MATERIALS SCIENCE RESEARCH Volume 4 KINETICS OF REACTIONS IN IONIC SYSTEMS MATERIALS SCIENCE RESEARCH Volume 1: Proceedings of the 1962 Research Conference on Structure and Properties of Engineering Materials - edited by H. H. Stadelmaier and W. W. Austin Volume 2: Proceedings of the 1964 Southern Metals/Materials Conference - edited by H. M. Qtte and S. R. Locke Volume 3: Proceedings of the 1964 Conference on the Role of Grain Bound aries and Surfaces in Ceramics - edited by W. Wurth Kriegel and Hayne Palmour III Volume 4: Proceedings of the 1967 International Symposium on Kinetics and Reactions in Ionic Systems - edited by T. J. Gray and V. D. Frechette MATERIALS SCIENCE RESEARCH. Volume 4 KINETICS OF REACTIONS IN IONIC SYSTEMS Proceedings of an International Symposium on Special Topics in Ceramics, held June 18-23, 1967, at Alfred University, Alfred, New York Edited by T. J. Gray Director, Atlantic Industrial Research Institute Nova Scotia Technical College Halifax, Nova Scotia and v. D. Frechette SUNY College of Ceramics Alfred University, Alfred, New York ~ Springer Science+Business Media, LLC 1969 Library of Congress Catalog Card Number 63-17645 © 1969 Springer Science+Business Media New York Originally published by Plenum Press in 1969. Softcover reprint of the hardcover 1st edition 1969 All rights reserved No part of this publication may be reproduced in any form without written permission from the publisher ISBN 978-1-4899-6224-9 ISBN 978-1-4899-6461-8 (eBook) DOI 10 .1007/978-1-4899-6461-8 Foreword The kinetics of reactions in ionic solids is of profound importance not only in the understanding of the fundamental principles involved but also in many aspects of industrial research and development. These relationships, which are necessarily complex, cover a very broad spectrum, from the initial inter action through all stages of reaction to nucleation and growth of each individual phase. Their academic and applied implications touch on every varied aspect of solid-state reactions and merit even more attention than they have yet been accorded. This Conference was held at Alfred University in June 1967 under the sponsorship of the U. S. Office of Naval Research and the U. S. Army Research Office, Durham, and was attended by more than 120 scientists. Ten foreign scientists attended and presented papers, including representatives of Sweden, Germany, France, the United Kingdom, Australia, and Canada. It was the fourth of a series of conferences on ceramic science. The previous conferences were titled "The Role of Grain Boundaries and Surfaces in Ceramics," at North Carolina State University at Raleigh, 1964, "Sintering," at the University of Notre Dame, 1965, and "Ceramic Microstructures," at the University of California at Berkeley, 1966. The subdivisions of the text were determined on a very broad basis. The introductory lecture by J. G. Cohn reviews the many implications of reaction kinetics and is followed by a historical paper by the one scientist preeminently qualified to review what in many respects is autobiographical, Professor J. A. Hedvall of the Silikatforskningsinstitut, GOteborg, Sweden. A group of analytical papers follows, covering the kinetics of generalized solid-state reactions, including diffusion, reaction, nucleation, and crystal-growth kinetics. The kinetics of sintering is the subject of a second group of papers, while a third group deals with specific solid-state reactions, including the oxidation process. We wish to express our sincere appreciation to the authors and other conference participants who made this volume possible. While preprinting for the conference was most arduous, our efforts were immeasurably assisted by C. H. Bloomquist of the State University of New York, College of Ceramics, who was responsible for the preparation of the photo-offset pre prints, which materially aided the lively discussions and were subsequently of considerable assistance to the Editors in producing the final manuscript. v vi Foreword The cooperation of the many faculty and staff members from both Alfred University and the State University of New York, Agricultural and Tech nical College, who contributed unstintingly of their time and efforts to make the conference a success, is most gratefully acknowledged. The support of the Air Preheater Corporation of Wellsville, N. Y. and the Corning Glass Center of Corning, N. Y., and of Mr. W. Taylor, Jr., of the Pleasant Valley Wineries of Hammondsport, N. Y., with respect to our social activities, was appreciated by all. A special acknowledgment is due Dr. H. M. Davis of AROD, Dr. W. G. Rauch and Dr. A. M. Diness of ONR, and Dr. Cyrus Klingsberg of the National Academy of Sciences, both as representatives of sponsoring agencies and for their personal interest and assistance. T. J. Grey V. D. Frechette Alfred, N. Y. October, 1968 Contents Chapter 1 General Introduction: Kinetics of Reactions in Ionic Systems by J. G. Cohn ........................................... . Chapter 2 A Historical Review of Solid-State Chemistry, Mechanisms, and Cor rosion Problems by J. A. Hedvall .......................................... 18 Chapter 3 Kinetics of the Thermal Decomposition of Solids by P. W. M. Jacobs ........................................ 37 Chapter 4 Phenomenological Observations During Solid Reactions by R. K. Stringer, C. E. Warble, and L. S. Williams 53 Chapter 5 Factors Affecting the Kinetics of Grain Growth and Densification in Ceramic Bodies Containing a Liquid Phase by J. White . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 Chapter 6 Dynamic Thermal Analysis by W. B. Campbell ........................................ 121 Chapter 7 Nucleation and Growth Processes in the Dehydration of Salt Hydrate Crystals by W. J. Dunning .......................................... 132 Chapter 8 Electronic Mechanisms in Solid-State Photolysis by P. W. Levy and P. J. HerJey . . . . . . . . . . . . . . . . . . . . . . . . . . .. 156 Chapter 9 Crystallization and Melting in Glass-Forming Systems by D. R. Uhlmann ........................................ 172 vii viii Contents Chapter 10 Role of Impurities in Precipitation of Potassium from Supersaturated KCI:K Systems by D. G. Muth and G. C. Kuczynski ......... . . . . . . . . . . . . . .. 198 Chapter 11 Nucleation and Kinetics of Ferroelectric Domains by H. F. Kay .............................................. 206 Chapter 12 Crystal Growth Kinetics and Morphology by K. A. Jackson .......................................... 229 Chapter 13 Crystal Growth in Ceramic Powders by H. J. Oel .............................................. 249 Chapter 14 Impurity Effects in Surface Diffusion on Aluminum Oxide by W. M. Robertson and F. E. Ekstrom . . . . . . . . . . . . . . . . . . .. 273 Chapter 15 Diffusion Path Networks in Oxides by R. H. Condit .......................................... 284 Chapter 16 Grain Boundary Grooving at a Solid-Solid Interface by A. H. Feingold, J. M. Blakely, and Che-Yu Li .............. 304 Chapter 17 Sintering of Two-Component Oxide Systems with Compound Formation by D. A. Venkatu and G. C. Kuczynski ...................... 316 Chapter 18 Powder Compact Studies of Initial Sintering by D. L. Johnson ........................................ 331 Chapter 19 Densification Kinetics During Nonisothermal Sintering of Oxides by C. S. Morgan .......................................... 349 Chapter 20 The Behavior of Oxygen in Oxides During Sintering by R. H. Condit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 362 Contents ix Chapter 21 The Role of Plastic Flow by Dislocation Motion in the Sintering of Calcium Fluoride by A. R. Hingorany, F. V. Lenel, and G. S. Ansell .............. 375 Chapter 22 A Reconsideration of Stress and Other Factors in the Kinetics of Densification by H. Palm our, III, R. A. Bradley, and D. R. Johnson .......... 392 Chapter 23 Glow Discharge Sintering of Alumina by C. E. G. Bennett and W. A. McKinnon .................... 408 Chapter 24 Vaporization of Cuprous Oxide and Other Dissociating Oxides by R. H. Campbell and M. O'Keeffe ........................ 413 Chapter 25 Kinetics and Mechanism of the Reaction Between Ti0 and SrC0 2 3 by S. F. Hulbert and M. J. Popowich ........................ 422 Chapter 26 Oxidation Kinetics by T. J. Gray and M. J. Pryor .............................. 446 Chapter 27 Considerations on the Atomistics of Oxidation by J. B. Lightstone and J. P. Pemsler ........................ 461 Chapter 28 Space Charge Distribution at Silver Chloride-Aqueous Solution Interface by C. A. Steidel, H. A. Hoyen, Jr., and Che-Yu Li .............. 475 Chapter 29 Reaction Kinetics of Wet Chemically Prepared Gadolinium-~ron Garnet by E. A. Giess and R. M. Potemski .......................... 493 Chapter 30 Kinetics of Crystallization in Ti0 -Opacified Porcelain Enamels 2 by R. A. Eppler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 501