Table Of ContentSUPERALLOYS, SUPERCOMPOSITES
AND SUPERCERAMICS
Edited by
JOHN K. TIEN
Center for Strategic Materials
Columbia University
New York, New York
THOMAS CAULFIELD
Philips Laboratories
Briar cliff Manor, New York
ACADEMIC PRESS, INC.
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Library of Congress Cataloging-in-Publication Data
Superalloys, supercomposites, and superceramics/edited by John K.
Tien, Thomas Caulfield.
p. cm.—(Materials science and technology series)
1. Heat resistant alloys. 2. Ceramic materials. 3. Composite
materials. I. Tien, John Κ. II. Caulfield, Thomas. III. Series:
Materials science and technology.
TA485.S95 1989
620.1'18-dc 19 88-30261
ISBN 0-12-690845-1
PRINTED IN THE UNITED STATES OF AMERICA
89 90 91 92 9 8 7 6 5 4 3 2 1
This volume
is dedicated to
Falih N. Darmara
now of the Principality of Andorra
and to
Ν. N. Hsu
late of Taipei
Contributors
Numbers in parentheses refer to the pages on which the authors' contributions begin.
STEPHEN D. ANTOLOVICH (363), Georgia Institute of Technology, School of
Materials Engineering, Mechanical Properties Research Laboratory,
Atlanta, Georgia 30332-0245
N. BIRKS (439), Metallurgy and Materials Science Department, University of
Pittsburgh, Pittsburgh, Pennsylvania
WILLIAM BOESCH (1), Special Metals Corporation, 16 Lin Road, Utica, New
York 13501
JANINE C. BOROFKA (237), Center for Strategic Materials, Henry Krumb
School of Mines, Columbia University, 520 W. 120th Street, New York,
New York 10027
G. K. BOUSE (99), Howmet Turbine Components Corporation, Whitehall
Technical Center, 699 Benston Road, Whitehall, Michigan 49461
THOMAS CAULFIELD (625), Philips Laboratories, 345 Scarborough Road,
Briar cliff Manor, New York 10510
WILLIS T. CHANDLER (491), Rockwell International, Rocketdyne Division,
6633 Canoga Avenue, Canoga Park, California 91303
C. I. CHEN (721), Materials R&D Center, Chung Shan Institute of Science and
Technology, Lungtan, Taiwan
WILFORD H. COUTS, Jr. (183), Wyman-Gordon Company, Worcester, Massa
chusetts
B. J. DALGLEISH (697), Materials Department, College of Engineering, Univer
sity of California, Santa Barbara, California 93106
DAVID N. DUHL (149), Pratt & Whitney, Engineering Division—North, 400
Main Street, East Hartford, Connecticut 06108
A. G. EVANS (697), Materials Department, College of Engineering, University
of California, Santa Barbara, California 93106
xv
xvi Contributors
LESLIE G. FRITZEMEIER (491), Rockwell International, Rocketdyne Division,
6633 Canoga Avenue, Canoga Park, California 91303
TIMOTHY E. HOWSON (183), Wyman-Gordon Company, Worcester, Massa
chusetts
S. E. Hsu (721), Materials R&D Center, Chung Shan Institute of Science and
Technology, Lungtan, Taiwan
ELIZABETH G. JACOBS (285), Center for Strategic Materials, Columbia Univer
sity, 520 W. 120th Street, New York, New York 10027
R. NATHAN KATZ (671), U.S. Army Materials Technology Laboratory, 405
Arsenal Street, Water town, Massachusetts 02172
Β. H. KEAR (545), Department of Mechanics and Materials Science, Rutgers
University, Piscataway, New Jersey
ROBERT D. KISSINGER (237), Engineering Materials, Technology Laborator
ies, General Electric Company, Cincinatti, Ohio
MASAKI KITAGAWA (413), Metallurgy Department, Research Institute, Ishik-
awajima-Harima Heavy Industries Co., Ltd., 1-15 Toyoshu 3-chome,
Koto-ku, Tokyo 135, Japan
G. L. LEATHERMAN (671), Mechanical Engineering Department, Worcester
Polytechnic Institute, Worcester, Massachusetts 01609
BRAD LERCH (363), Georgia Institute of Technology, School of Materials
Engineering, Mechanical Properties Research Laboratory, Atlanta,
Georgia 30332-0245
C. T. Liu (583), Metals and Ceramics Division, Oak Ridge National Labora
tory, PO Box X, Oak Ridge, Tennessee 37831-6115
GERNANT E. MAURER (49), Special Metals Corporation, Middle Settlement
Road, New Hartford, New York 13413
G. H. MEIER (439), Metallurgy and Materials Science Department, University
of Pittsburgh, Pittsburgh, Pennsylvania
J. R. MIHALISIN (99), Howmet Turbine Components Corporation, Dover Alloy
Division, Dover, New Jersey 07801
YOSHIO MONMA (339), National Research Institute for Metals (NRIM),
Tokyo 153, Japan
S. V. NAIR (301), Department of Mechanical Engineering, University of
Massachusetts, Amherst, Massachusetts 01003
V. C. NARDONE (301), United Technologies Research Center, Mail Stop 24,
Silver Lane, East Hartford, Connecticut 06108
DONALD W. PETRASEK (625), National Aeronautics and Space Administration,
Lewis Research Center, Cleveland, Ohio 44135
F. S. PETTIT (439), Metallurgy and Materials Science Department, University
of Pittsburgh, Pittsburgh, Pennsylvania
D. P. POPE (545, 583), Department of Materials Science and Engineering,
University of Pennsylvania, Philadelphia, Pennsylvania 19104-6272
Contributors xvii
J. M. SANCHEZ (525), Center for Strategic Materials, Columbia University, 520
W. 120th Street, New York, New York 10027
ROBERT A. SIGNORELLI (625), National Aeronautics and Space Administra
tion, Lewis Research Center, Cleveland, Ohio 44135
JOSEPH R. STEPHENS (9), National Aeronautics and Space Administration,
Lewis Research Center, Cleveland, Ohio 44135
MANABU TAMURA (215), Steel Research Center, Nippon Kokan Κ. K.,
Kawasaki, Japan
JOHN K. TIEN (237, 285, 301, 525, 625), Center for Strategic Materials, Henry
Krumb School of Mines, Columbia University, 520 W. 120th Street, New
York, New York 10027
N. C. Tso (525), Center for Strategic Materials, Columbia University, 520 W.
120th Street, New York, New York 10027
Preface
Progress in such strategic applications as jet engines, turbine power
generators, rockets and missiles is rate controlled by the development of
structural materials with ever higher temperature capabilities and reliability.
For the past forty years, superalloys have been the core material system
fulfilling such needs. Much has been learned through the years and super-
alloys have gone through many process advances—from air melting to
vacuum melting and refining, and onto double vacuum melting, directional
structural manipulation and extra ultra-clean alloys. Cast components are
now enjoying not only higher yield, precision vacuum investment shaping
and coring, but also the extra heat resistance benefits derived from directional
heat extraction and the resulting directionally solidified grain structures,
monocrystals, and more recently dense, clean and fine-grained structures that
may begin to compete with wrought superalloys.
Although the demand for superalloys, and, in general, the applications for
superalloys have grown, servicable high temperature limits for superalloys,
even with cooling schemes, are fast approaching. Accordingly, research and
development in alternative high temperature systems is and has been in full
swing for some time now. Such systems, like ODS and fiber reinforced
superalloys (FRS), can be considered direct derivatives of superalloy tech
nology. The aim of this volume is to review the state of superalloy technology
and concurrently cover some of the more salient aspects of alternative high
temperature systems such as superceramics and supercomposites. The no
menclature superceramic and supercomposite has been adopted from the use
of super to describe high temperature, structural alloys, i.e. superalloys. In
other words, we have extended the use of the prefix super to classify high
temperature, structural ceramic and composite systems.
We have asked the key players in the field to contribute chapters to this
volume. To this end the Table of Contents reads like a who's who in high
temperature materials. By no means do we intend for this volume to offer an
exhaustive review of the entire field. It does, however, address what we believe
to be the key issues of high temperature materials in a synergistic manner.
Superalloy topics range from resource availability, to discussions on ad
vanced processing such as VIM, VAR, VADAR, investment casting and
xix
XX Preface
single crystal growth, new superplastic forming techniques and powder
metallurgy (including HIP), to structure property relationships, important
strengthening mechanisms, oxidation, hydrogen embrittlement and phase
predictions. The alternative high temperature systems chapters cover inter-
metallics, fiber reinforced superalloys, and the processing and high tempera
ture properties of ceramics and C/C systems. Since high temperature
materials are no longer restricted to the confines of the U.S.A., the book
contains many contributions from the far east.
There are many people, mostly graduate students, to whom we are grateful
for their help in preparing this manuscript. It is impossible to thank them all
here, but their contributions do not go unnoticed. We are very appreciative of
the technical assistance given to us on many of the chapter contributions by
Dr. Edward Stover and Dr. Robert Kane. Their help has been invaluable. We
would also like to thank Mr. Robert Kaplan and his entire staff at Academic
Press for their efforts in publishing this text.
Finally, we are most proud to dedicate this volume to two distinguished
leaders in material research; Falih N. Darmara, the superalloy pioneer, and
for over forty years of outstanding contributions to superalloy development
and processing, and Ν. N. Hsu for his devoted service and pioneering
leadership in high temperature materials development in the far east.
Unfortunately, the untimely death of Dr. Hsu prevented the completion of his
chapter contribution.
John K. Tien
Thomas Caulfield
New York, April 1988
Foreword
It is a most unforeseen honor to be asked to write the foreword to the
volume Superalloys, Supercomposites and Superceramics. This sign of esteem
from my colleagues is specially touching as there are so many familiar names
of former co-workers among the contributors.
As I sit writing these lines there is in front of me one memento that seems
particularly appropriate. The inscription on the plaque is
Cross Section of J-48 Turbine Blade.
Heat AA-28
The World's First Production Heat of Vacuum Melted
High Temperature Alloy.
Melted December 31, 1952.
This particular heat of Waspalloy was the product of a six pound furnace!
The data is significant in that it is only thirty-six years old. Who could have
been brave enough in those days to prophesy not just the quantitative leap in
the volume of superalloys produced but the immense qualitative improve
ments in the properties of these alloys, the development of new and more
powerful investigative tools and the concomitant advances in our knowledge
of the laws controlling these properties.
The improvements in the properties led to increases in the efficiency and
power of the engines that used these materials. Consider the J-48 for which
the above mentioned heat of Waspaloy was made. If memory serves me right,
it was the first autonomously designed engine by Pratt & Whitney and was a
direct descendant of the Whittle engine. It had a centrifugal compressor and
very large forged turbine blades of Waspaloy. This alloy had been developed
by Rudy Thieleman then at Pratt & Whitney specifically for the J-48. This
relatively inefficient and clumsy engine could not have developed more than
three or four thousand pounds of thrust. The fuel efficiency was atrocious and
the blade life was at most a thousand hours.
This particular engine-alloy combination played a most seminal role in
the development of superalloy production. It may be worthwhile recounting
the occurrence as it may prove amusingly instructive to the younger and
nostalgic to the older generation. However before proceeding with that, it is
xxi
xxii Foreword
instructive to delve into the history of events up to that time. The advent of
the jet engine introduced an entirely new element in the attributes desirable in
either cast or wrought heat resistant alloys. Except for steam turbines and
turbocompressors for military piston engines, other uses were for stationay
applications, and weight-to-strength ratio at high temperature was not
critically important. But even in steam sturbines as they did not fly, lack of
creep resistance in the blading material could be compensated for by
increasing the cross section and reducing the stress. The only even remotely
comparable requirement to that of a jet engine was the turbo-compressor.
But even here the weight involved and the relatively low temperature of
operation did not set too high a priority on the strengths required.
Most of the wrought alloys used as heat resistant steels were Fe-Cr or Fe-
Cr—with some moly, or 300 series stainless steels, containing Ni in the
matrix. Alloys 321 Ti and 347 Cb were added but only for the purpose of
stabilizing the carbides, and so, were added as a multiple of the carbon
content. In some of the early Ni-Cr-Fe alloys the matrix composition was
modified by the addition of Co, and in some cases, varying amounts of W or
Mo. The one set of alloys that are in a class by themselves and were used for a
short period around 1944 as forged blades are the Hastalloy's. These, of
course consist of a Ni matrix with up to 30% Mo and no Cr, and hence
exhibit little high temperature oxidation resistance. This writer remembers
vividly the sight of a whole batch of forged blades reduced to brown
cardboard that, as a struggling heat treat metallurgist, he had ruined.
The only alloys that were precipitation hardened were Inconel Χ, K-42-B,
and Refractoloy 26. The preciptation mechanism was provided by the
varying amounts of Ti and Al which they contained. Inconel X was no doubt
a relative of the Nimonic series. Since the first was produced by Inco in the
U.S. and the other by Wiggin, an Inco subsidiary, in England. To this writer it
appears that most present day superalloys are direct descendants of these
alloys.
The first Jet engine brought to this country was one of the Whittle engines.
The task of designing an American version was given to General Electric
(Schenectady) since GE had a great deal of experience in the design and
construction of turbo compressors and turbines in general. The first engine to
issue from GE was the 1-40, in 1943-44. It was quite similar to the J-48 in
design, both being direct offsprings of the Whittle engine. The turbine blades
were forged from S-816, an alloy developed by Dr. Gunther Mohling at the
Watervliet plant of Allegheny Ludlum Co. and only a stone's throw from
Schenectady. The matrix was Cr-Ni-Co with additions of Mo-W-Cb and
fairly high carbon. The composition was easy to remember 20-20-20-4-4-4
with C0.40. The heat treatment involved a soak at the high temperature of
1260°C followed by a water quench and then aged 50 hours at 732-815°C. It
was obviously carbide strengthened.
