Chemical Processing of Ceramics Second Edition © 2005 by Taylor & Francis Group, LLC MATERIALS ENGINEERING 1. Modern Ceramic Engineering: Properties, Processing, and Use in Design. Second Edition, Revised and Expanded, David W. Richerson 2. Introduction to Engineering Materials: Behavior, Properties, and Selection, G. T. Murray 3. Rapidly Solidified Alloys: Processes • Structures • Applications, edited by Howard H. Liebermann 4. Fiber and Whisker Reinforced Ceramics for Structural Applications, David Belitskus 5. Thermal Analysis of Ceramics, Robert F. Speyer 6. Friction and Wear of Ceramics, edited by Said Jahanmir 7. Mechanical Properties of Metallic Composites, edited by Shojiro Ochiai 8. Chemical Processing of Ceramics, edited by Burtrand I. Lee and Edward J. A. Pope 9. Handbook of Advanced Materials Testing, edited by Nicholas P. Cheremisinoff and Paul N. Cheremisinoff 10. Ceramic Processing and Sintering, M. N. Rahaman 11. Composites Engineering Handbook, edited by P. K. Mallick 12. Porosity of Ceramics, Roy W. Rice 13. Intermetallic and Ceramic Coatings, edited by Narendra B. Dahotre and T. S. Sudarshan 14. Adhesion Promotion Techniques: Technological Applications, edited by K. L. Mittal and A. Pizzi 15. Impurities in Engineering Materials: Impact, Reliability, and Control, edited by Clyde L. Briant 16. Ferroelectric Devices, Kenji Uchino 17. Mechanical Properties of Ceramics and Composites: Grain and Particle Effects, Roy W. Rice 18. Solid Lubrication Fundamentals and Applications, Kazuhisa Miyoshi 19. Modeling for Casting and Solidification Processing, edited by Kuang-O (Oscar) Yu 20. Ceramic Fabrication Technology, Roy W. Rice 21. Coatings of Polymers and Plastics, edited by Rose A. Ryntz and Philip V. Yaneff © 2005 by Taylor & Francis Group, LLC 22. MicroMechatronics, edited by Kenji Uchino and Jayne Giniewicz 23. Ceramic Processing and Sintering, Second Edition, edited by M. N. Rahaman 24. Handbook of Metallurgical Process Design, edited by George Totten 25. Ceramic Materials for Electronics, Third Edition, Relva Buchanan 26. Physical Metallurgy, William F. Hosford 27. Carbon Fibers and Their Composites, Peter Morgan 28. Chemical Processing of Ceramics: Second Edition, Burtrand Lee and Sridhar Komarneni © 2005 by Taylor & Francis Group, LLC Chemical Processing of Ceramics Second Edition edited by Burtrand Lee Sridhar Komarneni Boca Raton London New York Singapore A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc. © 2005 by Taylor & Francis Group, LLC Published in 2005 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2005 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 987654321 International Standard Book Number-10: 1-57444-648-7 (Hardcover) International Standard Book Number-13: 978-1-57444-648-7 (Hardcover) Library of Congress Card Number 2004065504 This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright.com Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Chemical processing of ceramics.–2nd ed. / edited by Burtrand Lee and Sridhar Komarneni. p. cm.– (Materials engineering ; 28) Includes bibliographical references and index. ISBN 1-57444-648-7 (alk. paper) 1. Ceramics–Analysis. 2. Ceramic materials. I. Lee, Burtrand Insung. II. Komarneni, Sridhar. III. Title. IV. Series: Materials engineering (Marcel Dekker, Inc.) ; 28. TP810.5.C48 2005 666–dc22 2004065504 Visit the Taylor & Francis Web site at and the CRC Press Web site at Taylor & Francis Group is the Academic Division of T&F Informa plc. © 2005 by Taylor & Francis Group, LLC (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, http://www.taylorandfrancis.com http://www.crcpress.com Foreword The progress of civilization is often marked by naming ages, for example, the Stone Age, the Bronze Age, the Iron Age, the Steel Age. We are at the threshold of change from the Silicon or Information Age to the Age of Biology. A vital question is “What is the role of ceramics in an age of biology?” It is a challenging question and the future growth of the ceramics industry may well depend on how cleverly we approach the needs of the biological revolution and an aging popu- lation. Large segments of the population will need replacement parts before death. Can ceramics provide the additional survivability of these prostheses? Can bio- active ceramics with controlled release of ions and growth factors be used to turn on the body’s own regenerative potential? We are also at the threshold of a change from an energy-rich society to an energy-declining society. How will ceramics help industry respond to this need? Can we create recyclable ceramic products that are affordable? Can we make products with substantially lower power requirements? Again, these questions are difficult, but the creativity of our responses may determine the quality of life for the new age. This new edition of Chemical Processing of Ceramics offers a scientific and technological framework for achieving creative solutions to the questions posed above. It has been 20 years since the first Ultrastructure and Chemical Processing Conference proceedings were published. Enormous progress has been made in understanding the process mechanisms for chemical-based processing of new materials. The theoretical foundations are now well established and are being applied to an expanding range of materials. New process methods are being discovered. These new developments are all discussed in this new edition. The editors have made thoughtful selections from the leading researchers in the field. Their success makes this book a must for every serious investigator in the field of ceramic processing. Larry L. Hench Professor of Ceramic Materials Imperial College, London © 2005 by Taylor & Francis Group, LLC Preface Despite many recent advances in materials science and engineering, the perfor- mance of ceramic components in severe conditions is still far below the ideal limits predicted by theory. The emphasis on the relation between processing, structure, and behavior has been fruitful for ceramic scientists for several decades. It has been recently realized, however, that major advances in ceramics during the next several decades will require an emphasis on molecular-level or nanoscale control. Organic chemistry, once abhorred by ceramic engineers trained to define ceramics as “inorganic-nonmetallic materials,” has become a valuable asset in designing and synthesizing new ceramics. It has recently been established that as the structural scale in ceramics is reduced from macro- to micro- to nanocrys- talline regimes, the basic properties are drastically altered. Some brittle ceramic materials have been shown to be partially ductile. Quantum dot semiconducting ceramic particles emit different colors, depending on their size, and this property can be useful in various applications. The impetus and the ultimate goal in chemical processing of ceramic materials is to control physical and chemical variability by the assemblage of uniquely homogeneous structures, nanosized second phases, controlled surface composi- tional gradients, and unique combinations of dissimilar materials to achieve desired properties. Significant improvements in environmental stability and per- formance should result from such nanoscale or molecular design of materials. A number of books are available that deal with the chemical processing aspect of ceramic materials, but most of them are conference proceedings. This revised edition of Chemical Processing of Ceramics is written to update, enhance, and expand the topics in the first edition published in 1994. Many authors who are actively involved in the field of chemical processing of ceramic materials from all over the world contributed to the first edition. The authors in this edition are also from the international community—Australia, Japan, Germany, Korea, France, Russia, Switzerland, and the U.S.—practicing chemical principles in the fabrication of superior ceramic materials. Thus this book presents current developments and concepts in the chemical techniques for production and characterization of state-of-the-art ceramic mate- rials in a truly interdisciplinary fashion. The 27 chapters are divided into five parts reflecting topical groups. The first part discusses the starting materials—how to prepare and modify them in the nanoscale range. Powders are the most heavily used form of starting ceramic materials. The synthesis, characterization, and behavior of ceramic powders are presented in parts I and II. In the third part, processing of ceramic films via the sol-gel technique is discussed. Fabrication of © 2005 by Taylor & Francis Group, LLC nonoxide ceramics is covered in part IV. In the last part, several specific examples of classes of ceramic materials fabricated by chemical processing, including thin films, membranes, ferroelectrics, bioceramics, dielectrics, batteries, and super- conductors, are presented. These classes of examples are chosen on the basis of the current demand and active research. The topics on basic principles of the sol- gel technique, sintering, and postsintering processes are not included in this volume because there are other excellent books dealing solely with these topics. Although this book is edited, it is organized to reflect the sequence of ceramics processing and the coherent theme of chemical processing for advanced ceramic materials. Hence this book is suitable as a supplementary textbook for advanced undergraduate and graduate courses in ceramic science and materials chemistry, as well as an excellent reference book for practicing ceramists, chemists, materials scientists, and engineers. As shown by the data presented in this book, some of the interesting results from chemical processing have not yet made their way into real applications of ceramic materials. We are optimistic that, through further research, the full potential of chemical processing for high-performance ceramic materials can be realized. It is hoped that this book, through the authors’ and editors’ contributions, will bring researchers and engineers in the ceramics and chemical fields closer together to produce superior ceramic materials. Burtrand I. Lee Sridhar Komarneni © 2005 by Taylor & Francis Group, LLC Editors Burtrand Insung Lee, Ph.D. is a professor in the School of Materials Science & Engineering at Clemson University, Clemson, South Caro- lina. He obtained his B.S. degree in chemistry from Southern Adventist University, Tennes- see, and Ph.D. degree in materials science and engineering from the University of Florida, Gainesville, Florida in 1986. His industrial working experience includes Biospherics Inc., Gel Tech Inc., Kemet Electronics Materials Corp., Hitachi Ltd., and Samsung Electronics. Dr. Lee was a Fulbright Professor at Nor- wegian Institute of Technology in Norway in 1989. In 1993 he spent a sabbatical year at Hitachi Research Laboratory as a senior visiting researcher. He has published over 170 technical papers and other books on ceramic and polymer processing as well as several U.S. patents. He has co-organized many national/international technical symposia on materials and nano-processing. Dr. Lee received the MRS Award in 1986, Fulbright Scholar Award in 1989, Clemson Board of Trustee Faculty Excellence Awards in 2001 and 2004, and he was selected as a Lady Davis Fellow in 2004. Dr. Lee teaches colloidal and surface science as well as general materials processing at Clemson University. He is also director of Nanofabritech ® . His current research activities are focused on chemical processing of ceramic and polymeric materials, paying particular attention to surface and interfacial chemistry. © 2005 by Taylor & Francis Group, LLC Sridhar Komarneni, Ph.D. is a professor of clay mineralogy at The Pennsylvania State University, University Park, Pennsylvania. He conducts research on synthesis and pro- cessing of nanophases and nanocomposites by sol-gel and hydrothermal processing and on both basic and applied aspects of clay minerals. He has published over 415 refereed papers and edited or written 13 books during his career and received numerous awards. Dr. Komarneni was elected to The World Acad- emy of Ceramics, The European Academy of Sciences and Fellows of The American Asso- ciation for the Advancement of Science, The Royal Society of Chemistry, The American Society of Agronomy, The Soil Science Society of America, and The American Ceramic Society. He serves as the editor-in-chief of Journal of Porous Materials. © 2005 by Taylor & Francis Group, LLC [...]... for Ceramics 439 Markus Weinmann Chapter 19 Polymer Pyrolysis 491 Masaki Narisawa SECTION V Processing of Specialty Ceramics Chapter 20 Chemical Vapor Deposition of Ceramics 511 Guozhong Cao and Ying Wang Chapter 21 Ceramic Photonic Crystals: Materials, Synthesis, and Applications .543 Jeffrey DiMaio and John Ballato Chapter 22 Tailoring Dielectric Properties of Perovskite Ceramics. .. Group, LLC 18 I Chemical Processing of Ceramics, Second Edition HYDROTHERMAL SONOCHEMICAL METHOD Ultrasonic waves are often used in analytical chemistry for dissolving powder into solution.49 The hydrothermal sonochemical method is a new method for synthesizing materials.50 III IDEAL POWDERS AND REAL POWDERS The characteristics of ideal powders and real powders produced by hydrothermal processing are... One of the industrial applications of hydrothermal precipitation is ordinary alumina production The Bayer process is shown in Figure 1.7.29 T FIGURE 1.6 TEM of monoclinic zirconia powder using hydrothermal reaction (100 MPa at 400°C for 24 h) using 8 wt% KF solution © 2005 by Taylor & Francis Group, LLC 10 Chemical Processing of Ceramics, Second Edition TABLE 1.4 Phases Present and Crystallite Size of. .. is slightly modified 3 © 2005 by Taylor & Francis Group, LLC 4 Chemical Processing of Ceramics, Second Edition I INTRODUCTION Inorganic powders play a key role in many fields ceramics, catalysts, medicines, food, etc.—and many papers and books discuss powder preparation.1–5 Powder preparation is a very important step in the processing of ceramics Table 1.1 presents the methods used for preparing fine... Group, LLC 14 Chemical Processing of Ceramics, Second Edition FIGURE 1.12 TEM of BaTiO3 powders prepared by the hydrothermal electrochemical method (250°C, 0.5 N Ba(NO3)2, titanium plate) F REACTIVE ELECTRODE SUBMERGED ARC Reactive electrode submerged arc (RESA) is a totally new process for making powders.34,35 RESA produces extremely high temperatures (approximately 10,000 K) with a pressure of 1 atm H2O... for 4 h using 200 balls at 37 rpm © 2005 by Taylor & Francis Group, LLC 16 Chemical Processing of Ceramics, Second Edition FIGURE 1.16 Microwave-assisted reaction system (MARS 5) H MICROWAVE HYDROTHERMAL PROCESS Microwave-assisted hydrothermal synthesis is a novel powder processing technology for the production of a variety of ceramic oxides and metal powders under closed-system conditions Komarneni... Yonsei University Seoul, Korea Table of Contents SECTION I Chapter 1 Powder Synthesis and Characterization Hydrothermal Synthesis of Ceramic Oxide Powders .3 Shigeyuki Somiya, Rustum Roy, and Sridhar Komarneni Chapter 2 Solvothermal Synthesis 21 Masashi Inoue Chapter 3 Mechanochemical Synthesis of Ceramics 65 Aaron C Dodd Chapter 4 Cryochemical Synthesis of Materials 77 Oleg A Shlyakhtin,... Minnesota Robert Schwartz University of Missouri Rolla, Missouri Ying Wang University of Washington Seattle, Washington Oleg A Shlyakhtin Moscow State University Moscow, Russia Rainer Waser RWTH Aachen University of Technology Aachen, Germany Wolfgang Sigmund University of Florida Gainesville, Florida Shigeyuki Somiya Tokyo Institute of Technology and Teikyo University of Science and Technology Tokyo,... pressure, time, concentration of the metal solution, pH, etc The key result is crystallization reactions, which lead to faster kinetics by one or two orders of magnitude compared to conventional hydrothermal processing The use of microwaves in both solid and liquid states is gaining in popularity for many reasons, but especially because of the potential energy savings The use of microwaves under hydrothermal... Park SECTION III Sol-Gel Processing Chapter 16 Chemical Control of Defect Formation During Spin-Coating of Sol-Gels 411 Dunbar P Birnie, III © 2005 by Taylor & Francis Group, LLC Chapter 17 Preparation and Properties of SiO2 Thin Films by the Sol-Gel Method Using Photoirradiation and Its Application to Surface Coating for Display .421 Tomoji Ohishi SECTION IV Ceramics Via Polymers Chapter . number of books are available that deal with the chemical processing aspect of ceramic materials, but most of them are conference proceedings. This revised edition of Chemical Processing of Ceramics. questions are difficult, but the creativity of our responses may determine the quality of life for the new age. This new edition of Chemical Processing of Ceramics offers a scientific and technological. Composites, Peter Morgan 28. Chemical Processing of Ceramics: Second Edition, Burtrand Lee and Sridhar Komarneni © 2005 by Taylor & Francis Group, LLC Chemical Processing of Ceramics Second Edition edited