Table Of ContentTREATISE EDITOR
HERBERT HERMAN
Department of Materials Science and Engineering
State University of New York at Stony Brook
Stony Brook, New York
ADVISORY BOARD
J. W. CHRISTIAN, F.R.S. P. B. HIRSCH, F.R.S.
Oxford University Oxford University
Oxford, England Oxford, England
Μ. E. FINE R. I. JAFFEE
Northwestern University Electric Power Research Institute
Evanston, Illinois Palo Alto, California
J. FRIEDEL Ε. I. SALKOVITZ
Universite de Paris U.S. Office of Naval Research
Orsay, France Arlington, Virginia
A. GOLAND A. SEEGER
Department of Physics Max-Planck-Institut
Brookhaven National Laboratory Stuttgart, Germany
Upton, New York
J. J. HARWOOD J. B. WACHTMAN
Ford Motor Company National Bureau of Standards
Dearborn, Michigan Washington, D.C.
TREATISE ON MATERIALS SCIENCE
AND TECHNOLOGY
VOLUME 20
ULTRARAPID QUENCHING OF LIQUID ALLOYS
EDITED BY
1981
ACADEMIC PRESS
A Subsidiary of Harcourt Brace Jovanovich, Publishers
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COPYRIGHT © 1981, BY ACADEMIC PRESS, INC.
ALL RIGHTS RESERVED.
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ISBN 0-12-341820-8
PRINTED IN THE UNITED STATES OF AMERICA
81 82 83 84 9 8 7 6 5 4 3 2 1
List of Contributors
Numbers in parentheses indicate the pages on which the authors' contributions begin.
H. S. CHEN (215), Bell Laboratories, Murray Hill, New Jersey 07974
KOJI HASHIMOTO (291), The Research Institute for Iron, Steel, and
Other Metals, Tohoku University, Sendai, Japan
HERBERT HERMAN (183), Department of Materials Science and Engineer
ing, State University of New York at Stony Brook, Stony Brook,
New York 11794
R. W. K. HONEYCOMBE (117), Department of Metallurgy and Materials
Science, University of Cambridge, Cambridge, United Kingdom
K. A. JACKSON (215), Bell Laboratories, Murray Hill, New Jersey 07974
H. JONES (1), Department of Metallurgy, University of Sheffield,
Sheffield SI 3JD, United Kingdom
MARIA LASOCKA (261), Institute of Materials Science and Engineering,
Warsaw Technical University, Warsaw, Poland
J. C. M. Li (325), Department of Mechanical Engineering, University of
Rochester, Rochester, New York 14627, and Institut fur Werkstoffe,
Ruhr Universitat Bochum, D-4630 Bochum-1, West Germany
J. LIVAGE (73), Laboratoire de Chimie Appliquee de TEtat Solide, Ecole
Nationale Superieure de Chimie de Paris, Paris, France
ix
χ LIST OF CONTRIBUTORS
TSUYOSHI MASUMOTO (291), The Research Institute for Iron, Steel,
and Other Metals, Tohoku University, Sendai, Japan
HENRYK MATYJA (261), Institute of Materials Science and Engineering,
Warsaw Technical University, Warsaw, Poland
A. REVCOLEVSCHI (73), Laboratoire de Chimie Appliquee, Universite de
Paris-Sud-Bat. 414, 91405 Orsay, France
SAED SAFAI (183), Pratt and Whitney Aircraft Group, United Technolo
gies, West Palm Beach, Florida 33402
C. C. TSUEI (395), IBM Thomas J. Watson Research Center, Yorktown
Heights, New York 10598
J. V. WOOD (117), Faculty of Technology, The Open University, Walton
Hall, Milton Keynes MK7 6AA, United Kingdom
Foreword
Materials limitations are often the major deterrents to the achievement
of new technological advances. In modern engineering systems, materials
scientists and engineers must continually strive to develop materials that
can withstand extreme environmental conditions and maintain their
required properties. In the recent past we have seen the emergence of new
types of materials, literally designed and processed with specific uses in
mind. Many of these materials and the advanced techniques that were
developed to produce them came directly or indirectly from basic scien
tific research.
The "Treatise on Materials Science and Technology" is dedicated to
the relationship between the science and utility of materials. There can be
no better example of this relationship than that represented by this
twentieth volume of the treatise: "Ultrarapid Quenching of Liquid
Metals." Based on research started in the late 1950s, this field has cap
tured the imaginations of many scientists and engineers, giving rise to
hundreds of publications and numerous patents and industrial activities.
Embodied in rapid solidification science and technology is the essence of
innovational thrusts upon which the future will depend. It is our hope
that this volume as well as other volumes of this treatise will assist in the
growth of such new materials activities.
H. HERMAN
xi
Preface
When, in the distant future, histories are written on the origins of mate
rials processing, the relatively recent developments in ultrarapid solidifi
cation will most likely receive considerable attention. In fact, today's
rapid solidification technology originates from the eiforts of metallurgists
to trap highly metastable states through super-fast quenching of bulk al
loys. It was not so many years ago that five-figure cooling rates were
viewed as the upper limits, using, for example, cold-helium gas quench
ing, in a vacuum, of an electrically heated solid foil or wire specimen. Of
course, vapor phase quenching has been used, and remains important,
but, generally, physical vapor deposition techniques yield very thin
specimens.
It was Duwez and co-workers who, some 20 years ago, recognized that
the key to ultrarapid quenching depends on good physical contact be
tween the material and a low temperature, highly conductive substrate.
Effective and rapid contact was deemed essential. So, instead of quench
ing a solid, they proceeded to quench molten alloys. Thus was born liquid
quenching or splat cooling, both terms being apt descriptions of what is
becoming a major industrial process.
In the past few years the field of liquid quenching has seen hundreds of
publications on techniques of quenching, property measurements, and
industrial applications. A number of metal alloy systems have been
formed in amorphous condition through rapid solidification. Subsequent
studies are leading to both empirical criteria and theoretical understanding
for the bases upon which amorphous metals can be formed. Such studies
have indeed led to a number of industrial products based on special, and
sometimes unique, mechanical, electrical, and magnetic properties. More
recently, chemical properties of these unique materials have received
considerable attention.
In a field as active as rapid liquid quenching, covering so wide a range of
materials science, reviews can play an important role. This volume was
xiii
xiv
PREFACE
developed to enable an overview of certain prominent aspects of this field.
Jones, in his chapter, conveys a historical perspective, reviewing the
varieties of methods that have evolved for producing rapidly solidified
materials. He examines the criteria for the formation of highly metastable
states and how these relate to experiment. Rapid solidification of nonmet-
als is examined by Revcolevschi and Livage, who explore the limited
though exciting experiences in this evolving area. And the industrial imp
lications of rapid solidification of iron-based alloys become obvious in the
chapter by Wood and Honeycombe. In their chapter on plasma spraying,
Safai and Herman emphasize the utility of this industrial process for
producing rapidly solidified ceramics and metallic alloys. While this and
allied techniques have formerly been used principally to create protective
coatings, it is suggested that thermal spraying may indeed have a future
role to play in rapid solidification technology.
Metallic glasses have excited the imaginations of researchers and indus
trialists alike. Chen and Jackson review this rapidly evolving field.
Lasocka and Matyja examine what is known about annealing effects, and
Hashimoto and Masumoto explore corrosion behavior of this new class of
materials. The mechanical properties of the metallic glasses are reviewed
by Li, who relates the similarities and surprises that are encountered in
such studies. And finally, Tsuei examines what is known about the electri
cal properties of rapidly solidified materials.
An overall view of this field conveys excitement, surprise, and mul-
tidisciplinary aspects shared by few scientific activities. There is much of
the same ahead. It is hoped that this volume will contribute to the further
growth and expansion of rapid solidification science and technology.
TREATISE ON MATERIALS SCIENCE AND TECHNOLOGY, VOL. 20
1
Experimental Methods in Rapid Quenching
from the Melt
H. JONES
Department of Metallurgy
University of Sheffield
Sheffield, United Kingdom
I. Introduction 1
II. Historical Survey 3
III. Survey of Methods for Rapid Quenching from the Melt 7
A. Spray Methods 7
B. Chill Methods 16
C. Weld Methods 22
D. Factors Governing Choice of Method 26
IV. Cooling and Freezing 28
A. Predictions for Cooling and Freezing 29
B. Comparison with Experiment 33
V. Product Formation 37
A. Energetic Considerations 38
B. Effects of Cooling and Solidification 40
C. The Magnitude of Heat Transfer Coefficients 41
D. Some Considerations in Weld Methods 43
VI. Microstructure 45
A. General Features 46
B. Theory Compared with Experiment 47
C. Decomposition following Solidification 53
D. Quenching Efficiency 55
VII. Conclusion 58
List of Symbols 60
References 62
I. Introduction
Rapid quenching, molecular deposition, and external action are the
three basic alternative routes for achieving a nonequilibrium constitution
or a remorphologized or refined microstructure in a material.
Copyright © 1981 by Academic Press, Inc.
All rights of reproduction in any form reserved.
ISBN-0-12-341820-8
2 Η. JONES
External action, for example, by deformation, irradiation, or chemical
attack on solids, is very specific in its effects for particular materials and is
outside the scope of the present volume.
Molecular deposition includes formation from the vapor phase either by
thermal evaporation or sputtering, or by chemical reaction (e.g., CVD),t
or from salt solution by electroless displacement or electrodeposition.
Although widely applicable, it has limitations both in terms of production
rate and of energy efficiency.
Rapid quenching normally involves a rapid decrease of temperature,
fully or partially retaining the high-temperature structure, or else substan
tially refining the scale of any transformation products that do result.
Important limitations of the normal practice of quenching entirely within
the solid state are the highly specific initial structure and the difficulty of
achieving good contact with an effective heat sink, such as the surface of a
highly conducting solid chill, during the quench.
Rapid quenching from the melt (RQM), on the other hand, retains the
main merit of molecular deposition in significantly extending the range of
starting compositions that are not phase separated, while also generating a
wide range of possible product geometries at high throughputs and
quenching rates (through both liquid and solid phases) and with a much
lower energy consumption. The high cooling rate imposed by RQM plays
crucial roles in (a) promoting the increased supercooling necessary for
large departures from equilibrium, (b) achieving rapid completion of so
lidification:!: required, for example, to refine dendritic structures, and (c)
ensuring suppression of decomposition during cooling through the solid
state. Basic requirements for a high cooling rate in RQM are the rapid
formation of a thin layer or small particle of the melt in good contact with
an effective heat sink. Cooling rates in normal solidification processing
both for large-scale industrial production of standard castings, ingots, and
strands and for laboratory-scale steady-state solidification, are typically in
3
the range 10~ to 10°°K/s. Especially large sand castings and ingots freeze
6o
at cooling rates as low as 10" K/s, while thin strip, rod, and die casting
3o
can involve characteristic cooling rates as high as 10 K/s. The present
concern is primarily with methods for achieving cooling rates approaching
6o
or above 10 K/s during the solidification process and includes such di
verse approaches as gas cooling or spray deposition of atomized liquid
droplets, high-rate production of thin filaments or ribbons direct from the
melt, as well as rapid surface melting followed by rapid solidification as
given for example by a traversing laser or electron beam.
t Chemical vapor deposition—for a recent review, see Bryant (1977).
φ Rapid solidification processing (RSP) is thus a particularly important outcome of the
rapid quench.
