ANISOTROPY IN SINGLE-CRYSTAL REFRACTORY COMPOUNDS …978-1-4899-5307-0/1.pdf · ANISOTROPY IN...

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


Mas sachusetts Institute of Technology, Cambridge, Massachusetts

Franklin Institute, Philadelphia, Pennsylvania


O. N. E. R. A., Chatillon-sous-Bagneux (Seine) France


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


Institut "Ruder Bo~kovic", Zagreb, Yugoslavia


University of Uppsala, Uppsala, Sweden

RIAS, Division of Martin Company, Baltimore, Maryland

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


University of Caen, Caen, France

Imperial College, London, England


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.



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


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

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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

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