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England Telephone (+44) 1243 779777 Email (for orders and customer service enquiries): [email protected] Visit our Home Page on www.wileyeurope.com or www.wiley.com All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London W1T 4LP, UK, without the permission in writing of the Publisher. Requests to the Publisher should be addressed to the Permissions Department, John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England, or emailed to [email protected], or faxed to (+44) 1243 770571. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the Publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought. Other Wiley Editorial Offices John Wiley & Sons Inc., 111 River Street, Hoboken, NJ 07030, USA Jossey-Bass, 989 Market Street, San Francisco, CA 94103-1741, USA Wiley-VCH Verlag GmbH, Boschstr. 12, D-69469 Weinheim, Germany John Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons Canada Ltd, 22 Worcester Road, Etobicoke, Ontario, Canada M9W 1L1 Library of Congress Cataloging-in-Publication Data British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0471 49747 9 (hardback) ISBN 0471 49748 7 (paperback) Typeset by Dobbie Typesetting Ltd, Tavistock, Devon Printed and bound in Great Britain by T.J. International, Padstow, Cornwall This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production. www.iran-mavad.com اﯾﺮان ﻣﻮاد CONTENTS Preface xi Acknowledgements xv Glossary xvii 1: Introduction 1 2: Elementary Solid State Science 5 2.1 Atoms 5 2.2 The arrangement of ions in ceramics 10 2.3 Spontaneous polarization 17 2.4 Phase transitions 19 2.5 Defects in crystals 20 2.5.1 Non-stoichiometry 20 2.5.2 Point defects 21 2.6 Electrical conduction 24 2.6.1 Charge transport parameters 24 2.6.2 Electronic conduction 26 2.6.3 Ionic conduction 43 2.6.4 Summary 47 2.6.5 Schottky barriers to conduction 48 2.7 Charge displacement processes 52 2.7.1 Dielectrics in static electric fields 52 2.7.2 Dielectrics in alternating electric fields 60 2.7.3 Barium titanate – the prototype ferroelectric ceramic 71 2.7.4 Mixtures of dielectrics 72 2.7.5Impedancespectroscopy85 Problems 90 Bibliography 92 3: Processing of Ceramics 95 3.1 General 95 3.2 Cost 96 3.3 Raw materials 96 3.4 Powder preparation – mixing and grinding 97 3.4.1 The ‘mixed oxide’ or solid state route 100 3.4.2 The oxalate route 100 3.4.3 The alkoxide route 101 3.4.4 Hydrothermal synthesis 101 Electroceramics: Materials, Properties, Applications. 2nd Edition. Edited by A. J. Moulson and J. M. Herbert. & 2003 John Wiley & Sons, Ltd: ISBN 0 471 49747 9 (hardback) 0 471 49748 7 (paperback) www.iran-mavad.com اﯾﺮان ﻣﻮاد vi CONTENTS 3.5 Calcination 101 3.6 Shaping 103 3.6.1 Dry-pressing 104 3.6.2 Isostatic-pressing 106 3.6.3 ‘Jolleying’ 107 3.6.4 Extrusion 107 3.6.5 Colloidal processing: slip-casting 108 3.6.6 Tape-casting 109 3.6.7 Calendering and viscous polymer processing 110 3.6.8 Injection-moulding 111 3.6.9 Films and layers 111 3.7 High-temperature processing 114 3.7.1 Densification 114 3.7.2 Hot-pressing 115 3.7.3 Isostatic hot-pressing 116 3.7.4 Glass-ceramics 117 3.8 Finishing 118 3.9 Porous materials 119 3.10 Processing and electroceramics research and development 120 3.11 The growth of single crystals 121 Problems 130 Bibliography 133 4: Ceramic Conductors 135 4.1 High-temperature heating elements and electrodes 135 4.1.1 Silicon carbide 136 4.1.2 Molybdenum disilicide 141 4.1.3 Lanthanum chromite 141 4.1.4Tinoxide142 4.1.5 Zirconia 144 4.2 Ohmic resistors 145 4.2.1Thinfilms146 4.2.2 Thick films 147 4.3 Voltage-dependent resistors (varistors) 150 4.3.1 Electrical characteristics and applications 150 4.3.2 Silicon carbide 156 4.3.3 Zinc oxide 156 4.4 Temperature-sensitive resistors 159 4.4.1 Negative temperature coefficient resistors (NTC thermistors) 160 4.4.2 Positive temperature coefficient resistors (PTC thermistors) 167 4.5 Fuel cells and batteries 173 4.5.1 The stimulus for developing fuel cells and batteries 173 4.5.2 Basics of fuel cells and batteries 176 4.5.3 Electroceramics for fuel cells and batteries 184 4.6 Ceramics-based chemical sensors 198 4.6.1 Sensors based on solid electrolytes 199 4.6.2 Gas-sensors based on electronically conducting ceramics 207 4.6.3 Humidity sensors 214 4.7 High transition temperature superconductors 217 4.7.1 Overview 217 4.7.2 The phenomenon of superconductivity 218 4.7.3 Ceramic high-Tc superconductors (HTSs) 222 www.iran-mavad.com اﯾﺮان ﻣﻮاد CONTENTS vii 4.7.4 The properties, processing and applications of HTSs 225 4.7.5 Superconducting electronics – thin films 233 4.7.6 The future for HTSs 235 Problems 236 Bibliography 240 5: Dielectrics and Insulators 243 Part I Capacitative Applications 244 5.1 Background 244 5.2 Dielectric strength 245 5.2.1 Test conditions 246 5.2.2 Breakdown mechanisms 246 5.3 Thermal shock resistance 250 5.4 Capacitors 251 5.4.1 Capacitor characteristics 251 5.4.2 Non-ceramic capacitors 256 5.4.3 Ceramic capacitors 260 Part II Principal Ceramic Types and Applications 269 5.5 Low-permittivity ceramic dielectrics and insulators 269 5.5.1 Electrical porcelains 269 5.5.2 Alumina 276 5.5.3 Beryllia 285 5.5.4 Aluminium nitride 286 5.5.5 Ceramic ‘packaging’ technology 286 5.6 Medium-permittivity ceramics 289 5.6.1 Rutile ceramic 290 5.6.2 Degradation in titanium-containing oxides 293 5.6.3 High-power capacitors 295 5.6.4 Low-TCC low-loss capacitors 297 5.6.5 Microwave ceramics 300 5.7 High-permittivity ceramics 310 5.7.1 Modified barium titanate dielectrics 311 5.7.2 Relaxor ferroelectrics 320 5.7.3 Multilayer capacitors with base metal electrodes (BME) 323 5.7.4 Barrier layer caps (Class IV) 326 5.7.5 Ferroelectric memories 329 Problems 333 Bibliography 335 6: Piezoelectric Ceramics 339 6.1 Background theory 339 6.2 Parameters for piezoelectric ceramics and their measurement 344 6.3 General characteristics and fabrication of PZT 354 6.3.1 Effects of domains 354 6.3.2 Effects of aliovalent substituents 358 6.3.3 Fabrication of PZT 361 6.4 Important commercial piezoceramics 362 6.4.1 Barium titanate 362 6.4.2 Lead zirconate–lead titanate (‘PZT’) 364 www.iran-mavad.com اﯾﺮان ﻣﻮاد viii CONTENTS 6.4.3 Lead-based relaxor piezoelectric and electrostrictive ceramics 366 6.4.4 Lead niobate 369 6.4.5 Lithium niobate and lithium tantalate 371 6.4.6 Piezoceramic–polymer composites 373 6.4.7 Summary of properties 379 6.5 Applications 381 6.5.1 Generation of voltages 382 6.5.2 Generation of displacement – ‘actuators’ 386 6.5.3 High frequency applications 396 6.5.4 Piezoceramic–polymer composites 402 6.5.5 Summary 402 Appendix: Piezoelectric relations for ceramics poled in the 3 direction 404 Problems 407 Bibliography 409 7: Pyroelectric Materials 411 7.1 Background 411 7.2 Infrared detection 413 7.3 Effects of circuit noise 417 7.3.1 Johnson noise 418 7.3.2 Thermal fluctuations 418 7.4 Materials 419 7.5 Measurement of the pyroelectric coefficient 422 7.6 Applications 423 7.6.1 Radiometry 424 7.6.2 Pollutant control 425 7.6.3 Intruder alarm 425 7.6.4 Thermal imaging 426 Problems 431 Bibliography 432 8: Electro-optic Ceramics 433 8.1 Background optics 433 8.1.1 Polarized light 434 8.1.2 Double refraction 437 8.1.3 The electro-optic effect 440 8.1.4 Non-linear optics 445 8.1.5 Transparent ceramics 448 8.2 Lanthanum-substituted lead zirconate titanate 449 8.2.1 Structure and fabrication 449 8.2.2 Measurement of electro-optic properties 451 8.2.3 Electro-optic characteristics 454 8.3 Applications 459 8.3.1 Flash goggles 459 8.3.2 Colour filter 460 8.3.3 Display 460 8.3.4 Image storage 461 8.3.5 PLZT films 463 8.4 Optical non-linearity in glass and glass-ceramics 464 Problems 466 Bibliography 468 www.iran-mavad.com اﯾﺮان ﻣﻮاد CONTENTS ix 9: Magnetic Ceramics 469 9.1 Magnetic ceramics: basic concepts 470 9.1.1 Origins of magnetism in materials 470 9.1.2 Magnetization in matter from the macroscopic
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