Transport in Nonstoichiometric Compounds NATO ASI Series Advanced Science Institutes Series A series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics New York and London C Mathematical D Reidel Publishing Company and Physical Sciences Dordrecht, Boston, and Lancaster o Behaviora' and Social Sciences Martinus Nijhoff Publishers E Engineering and The Hague, Boston, and Lancaster Materials Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin. Heidelberg. New York. and Tokyo Recent Volumes in this Series Volume 123-Density Functional Methods in Physics edited by Reiner M. Dreizler and Joao da Providancia Volume 124-Nonequilibrium Phonon Dynamics edited by Walter E. Bron Volume 125-Supersymmetry edited by K. Dietz, A. Flume, G. v. Gehlen, and V. Rittenberg Volume 126-Perspectives in Particles and Fields: Cargese 1983 edited by Maurice Levy, Jean-Louis Basdevant, David Speiser, Jacques Weyers, Maurice Jacob, and Raymond Gastmans Volume 127-Phenomena Induced by Intermolecular Interactions edited by G. Birnbaum Volume 128-Techniques and Concepts of High-Energy Physics III edited by Thomas Ferbel Volume 129-Transport in Nonstoichiometric Compounds edited by George Simkovich and Vladimir S. Stubican Series 8: Physics Transport in Nonstoichiometric Compounds Edited by George Simkovich and Vladimir S. Stubican Pennsylvania State University University Park, Pennsylvania Plenum Press New York and London Published in cooperation with NATO Scientific Affairs Division Proceedings of the Third International Conference and NATO Advanced Research Workshop on Transport in Nonstoichiometric Compounds, held June 11-15, 1984, at Pennsylvania State University, University Park, Pennsylvania Library of Congress Cataloging in Publication Data International Conference on Transport in Nonstoichiometric Compounds (3rd: 1984: Pennsylvania State University) Transport in nonstoichiometric compounds. (NATO ASI series. Series B, Physics; v. 129) "Proceedings of the Third International Conference and NATO Advanced Research Workshop on Transport in Nonstoichiometric Compounds, held June 11-15, 1984, at Pennsylvania State University, University Park, Penn sylvania"-T.p. verso. "Published in cooperation with NATO Scientific Affairs Division." Includes bibliographical references and index. 1. Crystals-Defects-Congresses. 2. Mass transfer-Congresses. I. Simkovich, George. II. Stubican, Vladimir S. III. NATO Advanced Research Workshop on Transport in Nonstoichiometric Compounds (1984: Pennsylvania State University) IV. North Atlantic Treaty Organization. Scientific Affairs Divi sion. V. Title. VI. Series. OD921.15357 1984 530.411 85·17009 ISBN-13: 978-1-4612-9522-8 e-ISBN-13: 978-1-4613-2519-2 DOl: 10.1007/978-1-4613-2519-2 © 1985 Plenum Press, New York Softcover reprint of the hardcover 1s t edition 1985 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013 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 PREFACE Prior to the 9th International Conference on Reactivity Solids in Krakow, Poland a group of about 25 international scientists held a special conference entitled "Transport in Nonstoichiometric Compounds" in late Aug. 1980 in Mogilany, Poland (near Krakow). This conference was well received in view of the interaction between the participants, as well as the resulting publication of the proceedings (Elsevier Scientific Publishing Company, 1982, edited by J. Nowotny). At this first conference the participants decided that it would be desirable to organize similar conferences at about two year intervals. Thus, a second meeting was held in late June, early July at Alenya, Pyrenees Orientales, France. This conference had a larger number of participants, about 50, but still managed to promote excellent interaction between all the participants. These proceedings, with editors G. Petot-Ervas, Hj. Matzke and C. Monty, have also been published by Elsevier as a special edition of the journal, Solid State lonics, Vol. 12 (1984). In view of the success of the initial two conferences, a third meeting was organized and held at The Pennsylvania State University, University Park, PA., 16802, U.S.A. from 11 June 84 to 15 June 84. The proceedings of this conference are presented in the following text. It is perhaps well to note that the directors of this confer ence also limited the number of participants to about 50 in order to maximize mutual interaction. Additionally, because of the fact that the participants were essentially all internationally well recognized, presentation of all papers was held to about 30 minutes. This permitted sufficient interaction and discussion time during the 5 working days. At the end of the conference most participants felt that such a schedule appeared to work well. It is a pleasure for the conference chairmen to express their appreciation to: Mrs. Anna Dorman who aided extensively in our search for financing the meeting and Mrs. Gretchen Leathers who v aided much in carrying out the details of organlzlng the conference; to the organizing and international committee for their timely probes and aid; to Mrs. Linda Decker for her extensive typing aid; and especially to Prof. Emeritus W. O. Williamson for his thorough review of the published proceedings. We extend our best wishes to the organizers of future "Transport in Nonstoichiometric Compounds" meetings and it is with much pleasure that we look ahead to these stimulating, scientific interactions. George Simkovich Professor of Materials Science V.S. Stubican Professor of Ceramic Science vi CONTENTS ELECTRICAL PROPERTIES Transport in Materials Containing a Dispersed Second Phase J. Bruce Wagner, Jr. 3 Thermogravimetric and Electrical Conductivity Studies of Mg-Doped LaCr03 and La-Doped SrTi03 B. K. Flandermeyer, M. M. Nasrallah, D. H. Sparlin and H. U. Anderson .•. 17 Experimental Study of Mo03 Electrical Conductivity Changes Under Low Oxygen Pressures A. Steinbrunn, H. Reteno and J. C. Colson. 31 Electrical Properties of a Fez(Mo04)3 Catalyst C. M. Mari, P. Forzatti, P. L. Villa 43 Anisotropy of Electrical Properties in Pure and Doped aFeZ03 Driss Benjelloun, Jean-Pierre Bonnet and Marc Onil1on 51 Analysis of the Mobility of the Electronic Defects in COl_0° G. Petot-Ervas, P. Ochin and T. O. Mason 61 A++/Ti Nonstoichiometry in Alkaline Earth Titanates, ATi03 Y. H. Han, M. P. Harmer, Y. H. Hu and D. H. Smyth 73 Defect Structure and Transport in Oxygen Excess Cerium Oxide-Uranium Oxide Solid Solutions H. L. Tuller and T. S. Stratton ......• 87 vii Transport in Anion Deficient Fluorite Oxides A. N. Cormack and C. R. A. Catlow . 101 The Role of Dopant Ionic Radius in 02- - Conducting Solid Electrolytes R. Gerhardt-Anderson and A. S. Nowick . . . . . . III DIFFUSION PROPERTIES - PRIMARILY BULK The Haven Ratio in Terms of the Self-Diffusion of Charge Alfred R. Cooper . . . . . . . .. ..... 127 Use and Misuse of Chemical Diffusion Theory D. S. Tannhauser 139 Influence of Heterovalent Impurities on the Mass Transport in p-Type Semiconducting Oxides G. Petot-Ervas, F. Gesmundo and C. Petot 155 Concentration Distribution for Diffusion in a Temperature Gradient Han-Ill Yoo and B. J. Wuensch 169 Oxygen Self-Diffusion in Cubic Zr02 Solid Solutions Yasumichi Oishi and Ken Ando . . . . . . . . . . 189 Oxygen Self-Diffusion in Y203 and Y203-Zr02 Solid Solution Ken Ando and Yasumichi Oishi , . . . . . . . 203 Determination of Oxygen Diffusivities in Sand 8" Alumina by 180/160 Exchange A. E. McHale, J. A. Kilner and B.C.H. Steele 217 Chemical Diffusion in CoO Janusz Nowotny and Andrzej Sadowski . . . • 227 Alteration of CoO Wafers in an Oxygen Chemical Potential Gradient M. J. Shingler, K. M. Vedula and J. W. Halloran 243 Self Diffusion and Creep Studies of the Oxygen Sublattice Point Defects in CoO C. Clauss, R.-J. Tarento, C. Monty, A. Dominguez-Rodriguez, J. Castaing and J. Philibert 255 viii Mechanisms of Impurity Diffusion in Rutile N. L. Peterson and J. Sasaki ...•• 269 Diffusion of 51Cr Tracer in Cr203 and the Growth of Cr203 Films A. AtKinson and R. I. Taylor • • . • . • 285 Defect Structure and Transport Properties of the Manganese .. Oxides Manganosite (Mn1_~0) and Hausmannite (Mn3_804) Rudiger Dieckmann and Micha1e Keller . . . .. 297 The Thermodynamic Factors for the Cation Diffusion in a p-Type Oxide AO Doped with a Monovalent Impurity Francesco Gesmundo 315 Radiation Enhanced Diffusion in Nuclear Carbides Hj. Matzke ••••..•..••..•. 331 DIFFUSION PROPERTIES - PRIMARILY INTERFACIAL Volume, Grain Boundary and Surface Diffusion of an Isotope in Some Refractory Oxide Systems: A Comparison V. S. Stubican • • • • • . • • . . . . . •• 345 Diffusion of 180 Tracer in NiO Grain Boundaries A. Atkinson, F. C. W. Pummery and C. Monty. 359 Near-Surface Mass Transport in Nickel Oxide G. Dha1enne, A. Revco1evschi and C. Monty 371 Diffusion in Cr203 Via Initial Sintering Experiments Ming-Yih Su, Huan-Yeong Chang and George Simkovich 385 The Atomistic Simulation of Impurity Segregation at the Surfaces of MgO and CaO E. A. Co1bourn, P. W. Tasker and W. C. Mackrodt . 397 HIGH TEMPERATURE CORROSION Simultaneous Erosion and Oxidation of Nickel at High Temperatures C. T. Kang, F. S. Pettit and N. Birks .• 411 ix On the Phase Transformation During Reduction of Magnetite at High Temperatures Jan Janowski, Stanislawa Jasienska, Andrzej Sadowski and Andrzej Simon . . . . . • . . . . . 429 The Preparation of Non-Stoichiometric Sulphides by Solid-Gas Reactions M. Kizilyalli and H. M. Kizilyalli 441 The Reactions of Cobalt, Iron and Nickel in S02 Atmospheres: Similarities and Differences Nathan S. Jacobson and Wayne L. Worrell 451 The Influence of Ion Implantation of Reactive Elements on the Growth of Cr203 Scales on Ni-20% Cr at High Temperature F. H. Stott, J. S. Punni, G. C. Wood and G. Dearnaley 463 Diffusional Growth of A1203 Scales and Subscales on Ni-Al, Fe-Al and Fe-Mn-Al Alloys W. W. Smeltzer, P. R. S. Jackson and H. A. Ahmed 481 POINT DEFECT CONSIDEP~TIONS The Behaviour of Protons in Oxides A. N. Cormack, P. Saul and C. R. A. Catlow 497 Defect Structure and Transport Properties of Titanates Nicholas G. Eror . . . . . . . . . . . . . . 505 Structure and Stoichiometry in Lithium Inserted Metal Oxides R. J. Cava . . . . . . . . • . . . . . . . . . 517 A Predictive Molecular Orbital Theory Applied to Defects and Structures of Transition Metal Oxides Alfred B. Anderson, Robin W. Grimes and Arthur H. Heuer. • • • • • • • • • • • • 527 Defect Clustering in Rock-Salt Structured Transition Metal Oxides S. ~1. Tomlinson, C. R. A. Catlow and J. H. Harding 539 Photo of Participants 551 Participants 553 Compound Index 557 Index • • • • • 561 x