Refractory Glasses, Glass—Ceramics, and Ceramics: High Temperature Oxides, Part IV

260 Pages·1971·4.37 MB·English

by  Allen M. Alper (Eds.)

REFRACTORY MATERIALS
A SERIES OF MONOGRAPHS
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
Part I: Magnesia, Lime, and Chrome Refractories
Part II: Oxides of Rare Earths, Titanium, Zirconium,
Hafnium, Niobium, and Tantalum
Part III: Magnesia, Alumina, Beryllia Ceramics:
Fabrication, Characterization, and Properties
Part IV: Refractory Glasses, Glass—Ceramics, and
Ceramics
VOLUME 6. ALLEN M. ALPER, Editor
Phase Diagrams: Materials Science and Technology
Volume I: Theory, Principles, and Techniques of
Phase Diagrams
Volume II: The Use of Phase Diagrams in Metal,
Refractory, Ceramic, and Cement Technology
Volume III: The Use of Phase Diagrams in Electronic
Materials and Glass Technology
VOLUME 7. LOUIS E. TOTH
Transition Metal Carbides and Nitrides
High Temperature Oxides
Part IV
Refractory Glasses, Glass—Ceramics,
and Ceramics
Edited by
Allen M. Alper
Chemical and Metallurgical Division
Sylvania GTE Inc.
Subsidiary of General Telephone and Electronics
Towanda, Pennsylvania
ACADEMIC PRESS New York and London 1971
COPYRIGHT © 1971, 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.
Ill Fifth Avenue, New York, New York 10003
United Kingdom Edition published by
ACADEMIC PRESS, INC. (LONDON) LTD.
24/28 Oval Road, London NW1 7DD
LIBRARY OF CONGRESS CATALOG CARD NUMBER: 78-97-487
PRINTED IN THE UNITED STATES OF AMERICA
to
JOHN L. MARGRAVE
a good friend, who has had a
very strong influence on my technical
development
List of Contributors
Numbers in parentheses indicate the pages on which the authors' contri
butions begin.
Edward F. Adams, Lighting Products Division, Corning Glass Works, Corning,
New York (145)
George H. Beall, Research and Development Laboratories, Corning Glass
Works, Corning, New York (15)
Edward R. Begley, Laboratory Services, Corhart Refractories Company,
Louisville, Kentucky (185)
Robert F. Davis,* Department of Mineral Technology, College of Engineering,
University of California, Berkeley, California (37)
William H. Dumbaugh, Jr., Research and Development Laboratories, Corning
Glass Works, Corning, New York (1)
T. J. Gray, Atlantic Industrial Research Institute, Nova Scotia Technical
College, Halifax, Nova Scotia, Canada (77, 131)
Philip O. Herndon, Corhart Refractories Company, Louisville, Kentucky (185)
Joseph W. Malmendier, Research and Development Laboratories, Corning
Glass Works, Corning, New York (1)
Joseph A. Pask, Department of Mineral Technology, College of Engineering,
University of California, Berkeley, California (37)
Bert Phillips, LeMont Scientific, Inc., Lemont, Pennsylvania (109)
Harold T. Smyth, Department of Ceramics, Rutgers State University, New
Brunswick, New Jersey (209)
•Present address: Corning Research Center, Sullivan Park, Corning, New York.
xi
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 stoichiometrics, 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 published, will make the series of books on Refractory
Materials an indispensable tool for the modern high temperature scientist.
John L. Margrave
xiii
Preface
In recent years, whole new families of materials have been developed which
are composed of glass-ceramics and glass. These areas are discussed by the
scientists and engineers who have discovered and developed these new
materials.
Also discussed in this volume is slip-cast ceramics. This is one of the most
important methods of fabricating ceramics and refractories. The chapter on
this subject approaches slip-casting from a scientific point of view which
should help give ceramists and engineers much better understanding of this
complex process.
Mullite is one of the most common phases in ceramic materials. The chap
ter on mullite critically reviews the work that has been done on this important
material.
Also discussed in this volume are the recent advances in sintered and fusion-
cast glass-contact refractories such as Zr0 -Si0 -Al 03.
2 2 2
A very important chapter on the theory of the structure of glass has been
written in great depth. It will give glass scientists and technologists greater
insight into the structural reasons for the nature of glass.
Significant contributions on oxide spinels (including ferrites), zinc oxide,
and tungsten oxide phases are discussed.
Allen M. Alper
xv
Contents of Other Volumes
Part I
Magnesia, Lime, and Chrome Refractories
1. PITCH-BEARING MgO-CaO REFRACTORIES FOR THE BOP PROCESS
Κ. K. Kappmeyer
D. H. Hubble
2. MAGNESIA-BASED REFRACTORIES
James White
3. SINTERED AND CHEMICALLY BONDED MgO-CHROME 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
Part II
Oxides of Rare Earths, Titanium, Zirconium, Hafnium,
Niobium, and Tantalum
1. THORIA AND YTTRIA
Richard C. Anderson
2. REFRACTORY OXIDES OF THE LANTHANIDE AND ACTINIDE ELEMENTS
LeRoy Eyring
3. SINGLE-CRYSTAL TITANATES AND ZIRCONATES
M. Douglas Beals
4. ZIRCONIUM DIOXIDE AND SOME OF ITS BINARY SYSTEMS
R. C. Garvie
5. ZIRCON AND ZIRCONATES
William J. Baldwin
6. HAFNIUM OXIDE
C. T. Lynch
xvii
xviii CONTENTS OF OTHER VOLUMES
7. Nb 0 AND Ta O STRUCTURE AND PHYSICAL PROPERTIES
2 5 2 S
A. Reisman
F. Holtzberg
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
1
Refractory Glasses
William H. Dumbaugh, Jr., and Joseph W. Malmendier
I. INTRODUCTION
Interest in refractory glasses has increased enormously in recent years. The
requirements of the space program and new concepts for high-pressure vapor
lamps are among the major stimuli of this renewed interest. This chapter
presents the principles involved in formulating refractory glasses, reviews
some of the significant experimental work on such glasses, and gives compo
sitions, properties, and applications of some commercial refractory glasses.
Primary factors which limit the utility of glass at high temperatures are
chemical reaction, crystallization, and thermal deformation. Chemical reac
tivity and crystallization are dependent upon composition and application
and, therefore, are unsatisfactory bases for comparing glasses. Thermal
deformation measured as the viscosity at a given temperature is a more
universal standard. The temperature which best serves as an indication of the
refractoriness of a glass is the annealing point. It is defined as " that tem
perature at which the internal stress in a glass is substantially relieved in
a matter of minutes" (American Society for Testing Materials, 1968). The
viscosity of the glass at this point is ~ 10 13 poises.
The majority of the glasses of commercial importance have annealing points
in the range of 400-600°C (Corning Glass Works, 1965a). For example,
(1) Corning Code 9010—potash soda barium silicate, television bulb glass
—annealing point 445°C.
(2) Corning Code 0080—soda lime silicate, lamp bulb glass—annealing
point 514°C.
(3) Corning Code 7740—sodium borosilicate glass for Pyrex (trademark
of Corning Glass Works) laboratory ware—annealing point 560°C.
Such glasses constitute by far the largest volume of those manufactured and
are outside the scope of this discussion. Here, a refractory glass is defined as
one with an annealing point over 700°C.
1