High Temperature Oxides: Oxides of Rare Earths, Titanium, Zirconium, Hafnium, Niobium and Tantalum

284 Pages·1970·4.6 MB·English

by  Allen M. Alper (Eds.)

REFRACTORY MATERIALS
A SERIES OF M O N O G R A P HS
John L. Margrave, Editor
DEPARTMENT OF CHEMISTRY
RICE UNIVERSITY, HOUSTON, TEXAS
VOLUME 1. L. R. MCCREIGHT, H. W. RAUCH, SR., and W. H. SUTTON
Ceramic and Graphite Fibers and Whiskers
A Survey of the Technology
VOLUME 2. EDMUND K. STORMS
The Refractory Carbides
VOLUME 3. H. W. RAUCH, SR., W. H. SUTTON, and L. R. MCCREIGHT
Ceramic Fibers and Fibrous Composite Materials
VOLUME 4. LARRY KAUFMAN and HAROLD BERNSTEIN
Computer Calculation of Phase Diagrams
With Special Reference to Refractory Metals
VOLUME 5. ALLEN M. ALPER, Editor
High Temperature Oxides (In Four Parts)
VOLUME 6. ALLEN M. ALPER, Editor
Phase Diagrams: Materials Science and Technology (In
Three Volumes)
In Preparation
Louis E. TOTH
Transition Metal Carbides and Nitrides
High Temperature Oxides
Part II
Oxides of Rare Earths, Titanium,
Zirconium, Hafnium, Niobium
and Tantalum
Edited by
Allen M. Alper
Chemical and Metallurgical Division
Sylvania Electric Products Inc.
Subsidiary of General Telephone and Electronics
Towanda, Pennsylvania
ACADEMIC PRESS New York and London 1970
COPYRIGHT © 1970, BY ACADEMIC PRESS, INC.
ALL RIGHTS RESERVED.
NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM,
BY PHOTOSTAT, MICROFILM, RETRIEVAL SYSTEM, OR ANY
OTHER MEANS, WITHOUT WRITTEN PERMISSION FROM
THE PUBLISHERS.
ACADEMIC PRESS, INC.
111 Fifth Avenue, New York, New York 10003
United Kingdom Edition published by
ACADEMIC PRESS, INC. (LONDON) LTD.
Berkeley Square House, London W1X 6BA
LIBRARY OF CONGRESS CATALOG CARD NUMBER: 78-97487
PRINTED IN THE UNITED STATES OF AMERICA
to
PROFESSOR CHARLES H. BEHRE, JR.
for the guidance and instruction he gave me in economic geology
when I was a student at Columbia University
List of Contributors
Numbers in parentheses indicate the pages on which the authors' contribu-
tions begin.
Allen M. Alper, Chemical and Metallurgical Division, Sylvania Electric
Products Inc., Subsidiary of General Telephone and Electronics, To-
wanda, Pennsylvania (xi)*
Richard C. Anderson, Research and Development Center, General Electric
Company, Schenectady, New York (1)
William J. Baldwin, Ceramic Division, National Lead Company, ΤΑΜ
Division, Niagara Falls, New York (167)f
M. Douglas Beals, Single Crystals, Titanium Division, National Lead Com-
pany, South Amboy, New Jersey {99)%
LeRoy Eyring, Department of Chemistry, Arizona State University, Tempe,
Arizona (41)
R. C. Garvie, Research and Development Laboratories, Corning Glass
Works, Corning, New York (117)
F. Holtzberg, IBM Watson Research Center, Yorktown Heights, New York
(217)
C. T. Lynch, Metals and Ceramics Division, Wright-Patterson Materials
Laboratory, Wright-Patterson Air Force Base, Ohio (193)
A. Reisman, IBM Watson Research Center, Yorktown Heights, New York
(217)
* Former address: Research and Development Laboratories, Corning Glass Works,
Corning, New York.
fPresent address: 15 Huxley Drive, Buffalo, New York.
$ Present address: Quantel Corporation, Princeton, New Jersey.
vii
Foreword
The Refractory Materials Series was initiated in the hope of filling some
serious voids in the literature available for high temperature scientists, and
this new publication, High Temperature Oxides, edited by Dr. Allen M.
Alper, will clearly perform this function. For thousands of years, men have
worked with oxides at high temperatures—ceramics, cements, bricks, tiles,
glazes, etc. were widely applied long before their basic chemistry and physics
were understood. The application of modern methods has led to hundreds
of new oxide materials and thousands of new applications as ultra-pure
compounds, variable stoichiometries, and a great variety of physical and
chemical properties have been measured and characterized on the basis of
current theories.
In this sequence of volumes on High Temperature Oxides, Dr. Alper has
drawn on his own experience in geochemistry, ceramics and glass technology
to define the broadest coverage of this most important group of Refractory
Materials yet available in the literature. His co-authors include experts from
a variety of laboratories—industrial, government and academic. This group
of outstanding scientists has made an extensive yet critical coverage of oxides
and systems of oxides with emphasis on fundamental properties as well as
the important new technological developments.
It is my hope that this publication, joined by the earlier volumes of this
series, and those yet to be printed, will make the series of books on
Refractory Materials an indispensable tool for the modern high temperature
scientist.
John L. Margrave
February 1970
Houston, Texas
ix
Preface
In the past five years, transition metal oxides have grown in technical and
economic importance. They are now being widely used in chemistry and in
electronic, refractory, and aerospace applications. The following are dis-
cussed: yttria, thoria, lanthanide and actinide oxides, titanates, zirconia,
zirconates, zircon, hafnia and tantalum and niobium oxides.
Thoria-doped yttria ceramics are now becoming important specialty
ceramics. In the past few years, these materials have been perfected into
high-temperature, transparent ceramics. Lanthanide and actinide oxides are
now being widely used in chemicals, phosphors, lasers, and ceramics; these
oxides are discussed in depth. Titanates and some zirconates are being widely
used in electronic applications. Zirconia and zirconia-containing compounds
are some of the most widely used refractories. Since zirconia-containing com-
pounds are very important in complex refractories, much work has been
done to gain a better understanding of them. This work is reviewed to show
the relationship of these Zr0 solid solutions and compounds to composition
2
and temperature. The cost of Hf0 is decreasing and, consequently, this
2
very refractory oxide is becoming increasingly important. Recent research
on tantalum and niobium oxide-containing compounds is also reviewed.
For information on the transitional metal oxides of Cr, Μη, Fe, Co, Ni,
see Part I, entitled Magnesia, Lime, and Chrome Refractories. Those oxides
were included in Part I because they are extremely important in the manu-
facture of steel.
Part III will discuss the properties and fabrication of the more stable
oxides such as MgO, A1 0 , and BeO, which are widely used in ceramics
2 3
and glasses.
Part IV will review the most recent research and advances that have been
made in refractory glasses and glass-ceramics. Compounds containing
A1 0 , such as mullite and spinel, are discussed, and research work on
2 3
tungsten and zinc oxides is brought up to date. There is also an in-depth
chapter on slip-casting ceramics.
The editor wishes to thank Prof. John L. Margrave of Rice University
and Mrs. Thyrza C. Hanson and Dr. John H. Munier of Corning Glass
Works. Thanks are also given to all the contributors who made this volume
possible. Corning Glass Works and Sylvania Electric Products Inc. are also
acknowledged for their support.
Allen M. Alper
March 1970
Towanda, Pennsylvania
xi
Contents of Previous Volume
Parti
Magnesium, Lime, and Chrome Refractories
1. PITCH-BEARING MgO-CaO REFRACTORIES FOR THE BOP PROCESS
K. K. Kappmeyer
D. H. Hubble
2. MAGNESIA-BASED REFRACTORIES
James White
3. SINTERED AND CHEMICALLY BONDED MgO—CHROM Ε ORE
REFRACTORIES
J. Laming
4. REBONDED FUSED MgO—CHROME ORE GRAIN REFRACTORIES
R. F. Patrick
5. BASIC FUSION-CAST STEEL REFRACTORIES
A. M. Alper
R. C. Doman
R. N. McNally
6. CHROMITE SPINELS
Gene C. Ulmer
7. OXIDES OF TRANSITION ELEMENTS
Arnulf Muan
xv
Contents of Future Volumes
Part III
Magnesia, Alumina, Beryllia Ceramics: Fabrication, Characterization
and Properties
1. BERYLLIUM OXIDE
D. T. Livey
2. MECHANICAL BEHAVIOR OF SINGLE-CRYSTAL AND
POLYCRYSTALLINE MGO
Terence E. Langdon
Joseph A. Pask
3. SINTERED ALUMINA AND MAGNESIA
Ivan B. Cutler
4. HOT-PRESSED OXIDES
Richard M. Spriggs
5. HOT-WORKING OF OXIDES
Roy W. Rice
Part IV
Refractory Glasses, Glass-Ceramics, Ceramics
1. REFRACTORY GLASSES
William H. Dumbaugh, Jr.
Joseph W. Malmendier
2. REFRACTORY GLASS-CERAMICS
George H. Beall
3. MULLITE
Joseph A. Pask
Robert F. Davis
4. OXIDE SPINELS
Thomas J. Gray
5. OXIDES CONTAINING TUNGSTEN
Bert Phillips
6. ZINC OXIDE
Thomas J. Gray
7. SLIP-CAST CERAMICS
Edward F. Adams
xvii
xviii
CONTENTS
8. ZIRCONIA-ALUMINA-SILICA REFRACTORIES
Edward R. Begley
9. FUSION-CAST ALUMINA REFRACTORIES
William H. Bauer
Richard G. LaBar
10. GLASS NETWORK STRUCTURES
Harrold T. Smyth