DEFECTS AND TRANSPORT IN OXIDES

BATTELLE INSTITUTE MATERIALS SCIENCE COLLOQUIA

Published by Plenum Press

1972: Interatomic Potentials and Simulation of Lattice Defects Edited by Pierre C. Gehlen, Joe R. Beeler, Jr., and Robert I. Jaffee

1973: Deformation and Fracture of High Polymers Edited by H. Henning Kausch, John A. Hassell, and Robert I. Jaffee

1974: Defects and Transport in Oxides Edited by Martin S. Seltzer and Robert I. Jaffee-

In preparation:

1975: The Physical Basis for Heterogeneous Catalysis

Edited by

DEFECTS AND TRANSPORT IN OXIDES

MARTIN S. SELTZER Materials Science Department Battelle Memorial Institute, Columbus Laboratories

ROBERT I. JAFFEE Materials Science Department Battelle Memorial Institute, Columbus Laboratories

BATTELLE INSTITUTE MATERIALS SCIENCE COLLOQUIA

Columbus and Salt Fork, Ohio September 17-22, 1973

Robert I. Jaffee, Chairman

SPRINGER SCIENCE+ BUSINESS MEDIA, LLC

Library of Congress Cataloging in Publication Data

Battelle Institute Materials Science Colloquia, 8th, Columbus and Salt Fork, Ohio, 1973. Defects and transport in oxides.

Includes bibliographical references. 1. Crystals-Defects-Congresses. 2. Mass transfer-Congresses. 3. Oxides-Congresses.

1. Seltzer, Martin S., ed. II. Jaffee, Robert Isaac, 1917- ed. III. Title. QD921.B35 1973 548'.842 74-19162 ISBN 978-1-4615-8725-5 ISBN 978-1-4615-8723-1 (eBook) DOI 10.1007/978-1-4615-8723-1

© 1974 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1974 Softcover reprint of the hardcover 1 st edition 197 4

All rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

To the late PROFESSOR JOHN E. DORN

whose contributions to the science of deformation of solids via thermal activation and climb of defects has been part of the broad foundation of transport processes by defects described for oxides in this volume.

J. S. ANDERSON University of Oxford, Oxford, England P. CARO CNRS, Bellevue-Meudon, France

PARTICIPANTS

T. D. CIDKALLA Battelle, Pacific Northwest Laboratories, Rich/and, Washington, U.S.A.

A. H. CLAUER Battelle, Columbus Laboratories, Columbus, Ohio, U.S.A. J. B. COHEN Northwestern University, Evanston, Illinois, U.S.A. R. CONDIT University of California, Livermore, California, U.S.A. J. M. COWLEY Arizona State University, Tempe, Arizona, U.S.A. A. L. DRAGOO National Bureau of Standards, Washington, D.C. .. U.S.A. L. EYRING Arizona State University, Tempe, Arizona, U.S.A. P. L. F ARNSWORTH Exxon Nuclear Company, Richland, Washington, U.S.A. A. D. FRANKUN National Bureau of Standards, Washington, D. C., U.S.A. J. B. GOODENOUGHMassachusetts Institute of Technology, Cambridge, Massachusetts,

U.S.A. H. C. GRAHAM Aerospace Research Laboratories, Wright-Patterson Air Force Base,

Ohio, U.S.A. K. HAGEMARK 3M Company, St. Paul, Mhnesota, U.S.A. P. E. HART Battelle, Pacific Northwest Laboratories, Richland, Washington, U.S.A. K. HAUFFE Institut fur Physikalische Chemie der Universitiit Gottingen, Gottingen,

West Germany A. H. HEUER Case Western Reserve University, Cleveland, Ohio, U.S.A. J. M. HOI\ilG Purdue University, Lafayette, Indiana, U.S.A. R A. HUGGINS Stanford University, Stanford, California, U.S.A.

vii

viii PARTICIPANTS

J. C. HURT Army Research Office, Durham, North Carolina, U.S.A. B. ILSCHNER Universitiit Erlangen-Nurnberg, Erlangen, West Germany R I. JAFFEE Battelle, Columbus Laboratories, Columbus, Ohio, U.S.A. D. L. JOHNSON Northwestern University, Evanston, Illinois, U.S.A. P. J. JORGENSEN Stanford Research Institute, Menlo Park, California, U.S.A. P. KOFSTAD Central Institute for Industrial Research, Blindern-Oslo, Norway F. A. KROGER University of Southern California, Los Angeles, California, U.S.A. RA. LAD NASA Lewis Research Center, Cleveland, Ohio, U.S.A. G. G. LIBOWITZ Allied Chemical Corporation, Morristown, New Jersey, U.S.A. A. B. LIDIARD Atomic Energy Research Establishment, Harwell, Didcot, Berks.,

England P. LINDENMEYER National Science Foundation, Washington, D.C., U.S.A. B. LUX Battelle, Geneva Research Centre, Geneva, Switzerland A. J. MARKWORTH Battelle, Columbus Laboratories, Columbus, Ohio, U.S.A. F. A. NICHOLS Westinghouse Electric Corporation, West Mifflin, Pennsylvania, U.S.A. A. S. NOWICK Columbia University, New York, New York, U.S.A. M. O'KEEFFE Arizona State University, Tempe, Arizona, U.S.A. R A. RAPP The Ohio State University, Columbus, Ohio, U.S.A. H. SCHMALZRIED Technische Universitiit Clausthal, Zellerfeld, West Germany M. S. SELTZER Battelle, Columbus Laboratories, Columbus, Ohio, U.S.A. P. G. SHEWMON National Science Foundation, Washington, D.C., U.S.A. W. W. SMELTZER McMaster University, Hamilton, Ontario, Canada H. G. SOCKEL Institut fiir Werkstoffwissenschaften I der Universitiit Erlangen­

Nurnberg, Erlangen, West Germany J. STRINGER University of Liverpool, Liverpool, England V. S. STUBICAN The Pennsylvania State University, University Park, Pennsylvania,

U.S.A. N. M. T ALLAN Aerospace Research Laboratories, Wright-Patterson Air Force Base,

Ohio, U.S.A. D. S. TANNHAUSER Technion-Israel Institute of Technology, Haifa, Israel R P. TURCOTTE Battelle, Pacific Northwest Laboratories, Rich/and, Washington,

U.S.A. H. J. VINK Philips Research Laboratories, Eindhoven, Netherlands J. B. WAGNER, JR Northwestern University, Evanston, Illinois, U.S.A. D. D. WELSH Brookhaven National Laboratory, New York, New York, U.S.A. J. E. WERTZ University of Minnesota, Minneapolis, Minnesota, U.S.A. J. M. WIMMER Aerospace Research Laboratories, Wright-Patterson Air Force Base,

Ohio, U.S.A. I. G. WRIGHT Battelle, Columbus Laboratories, Columbus, Ohio, U.S.A.

PREFACE

DEFECTS AND TRANSPORT IN OXIDES is the proceedings of the eighth Battelle Colloquium in the Materials Sciences, held in Columbus and Salt Fork, Ohio, September 17-22, 1973. It took as its theme the relationship between defects and transport of both mass and charge in oxides. Applications of defect-controlled transport to a number of important processes in oxides also were covered. In selecting this topic, the Organizing Committee thought that 1973 was timely to bring together the leading theoretical and experimental researchers in the oxide transport field to review its status in a critical way, and to consider current major research directions and how research in the future might be guided into fruitful areas.

The meeting was highlighted by the presentation of several papers which suggest that major advances in our understanding of transport in oxides appear to be imminent. These papers dealt with the results of new theoretical approaches whereby the energies and configurations of defects may be calculated, and with new experimental techniques for indirectly observing these defects, previously thought to be below the limits of experimental resolving power. Other papers, dealing with the application of defect chemistry to technological processes, served to demonstrate the successes and to point out yet unresolved problems associated with

ix

x PREFACE

understanding the chemistry of imperfect crystals. As the usual custom, the Colloquium started with a first day of

introductory lectures by major contributors to the field. In the evening of the first day an address was given by Dr. H. J. Vink, one of the important early contributors. The first intrcductory lecture by Dr. F. A. Kroger provided the Colloquium with an excellent historical review of defect thermodynamics and the various means for characterizing defects. Dr. J. S. Anderson then introduced the topic of the real structure of defect solids. Dr. John B. Goodenough introduced charge transport, and Dr. H. Schmalzried discussed mass transport involved in solid-solid reactions. Finally, Dr. A. B. Lidiard introduced the theoretical calculation of defect configurations through the use of interatomic potentials.

On the following days, the overall field was divided into the follow­ing sessions: Theory and Characterization, Transport of Mass and Charge, and Defect-Dependent Processes (in two groups). Each session was introduced by a morning presentation of research papers and, after a free afternoon, ended with an evening agenda-discussion session covering the critical issues in each of the subtopics. Finally, a concluding agenda discussion covering issues in the overall field was led by Dr. A. S. Nowick. The reader is commended to these discussions for an up-to-date statement of the status of research in oxide transport.

Each Colloquium customarily honors one of the distinguished partici­pants by inscribing the proceedings in his name. At Salt Fork, we deviated from this custom by honoring the late Professor John E. Dom of the University of California at Berkeley. Although Professor Dorn had not worked on defects and transport in oxides, he was an important con­tributor to the field of defect transport in solids. He was a great friend of Battelle, and had participated in many of the early Colloquia. His untimely death in September of 1971, several months after contracting pneumonia while participating in the June 1971 Colloquium on "Inter­atomic Potentials and Simulation of Lattice Defects", prevented us from honoring him as a participant during his lifetime. The Colloquium on "Defects and Transport in Oxides" is the first opportunity Battelle has had to acknowledge its great admiration for Professor Dorn and his many contributions to the science of materials. We were happy that Mrs. Dom was able to attend the concluding banquet on September 22 held in Professor Dorn's honor and memory.

We also wish to thank our Battelle colleagues who have supported the Colloquia. In particular, we wish to thank Dr. Sherwood L. Fawcett, President of Battelle Memorial Institute, and Dr. William H. Jones, Jr., Director of Research in the Physical Sciences of Battelle Institute, under whose auspices these Colloquia are a continuing activity. We are grateful to Dr. John M. Batch, Director of Battelle's Columbus Laboratories, for

PREFACE xi

his participation in the opening and closing events of the Colloquium, and for the excellent support provided by members of the Battelle-Columbus staff: Duane Yothers, in charge of local arrangements; the secretariat headed by Darlene Weaver, including Rose Bowman and Dahlene Walnoha, who provided excellent secretarial assistance; Phillip La Mori, responsible for coordinating meals and wines, bringing haut cuisine to central Ohio; Philip Me Rury, in charge of sound and lighting arrangements; and Lew De Walt, in charge of transportation and slide projection. Edna Jaffee was in charge of the Ladies Program and hospitality. To all these, and many others, we wish to extend our sincere thanks.

The Organizing Committee is grateful to J. S. Anderson, I. G. Austin, L. Eyring, P. Kofstad, F. A. Kroger, G. G. Libowitz, A.·H. Heuer, H. Schmillzried, and C. Wagner for their advice and the choice of subject and participants for this Colloquium.

This book dealing with the transport behavior of oxides is the first in the Battelle Colloquia series that has been concerned with oxides. We trust it will not be the last, and that it will be useful to old and new workers in the field. If new advances in oxides result from having held this Colloquium, our purposes will have been served well.

The Organizing Committee R. I. Jaffee, Chairman T. D. Chikalla P. L. Farnsworth R. A. Rapp M. S. Seltzer N M. Tallan B. A. Wilcox

Participants Preface . .

Part One INTRODUCTORY LECTURES

CONTENTS

vii ix

1. Defect Thermodynamics - Historical F. A. KROGER . 3 DISCUSSION . . . . . . . . . . . . . . . 23

2. The Real Structure of Defect Solids J. S. ANDERSON 25 DISCUSSION . . . . . . . . . . . . . . . 49

3. Electron Transport in Transition-Metal and Rare-Earth Oxides J. B. GOODENOUGH . . . . . . . . . . . . . 55 DISCUSSION . . . . . . . . . . . . . . . . 80

4. Solid-State Reactions Between Oxides H. SCHMALZRIED 83 DISCUSSION . . . . . . . . . . 106

5. Point Defects in Oxides A. B. LIDIARD 109 DISCUSSION . . . . . . . . . . 123

Banquet Address: Scientific Understanding of the Manufacture and Properties of Solid Oxidic Industrial Materials H. J. Vink . . . . 127

Part Two THEORY AND CHARACTERIZATION

1. Calculation of Defect-Formation Energies in Alkaline-Earth Oxides: Interionic Forces A. D. FRANKLIN AND A. L. DRAGOO 141 DISCUSSION . . . . . . . . . . . . . . . . . . 155

xiii

xiv CONTENTS

2. Concentrated Defects in Pu02 R. P. TURCOTTE AND T. D. CHIKALLA . . . . . . . . . . . . 159 DISCUSSION . . . . . . . . . . . . . . . 173

3. The Defect Structure of Transition-Metal Monoxides M. HAY AKA WA, M. MORINAGA, AND J. B. CO HEN . 177 DISCUSSION . . . . . . . . . . . . . . . 199

4. High-Resolution Electron Microscopy of Defects and Disorder in Crystals J. M. COWLEY AND S. IIJIMA 205 DISCUSSION . . . . . . . . . . . . . . 220

5. Vacancy-Related Defects in the Alkaline-Earth Oxides J. E. WERTZ 225 DISCUSSION . . . . . . . . . . . . . . 236

6. Defect Characterization by Indirect Experimental Techniques N. M. TALLAN 239 DISCUSSION . . . . . . . . . . . . . . . . . 247

Agenda Discussion: Theory and Characterization of Defects and Transport in Oxides Chairman, L. Eyring Secretary, A. L. Dragoo . . . 251

Part Three TRANSPORT OF MASS AND CHARGE

1. Electrical Conductivity and, Diffusion in Some Transition-Metal Oxides J. B. WAGNER, JR. . . _ . .. . . .. . . . . 283 DISCUSSION . . . . . . . . . . . . . . . . . . 298

2. Diffusion-Path Networks in the Wurtzite Lattice R. H. CONDIT. 303 DISCUSSION . . . . . . . . . . . . . . . . . . 312

3. Some Aspects of Electrical Properties of Metal Oxides J. M. HONIG 315 DISCUSSION . . . . . . . . . . . . . . . . . 330

4. Growth of Pure Crystals of NiO and Measurement of Their Drift Mobility D: S. TANNHAUSER . . . . . . . 333 DISCUSSION . . . . . . . . . . . . . . . . 339

5. Defect Structure and Electrical Conductivity of Crystalline Ferrous Silicate H. G. SOCKEL 341 DISCUSSION . . . . . . . . . . . . . 355

Agenda Discussion: Transport of Mass and Charge Chairman, P. Kofstad Secretary, J. M. Wimmer . . . . . . . . . . 357

Part Four DEFECT DEPENDENT PROCESSES I (Creep & Sintering)

1. Nonstoichiometry and Doping in the Sintering of Oxides D. L. JOHNSON . . . . . . . . . . . . DISCUSSION . . . . . . . . . . . . .

2. Final Stage Sintering and Grain Growth in Oxides P. J. JORGENSEN DISCUSSION . . . . . . . . . . . . .

365 377

379 393

CONTENTS xv

3. Approaches to Describing the Kinetic Behavior of Distributions of Second-Phase Inclusions A. J. MARKWORTH . . . . 397 DISCUSSION . . . . . . . . . . . . . . . . 411

4. Precipitation Hardening in Ceramics A. H. HEUER AND G. K. BANSAL . . . . . . . . . . . . . . . 415 DISCUSSION . . . . . . . . . . . . . . . . 422

5. Development of Substructures During Creep and Effect of Ionic Defects and Precipitates on the Strength of Magnesium Oxide B. ILSCHNER AND B. REPPICH . . . . . . . . 425 DISCUSSION . . . . . . . . . . . . . . . 438

6. The Influence of Stoichiometric Defects on the Creep of Oxides With the Fluorite Structure M. S. SELTZER, B. A. WILCOX, AND A. H. CLAUER 443 DISCUSSION . . . . . . . . . . . . . . 455

Agenda Discussion: Creep and Sintering Chairman, F. A. Nichols Secretary, P. E. Hart . . . . . . . . . . . . . . . . . 459

Part Five DEFECT DEPENDENT PROCESSES 11 (Oxidation, Solid State Reactions, Electrochemistry)

I. Diffusional Growth of Oxide Scales on Binary Alloys W. W. SMELTZER . . . . . . . . . . . .

2. The Importance of Short-Circuit and Related Transport Processes 475

in High-Temperature Oxidation J. STRINGER . . . . . 495 DISCUSSION . . . . . . . . . . . . . . . . . 515

3. Defects and Impurities Influences on Phase Transformations in Rare Earth Oxides P. E. CARO, G. SCHIFFMACHER, C. BOULESTEIX, CH. LOIER, AND R. PORTIER . . . . 519

4. Interdiffusion and Association Phenomena in Some Oxide Systems V. S. STUBICAN AND W. J. MINFORD . . . . . . . . . 537

5. Ionic Conduction in Oxides at Low Temperatures R. A. HUGGINS 549 DISCUSSION . . . . . . . . . . . . . . . . . . 562

Agenda Discussion: Oxidation, Solid Reactioms, Electrochemistry Chairman, R. A. Rapp Secretary, H. C. Graham . . . . . . . . . 567

Part Six CONCLUDING DISCUSSION: CRITICAL ISSUES

Concluding Discussion: Critical Issues Chairman, A. S. Nowick Secretary, G. G. Libowitz .

Author Index .

Subject Index .

Chemical Index

583

601

605

609