THE OXIDE HANDBOOK. Institute of Problems in Materials Science Academy of Sciences of the Ukrainian SSR Kiev, USSR. Translated from Russian by

Transcription

1 THE OXIDE HANDBOOK

2 THE OXIDE HANDBOOK Edited by G. V. Samsonov Institute of Problems in Materials Science Academy of Sciences of the Ukrainian SSR Kiev, USSR Translated from Russian by C. Nigel Turton and Tatiana I. Turton IFI/PLENUM NEW YORK-WASHINGTON-LONDON 1973

3 The original Russian edition, published by Metallurgiya Press in Moscow in 1969, has been revised and corrected for this edition. The English translation is published under an agreement with Mezhdunarodnaya Kniga, the Soviet book export agency. r. B. CAMCOHOB <P1-13I-1KO XI-1MI-14ECKI-1E CBoClcTBA OKI-1ClIOB FIZIKO-KHIMICHESKIE SVOISTV A OKISLOV Library of Congress Catalog Card Number ISBN-13: e-1sbn-13: DOl: IFI/Plenum Data Corporation Softcover reprint of the hardcover 1st edition 1973 A Subsidiary of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company, Ltd. Davis House (4th Floor), 8 Scrubs Lane, NW10 6SE, London, England All rights reserved No part of this publication may be reproduced in any form without written permission from the publisher

4 PREFACE TO AMERICAN EDITION Oxides of metals and nonmetals constitjte one of the most important classes of inorganic compounds. They are starting materials for the production of elements, are used widely in technology in refractory materials and as catalysts, semiconductors, and components of various construction materials, and are widely distributed in nature. This handbook offers the American reader a systematic presentation of basic information on the properties of oxides in the form of tabular data for the widest possible range of temperatures and other external conditions. Errors in the Soviet edition of this handbook have been corrected, and many additions have been made, with particular attention to the expansion of the section on phase diagrams of systems in which oxide phases are formed and information on properties at high temperatures. In expressing our gratitude to Plenum Press for publishing this book, the authors hope that it will be useful to A merican readers who are in any way connected with research on or the use of oxides. G. V. Samsonov v

5 PREFACE The continuous and ever expanding development of high-temperature technology involves the use of high -temperature refractory materials and one of the most important classes of these is the oxides, i.e., compounds of elements with oxygen. Oxides are the oldest refractory compounds known in technology and this is connected with their high chemical stability and abundance in nature. In addition to the use of oxides as raw materials for metallurgical processes, the refractoriness, chemical stability, and magnetic and other technically important properties of oxides have been put to use since antiquity. At the present time the importance of oxides as bases of many materials for new technology is substantial and is growing rapidly with the development of processes for the direct conversion of various forms of energy into electrical energy, the development of nuclear technology, electronics, semiconductor and dielectric technology, and cosmic technology, where the refractoriness and chemical stability of oxides are used in combination with their specific physical properties. Oxides are the foundation of the so-called oxygen -containing or oxygen refractory materials, which are fundamental to high-temperature technology. Oxides are no less important as the bases of practically all structural materials and rocks. A number of oxides are involved in biological processes. Despite the great importance of oxides in technology and human life, many of their physicochemical properties have been investigated only recently and data on these properties are not only few, but also scattered through many sources, making it difficult to use them. Collections of data on individual properties of oxides are often very narrow in nature, giving only those properties which are specific for a given technical application. In the Soviet literature there exist particularly complete collections of thermodynamic properties (U. D. Veryatin et al., Thermodynamic Properties of Inorganic Substances, Atomizdat, 1965; V. I. Babushkin et al., Thermodynamics of Silicates, Stroiizdat, 1965; Thermal Constants of Substances, edited by V. P. Glushko; Thermodynamic Properties of Individual Substances, Izd. AN SSSR, 1962; etc.) and some thermal properties (for example, I. S. Kulikov, Thermal vii

6 viii PREFACE Dissociation of Compounds, Izd. Metallurgiya, 1966). A review of the properties of a series of oxides is given in the monograph of A. M. Cherepanov and S. G. Tresvyatskii, High-Temperature Materials and Components from Oxides, Izd. Metallurgiya, However, up to now there has been no publication in which practically all the properties of most of the known oxides have been gathered together. Taking this into account, the authors of this handbook have attempted to collect together in a quite compact form the properties of the oxides known at the present time so that this handbook may be used by a wide range of scientific workers, engineers, teachers, and designers. Naturally, the first attempt to compile such a handbook must have shortcomings, but nonetheless the authors hope that it will be of value and will be grateful for critical comments and recommendations from readers. Colleagues from the Refractory Materials Department of the Red Banner of Labor Institute for Materials Science Problems of the Academy of Sciences of the Ukrainian SSR and Colleagues from the Physics Department of the Zhdanov Metallurgical Institute participated in the compilation of the handbook. The authors are grateful to S<wiet and foreign scientists who provided copies of their papers which were used in compiling the handbook.

7 CONTENTS Introduction Chapter I. General Data, Stoichiometry, and Crystal Chemical Properties Electronic Structure of Isolated Atoms Ionization Potentials of Atoms Geometric Constants of Atoms and Ions Composition of Oxides Regions of Homogeneity Crystal Structure Densi ty Chapter II. Thermal and Thermodynamic Properties Standard Heat of Formation Entropy Free Energy of Formation of Oxides Thermodyna mic Potentials of Oxide Formation Reactions Melting and Boiling Points Heats of Fusion, Evaporation, and Sublimation Thermal Conductivity Linear Coefficient of Thermal Expansion Molar Heat Capacity Specific Heat Capacity Heat of Combustion Chemical Bond Energy (Heat of Dissociation) Heat of Decomposition Heat of Phase Change Temperature and Heat of Polymorphic Conversion Characteristic Temperature Crystal Lattice Energy Oxidation Rates Diffusion Parameters for Oxygen into Metals and Nonmetals Diffusion Parameters for Elements into Oxides Rate of Eva para tion Vapor Pressure ix

8 x CONTENTS 23. Dissociation Pressure Thermal Stability Characteristics Free Energy Function of Gaseous Oxides. 223 Cha pter III. Mechanical Properties Modulus of Normal Elasticity Shear Modulus Poisson IS Ratio Tensile Strength Compressive Strength Bending Strength Dynamic Viscosity Hardness on Mineralogical Scale Microhardness Compressibility Elastic Constants 262 Chapter IV. Electrical and Magnetic Properties Electrical Conductivity Thermoelectric Properties Galvanomagnetic Properties Magnetic Properties Thermal Emission Properties Width of Forbidden Band Dielectric Properties Cha pter V. Optical Properties Color of Oxides Emissivity Refractive Index Velocity of Sound in Oxides Molecular Data Van der Waals Constants Critical Properties Cha pter VI. Nuclear Properties Nuclear Properties of Oxides Effect of Fast Neutron Radia tion on Oxides. 339 Chpater VII. Chemical and Catalytic Properties Chemical Properties of Oxides Catalytic Properties of Oxides. 411 Chapter VIII. Refractory Properties Solid Phase Reactions of Oxides. 441

9 CONTENTS xi 2. Wetting of Oxides by Liquid Metals Resistance to the Action of Molten Metals, AllOYS, and Slags. 458 Chapter IX. Applications of Oxides in Technology. 464 Chapter X. Phase Diagrams of Element-Oxygen Binary Systems. 468 References