Nonequilibrium Phase Diagrams of Ternary Amorphous Alloys

640 Pages·1997·4.97 MB·English

by  Y. Kawazoe

Landolt-Börnstein
Numerical Data and Functional Relationships in Science and
Technology
New Series / Editor in Chief: W. Martienssen

Group III: Condensed Matter
Volume 37

Phase Diagrams and Physical
Properties
of Nonequilibrium Alloys

Subvolume A
Nonequilibrium Phase Diagrams of Ternary
Amorphous Alloys

Editor in Chief:
Y. Kawazoe

Editors:
J.-Z. Yu, A.-P. Tsai, T. Masumoto

Authors:
Y. Kawazoe, T. Masumoto, K. Suzuki, A. Inoue, A.-
P. Tsai, J.-Z. Yu,
T. Aihara Jr., T. Nakanomyo
Editor in Chief

Y. Kawazoe
Institute for Materials Research
Materials Science Information Center
Tohoku University
Sendai 980-77, Japan

Editors

J.-Z. Yu
T. Masumoto
Institute for Materials Research
Materials Science Information Center
Tohoku University
Sendai 980-77, Japan

A.-P. Tsai
National Research Institute for Metals
Tsukuba 305, Japan

Authors

Y. Kawazoe
T. Masumoto
K. Suzuki
A. Inoue
J.-Z. Yu
T. Aihara Jr.
T. Nakanomyo
Institute for Materials Research
Materials Science Information Center
Tohoku University
Sendai 980-77, Japan

A.-P. Tsai
National Research Institute for Metals
Tsukuba 305, Japan
Preface

In the 80-year-long history of the Institute for Materials Research (IMR), Tohoku University, the metallic
alloy systems have always been the most important subject studied. The founder of the Institute, Professor
Koutarou Honda, aimed to establish a research environment which was named "physical metallurgy". He
not only experimentally found the strongest magnetic material, KS steel, but also provided the basic
understanding of its physical properties. In the early years of the Institute, when it was called Research
Institute for Iron, Steel and Other Metals, the researchers worked mainly on the crystalline phases of
metallic alloy systems. Recently, we changed the name of the Institute into IMR and started to expand
research into modern areas covering most of the important materials which meet present-day high-
technology demands, including amorphous alloys, superconducting materials, gradient functional
materials, ceramics, biomaterials, magnetic superlattices, nano-scale materials such as fullerenes, and so
on.
The research activity of the Institute is measured by the number of publications per year which exceeds
500. All the published papers by IMR in the past 16 years have been augmented with complementary
papers selected from various journals to form the computerized database KIND (KINKen materials
Database corresponding to the Japanese name of the Institute with a total of more than 50000 papers
including those by other institutions both inside and outside Japan in the research are as mentioned above)
which is open to the materials researchers via computer network. The Information Science Group of the
Institute deals with the extraction of the factual data from KIND.
As the first step, we extracted the formation data of Fe, Ni, Al, Mg, Ti and other metal-based ternary
amorphous alloys for which better mechanical, physical and chemical properties than those of crystalline
alloys are expected. On the basis of the extraction results, we have constructed and are expanding the so-
called Amorphous Alloys Factual Database, named AMOR. The amorphous alloys mentioned above were
mainly prepared by the melt-spinning method and their physical and chemical properties have been exten-
sively studied, from both a basic and an application points of view, by the research group at our Institute
under the leadership of Prof. Tsuyoshi Masumoto. It was Prof. Masumoto who 1969 invented the methods
for producing amorphous alloys in form of ribbons or tapes, which greatly promoted the research work
in this field worldwide. In order to manifest his great contribution to the research and development
work on amorphous alloys, we planned to publish a databook of amorphous alloys dedicated to
Prof. T. Masumoto in Japan.
It was in early Spring of 1994 when we came into contact with the Springer-Verlag. The Managing
Editor, Dr. R. Poerschke, and the Editor-in-Chief of the Landolt-Börnstein, Prof. Dr. W. Martienssen,
asked us to make a contribution to a new volume of Condensed Matter. Accordingly, we revised and
enlarged our project to publish a databook of nonequilibrium alloys in a series of subvolumes and take
"Nonequilibrium Phase Diagrams of Ternary Amorphous Alloys" as the first subvolume. After nearly 3
years of hard work, this first subvolume has been completed. It is the result of the close and efficient co-
operation between our editorial committee at IMR and the Springer-Verlag. We are now preparing the
remaining subvolumes which we hope can be presented to the readers in the very near future.

Sendai, October 1996 Y. Kawazoe
This Book is Dedicated to

DR. TSUYOSHI MASUMOTO

Professor of Tohoku University
and Former Director
of the Institute for Materials Research
1 Introduction 1
1 Introduction

1.1 IMR data project

The modern research area of the Institute for Materials Research (IMR) of Tohoku University covers most
of the advanced materials, such as amorphous metallic materials, superconducting materials, gradient
functional materials, high-temperature ceramics, biomaterials, nanoscale materials, magnetic multilayers
(superlattice), and so on. Since 1987, when IMR was reorganized as a collaborative research institute
which is open not only to Japanese but also to foreign scientists, the research work has become quite
extensive and rapid progress has been and is being made. As a result, more than 500 papers are published
yearly.
In order to contribute an original materials database on the variety of research subjects at IMR, the
computerized materials database project KIND was also initiated in 1987 as an institute-wide activity
which is open to the world via computer network. It was at first a collection of papers published by the
members of IMR and later expanded to include the papers published both inside and outside Japan, cover-
ing the subjects of main interests at IMR, such as high-T superconducting materials, magnetic materials,
c
microclusters and nonequilibrium metallic materials.
In 1993, the factual database project AMOR was started. As is clearly seen from the name AMOR,
which are the first four characters of "amorphous", this project aimed at extracting and utilizing numerical
data of formation ability and physical properties of metallic amorphous materials. At first, special
attention was paid to ternary amorphous alloys. To date, 8327 points of formation data of 1532 ternary
amorphous alloys consisting of 351 ternary systems have been extracted, classified and evaluated and are
presented in this subvolume A. The next step is to extract, classify and evaluate numerical data of me-
chanical, physical, chemical and other important properties for these 351 ternary systems which will be
presented in the subvolume B. Therefore, the two subvolumes provide complete information concerning
the ternary amorphous alloys.
Together with the treatment of the data of ternary amorphous alloys, the data for multicomponent, i.e.
quaternary, quinary, ... metallic amorphous materials are also under preparation, as they are even more
important from the viewpoint of industrial application. The data of these multicomponent systems are ex-
pected to be presented in subvolume C.
As is commonly known, metallic amorphous materials are of high strength, high corrosion resistance,
high permeability, and other industrially important and useful properties. Furthermore, new metallic ma-
terials can be produced from metallic amorphous materials by proper crystallization processes, usually
heat treatment, to meet the various industrial demands. For instance, materials with micro- or nano-
crystals dispersed in the amorphous matrix are of high strength-ductility; materials consisting of pure
micro- or nano-crystals are not only high strength-ductile but also high-magnetization soft materials. Some
metallic materials of pure crystalline phase made from the amorphous phase show much better properties
than those made conventionally, strong permanent magnets of B-Fe-Nd are a good example.
Crystallization of the amorphous phase is also a good way to obtain the very special and stable phases,
i.e. quasi-crystals, which are important for basic research in physics.
The data of all these materials made from amorphous alloys by a crystallization process are being
extracted, classified and evaluated and are expected to appear in subvolume D.
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2 1 Introduction
From the above, it is clear that the combination of the four complemental subvolumes, i.e.
subvolume A, Nonequilibrium Phase Diagrams of Ternary Amorphous Alloys,
subvolume B, Physical Properties of Ternary Amorphous Alloys,
subvolume C, Physical Properties of Multicomponent Amorphous Alloys and
subvolume D, Physical Properties of Quasi-, Micro- and Nano-crystalline Alloys,
constitutes the complete volume and provides necessary and sufficient information of formation and prop-
erty data of nonequilibrium alloys to the readers.
It should be noted that another new data project of IMR, MAGNE, has been started. As mentioned
above, magnetic multilayer (superlattice) is one of the modern research areas at IMR. A large amount of
literature information has been collected and stored in our materials database KIND and at present there
are more than 5000 papers containing numerical data which are important to both basic and application
research and are now being extracted.
The next data project to be initiated will be the construction of a factual database for nanoscale materi-
als. There is a special research group at IMR working exclusively on nanoscale materials with both
experimental and ab initio computer simulation methods and several hundred papers have been published
and accumulated.
The final aim of IMR Data projects is to provide fundamental information on the highly specialized
materials industrially useful.

1.2 Introductory remarks

As the first subvolume A of volume III/37 of Landolt-Börnstein New Series, this book mainly consists of
formation data of ternary amorphous alloys. This chapter gives a brief introduction of the source and
distribution of the data, classification of the data on the basis of preparation methods for the alloys and the
presentation of the data. Finally are acknowledged the main contributors except the editors and authors of
this subvolume.

1.2.1 Data source and distribution

This book contains 8327 entries of formation data of 1532 ternary amorphous alloys consisting of 351
alloy systems (ternary element combinations) of which some of the data has not been published before. In
order to obtain all these data, we have made a survey of all publications, including internal reports and
regular journals worldwide. The publications are summarized in Table 1. It should be noted that, to the
best of the knowledge of the editors and authors, all the experimentally observed formation data of ternary
amorphous alloys reported in these publications have been collected and adopted to meet the requirement
of completeness of Landolt-Börnstein.

Table 1. List of Publications.
Theses and Dissertations
1. T. Minemura, Master Dissertation, Tohoku University, 1977
2. Y. Takahashi, Master Dissertation, Tohoku University, 1982
3. M. Komuro, Master Dissertation, Tohoku University, 1984
4. M. Otsuki, Graduation Thesis, Miyagi National College of Technology, 1986
5. M. Kumagai, Graduation Thesis, Miyagi National College of Technology, 1986
6. M. Nose, Doctor Thesis, Tohoku University, 1988
7. T. Zhang, Master Dissertation, Tohoku University, 1990
8. M. Kohinata, Master Dissertation, Tohoku University, 1990
9. S.-G. Kim, Doctor Thesis, Tohoku University, 1992
10. T. Zhang, Doctor Thesis, Tohoku University, 1993
11. C. Fan, Master Dissertation, Tohoku University, 1995

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1 Introduction 3
Book
1. Amorphous Magnetism II, R.A. Levy, R. Hasegawa, (eds.), Plenum Press, New York, 1977

Conference Proceedings
1. AIP Conf. Proc., from Vol. 24, 1974
2. MRS Symp. Proc., from Vol. 58, 1986
3. MRS Int. Meet. Advanced Materials, Vol. 3, 1989
4. Proc. 2nd Int. Conf. RQM, Massachusetts, 1976
5. Proc. 3rd Int. Conf. RQM, London, 1978
6. Proc. 4th Int. Conf. RQM, Sendai, 1982
7. Proc. 5th Int. Conf. RQM, Würzburg, 1985
8. Proc. 3rd Int. Conf. Aluminum Alloys, Trondheim, Norway, 1992
9. Proc. Symp. Corrosion, Electrochem., Catalysis of Metallic Glasses, R.B. Diegle,
K. Hashimoto, (eds.), The Electrochem. Soc., Pennington, 1988
10. Proc. Symp. Corrosion, Electrochem., Catalysis of Metastable Metals, Intermetallics, by C.R.
Clayton, K. Hashimoto, (eds.), The Electrochem. Soc., Pennington, 1993

Journals
1. Acta Metall., from Vol. 17 (1969)
2. Appl. Phys. Lett., from Vol. 10 (1967)
3. Boshoku Gijyutsu (in Japanese), from Vol. 28 (1979)
4. Chem. Lett. from 1975
5. Corros. Sci., from Vol. 23 (1983)
6. Electrochim. Acta, from Vol. 25 (1980)
7. Europhys. Lett., from Vol. 9 (1989)
8. High Pressure Res., from Vol. 1 (1989)
9. IEEE Trans. on Magnetics, from MAG-12 (1976)
10. J. Alloys Compounds, from Vol. 191 (1993)
11. J. Appl. Phys., from Vol. 38 (1967)
12. J. Electrochem. Soc., from Vol. 127 (1980)
13. J. Jpn. Inst. Met. Sendai (in Japanese), from Vol. 54 (1990)
14. J. Jpn. Soc. Powder Powder Metall. (in Japanese), from Vol. 38 (1991)
15. J. Magn. Magn. Mater., from Vol. 31 (1983)
16. J. Magn. Soc. Jpn., 11, Suppl., S1 (1987)
17. J. Mater. Sci. Lett., from Vol. 2 (1983)
18. J. Mater. Sci., from Vol. 16 (1981)
19. J. Non-Cryst. Solids, from Vol. 5 (1971)
20. J. Phys. Chem. Solids, from Vol. 32 (1971)
21. J. Phys. F, from Vol. 18 (1988)
22. J. Phys. Soc. Jpn., from Vol. 37 (1974)
23. J. Phys., Colloq., from Vol. 39 (1978)
24. J. Phys. Condens. Matter, from Vol. 1 (1989)
25. Jpn. J. Appl. Phys., from Vol. 10 (1971)
26. KENS Rep., from Vol. 7 (1987)
27. Mater. Lett., from Vol. 15 (1993)
28. Mater. Sci. Eng., Vol. 13 (1974)
29. Mater. Sci. Forum, from Vol. 88 (1992)
30. Mater. Trans. JIM, from Vol. 17 (1976)
31. Metall. Trans. A, from Vol. 12A (1981)
32. Nippon Oyo Jiki Gakkaishi (in Japanese), from Vol. 17 (1993)
33. Nucl. Instrum. Methods Phys. Res., Sect. B, from Vol. 76 (1993)
34. Philos. Mag. A, from Vol. 44 (1981)
35. Phys. Lett., from Vol. 51A (1975)
36. Phys. Rev. B, from Vol. 2 (1970)
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4 1 Introduction
Table 1. (cont.)

Journals (cont.)
37. Phys. Status Solidi (a), from Vol. 17 (1973)
38. Sci. Rep. Res. Inst. Tohoku Univ. Ser. A, from Vol. 26 (1976)
39. Scr. Metall., from Vol. 9 (1975)
40. Solid State Commun., from Vol. 16 (1975)
41. The Minerals Metals Mater. Soc. 1994
42. Z. Naturforsch. A, from Vol. 43 (1988)
43. Z. Phys. B, from Vol. 21 (1975)

Table 2. Distribution of data worldwide.
No. Country Institution Paper Ternary Alloys
1. Australia 3 6 7
2. Austria 1 2 2
3. Belgium 2 3 6
4. Brazil 1 1 1
5. Bulgaria 2 3 4
6. Canada 12 17 19
7. China 14 26 32
8. Czechoslovakia 4 11 12
9. Denmark 2 2 2
10. Egypt 1 1 1
11. France 16 22 25
12. Germany 44 98 132
13. Hungary 2 13 15
14. India 12 15 20
15. Ireland 1 1 1
16. Israel 2 2 3
17. Italy 9 11 28
18. Japan 88 432 794
19. Korea 9 9 16
20. Mexico 1 1 1
21. Netherlands 8 16 18
22. Norway 2 1 1
23. Poland 9 22 23
24. Romania 4 3 5
25. Singapore 1 1 1
26. Spain 6 7 8
27. Sweden 10 13 18
28. Switzerland 9 18 25
29. Taiwan 2 1 1
30. U.K. 14 34 47
31. Ukraine 1 1 1
32. U.S.A. 66 146 247
33. U.S.S.R. 7 6 7
34. Yugoslavia 5 9 12
Total 370 954 1535

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1 Introduction 5
Of the publications, Mater. Sci. Eng., J. Non-Cryst. Solids, Scr. Metall., Sci. Rep. Res. Inst. Tohoku
Univ. Ser. A, Mater. Trans. JIM, Proc. 4th Int. Conf. RQM and Proc. 5th Int. Conf. RQM are the most
important. As a matter of fact, about half of the data have been collected from these five journals and two
proceedings. All the unpublished data, of course, have been collected from the theses and dissertations.
As Landolt-Börnstein requires a full representation of data worldwide, a detailed investigation of data
distribution has been conducted and the result is shown in Table 2.
From Table 2, it is clear that the contributors of formation data of ternary amorphous alloys come from
370 research institutions in 34 countries and regions. It can also be seen that Japan makes the most
contributions (45% of the published papers and 52% of the number of alloy systems); followed by United
States of America, Germany, the United Kingdom and China.
It should be noted that the Institute for Materials Research (IMR) published 326 papers concerning
609 ternary amorphous alloy systems, which is about 75% of all publications within Japan and 40%
worldwide.
It is perhaps of significance to know the yearly tendency in the research work. Table 3 shows the
development of numbers of papers and ternary amorphous alloy systems per year. The data for 1995 are
under preparation and not included in the table.

Table 3. List of papers and ternary amorphous alloy systems published yearly
Year Paper System Year Paper System Year Paper System
1967 2 2 1977 18 32 1987 11 23
1968 0 0 1978 28 39 1988 98 160
1969 2 6 1979 30 60 1989 15 25
1970 1 2 1980 31 49 1990 13 15
1971 3 3 1981 19 32 1991 82 114
1972 2 4 1982 106 175 1992 32 39
1973 2 2 1983 29 43 1993 48 116
1974 6 13 1984 36 72 1994 123 187
1975 11 12 1985 97 130
1976 19 28 1986 14 16
Total 48 72 Total 408 648 Total 422 679

From Table 3 it can be clearly seen that the first 10-year period (from 1967 to 1976) is a preparation
or warm-up stage, and the next 10-year period belongs to rapid development stage in which the published
number of papers and ternary amorphous alloy systems is 9 times of that of the first 10-year period. The
3rd 10-year period (from 1987 to 1994, strictly speaking it is 8 years) is also a rapid development stage. It
seems in this period that the number of papers and ternary amorphous alloy systems has not increased as
much as expected compared with that of the second 10-year period. As a matter of fact, in the 3rd period,
much attention was paid to multi-component (quaternary, quinary, ...) amorphous alloy systems.
Furthermore, it can also be seen from Table 3 that there are five peaks in the numbers of paper and
ternary amorphous alloy systems in the years 1982, 1985, 1988, 1991 and 1994, which correspond to the
4th, 5th, 6th, 7th and 8th International Conference on Rapidly Quenched Metals, respectively.
It should be pointed out that the total number of papers and ternary amorphous alloy systems shown in
Table 3 are slightly smaller than those in Table 2, which is reasonable, as the latter is based on the
counting of papers or ternary amorphous alloy systems published by each country or institution. In the
case that a paper is published co-operatively by several institutions, it is counted several times.
Landolt-Börnstein
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6 1 Introduction
1.2.2 Classification of preparation methods and formation data

As mentioned above, 8327 entries of formation data of 1532 ternary amorphous alloys are collected in this
subvolume and by element combination these alloys are classified in 351 ternary systems, which means
that some ternary alloys belong to the same ternary alloy system, or in other words, there must be such
ternary alloy systems of which the formation data have been reported by multiple researchers or research
groups. The experimental observation range and/or the preparation and measurement methods may be the
same or different. If the preparation and/or measurement methods, especially if the preparation methods
are different in nature, then it is possible for the same ternary alloy system to have a different formation
range of amorphous and other phases such as crystalline, quasicrystalline or a mixture of the three phases.
In such a case, the formation data should be classified on the basis of principal preparation methods of the
alloy.
There are usually two stages for the preparation of amorphous alloys. In the first stage, a master alloy
should be prepared. In principle, the preparation of the master alloy is the melting of the necessary three
constituent metallic elements or some binary alloys in a desired chemically appropriate proportion.
Repeating the melting process is usually necessary to obtain a homogeneous master alloy, i.e. an alloy
without any severe compositional and/or organizational segregations.
The melting methods are classified by the heating source. The main melting methods are currently as
follows: (i) radio frequency melting; (ii) arc melting; (iii) resistancy-heat melting; (iv) levitation melting;
(v) electron beam melting; (vi) laser beam melting and (vii) plasma melting. Both radio frequency melting
and levitation melting are indirect heating methods, i.e. the mixtures of pure metallic elements or alloys
are heated by an inductive electrical current; all the others are direct heating methods. For the amorphous
alloys collected in this subvolume, about 67% of the master alloys are prepared by radio frequency melt-
ing; 30% by arc melting and the remaining 3% by the other melting methods.
In the second stage, the desired amorphous alloys are prepared from the master alloys of the same
chemical compositions. Unlike those for master alloys, there are a great number of methods, from the
viewpoint of technology, for preparing the final amorphous alloys. However, the variety of methods can
be classified into three main groups according to the physicochemical principles, i.e. solid reaction (from
solid to solid), liquid condensation (from liquid to solid) and gas condensation (from gas - atomic vapor -
to solid). In the solid reaction group, there are the following methods: (i) mechanical alloying;
(ii) hydrogen absorption; (iii) irradiation and (iv) chemical reduction (coating). Although these four
methods belong to the same group, they are usually applied to different special alloy systems. Even if they
are applied to the same alloy system, the formation data of amorphous alloys are quite different.
In the liquid condensation group there are (i) melt-spinning including single- or twin-roller spinning
and in-rotating water spinning; (ii) water quenching; (iii) gas atomization; (iv) chill-casting including
metallic mold casting; (v) piston-anvil method (splat cooling) and (vi) other liquid quenching methods. In
this group, different methods are applied to obtain different shapes and sizes of the desired amorphous
alloys. For the same alloy system the formation data of the amorphous phase are usually not significantly
different.
The gas condensation group includes: (i) sputtering and (ii) vapor deposition methods. When applied
to the same alloy system, the formation ability of the amorphous phase of these two gas condensation
methods is usually greater than that of liquid condensation. For some alloy systems, it is impossible to
achieve the amorphous phase by liquid condensation, but possible by gas condensation.
From the above it is clear that the formation data of amorphous phases are dependent upon the
preparation methods and that the data by the methods different in principle should not be merged. For the
formation data of other nonequilibrium phases, the situation is similar to that of an amorphous phase.
For some details of the most important preparation methods of amorphous alloys, the readers are
referred to section 1.3 Process and technology .
It should be pointed out that about 90% of the ternary amorphous alloys collected in this subvolume
are prepared by liquid condensation methods, while the percentage of solid reaction methods and gas
condensation methods share almost the same, i.e. about 5%. In the liquid condensation group, melt-
spinning methods occupy about 90%.

Landolt-Börnstein
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