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ANISOTROPY IN SINGLE-CRYSTAL REFRACTORY COMPOUNDS
Volume I
ANISOTROPY IN SINGLE-CR YST AL REFRACTORY COMPOUNDS
Edited by Fred W. Vahldiek and Stanley A. Mersol
VOLUME 1 • Crystal Structure and Chemistry • Electronic Structure and Bonding • Non-Stoichiometry and Phase Relations • Physical-Chemical Properties
VOLUME 2 • Defect Structure • Mechanical Properties
ANISOTROPY IN SINGLE-CRYSTAL REFRACTORY COMPOUNDS
Edited by
Fred W. Vahldiek and Stanley A. Mersol Metals and Ceramics Division Air Force Materials Laboratory Wright Patterson Air Force Base, Ohio
Proceedings of an International Symposium on Anisotropy in Single-Crystal Refractory Compounds, held on June 13-15, 1967, in Dayton Ohio. Sponsored by the Ceramics and Graphite Branch of the Air Force Materials Laboratory, United States Air Force.
Volume 1
<±> Springer Science+Business Media, LLC 1968
Library of Congress Catalog Card Number 68-20273
ISBN 978-1-4899-5309-4 ISBN 978-1-4899-5307-0 (eBook) DOI 10.1007/978-1-4899-5307-0
© 1968 Springer Science+Business Media New York Originally published by Plenum Press in 1968.
Softcover reprint of the hardcover 1st edition 1968
No part of this publication may be reproduced in any form without written permission from the publisher
FOREWORD
An International Symposium on Anisotropy in Single-Crystal Refractory Compounds, sponsored by the Ceramics and Graphite Branch, Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio, in commemoration of the fiftieth anniversary of materials research in the United States Air Force, was held on 13-15 June 1967 at the Sheraton-Dayton Hotel, Dayton, Ohio. General chairman of the Symposium was Fred W. Vahldiek, assisted by the program chairmen Charles T. Lynch and Stanley A. Mersol, all three being materials research engineers from the Air Force Materials Laboratory. The Symposium coordinator was James M. Miller, University of Dayton Research Institute, who, assisted by his staff, handled the administrative details of the Symposium. Approximately one-hundred and twenty scientists and engineers, representing the United States, Belgium, Canada, France, India, Sweden, West Germany, and Great Britain attended the Symposium. Approximately forty invited papers were presented. An attempt was made to bring together scientists working in the area of anisotropy on single-crystal refractory compounds and in related areas in order to review the state-of-theart in this important area of research and to insure widespread dissemination of recent findings and ideas.
The welcoming address, given by Alan M. Lovelace, Director of the Air Force Materials Laboratory, emphasized the role of the United States Air Force as the host at this Symposium and set the informal tone for the seven technical sessions of the Symposium. In his opening address, Harris M. Burte, Chief of the Metals and Ceramics Division, Air Force Materials Laboratory, reemphasized the need for proper characterization of materials, especially refractory compounds, and outlined the main reasons for holding this first International Symposium on Anisotropy in Single-Crystal Refractory Compounds. The purpose for holding the Symposium thus firmly crystalized, Fred W. Vahldiek, general chairman, then said a few introductory remarks, and the Symposium was in session.
An attempt was made at this Symposium to cover the principal parameters on anisotropy of refractory compounds relative to their structure, bonding, non-stoichiometry, and thermal and mechanical behavior. Special emphasis was placed on the role of imperfections in crystals, including dislocations, slip, twinning, and stacking faults, and correlating these with the anisotropy in properties observed. Materials primarily discussed were refractory oxides, carbides, borides, silicides, and nitrides of the transition metals. Several contributions necessitated, on fundamental grounds, the discussion of other metallic and nonmetallic materials in order to have a homogeneous understanding of anisotropy. Although many of the papers presented stimulated heated oral discussions, no attempt was made to record
v
vi FOREWORD
these, and thus they are not included in this Proceedings. In general, the questions asked dealt with controversial points, or were the type that required an explanation or further data from the respective speakers, and a relatively select few conferees were involved. It is presumed that many of these points of controversy and/ or explanation are being further pursued by the scientists directly concerned.
The overall assessment of the Symposium could be stated as follows: It was brought out during the course of the Symposium that there
is a considerable gap at the moment in relating basic concepts, such as dislocations, electronic crystal structure, etc. to the bulk physical, chemical and mechanical properties of refractory compounds. Whereas considerable progress has been made in the last decade or so on the understanding of these compounds, the state-of-the-art as to the basic properties and behavior of these materials is still lagging far behind metallic systems. The key to many of the inherent problems associated with refractory compounds such as how to make them more ductile, how to increase their high-temperature insulation and thermal shock resistance properties, and how to improve the strength and load-carrying capabilities seems to lie in the controlled changes in the stoichiometry, impurity content, and especially the electronic structure of these materials. Much can be learned about the refractory compounds by referring to the behavior and properties of the respective "host" metals.
It was pointed out that in refractory inorganic nonmetallic or ceramic materials research the problems are often associated with the difficulty in obtaining suitable thin single-crystal specimens for study. Recent developments in transmission electron microscopy, electron microprobe, and microfocus x-ray techniques should allow a careful compositional and structure analysis as well as purity and homogeneity control of refractory compounds, such as are essential if single-crystal and polycrystalline refractories are to be meaningfully compared. Of course, much more work is needed on the physical, chemical, and mechanical properties of the refractory compounds.
Among the principal recommendations are the following: (1) Work in single-crystal refractory compounds such as exemplified by this Symposium is essential, and should be continued at an ever increasing rate if one is ever to understand the behavior and the inherent nature of these materials and how to properly modify them so that they may fulfill a useful function in the presently existent and newly developed aerospace and other systems. In this, fundamental studies, such as for example the understanding and changing of the basic electronic structure, play an increasingly important role. (2) Specialized symposia of this type should be held periodically - perhaps every two or three years - sponsored by the United States Air Force and/or by other interested agencies, in order to insure the best advancement of the state-of-the-art relative to the anisotropy in refractory materials research.
Special thanks are extended to all who substantially contributed to the success of this Symposium: Alan M. Lovelace, Director of the Air Force Materials Laboratory, for his welcoming address; Harris M. Burte, Chief of the Metals and Ceramics Division, Air Force Materials Laboratory, for his opening address; J. Allen Hynek, Director
FOREWORD
of Northwestern University's Dearborn Observatory and a long-time Air Force consultant on unidentified objects, who was the banquet speaker, for his interesting talk on the UFO's; Mrs. Anna G. Blackwell, Ceramics and Graphite Branch, Air Force Materials Laboratory, for her professional piano recital during the social hour preceding the banquet;
vii
James M. Miller, Symposium coordinator, Mrs. Audrey Sachs, Symposium secretary, University of Dayton Research Institute and staff for taking care of the administrative arrangements; Mrs. Jean Gwinn, University of Cincinnati, Symposium secretary and editorial assistant, for helping with setting up the Symposium and editing the manuscripts for the Proceedings, and for taking care of the numerous details associated with a Symposium of this type; and above all, to the conferees themselves who most of all had to do with the success of the Symposium.
The Proceedings of the Symposium are presented in two parts. Part I contains paper s of Se s sions I-IV, dealing with Crystal Structure and Chemistry, Electronic Structure and Bonding, Non-stoichiometry and Phase Relations, and Physical-Chemical Properties. Part II contains papers of Sessions V-VII, dealing with Defect Structure, and Mechanical Properties.
Dayton, Ohio October 7, 1967
FRED W. VAHLDIEK STANLEY A. MERSOL
CONTRIBUTORS
AMELINCKX, S.
ARONSSON, BER TIL
AUTIO, G. W.
BERMAN, 1.
BERNSTEIN, H.
BLUMENTHAL, R. N.
BRITTAIN, J. O.
BROOKES, C. A.
BRUNO, G. W.
BUESSEM, W. R.
CARTZ, L.
CHUNG, D.H.
CONRAD, H.
CONSIDINE, D. P.
COSTA, P.
DAMIANO, V.
Studiecentrum voor Kernenergie, Mol, Belgium
Swedish Institute for Metal Research, Stockholm, Sweden
Cornell University, Ithaca, New York
Air Force Cambridge Research Laboratories, Bedford, Massachusetts
ManLabs Inc., Cambridge, Massachusetts
Marquette University, Milwaukee, Wisconsin
Northwestern University, Evanston, Illinois
University of Bradford, Bradford, Yorkshire, Great Britain
Advanced Metals Research Corporation, Burlington, Massachusetts
The Pennsylvania State University, University Park, Pennsylvania
Marquette University, Milwaukee, Wisconsin
Mas sachusetts Institute of Technology, Cambridge, Massachusetts
Franklin Institute, Philadelphia, Pennsylvania
Air Force Cambridge Research Laboratories, Bedford, Massachusetts
O. N. E. R. A., Chatillon-sous-Bagneux (Seine) France
Franklin Institute, Philadelphia, Pennsylvania
ix
x
DAY. R.B.
DELA VIGNETTE. P.
ENGSTROM. INGVAR
FLEISCHER. L. R.
FREISE. E. J.
FRENCH. D. N.
GARDNER. W.
GIBBONS. D. F.
HARROD. D. L.
HASSELMAN. D. P. H.
HAWLEY. J. J.
HIRTHE. W. M.
HOCH. MICHAEL
HOLLOX. G. E.
HOSE MANN. R.
HULSE. C.O.
HYMAN. A.
JAIN. R. K.
JAIN. S. C.
JORGENSEN. P. J.
CONTRIBUTORS
Western Michigan University. Kalamazoo. Michigan
Studiecentrum voor Kernenergie. Mol. Belgium
University of Uppsala. Uppsala. Sweden
Westinghouse Astronuc1ear Laboratory. Pittsburgh. Pennsylvania
Northwestern University. Evanston. Illinois
Ingersoll-Rand Research Center. Princeton. New Jersey
Texas Instruments. Dallas. Texas
Case Western Reserve University. Cleveland. Ohio
Westinghouse Astronuc1ear Laboratory. Pittsburgh. Pennsylvania
Stanford Research Institute. Menlo Park. California
Air Force Cambridge Research Laboratories. Bedford. Massachusetts
Marquette University. Milwaukee. Wisconsin
University of Cincinnati. Cincinnati. Ohio
RIAS. Division of Martin Company. Baltimore. Maryland
Fritz-Haber Institut. Berlin. Germany
United Aircraft Corporation. East Hartford. Connecticut
University of Maryland. Baltimore. Maryland
National Physical Laboratory. New Delhi. India
National Physical Laboratory. New Delhi. India
General Electric Company. Schenectady. New York
CONTRIBUTORS
KAUFMAN, L.
LAUBACH, J. E.
LOBODA-CACKOVIC, J.
LONDON, G.
LUNDSTRdM, TORSTEN
LYE, R.G.
LYNCH, C. T.
MARSHALL, R. C.
MERSOL, S.A.
MOLL, SHELDON H.
MOORE, J. W.
MURRAY, M. J.
NADEAU, J. S.
NEWEY, C. W.A.
O'NEILL, J. B.
P ALMOUR, HAYNE III
PINZ, B.A.
PONS, L.
RADFORD, K. C.
RYAN, C.E.
SATO, Y.
xi
ManLabs Inc., Cambridge, Massachusetts
Marquette University, Milwaukee, Wisconsin
Institut "Ruder Bo~kovic", Zagreb, Yugoslavia
Franklin Institute, Philadelphia, Pennsylvania
University of Uppsala, Uppsala, Sweden
RIAS, Division of Martin Company, Baltimore, Maryland
Air Force Materials Laboratory, WrightPatterson Air Force Base, Dayton, Ohio
Air Force Cambridge Research Laboratories, Bedford, Massachusetts
Air Force Materials Laboratory, WrightPatterson Air Force Base, Dayton, Ohio
Advanced Metals Research Corporation, Burlington, Massachusetts
E. I. Dupont Company, Wilmington, Delaware
Cavendish Laboratory, Cambridge, England
General Electric Company, Schenectady, New York
Imperial College, London, England
University of Bradford, Bradford, Yorkshire, Great Britain
North Carolina State University, Raleigh, North Carolina
Marquette University, Milwaukee, Wisconsin
University of Caen, Caen, France
Imperial College, London, England
Air Force Cambridge Research Laboratories, Bedford, Massachusetts
University of Minnesota, Minneapolis, Minnesota
xii
SAUER, R. W.
SCALA, E.
SMAKULA, A.
STOKES, R. J.
STRAUMANIS, M. E.
THOMAS, D. A.
TIGHE, N. J.
TOTH, L.E.
VAHLDIEK, F. W.
VAN V LACK, L. H.
VENABLES, J. D.
WESTBROOK, J. H.
WILKE, W.
WILLIAMS, WENDELL S.
WITTER, D. E.
ZBASNIK, J.
CONTRffiUTORS
Northwestern University, Evanston, Illinois
Cornell University, Ithaca, New York
Massachusetts Institute of Technology, CaIYlbridge, Massachusetts
Honeywell Corporate Research Center, Hopkins, Minnesota
University of Missouri, Rolla, Missouri
Ingersoll":Rand Research Center, Princeton, New Jersey
National Bureau of Standards, Washington, D. C.
University of Minnesota, Minneapolis, Minnesota
Air Force Materials Laboratory, WrightPatterson Air Force Base, Dayton, Ohio
The University of Michigan, Ann Arbor, Michigan
RIAS, Division of Martin COIYlpany, BaltiIYlore, Maryland
General Electric COIYlpany, Schenectady, New York
Fritz-Haber Institut, Berlin, GerIYlany
University of Illinois, Urbana, Illinois
North Carolina State University, Raleigh, North Carolina
University of Minnesota, Minneapolis, Minnesota
CONTENTS
Volume 1
Contents of Volume 2 • • • • . • . • . • • • • • • • . • . . • • . • • • • • . . . • • . . • . •. xvii
SESSION I
Crystal Structure and Chemistry
Some Aspects of the Crystal Chemistry of Borides, Boro-carbides, and Silicides of the Transition Metals ................... .
Bertil Aronsson, Torsten Lundstrom, and Ingvar Engstrom
Application of the Electron Microprobe to the Study of Refractory Metal Carbides, Oxides, and Silicides ................ .
Sheldon H. Moll and George W. Bruno
Equilibrium Particle Size and Paracrystalline Distortions
R. Hosemann, J. Loboda-6ackovi6, and W. Wilke
Crystallographic Polarity of WC ....•..
D. N. French and D. A. Thomas
Tabulation of Indices and Interplanar Angles for Rapid Identification of Crystallographic Planes ........................ .
David Emmett Witter and Hayne Palmour III
SESSION II
Electronic Structure and Bonding
The Electronic Structure of Refractory Metals, Compounds, and Alloys
D. F. Gibbons
xiii
3
23
37
55
67
105
xiv CONTENTS
Bonding, Imperfect Structure, and Properties of the Refractory Nitrides of Titanium, Zirconium, and Hafnium. • • . • • . . • . • • . . • . • • . . . • • • • 121
M. E. Straumanis
The Nature of the Electrical Conduction Transient Behavior of Rutile. . . . . . • 139
R. N. Blumenthal, W. M. Hirthe, and B. A. Pinz
Electronic Structure of Transition Carbides, Nitrides, and Borides
P. Costa
SESSION III
Non-stoichiometry and Phase Relations
Non-stoichiometry and Bonding in Refractory Monocarbides ••...
Michael Hoch
The Conversion of Cubic and Hexagonal Silicon Carbide as a Function
151
163
of Temperature and Pressure. . • . . . . . . . . . . • . • • . . . . • . . • • • . • • 177
C. E. Ryan, R. C. Marshall, J. J. Hawley, I. Berman, and D. P. Considine
Phase Relationships and Defect Structure in Dimolybdenum Carbide.
F. W. Vahldiek and S. A. Mersol
Influence of Octahedral Subcells on the Electrical Properties and Bonding Characteristics of Molybdenum Carbides ..••.•........•.•.
L. E. Toth, J. Zbasnik, Y. Sato, and W. Gardner
SESSION IV
Physical-Chemical Properties
199
249
Thermodynamic Properties of Refractory Transition Metal Compounds. . . • • • 269
Larry Kaufman and Harold Bernstein
Some Properties of Eutectic IICrystals!! of MnO-MnS • • • • . . . . . . . . . . • • . 299
John W. Moore and Lawrence H. Van Vlack
Selected Problems in the Analysis of Refractory Materials. . . • . . . . . . . . . • 317
C. T. Lynch, F. W. Vahldiek, and S. A. Mersol
On the Role of Diffusion in the Plastic Deformation of Transition Metal Carbides 341
D. L. Harrod and L. R. Fleischer
CONTENTS xv
Anisotropy in Emissivity of Single-Crystal Refractory Materials. . . • . • • • • • 357
G. W. Autio and E. Scala
Anisotropic Thermal Expansion Characteristics of Some Crystal Structures 383
L. Cartz
Electron Paramagnetic Resonance Absorption and Other Physical Properties of Chromium Oxide and Other Crystals Containing Chromium as Impurity. . . • . 391
S. C. Jain and R. K. Jain
Subject Index • . • • • . . • • . • • • • . • • • • . • • . . • . • . • • • • • . . • • . • . • • • . 401
CONTENTS Volume 2
Contents of Volume 1 •• • • • • • • • • • • • • • • . • • • • • • • • • • • • • . • • • • • • • • ix
SESSION V
Defect Structure
Electron Microscopy of High Temperature Materials. . • . . • . . • . • . . • • • • • 3
P. Delavignette and S. Amelinckx
Defects in Crystal Growth of Transition Metal Oxides . • • • • . • . • . . . • . • • . 27
A. Smakula
Defect Structure of Single-Crystal Titanium Diboride .••.••..••...•••• 41
S. A. Mersol, C. T. Lynch, and F. W. Vahldiek
Defect State and the Properties of Some Solids. • • . • • . • . • • • • . • • . • . . . . 95
J. 0. Brittain
Transmission Electron Microscopy of Alumina Ceramics. • . • . . • . . . . • • • • 121
N. J. Tighe and A. Hyman
The Defect Structure of Non-stoichiometric Ce02-X' . . • • . • • • • • • • • • • • • . 137
R. N. Blumenthal and J. E. Laubach
SESSION VI
Mechanical Properties. PART 1
Anisotropy in the Mechanical Properties of Beryllium Single Crystals . • . • • • 153
H. Conrad, G. London, and V. Damiano
xvii
xviii CONTENTS
The Elastic Anisotropy of Crystals ..... 217
D. H. Chung and W. R. Buessem
Single-Crystal Elastic Anisotropy and the Mechanical Behavior of Polycrystalline Brittle Refractory Materials ............ . 247
D. P. H. Hasselman
High Temperature Deformation, Polygonization, and Recrystallization of Magnesium Oxide Single Crystals. . . . • • . . . . . . . . . . . . . . . . . . . . 267
R. B. Day and R. J. Stokes
Frictional Anisotropy in Magnesium Oxide. . . . . . . . . . . . . . . . . . . . . . • . . 291
C. A. Brookes and J. B. O'Neill
Plastic Anisotropy in MgO and Other NaCl-type Crystals. . . . . . . . . . . . . • . 307
C. O. Hulse
Plastic Deformation of Magnesium Aluminate Single Crystals. . . . . . . . . . . . 321
C. W. A. Newey and K. C. Radford
High Pressure Electrical Resistance and Compressive Strength of TiB2
F. W. Vahldiek
SESSION VII
M ec han i cal Pro per tie s • PAR T 2
Effects of Adsorbed Water on Indentation Hardness Anisotropy in Crystals
J. H. Westbrook and P. J. Jorgensen
The Strength of Nonstoichiometric Oxides
John S. Nadeau
339
353
361
Stress-Velocity Relation for Dislocations in TiC (Abstract only). . . . . . . • . . 391
Wendell S. Williams
Plastic Properties in Tungsten Monocarbide
L. Pons
Bonding, Structure, and Mechanical Behavior of VC Single Crystals ...
R. G. Lye, G. E. Hollox, and J. D. Venables
393
445
CONTENTS xix
The Deformation Modes of the Cobalt Silicides . • • • • • • . • . . . • . • . • . • • . 459
R. W. Sauer and E. J. Freise
Observations on the Kinetics of Cleavage Cracks in Magnesium Oxide • • • • . 479
M. J. Murray
Subject Index. . . • . • • . . . • . • • . . . . . . . . • • . • . • . . . • . . • • . • . . . • • . 489