Non-Ferrous Metal Systems. Part 2 Selected Copper Systems

Landolt-Brnstein
Numerical Data and Functional Relationships in Science and Technology

New Series / Editor in Chief: W. Martienssen
Group IV: Physical Chemistry

Volume 11
Ternary Alloy Systems

Phase Diagrams, Crystallographic and
Thermodynamic Data
critically evaluated by MSIT
Subvolume C
Non-Ferrous Metal Systems
Part 2
Selected Copper Systems
Editors
G. Effenberg and S. Ilyenko
Authors
Materials Science International Team, MSIT
ISSN 1615-2018 (Physical Chemistry)
ISBN 978-3-540-25776-9 Springer Berlin Heidelberg New York
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Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie
Editor in Chief: W. Martienssen
Vol. IV/11C2: Editors: G. Effenberg, S. Ilyenko
At head of title: Landolt-Brnstein. Added t.p.: Numerical data and functional relationships in science and technology.
Tables chiefly in English.
Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Brnstein of which the 6th ed. began publication in 1950 under title:
Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik.
Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag
Includes bibliographies.
1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables.
I. Brnstein, R. (Richard), 1852-1913. II. Landolt, H. (Hans), 1831-1910.
III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology.
QC61.23 502'.12 62-53136
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Editors: Gnter Effenberg
Svitlana Ilyenko
MSI, Materials Science International Services GmbH

Postfach 800749, D-70507, Stuttgart, Germany
http://www.matport.com
Authors: Materials Science International Team, MSIT

The present series of books results from collaborative evaluation programs performed by MSI and authored
by MSIT. In this program data and knowledge are contributed by many individuals and accumulated over
almost twenty years, now. The content of this volume is a subset of the ongoing MSIT Evaluation
Programs. Authors of this volume are:
Christian Btzner, Stuttgart, Germany Viktor Kuznetsov, Moscow, Russia

Suray Bhan, Tronoh, Malaysia Nathalie Lebrun, Lille, France
Nataliya Bochvar, Moscow, Russia Hans Leo Lukas, Stuttgart, Germany

Oksana Bodak , L'viv, Ukraine Evgenia Lysova, Moscow, Russia
Gabriele Cacciamani, Genova, Italy Dirk Matusch, Stuttgart, Germany
Lesley Cornish, Randburg, South Africa Pierre Perrot, Lille, France
Zhenmin Du, Beijing, China Paola Riani, Genova, Italy
Gnter Effenberg, Stuttgart, Germany Peter Rogl, Wien, Austria
Olga Fabrichnaya, Stuttgart, Germany Lazar Rokhlin, Moscow, Russia
Riccardo Ferro, Genova, Italy Rainer Schmid-Fetzer, Clausthal-Zellerfeld, Germany
Gautam Ghosh, Evanston, USA Julius C. Schuster, Wien, Austria
Joachim Grbner, Clausthal-Zellerfeld, Germany Mikhail Turchanin, Kyiv, Ukraine
Svitlana Ilyenko, Stuttgart, Germany Vladimir Turkevich, Kyiv, Ukraine
Volodymyr Ivanchenko, Kyiv, Ukraine Tamara Velikanova, Kyiv, Ukraine
Boris Kasper, Stuttgart, Germany Jean-Claude Tedenac, Montpellier, France
Kostyantyn Korniyenko, Kyiv, Ukraine Vasyl Tomashik, Kyiv, Ukraine
Ortrud Kubashewski, Aachen, Germany Andy Watson, Leeds, U.K.
K.C. Hari Kumar, Chennai, India Matvei Zinkevich, Stuttgart, Germany
Armin Kussmaul, Stuttgart, Germany
Institutions
The content of this volume is produced by Materials Science International Services GmbH and the
international team of materials scientists, MSIT. Contributions to this volume have been made from the
following institutions:
The Baikov Institute of Metallurgy, Academy of National University of L'viv, Cathedra of

Sciences, Moscow, Russia Inorganic Chemistry, L'viv, Ukraine
Donbass State Mechanical Engineering Academy, RWTH Aachen, Germany

Kramatorsk, Ukraine
I.M. Frantsevich Institute for Problems of Materials Technische Universitt Clausthal,

Science, National Academy of Sciences, Kyiv, Metallurgisches Zentrum, Clausthal-Zellerfeld,
Ukraine Germany
Indian Institute of Technology Madras, Department Universit di Genova, Dipartimento di Chimica,

of Metallurgical Engineering, Chennai, India Genova, Italy
Institute for Semiconductor Physics, National Universit de Lille I, Laboratoire de Mtallurgie

Academy of Sciences, Kyiv, Ukraine Physique, Villeneuve dASCQ, Cedex, France
Institute for Superhard Materials, National Academy Universitt Wien, Institut fr Physikalische
of Sciences, Kyiv, Ukraine Chemie, Wien, Austria
G.V. Kurdyumov Institute for Metal Physics, University of Cambridge, Department of

National Academy of Sciences, Kyiv, Ukraine Materials, Cambridge, U.K.
Laboratoire de Physicochimie de la Matire Condense, University of Florida, Gainesville, USA

Universit de Montpellier II, Montpellier, France
Materials Science International Services GmbH, University of Leeds, Department of Materials,

Stuttgart, Germany School of Process, Environmental and Materials
Engineering, Leeds, UK
Max-Planck-Institut fr Metallforschung, Institut fr Universiti Sains Malaysia, School of Materials

Werkstoffwissenschaft, Pulvermetallurgisches and Mineral Sources, Tronoh, Malaysia
Laboratorium, Stuttgart, Germany
Moscow State University, Department of General University of Science and Technology Beijing,
Chemistry, Moscow, Russia Department of Materials Science and
Engineering, Beijin, China
Mintek, Physical Metallurgy Division
Preface
The sub-series Ternary Alloy Systems of the Landolt-Brnstein New Series provides reliable and
comprehensive descriptions of the materials constitution, based on critical intellectual evaluations of all
data available at the time, and critically weights the different findings, also with respect to their
compatibility with todays edge binary phase diagrams. Selected are ternary systems of importance to
industrial alloy development and systems which gained scientific interest in the recent years otherwise. In
a ternary materials system, however, one may find alloys for various applications, depending on the
chosen composition.
Reliable phase diagrams provide scientists and engineers with basic information of eminent
importance for fundamental research and for the development and optimization of materials. So
collections of such diagrams are extremely useful, if the data on which they are based have been
subjected to critical evaluation, like in these volumes. Critical evaluation means: where contradictory
information is published data and conclusions are being analyzed, broken down to the firm facts and re-
interpreted in the light of all present knowledge. Depending on the information available this can be a
very difficult task to achieve. Critical evaluations establish descriptions of reliably known phase
configurations and related data.
The evaluations are performed by MSIT, Materials Science International Team, a group which has
been working together for 20 years now. Within this team skilled expertise is available for a broad range
of methods, materials and applications. This joint competence is employed in the critical evaluation of the
often conflicting literature data. Particularly helpful in this are targeted thermodynamic calculations for
individual equilibria, driving forces or complete phase diagram sections.
Insight in materials constitution and phase reactions is gained from many distinctly different types of
experiments, calculation and observations. Intellectual evaluations which interpret all data simultaneously
reveal the chemistry of a materials system best. The conclusions on the phase equilibria may be drawn
from direct observations e.g. by microscope, from monitoring caloric or thermal effects or measuring
properties such as electric resistivity, electro-magnetic or mechanical properties. Other examples of
useful methods in materials chemistry are mass-spectrometry, thermo-gravimetry, measurement of
electro-motive forces, X-ray and microprobe analyses. In each published case the applicability of the
chosen method has to be validated, the way of actually performing the experiment or computer modeling
has to be validated and the interpretation of the results with regard to the materials chemistry has to be
verified.
An additional degree of complexity is introduced by the material itself, as the state of the material
under test depends heavily on its history, in particular on the way of homogenization, thermal and
mechanical treatments. All this is taken into account in an MSIT expert evaluation.
To include binary data in the ternary evaluation is mandatory. Each of the three-dimensional ternary
phase diagrams has edge binary systems as boundary planes; their data have to match the ternary data
smoothly. At the same time each of the edge binary systems A-B is a boundary plane for many ternary A-
B-X systems. Therefore combining systematically binary and ternary evaluations can lead to a new level
of confidence and reliability in both ternary and binary phase diagrams. This has started systematically
for the first time here, by the MSIT Evaluation Programs applied to the Landolt-Brnstein New Series.
The multitude of correlated or inter-dependant data requires special care. Within MSIT an evaluation
routine has been established that proceeds knowledge driven and applies both human based expertise and
electronically formatted data and software tools. MSIT internal discussions take place in almost all
evaluations and on many different specific questions, adding the competence of a team to the work of
individual authors. In some cases the authors of earlier published work contributed to the knowledge base
by making their original data records available for re-interpretation. All evaluation reports published here
have undergone a thorough review process in which the reviewers had access to all the original data.
In publishing we have adopted a standard format that provides the reader with the data for each
ternary system in a concise and consistent manner, as applied in the MSIT Workplace: Phase Diagrams
Online. The standard format and special features of the Landolt-Brnstein compendium are explained in
the Introduction to the volume.
In spite of the skill and labor that have been put into this volume, it will not be faultless. All criticisms
and suggestions that can help us to improve our work are very welcome. Please contact us via
effenberg@msiwp.com. We hope that this volume will prove to be an as useful tool for the materials
scientist and engineer as the other volumes of Landolt-Brnstein New Series and the previous works of
MSIT have been. We hope that the Landolt-Brnstein Sub-series Ternary Alloy Systems will be well
received by our colleagues in research and industry.
On behalf of the participating authors we want to thank all those who contributed their comments and
insight during the evaluation process. In particular we thank the reviewers Andy Watson, Pierre Perrot,
Rainer Schmid-Fetzer, Peter Rogl, Olga Fabrichnaya, Lazar Rokhlin, Nataliya Bochvar, Nathalie Lebrun,
Hari Kumar, Tamara Velikanova, Anatoliy Bondar, Gabriele Cacciamani, Matvei Zinkevich, Artem
Kozlov, Ludmila Tretyachenko, Joachim Grbner, Marina Bulanova, Volodymyr Ivanchenko, Paola
Riani.
We all gratefully acknowledge the dedicated desk editing by Dr. Oleksandra Berezhnytska, Mrs.
Tatiana Whrle and Dr. Oleksandr Rogovtsov.
Gnter Effenberg and Svitlana Ilyenko Stuttgart, December 2005

Contents
IV/11 Ternary Alloy Systems

Phase Diagrams, Crystallographic and Thermodynamic Data
Subvolume C: Non-Ferrous Metal Systems
Part 2: Selected Copper Systems
Introduction
Data Covered ..................................................................................................................................XI
General............................................................................................................................................XI
Structure of a System Report ..........................................................................................................XI
Introduction..........................................................................................................................XI
Binary Systems ....................................................................................................................XI
Solid Phases ....................................................................................................................... XII
Quasibinary Systems......................................................................................................... XIII
Invariant Equilibria ........................................................................................................... XIII
Liquidus, Solidus, Solvus Surfaces................................................................................... XIII
Isothermal Sections........................................................................................................... XIII
Temperature Composition Sections ............................................................................... XIII
Thermodynamics .............................................................................................................. XIII
Notes on Materials Properties and Applications............................................................... XIII
Miscellaneous ................................................................................................................... XIII
References.........................................................................................................................XVI
General References .................................................................................................................... XVII
Ternary Systems
Al Cu Li (Aluminium Copper Lithium) ................................................................................1
Al Cu Ru (Aluminium Copper Ruthenium) ........................................................................43
Be Cu Mg (Beryllium Copper Magnesium)........................................................................58
Be Cu Ni (Beryllium Copper Nickel) .................................................................................64
Be Cu Si (Beryllium Copper Silicon) .................................................................................73
Ce Cu Ge (Cerium Copper Germanium).............................................................................77
Ce Cu In (Cerium Copper Indium) .....................................................................................92
Ce Cu Ni (Cerium Copper Nickel)....................................................................................105
Ce Cu Si (Cerium Copper Silicon)....................................................................................112
Ce Cu Sn (Cerium Copper Tin) ........................................................................................128
Ce Cu Zn (Cerium Copper Zinc) ......................................................................................152
Co Cu Si (Cobalt Copper Silicon).....................................................................................159
Co Cu Sm (Cobalt Copper Samarium)..............................................................................167
Cr Cu Fe (Chromium Copper Iron)...................................................................................183
Cr Cu Ni (Chromium Copper Nickel)...............................................................................210
Cr Cu Si (Chromium Copper Silicon)...............................................................................222
Cr Cu Zr (Chromium Copper Zirconium).........................................................................228
Cu Fe Pt (Copper Iron Platinum) ......................................................................................243
Cu Ga Mn (Copper Gallium Manganese) .........................................................................252
Cu Gd Sn (Copper Gadolinium Tin).................................................................................261
Cu Ge Mn (Copper Germanium Manganese) ...................................................................268
Cu Ge Ni (Copper Germanium Nickel) ............................................................................279
Cu H Ni (Copper Hydrogen Nickel) .................................................................................287
Cu In Yb (Copper Indium Ytterbium) ...............................................................................300
Cu La Ni (Copper Lanthanum Nickel)..............................................................................318
Cu Mg Zr (Copper Magnesium Zirconium)......................................................................328
Cu Mn Si (Copper Manganese Silicon) ............................................................................332
Cu Mn Zn (Copper Manganese Zinc) ...............................................................................346
Cu Nb Si (Copper Niobium Silicon).................................................................................358
Cu Nb Sn (Copper Niobium Tin)......................................................................................364
Cu Ni Si (Copper Nickel Silicon) .....................................................................................374
Cu Ni Zr (Copper Nickel Zirconium) ...............................................................................382
Cu Pb Sb (Copper Lead Antimony) ..................................................................................396
Cu Pb Zn (Copper Lead Zinc)...........................................................................................408
Cu Sb Sn (Copper Antimony Tin) ....................................................................................420
Cu Sb Zn (Copper Antimony Zinc) ..................................................................................437
Cu Si Zr (Copper Silicon Zirconium) ...............................................................................443
Cu Ti Zn (Copper Titanium Zinc).....................................................................................451
Free WEB Access to update information and more.

Content updates of the Landolt-Brnstein sub-series IV/11 plus supplementary information are available
from MSI, including:
Links to Literature (up-to-date bibliographic data base)

Diagrams as Published (not MSIT-evaluated diagrams)
Research Results (published and proprietary data)
Ternary Evaluations: These are LB IV/11 contents and their
updates (if any) as interactive live diagrams & documents.
This service is free of charge for Landolt-Brnstein subscribers and applies for material systems included
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license@msiwp.com .
Contents and supplementary information to the Landolt-Boernstein sub-series IV/11 are made by MSI,
Materials Science International Services, GmbH, Stuttgart and its global team MSIT, as part of their
ongoing Phase Diagram Evaluation Programs. For details on MSIT Workplace, Phase Diagrams
Online see: http://www.matport.com .
Introduction XI
Introduction
Data Covered
The series focuses on light metal ternary systems and includes phase equilibria of importance for alloy
development, processing or application, reporting on selected ternary systems of importance to industrial
light alloy development and systems which gained otherwise scientific interest in the recent years.
General
The series provides consistent phase diagram descriptions for individual ternary systems. The
representation of the equilibria of ternary systems as a function of temperature results in spacial diagrams
whose sections and projections are generally published in the literature. Phase equilibria are described in
terms of liquidus, solidus and solvus projections, isothermal and pseudobinary sections; data on invariant
equilibria are generally given in the form of tables.
The world literature is thoroughly and systematically searched back to the year 1900. Then, the
published data are critically evaluated by experts in materials science and reviewed. Conflicting information
is commented upon and errors and inconsistencies removed wherever possible. It considers those, and only
those data, which are firmly established, comments on questionable findings and justifies re-interpretations
made by the authors of the evaluation reports.
In general, the approach used to discuss the phase relationships is to consider changes in state and phase
reactions which occur with decreasing temperature. This has influenced the terminology employed and is
reflected in the tables and the reaction schemes presented.
The system reports present concise descriptions and hence do not repeat in the text facts which can
clearly be read from the diagrams. For most purposes the use of the compendium is expected to be self-
sufficient. However, a detailed bibliography of all cited references is given to enable original sources of
information to be studied if required.
Structure of a System Report

The constitutional description of an alloy system consists of text and a table/diagram section which are
separated by the bibliography referring to the original literature (see Fig. 1). The tables and diagrams carry
the essential constitutional information and are commented on in the text if necessary.
Where published data allow, the following sections are provided in each report:
Introduction
The opening text reviews briefly the status of knowledge published on the system and outlines the
experimental methods that have been applied. Furthermore, attention may be drawn to questions which are
still open or to cases where conclusions from the evaluation work modified the published phase diagram.
Binary Systems
Where binary systems are accepted from standard compilations reference is made to these compilations.
In other cases the accepted binary phase diagrams are reproduced for the convenience of the reader. The
selection of the binary systems used as a basis for the evaluation of the ternary system was at the discretion
of the assessor.
Landolt-Brnstein
New Series IV/11C2
MSIT
XII Introduction
Heading
Introduction
Binary Systems
Solid Phases
Quasibinary Systems
Invariant Equilibria
Text
Liquidus, Solidus, Solvus Surfaces
Isothermal Sections
Temperature-Composition Sections
Thermodynamics
Notes on Materials Properties and Applications
Miscellaneous
References
Miscellaneous
Thermodynamics
Temperature-Composition Sections
Tables and Isothermal Sections
diagrams
Quasibinary Systems
Solid Phases
Binary Systems
Fig. 1: Structure of a system report
Solid Phases
The tabular listing of solid phases incorporates knowledge of the phases which is necessary or helpful
for understanding the text and diagrams. Throughout a system report a unique phase name and abbreviation
is allocated to each phase.
Phases with the same formulae but different space lattices (e.g. allotropic transformation) are
distinguished by:
small letters (h), high temperature modification (h2 > h1)
(r), room temperature modification
(1), low temperature modification (l1 > l2)
Greek letters, e.g., J, J'
Roman numerals, e.g., (I) and (II) for different pressure modifications.
In the table Solid Phases ternary phases are denoted by * and different phases are separated by
horizontal lines.
MSIT Landolt-Brnstein
New Series IV/11C2
Introduction XIII
Quasibinary Systems
Quasibinary (pseudobinary) sections describe equilibria and can be read in the same way as binary
diagrams. The notation used in quasibinary systems is the same as that of vertical sections, which are
reported under Temperature Composition Sections.
The invariant equilibria of a system are listed in the table Invariant Equilibria and, where possible, are
described by a constitutional Reaction Scheme (Fig. 2).
The sequential numbering of invariant equilibria increases with decreasing temperature, one numbering
for all binaries together and one for the ternary system.
Equilibria notations are used to indicate the reactions by which phases will be
decomposed (e- and E-type reactions)
formed (p- and P-type reactions)
transformed (U-type reactions)
For transition reactions the letter U (bergangsreaktion) is used in order to reserve the letter T to denote
temperature. The letters d and D indicate degenerate equilibria which do not allow a distinction according
to the above classes.

The phase equilibria are commonly shown in triangular coordinates which allow a reading of the
concentration of the constituents in at.%. In some cases mass% scaling is used for better data readability
(see Figs. 3 and 4).
In the polythermal projection of the liquidus surface, monovariant liquidus grooves separate phase
regions of primary crystallization and, where available, isothermal lines contour the liquidus surface (see
Fig. 3).
Isothermal Sections
Phase equilibria at constant temperatures are plotted in the form of isothermal sections (see Fig. 4).
Temperature Composition Sections

Non-quasibinary T-x sections (or vertical sections, isopleths, polythermal sections) show the phase
fields where generally the tie lines are not in the same plane as the section. The notation employed for the
latter (see Fig. 5) is the same as that used for binary and pseudobinary phase diagrams.
Thermodynamics
Experimental ternary data are reported in some system reports and reference to thermodynamic
modelling is made.

Noteworthy physical and chemical materials properties and application areas are briefly reported if they
were given in the original constitutional and phase diagram literature.
Miscellaneous
In this section noteworthy features are reported which are not described in preceding paragraphs. These
include graphical data not covered by the general report format, such as lattice spacing composition data,
p-T-x diagrams, etc.
Landolt-Brnstein
New Series IV/11C2
MSIT
XIV
second binary first binary eutectic reaction
MSIT
eutectic reaction (highest temperature) ternary maximum
Ag-Tl Tl-Bi Ag-Tl-Bi Bi-Ag
303 e1
l (Tl)(h)+Tl3Bi 294 e2 (max) reaction
291 e3 temperature
L (Ag) + Tl3Bi
l (Ag)+(Tl)(h) of 261C
289 L + Tl3Bi (Ag) + (Tl)(h) U1
289 e4 (min) (Ag) + (Tl)(h) + Tl3Bi

261 e5
L (Ag) + (Tl)(h)
234 d1 l (Ag) + (Bi)
(Tl)(h) (Tl)(r),(Ag)
207 e6 (max)
202 e7
L (Ag) + Tl2Bi3
l (Bi)+Tl2Bi3
197 L (Ag)+(Bi)+Tl2Bi3 E1
192 e8
l Tl3Bi+Tl2Bi3 (Ag)+(Bi)+Tl2Bi3
Introduction
monovariant
equilibrium stable
188 L (Ag)+Tl3Bi+Tl2Bi3 E2 down to low
temperatures
(Ag)+Tl3Bi+Tl2Bi3
second
ternary
144 e9 eutectic
144 (Tl)(h) Tl3Bi + (Tl)(r),(Ag) D1 reaction
(Tl)(h) Tl3Bi+(Tl)(r)
(Ag)+(Tl)(r)+Tl3Bi
equation of eutectoid
reaction at 144C
Fig 2: Typical reaction scheme
New Series IV/11C2

Landolt-Brnstein
Introduction XV
C Data / Grid: at.%

Axes: at.%

p1
700
20
80
500C isotherm, temperature is usually in C
50
primary -crystallization 0
40 400C
60 liquidus groove to
decreasing temperatures
40
binary invariant
0
reaction 300 estimated 400C isotherm
e2
60 U e1
ternary invariant 40
reaction
300
(h)
300
400
0
50
0
70
40
80
20
0
limit of known region
20 40 60 80
A B
Fig. 3: Hypothetical liquidus surface showing notation employed
C Data / Grid: mass%

Axes: mass%
phase field notation
estimated phase boundary

20
80
40 + (h)
60
phase boundary three phase field
(partially estimated)
experimental points
L+ (occasionally reported)
60
40
tie line L+ + (h)
80 L (h)
20
L+ (h)
L+ limit of known region
20 40 60 80
Al B
Fig. 4: Hypothetical isothermal section showing notation employed
Landolt-Brnstein
New Series IV/11C2
MSIT
XVI Introduction
750
L phase field notation

Temperature, C
500
L+ (h)
L+ 32.5% concentration of
abscissa element
250
L+ + (h)
(h) temperature, C
(h) - high temperature
188 modification
(r) - room temperature
modification
+ (h) (r)
alloy composition
0 in at.%
A 80.00 60 40 20 A 0.00
B 0.00 B 80.00
C 20.00 Al, at.% C 20.00
Fig. 5: Hypothetical vertical section showing notation employed
References
The publications which form the bases of the assessments are listed in the following manner:
[1974Hay] Hayashi, M., Azakami, T., Kamed, M., Effects of Third Elements on the Activity of Lead
in Liquid Copper Base Alloys (in Japanese), Nippon Kogyo Kaishi, 90, 51-56 (1974) (Experimental,
Thermodyn., 16)
This paper, for example, whose title is given in English, is actually written in Japanese. It was published
in 1974 on pages 51- 56, volume 90 of Nippon Kogyo Kaishi, the Journal of the Mining and Metallurgical
Institute of Japan. It reports on experimental work that leads to thermodynamic data and it refers to 16 cross-
references.
Additional conventions used in citing are:
# to indicate the source of accepted phase diagrams
* to indicate key papers that significantly contributed to the understanding of the system.
Standard reference works given in the list General References are cited using their abbreviations and
are not included in the reference list of each individual system.
New Series IV/11C2
Introduction XVII
General References
[C.A.] Chemical Abstracts - pathways to published research in the world's journal and patent
literature - http://www.cas.org/
[Curr.Cont.] Current Contents - bibliographic multidisciplinary current awareness Web resource -
http://www.isinet.com/products/cap/ccc/
[E] Elliott, R.P., Constitution of Binary Alloys, First Supplement, McGraw-Hill, New York
(1965)
[G] Gmelin Handbook of Inorganic Chemistry, 8th ed., Springer-Verlag, Berlin
[H] Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York
(1958)
[L-B] Landolt-Boernstein, Numerical Data and Functional Relationships in Science and
Technology (New Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P.,
Kandler, H. and Stegherr, A., Structure Data of Elements and Intermetallic Phases (1971);
Vol. 7, Pies, W. and Weiss, A., Crystal Structure of Inorganic Compounds, Part c, Key
Elements: N, P, As, Sb, Bi, C (1979); Group 4: Macroscopic and Technical Properties of
Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic and Thermodynamic Data of
Binary Alloys, Subvol. a: Ac-Au ... Au-Zr (1991); Springer-Verlag, Berlin.
[Mas] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, ASM, Metals Park, Ohio (1986)
[Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International,
Metals Park, Ohio (1990)
[P] Pearson, W.B., A Handbook of Lattice Spacings and Structures of Metals and Alloys,
Pergamon Press, New York, Vol. 1 (1958), Vol. 2 (1967)
[S] Shunk, F.A., Constitution of Binary Alloys, Second Supplement, McGraw-Hill, New
York (1969)
[V-C] Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for
Intermetallic Phases, ASM, Metals Park, Ohio (1985)
[V-C2] Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for
Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)
Landolt-Brnstein MSIT
New Series IV/11C2
IV/11 Ternary Alloy Systems
Phase Diagrams, Crystallographic and Thermodynamic Data
Subvolume C: Non-Ferrous Metal Systems
Part 2: Selected Copper Systems
Ternary Systems Al - Ternary Systems Be - Ternary Systems Ce -
Al - Cu - Li Be - Cu - Mg Ce - Cu - Ge
Al - Cu - Ru Be - Cu - Ni Ce - Cu - In
Be - Cu - Si Ce - Cu - Ni
Ce - Cu - Si
Ce - Cu - Sn
Ce - Cu - Zn
Ternary Systems Co - Ternary Systems Cr - Ternary Systems Cu -
Co - Cu - Si Cr - Cu - Fe Cu - Fe - Pt
Co - Cu - Sm Cr - Cu - Ni Cu - Ga - Mn
Cr - Cu - Si Cu - Gd - Sn
Cr - Cu - Zr Cu - Ge - Mn
Cu - Ge - Ni
Cu - H - Ni
Cu - In - Yb
Cu - La - Ni
Cu - Mg - Zr
Cu - Mn - Si
Cu - Mn - Zn
Cu - Nb - Si
Cu - Nb - Sn
Cu - Ni - Si
Cu - Ni - Zr
Cu - Pb - Sb
Cu - Pb - Zn
Cu - Sb - Sn
Cu - Sb - Zn
Cu - Si - Zr
Cu - Ti - Zn
AlCuLi 1
Aluminium Copper Lithium

Matvei Zinkevich, Tamara Velikanova, Mikhail Turchanin, Zhenmin Du
Introduction
The experimental data for the Al-Cu-Li system are mostly concentrated in the Al rich corner. Table 1
summarizes experimental investigations pertaining to phase relations, structure, and thermodynamics
reported in the literature. [1955Har] were the first to carry out a systematic study of phase equilibria in the
Al-Cu-Li system. By means of X-ray and optical microscopy techniques designed to minimize the effects
of oxidation they provided extensive data for the Al corner at 500 and, tentatively, at 350C. In the
composition range extending up to 60 mass% Cu and 20 mass% Li they identified for the first time a total
of six ternary solid phases, designated as -B, -1, -2, R (in this assessment -3), Q (-4), and P (-5). The three
ternary intermetallic compounds, -B, -1 and -2, were found to be in equilibrium with the Al rich solid
solution (Al). The structure of -2, -3, -4, and -5 remained undetermined at that time. Subsequently,
[1961Fri] studied the combined solubility of Cu and Li in (Al) at 200 and 500C. Further experimental
investigations of the equilibria in the ternary system were reported by [1960Mik, 1963Sha, 1965Boc,
1986Smi, 1986Rio, 1987Che, 1988Dor, 1989Dub, 1990Tak, 1991Che1]. [1960Mik] reported three vertical
sections CuAl2-LiAl, Al-Cu:Li = 4:1 (mass%), and Al-Cu:Li = 9:1 (mass%) but they did not observe the
existence of -B. Several errors in the CuAl2-LiAl section [1960Mik] were pointed out by [1988Zak]. Some
inconsistencies were observed by [1988Riv] in the liquidus surface proposed by [1960Mik, 1963Sha]. Four
vertical sections (at 4, 5 and 6 mass% Cu and 95 mass% Al) were reported by [1965Boc]. Two invariant
reactions were proposed by [1977Dri] near the Al-Cu side. The phase equilibria in the ternary Al-Cu-Li
system were reviewed subsequently by [1968Age, 1968Dri, 1969Wat, 1976Mon, 1977Dri, 1980Zak,
1987Flo, 1987Lav, 1988Riv, 1991Har, 1995Bod]. The critical evaluation by [1991Har] included reaction
scheme, liquidus surface and isothermal section at 500C in the Al rich region. Since then many papers were
devoted to the Al-Cu-Li alloys. Solidus and solvus temperatures were metallographically determined for 4
alloy compositions by [1988Dor]: 1.96Li, 2.68Cu, ~95 mass% Al; 2.23Li, 2.76Cu, ~95 mass% Al; 2.40Li,
2.66Cu, ~95 mass% Al; 2.67Li, 2.83Cu, ~95 mass% Al. The homogeneity range of the (Al) ternary solid
solution at 500C proposed by [1988Dor] is larger than that suggested by [1976Mon]. A new experimental
determination of the phase equilibria of the Al rich alloys was carried out by [1991Che1]. The primary
phases, reaction sequences, and solidification temperatures were studied. In the calculations, -2 and -3
phases were treated as stoichiometric compounds. A liquidus projection was also calculated.
The thermodynamic properties of phases were studied by many researchers. The enthalpy of formation of
compounds and liquid alloys as well as enthalpy of fusion of ternary compounds were studied
calorimetrically by [1987Che, 1988Dub, 1989Dub, 2002Mos]. Thermodynamic properties of liquid alloys
and phases in equilibrium were studied by [2002Mos] using electromotive force method. Low-temperature
heat capacity of the -2 phase was investigated by [1988Wag, 1997Wan].
The Al rich part of the phase diagram was thermodynamically assessed by [1989Dub, 1991Che2, 1990Ans,
1992Sau, 1998Ans, 2002Mos] using the CALPHAD method. A detailed experimental analysis of the
constitution and thermodynamics of the Al-Cu-Li system coupled with thermodynamic calculation of the
equilibrium phase diagram, with emphasis on Al rich region, was carried out by [1988Dub, 1989Dub]
allowing them to present a liquidus surface focusing on the -2 and -3 phases. Yet another thermodynamic
calculation of the system in the Al rich corner was attempted by [1991Che2]. Values of the enthalpies of
formation for the ternary intermetallic phases -B, -1, -2, and -3 were determined experimentally as 17 1,
20.6 1, 20.4 1, 22.1 1 kJ#mol1 [1988Dub, 1989Dub]. The calculated values of enthalpy of
formation of -B, -1, and -2 are 21, 20 and 17 kJ#mol1, respectively [1991Che2]. Unfortunately,
probable misprints are responsible for the incorrect values (27, 30 and 29 kJ#mol1, respectively) quoted
by [1991Che2] for [1989Dub].
[1991Che2] did not differentiate between the -2 and -3 phases. This differs from the assessment of others,
where these phases are modeled separately. A problem for [1989Dub, 1990Ans, 1991Che1, 1992Sau,
Landolt-Brnstein
New Series IV/11C2
MSIT
2 AlCuLi
1998Ans] was the lack of thermodynamic data on the liquid phase. [2002Mos] used their own data for
enthalpy of mixing of the liquid phase in the modeling of phase equilibria. The results of optimization by
[1989Dub, 1990Ans, 1998Ans, 2002Mos] can be considered as a consequent development of models where
the last one demonstrates good agreement with majority of experimental results on phase equilibria and
thermodynamics. In the current assessment the results of [2002Mos] are taken as the basis for the evaluation
of the phase equilibria.
A number of investigations of quasicrystalline -2 together with the related -3 phase were performed after
1985. The ternary phase -2 was unambiguously identified as an icosahedral quasicrystalline phase by
[1986Dub] and considered as a stable quasicrystalline phase. The icosahedral quasicrystalline -2 phase can
be obtained by rapid or slow cooling from the melt [1986Dub, 1986Sai, 1987Lan, 1987Mai, 1987Rao,
1988Par, 1989Kor, 1989She, 1993Deg]. Quasicrystal growth processes were studied by [1987Gay,
1987Lan, 1988She2, 1988Par]. Slowly solidified icosahedral -2 quasicrystals can grow as facetted dendrites
with an apparent rhombic triacontahedral habit [1987Gay]. Quasicrystalline grains can grow along the
5-fold axis [1987Lan], and formation of a texture was observed in melt-spun quasicrystals with a 5-fold axis
aligned perpendicular to the ribbon surface [1989Sug]. [1988Par] and [1993Deg] have grown
centimeter-sized single-grained -2 quasicrystals using the Bridgman method. Easy nucleation of
icosahedral particles combined with the slow kinetics of the -2 -3 transformation is probably the reason
for growth of large icosahedral crystals [1988She2]. The icosahedral quasicrystalline -2 phase can also be
formed by solid-state reaction from the supersaturated (Al) solid solution [1985Sai2, 1986Cas1, 1986Cas2,
1987Cas1, 1991Lar]. DSC was used for studying the stability of the icosahedral quasicrystalline -2 phase
[1987Che, 1988She2, 1991Lar] and of the -3 phase [1987Che, 1988She2]. Salient feature in the thermal
behavior of icosahedral quasicrystalline -2 is the absence of exothermic transition characteristics of
metastable phases [1987Che, 1988She2, 1991Lar]. The reversibility of the formation of icosahedral -2 on
ageing at room temperature after its partial destruction during annealing at 400C was observed by
[1991Lar]. The results obtained by [1955Har, 1960Mik, 1963Sha, 1965Boc, 1987Che, 1988Dub,
1991Che1] show that the phase equilibria in the Al-Cu-Li system are complex and still need careful
experimental work for a satisfactory interpretation. Some of these investigators found that the lithium
content changed in the course of their experiments. [1960Mik] analyzed the chemical compositions of three
alloys after solidification and found that the lithium loss varied from 10 to 23 mass%.
Binary Systems
Assessments of the Al-Cu system by [2004Gro], the Al-Li system by [2002Gro], and the Cu-Li system by
[2006Boc] are accepted. They are based on [1994Mur, 1998Liu] for Al-Cu, [1982McA] for Al-Li and
[1994Pel] for Cu-Li. The thermodynamic data set of the COST 507 action [1998Ans, 1991Sau] for the
corresponding binary systems was used to calculate figures and the reaction scheme in the present
assessment. The agreement between calculated and evaluated diagrams is very good. The only differences
are minor shifts in the temperatures of invariant equilibria and the treatment of 0 1 phase transition in
the Al-Cu system (first order in [1998Ans] and second order in [2004Gro]). In addition, the !, , Li3Al2,
Li9Al4, -B, -1, -2, and -3 phases are treated as stoichiometric, while 1 and 2 as well as Li9Al4(h) and
Li9Al4(r) are not differentiated and called and Li9Al4, respectively.
Solid Phases
The crystal data for solid phases are listed in Table 2. The cubic -B, LiCu4Al7.5 phase forms peritectically
at about 550C according to the experimental data of [1963Sha]: the value calculated in the present
assessment is somewhat higher, P3, 584C (see section Invariant Equilibria and Table 3). The -B phase also
crystallizes on ageing Al rich commercial alloys between room temperature and 350C [1959Sil, 1973Sch1,
1991Lud]. The -1 phase, LiCuAl2, is formed congruently at about 695C [1963Sha, 1989Dub] (693C after
thermodynamic calculation). It also precipitates from aged alloys with a well-defined plate-shaped
morphology [1955Har]. The hexagonal crystal structure of -1 was first proposed by [1955Har]. The
existence of the -1 phase was reported without details by [1966Che]. The -1 phase formation was assumed
to occur via direct nucleation and growth from the saturated (Al) solid solution following a stacking fault
New Series IV/11C2
AlCuLi 3
mechanism [1972Nob]. This point of view was confirmed by [1987Cas2]. After some debates among
[1988How, 1987Hua1, 1987Rad, 1992Hua], the -1 phase was confirmed to be of a hexagonal structure with
space group P6/mmm [1987Hua1, 1988Vec3, 1990Sma]. High-resolution TEM examination and simulation
[1987How, 1987Rad, 1992Hua] yielded results consistent with the hexagonal structure, though the exact
atom positions were assigned slightly differently by [1987How, 1987Rad] compared to [1987Hua1].
Refinement of the hexagonal structure of LiCuAl2 was carried out using single crystal X-ray diffraction
[1990Sma]. Positron lifetime measurements were carried out during in-situ annealing of quenched samples
of an alloy with composition 7.5Li-1.1Cu-91.4 (at.%) Al. Semicoherent and incoherent precipitation of the
-1 phase was detected, but no quenched-in vacancies were found [1992Dlu]. The presence of the -1 phase
in Al rich alloys can facilitate hydrogen entry and cause embrittlement of the alloys [1991Mel]. The
structure of the -3 phase, Li3CuAl5 (R phase after [1955Har]) was first determined by [1963Che] and found
to be based on the Frank-Kasper Mg32(Zn,Al)49 structure. Using X-ray and neutron diffraction, the atomic
arrangement in the -3 (R) phase was redetermined [1988Aud1, 1988Gur, 1989Aud, 1990Gur]. The atom
positions proposed by [1988Aud1, 1988Gur, 1990Gur, 1992Tam] are slightly different from [1963Che] but
confirm the successive icosahedral and dodecahedral shells. The -3 phase, Li3CuAl5, is a bcc crystalline
phase (space group Im3m) with 162 atoms per unit cell (see Table 2) [1988Aud1, 1992Tam]. The origin is
unoccupied. The body-centered sites are surrounded by successive atomic shells with almost icosahedral
symmetry: a small Al, Cu icosahedron (r = 251.8 pm), a Li pentagonal dodecahedron (r = 453.2 pm) and a
second Al,Cu icosahedron (r = 504.8 pm) [1992Tam]. The set of the last two shells forms a small
triacontahedron. The next shells are an Al, Cu pentakisdodecahedron [1992Tam] (r = 668.6 pm), a second
Li dodecahedron (r = 750.5 pm) and a Li icosahedron (r = 812.3 pm). The last two shells form a large
triacontahedron. The -3 phase is therefore described as a bcc stacking of these large triacontahedra.
Translational planar defects are characteristic of the microstructure of Li3CuAl5 crystals [1991Don,
1992Don]. When these defects have a high density, they become periodically organized what leads to
pseudo-fivefold diffraction patterns [1992Don], which are used for identifying the icosahedral
quasicrystalline -2 phase [1991Don]. The -3 phase can be therefore presented as an interlinking crystal in
the whole family from large-parameter crystals to the quasicrystal -2. Imperfections in the -3 phase crystal
structure were also analyzed by [1991Shi]. Intermediate states between the icosahedral quasicrystal -2 and
the -3 phase were observed at the interface -2--3 by TEM investigations [1993Don] on annealing and
attributed to the chemical diffusion between -2 and -3. The defect network, randomly organized at low
defect density in the -3 phase, becomes a periodic when the defect density increases. This complex
organization suggests that diffusion rates are very low in the quasicrystalline -2 phase and the equilibrium
state is difficult to reach. This can explain some inconsistencies in the TEM and X-ray results obtained by
several authors [1993Nis]. A new rhombohedral approximant crystal is also suggested by [1993Don]. The
close structural relationship between the icosahedral phase -2 and the cubic -3 phase was established by
[1989Aud] and is also proved by the results obtained using either scanning electron microscopy [1986Aud],
X-ray diffraction [1986Mar, 1987Dmo, 1987She, 1987Sma, 1988Aud1, 1988Els, 1988Gur, 1988She1,
1989She, 1991Boi, 1993Qiu, 1993Ara], high-resolution X-ray scattering experiments [1987Poo], X-ray
absorption fine structure spectroscopy (XAFS) [1987Ma, 1987Ste], pulsed neutron scattering [1988She1,
1989She] or inelastic neutron scattering measurements [1991Gol, 1992Gol] as well as nuclear magnetic
resonance measurements [1988Lee]. Both phases have compositions, which are very close [1987Che,
1989Aud, 1988Dub] (see Table 2). A comparison between high-resolution electron microscopy (HREM)
image simulations on the -3 phase with experimental HREM images of the icosahedral -2 phase also
showed a strong similarity in the local order arrangements between the two phases [1992Tam]. The
structure of the icosahedral phase -2 has also been shown to be related not only to the cubic -3 phase but
also to several stable intermetallic compounds (Li,Mg)0.3(Cu,Zn)0.1Al0.6 with chemical compositions close
to -2 and -3 [1989Aud]. Neutron diffraction data strongly suggest that short- and medium-range orders are
almost the same in the -2 and -3 phases [1989Aud]. The Friauf polyhedron could be the only structural unit
common to quasicrystalline and related crystalline Li-(Cu,Zn,Mg)-Al phases [1987Fru, 1989Aud,
1991LeB, 1991Leb, 1993Don]. Small changes in the composition or in the defect network of the periodic
-3 phase can produce the -2 aperiodic network [1993Don]. The strong similarities, which exist between the
structures of -2 and -3 (R after [1955Har, 1989Aud]) as well as the existence of intermediate states between
Landolt-Brnstein
New Series IV/11C2
MSIT
4 AlCuLi
-2 and -3 structures [1991Don, 1992Don, 1993Don] are considered as support to the point of view that a
unique symbol, -2(R), can be used for both -3 and -2 phases. The absence of exothermic thermal effect for
the -2 -3 transition [1987Che, 1988She2, 1991Lar] and the fact that the values of the enthalpies of
formation are almost the same for -2 and -3 [1988Dub, 1989Dub] can be attributed to very close
compositions and very similar crystal structures of the compounds.
The TEM observation of microcrystals in association with the icosahedral quasicrystalline -2 phase caused
some controversy about its stability and existence range [1987Bar, 1987Hua2, 1988Mic, 1988Sad,
1988Vec1, 1988Vec2, 1989Tos, 1989How, 1990Mic1, 1990How]. A tentative interpretation of the X-ray
diffraction patterns of the icosahedral -2 phase with a tetragonal unit cell was proposed by [1988Ana]. X-ray
precession and electron diffraction data indicated a perfect icosahedral symmetry [1987Den], while others
revealed deviations from an icosahedral symmetry [1987Mai, 1988Yu, 1993Nis]. Comparison between the
electron diffraction patterns of the as-quenched and the annealed -2 phase revealed a pronounced deviation
from the perfect icosahedral symmetry after annealing [1987Yu]. Convergent beam electron diffraction of
the -2 and -3 phases indicated that the quasicrystalline and crystalline structures seem to occur
simultaneously [1988Las]. Structural models were developed for the icosahedral -2 phase. Most of them
consider the structure as the three-dimensional cut of a six-dimensional crystal [1988Els, 1991Boi,
1991Sma, 1992Yam]. The icosahedral quasicrystalline -2 phase is also viewed as the result of competition
between antisymmetric coupling of Friauf polyhedra forming prolate Penrose rhombohedra and symmetric
coupling forming 5-fold rings of prolate rhombohedra. Antisymmetric couplings do not exist in the -3
crystalline phase [1987Fru]. They initiate multiple twinning, which produces an average icosahedral
symmetry [1987Fru]. The atomic structure of a perfect icosahedral quasicrystal can also be achieved in a
three-dimensional Penrose and the structure may be understood in terms of four zonohedra [1987Guy1,
1987Guy2, 1988Aud2]. The powder and single crystal neutron and X-ray diffraction data were obtained for
the icosahedral quasicrystal -2 by [1991Boi] and used by [1994Elc] for refining the structure. Structure
factors of the icosahedral -2 phase were determined by [1993Qiu], in good agreement with previous
structural investigations and models [1988Els, 1991Boi].
Quantum structural diagrams successfully predict the existence of the -2 phase [1986Vil]. Using a
molecular dynamics simulations, [1993Win] found that the structure of the icosahedral -2 phase may be
stable. The same conclusion was reached by [1993Nie] who calculated the total energies of the -2 and -3
phases and compared them with fictitious ternary solid solutions and mixtures. However, the -2 phase was
observed to transform to the -3 phase after an isothermal heat treatment at 400C for 20 min [1992Yan] or
during argon-ion bombardment [1988Sad]. A defect network and translation domains could be formed
during the -2 -3 phase transformation [1991Shi].
The -4(Q) and -5(P) phases were additionally reported by [1955Har] in alloys annealed at 500 and 350C.
Only some X-ray lines but no compositions are given for them. The composition of -5 appears to be close
to that of -B phase since the alloys in the <35 at.% Cu, <15 at.% Li range contained this phase together with
-B: +-B+-5 / -B+-5/-5+-B+-1. The composition 30Li-30Cu-40Al (at.%) reported by [1970Ole] for -4 does
not contradict with phase constituents of alloys near the -1+LiAl tie-line of the -1+-3+LiAl phase triangle
[1955Har]. The ternary phases LiCu2Al (-6) and Li3Cu3Al4 (-7) were reported in the only short publication
by [1966Che]. Further investigation is needed to obtain a complete picture concerning a number of ternary
compounds in the system and crystal structure of the new ternary phases. The data on an extension of solid
solutions based on binary phases are also very scarce.
Quasibinary Systems
Two maxima of three phase equilibria, both quasibinary eutectics, e2 and e3: L -1 + J2 and L -1 + LiAl,
respectively are found by calculation in the current assessment (see Table 3). The -1 - LiAl section (Fig. 1)
is the only quasibinary system because -1 and LiAl are congruently melting phases. This section was never
presented in experimental reports, it is calculated in the present assessment. The quasibinary peritectic
L + LiAl -3 reported by [1991Har, 1995Bod] is not confirmed. The partial quasibinary system proposed
by [1987Che, 1988Par] within the composition range Li3CuAlx where 4.5 < x < 10 is not accepted because
it does not follow the thermodynamic criteria for quasibinary systems.
New Series IV/11C2
AlCuLi 5
The invariant reactions and the reaction scheme resulting from the thermodynamic calculation for
solid-liquid phase equilibria are given in Table 3 and Fig. 2, respectively. Only the -B, -1, -2 and -3 ternary
intermediate phases were involved in the calculation. There is good agreement between the calculated four
phase invariant equilibria and experimental data published by [1965Boc, 1988Dub, 1989Dub] for the range
of >50 at.% Al (reactions P1, P2, U3, U5, U7, U8, U9, and E1) as well as between the calculated and
experimental temperatures of congruent melting of the -1 phase. Two maxima of three-phase invariant
equilibria of the eutectic type (e2, e3) are found. Moreover, there is a good agreement between calculations
and the experimental data of [1963Sha, 1977Dri, 1991Che1] for the above mentioned invariant reactions,
on one hand, and of [1965Boc, 1988Dub, 1989Dub] for U9 (L + (Al) + -B), on the other hand, as well
as between the calculations and experimental data of [1960Mik, 1963Sha, 1965Boc, 1977Dri, 1988Dub,
1989Dub, 1991Che1] for E1 (L + (Al) + -B + -1). However, the calculated temperatures for the reactions
L + + -1 -B (P3, 584C) and L + + -B (U6, 574C) are markedly higher than ones reported by
[1963Sha] (the only who investigated them): 550 and 542C, respectively.
The liquid compositions for all the U-type transition reactions given by [1991Che1] in figure 7 of their work
are inconsistent with the reactions, which are proposed there [1991Che1], because they are located inside
the triangles formed by the compositions of solid phases participating in succeeding equilibria shown in
figure 6 of [1991Che1]. Unfortunately, [1991Che1] did not report the numerical data on the composition of
phases at the invariant equilibria. The temperatures reported by [1960Mik] are drastically different from
those of other authors and cannot be accepted. The congruent melting of the -3 phase proposed by
[1987Che, 1988Par, 1989Dub] is not confirmed by thermodynamic calculations. As it follows from the
relative position of compositional points, which participate in the equilibrium, congruent melting of the -3
phase turns out to be impossible, even though the narrow homogeneity ranges of -2 and -3 phases are taken
into account. It is worth noting that the composition of the -3 phase is very close to that of the liquid phase
composition at P1 (see Table 3). The calculated liquid phase compositions for P1, P2, U5, P3, U6, U7, U8,
U9, and E1 invariant equilibria and the data according to the critical evaluation of [1991Har, 1995Bod]
based on the experimental data of [1960Mik, 1963Sha, 1965Boc, 1987Che, 1988Dub] as well as the
calculated data of [1992Sau, 2002Mos] appear to be in satisfactory agreement, because the deviations are
below 3 at.%. However, in some cases these differences cause the change of the proposed type of equilibria
as one can see in the case of the reactions L + LiAl -1 + -3 by [1991Har, 1995Bod] as well as
L + -3 LiAl + -2, L + -B + -1, and L + + -B by [2002Mos] instead of P1, P2, P3 and U6,
respectively, after the current assessment.
Both the -2 and -3 phases are considered in the current assessment as separate and stable phases according
to [1988Dub, 1988Riv, 1989Dub, 1991Har, 1995Bod, 2002Mos]. In contrast to this point of view a
continuous transition between the -2 and R (-3) structures was reported [1991Don, 1992Don, 1993Don] and
the unique symbol, -2 (R), was proposed for designation of these phases.
The region of the phase diagram, where Al content is below 50 at.% has not been experimentally
determined. The conclusion of [1960Mik] concerning the equilibria of the (Cu) solid solution with the
phases LiAl, -1, and J2 can not be considered enough justified because it is based only on the investigation
of nonequilibrated alloys using the DTA and microstructural methods. In addition, the results of [1960Mik]
contradict with all other experimental data on phase relations in the ternary system and cannot be accepted.
Phase equilibria in this composition range were calculated by only taking into account the data for boundary
binary systems and thermodynamic data for the liquid at high Al content. Equilibria involving (Cu) reported
by [1960Mik] were not confirmed by thermodynamic calculations.
The existence of four phase monotectic reactions (U4 and E2) is the most interesting result for this
composition range of the system (<50 at.% Al). They arise from the stabilization of the metastable
liquid-liquid miscibility gap from the binary Cu-Li system reported by [1994Pel, 2006Boc]. The stable
ternary miscibility gap maximum according to the calculation (at ~960C, ~30 at.% Cu and ~60 at.% Li) is
markedly higher than that assumed in the binary Cu-Li. Certainly, in future analysis of this system, the
ternary -4, -5 and possibly other phases should be considered. Also, it is desirable to take the ranges of
homogeneity for the ternary solutions based on binary and ternary compounds into consideration.
Landolt-Brnstein
New Series IV/11C2
MSIT
6 AlCuLi
Liquidus Surface
The liquidus surface calculated according to the thermodynamic description of [2002Mos] in the whole
range of compositions is presented in Figs. 3 a, b. Additionally, the 0 1 phase transition is shown
(dashed line) since it is accepted to be of second-order in the Al-Cu system [2004Gro], but this feature is
not modeled in [1998Ans, 2002Mos]. For the Al rich part of the system it is in satisfactory agreement with
that given in critical evaluation of [1991Har, 1995Bod] based on the results obtained by [1963Sha,
1965Boc, 1988Dub, 1989Dub]. The Al rich, Cu rich and Li rich regions of the liquidus projection are shown
in Figs. 3 c, d, e and f.
Isothermal Sections
The calculated partial isothermal sections at Al content 50 to 100 at.% are given in Figs. 4 to 8. The
homogeneity range of the (Al) solid solution at 350C according to the current assessment is shown in
Fig. 4. The calculation is in good agreement with the experimental data for 350C. Isothermal section at
400C is given in Fig. 5 and shows good compliance with that of [1989Dub]. The isothermal section of the
Al corner at 500C according to the current assessment (Fig. 6) agrees well with that given in the critical
evaluations of [1988Riv, 1991Har, 1995Bod] mainly based on [1955Har] and with the experimental ones
determined by [1989Dub]. The homogeneity range of the (Al) solid solution agrees fairly well with that of
[1961Fri], but initial slopes of the (Al) phase boundaries after [1961Fri] contradict van't Hoff relation, so
that these data cannot be accepted. For -2 and -3, the compositions determined by [1988Dub] were selected,
which agree with those given by [1987Che] and [1955Har] within the given error of 3%.
It should be noted that there is a significant temperature dependence of the homogeneity range of the (Al)
solid solution, and a wide range of coexistence of the -1 and -2 phases with the (Al) phase. The phase
relations at 555 and 615C are shown in Figs. 7, 8 according to the current calculation. The -2 phase is
predicted to be the predominant phase in equilibrium with the (Al) matrix in the ternary Al rich alloys
annealed below 500C. The -2 phase is expected to precipitate together with the -1 phase in alloys located
on the Cu rich side of the (Al) + -2 field. The LiAl compound should precipitate with -2 in the ternary alloys
located between the Li rich side of the (Al) + -2 domain and the Al-Li side. Despite the difficulty in
achieving thermodynamic equilibrium at the lower temperatures (e.g. below 400C), this trend appears to
be in good qualitative agreement with the observed equilibrium precipitation in extensively overaged alloys
[1986Cas2, 1986Cas3, 1986Tos, 1989Dub].

Ten temperature-composition sections studied experimentally are reported: CuAl2-LiAl, Al-(Cu:Li = 4:1,
mass%) and Al-(Cu:Li = 9:1, mass%) by [1960Mik]; CuAl2--B/-B--1 and -1-Al by [1963Sha]; at 95 Al
mass% and at 4, 5 and 6 Li (mass%) by [1965Boc]; and Al--2 by [1988Dub]. All of them were revised in
the current assessment by computation using the CALPHAD method. The results are given in Figs. 9 to 18.
Additionally, the calculated vertical section Al-67Li33Cu (at.%) and one through the critical points of the
miscibility gap in the liquid are given in Figs. 19, 20a, 20b.
There is a good agreement between the experimental data of [1965Boc] and calculated sections along the
same composition lines at 95 mass% Al, 4, 5 and 6 mass% Li, which are given in Figs. 9 to 12, respectively.
The significant temperature dependence of the (Al) + LiAl + -2 / (Al) + LiAl phase boundary according to
the calculation shown in Fig. 9 correlates well with the significant temperature dependence of the (Al) / (Al)
+ LiAl boundary in the Al-Li binary system.
The phase regions and the temperature of the isotherms corresponding to the invariant equilibria E1 and P3
shown in the section CuAl2--B / -B--1 and Al--1 by [1963Sha], generally, are in agreement with the
calculated vertical sections CuAl2--1 and -1-Al given in Figs. 13, 14, respectively. The details are not
discussed here, because the compositions of the alloys under investigation in [1963Sha] do not correspond
to the claimed sections. They were shifted from the nominal composition to the Al corner according to the
chemical analysis data after [1963Sha]. An interpretation of the phase relations in the vertical sections
CuAl2-LiAl, Al-(Cu:Li = 4:1, mass%) and Al-(Cu:Li = 9:1, mass%) by [1960Mik] cannot be accepted.
New Series IV/11C2
AlCuLi 7
These sections are based only on the investigation of as-cast alloys using DTA and microscopical methods.
The calculated ones are given in Figs. 15 to 17 along the same composition lines. Experimental data on
liquidus for alloys along the section Al--2 reported by [1988Dub] agree with the calculated diagram given
in Fig. 18. Only preliminary picture of the phase relations at lower temperatures are reported by [1988Dub].
The congruent melting of -1 and incongruent melting of -2 and -3 phases as well as the dome of the liquid
phase immiscibility near the Cu-Li edge of the Al-Cu-Li composition triangle are exhibited by the
calculated vertical section Al-67Li33Cu (at.%) in Fig. 19. Vertical sections through the critical points of the
miscibility gap in the vicinity of c1 and c2 are given in Figs. 20a and 20b, respectively.
Thermodynamics
The enthalpies of fusion for the -2 and -3 phases were measured by differential scanning calorimetry (DSC)
[1987Che]. The values were reported to be same and equal to mH = 13.4 kJ#mol1. This is perhaps due to
the compositional and structural similarity between -2 and -3. [1988Dub, 1989Dub] determined the
enthalpies of formation of -B, -1, -2 and -3 phases by means of solution calorimetry in liquid aluminium.
The samples consisted of nearly single phases of the compounds and were annealed for 72 h at 500C. The
enthalpy of formation of phases at 25C are fH(-B) = 17 1 kJ#mol1, fH(-1) = 20.6 1.0 kJ#mol1,
fH(-2) = 20.4 1.0 kJ#mol1and fH(-3) = 22.0 1.0 kJ#mol1. Electromotive force and calorimetric
studies of liquid and solid alloys were performed by [2002Mos]. Electromotive force studies were made for
four sets of alloys at the following temperatures and compositions: T = 888 K (615C), xAl/xCu = 9,
0.001 xLi 0.639; T = 888 K (615C), xAl/xCu = 4, 0.013 xLi 0.815; T = 828 K (555C), xAl/xCu = 7/3,
0.0001 xLi 0.5; T = 778 K (505C), xAl/xCu = 7/3, 0.0032 xLi 0.069. Drop calorimetric studies were
carried out to determine mixing enthalpies for liquid alloys. At 986 K (713C), copper was dropped into the
Al-Li bath with xAl/xLi = 4 to obtain alloys with 0.02 xCu 0.285, and, at 945 K (672C), lithium was
dropped into an Al-Cu bath with xAl/xLi = 6.07 to obtain alloys with 0.023 xLi 0.265.
The thermodynamic information obtained by [1987Che, 1988Dub, 1989Dub, 2002Mos] along with the
information on the phase equilibria updated by [1987Che] were combined to calculate the isothermal
sections at 828 (555C) and 888 (615C) K in aluminium rich corner of the Al-Cu-Li phase diagram
[2002Mos]. The optimized parameters of constituent binary Al-Li, Al-Cu, and Cu-Li systems were taken
from [1998Ans]. For pure aluminium, copper and lithium the thermodynamic parameters from COST 507
database [1991Sau] were used. The -4 and -5 phase were not considered in the calculation as well as lithium
solubility in the phase. Excess Gibbs energy of the liquid phase was described by equation [2002Mos]
Gex = xAlxCu( 66622 + 8.1T + (xAl xCu)(46800 90.8T + 10TlnT) + (xAl xCu)2( 2812))
+ xAlxLi( 41500 + 20.96T + (xAl xLi)(10000 5.8T) + (xAl xLi)2(15902 9.386T) 250(xAl xLi)3) +
xCuxLi(66000 44.723T) + xAlxCuxLi (xAl (235832 + 169.7897T)
163397.43 xCu + xLi(264994.13 + 186.6438T)) J#mol1.
According to this model wide range of immiscibility of liquid alloys can be predicted near Cu-Li side of the
diagram. The dome of the miscibility gap has a flat maximum at ~960C and ~30 at.% Cu, ~60 at.% Li.
Gibbs energy of formation of ternary phases was described as:
fG(-B) = 18924.73 + 2.93494T J#mol1,
fG(-1) = 22354.21 + 3.33970T J#mol1,
fG(-2) = 18637.75 + 3.94024T J#mol1,
fG(-3) = 19442.97 + 4.24074T J#mol1.
No ternary parameters were used for (Al) solid solution. Good agreement between majority of
electrochemical and calorimetric results and the optimized thermodynamic parameters were observed.
However, for alloys with xAl/xCu = 7/3 differences between experimental [2002Mos] and calculated values
were observed in one-, two- and three phase fields.
The low temperature heat capacity of rapidly quenched, annealed and single crystal samples of the -2 phase
was measured in the temperature range 0.7-10 K using the thermal relaxation method [1988Wag]. In
[1997Wan], the low temperature heat capacity of the -2 phase was investigated using an AC calorimetric
method in temperature range 1-6 K for as-cast and annealed samples. It was found that preparation methods
could greatly affect the electronic and vibrational properties.
Landolt-Brnstein
New Series IV/11C2
MSIT
8 AlCuLi

Al-Cu-Li alloys offer a combination of high elastic modulus, low density and high strength, which make
them attractive for aerospace applications. The development of such alloys, which are weight saving in the
aerospace structures was reviewed, including ingot metallurgy, rapid solidification, physical metallurgy and
mechanical properties [1987Lav].
A summary of main and recent investigations of the properties of Al-Cu-Li alloys is given in Table 4.
Aluminium alloys have undergone a series of developments for aircraft and aerospace applications since the
1970s [1960Ter, 1973Sch1, 1973Sch2, 1976Shc]. The demand for high specific strength without prior cold
stretching, a very strong and rapid natural aging capability, good fracture toughness at room and cryogenic
temperature, good weldability, and stress-corrosion-cracking resistance led to the further development of
Al-Cu-Li-based alloys since the late 1980s [1991Bal, 1992Flo, 1995Yam, 1997Gil, 1998Rad, 2000Cso,
2000Dav, 2001Dut, 2002Gab, 2003Fra, 2003Sal]. Depending on composition and aging treatment, the
high-strength is due to one or more of three different precipitates: -LiAl3, - CuAl2, -1-LiCuAl2 and
Guinier-Preston (GP) zones [1976Shc, 1993Sta, 1993Yu, 1995Yam, 2003Fra].
The precipitation behaviour of aged 1.6Li-3.2Cu-95.2Al (mass%) and 2.4Li-3.2Cu.94.4Al (mass%) was
investigated using conventional TEM, high resolution transmission electron microscopy (HREM) and high
angle annular detector dark-field-scanning transmission electron microscopy (HAADF-STEM) [2003Yos2,
2003Yos1]. The addition of small amounts of Zn, 0.50 mass%, to Al-Cu-Li alloys was shown to have a
significant effect on their corrosion resistance or environmental properties [2002Gab]. A study was made
on how additions of In, Mg and Si and impurities Na and K affect the microstructure and related mechanical
properties of an Al-Cu-Li alloy [1997Gil]. The stress-corrosion cracking susceptibility of
2.05Li-2.15Cu-95.8Al alloy in 0.5 M NaCl solution was measured [1991Bal]. A theoretical model
describing the evolution of the hardness profiles in the heat-affected zones of the Al-Cu-Li 2095 alloy was
established [1998Rad]. The effect of quenching rate on the microstructure and mechanical properties of the
Al-Cu-Li alloy AF/C 458 (1.8Li.2.7Cu-95.5Al, mass%) was investigated [2000Cso], and the
microstructural features of AF/C 458 alloy were characterized to determined the average size, distribution,
number density, spacing and volume fraction of the intermetallic strengthening precipitates -LiAl3 and
-1-LiCuAl2 [2003Fra]. The kinetics and mechanism of decomposition process of an 3.6Li-2.0Cu-94.4Al
alloy, whose melt spun ribbons were cast at a linear rate of 10-20 m#s1 and aged at 200C, were analysed
[2001Dut].
The electronic properties of icosahedral Al-Cu-Li quasicrystals were studied experimentally and the role of
the interaction effect between the Fermi surface and Jones zone [1988Wag, 1992Hip, 1991Miz, 1993Fuj]
were shown. The icosahedral -2 phase and the Frank-Kasper R phase (-3) show similar electronic,
vibrational and transport properties [1988Wag]. The electronic properties of the R (-3) and -2 phases have
also been studied by nuclear magnetic resonance (NMR) [1992Hip]. Low values of the density of states at
the Fermi level were observed for the R (-3) phase as well as for the icosahedral -2 phase. The existence of
a pseudogap at the Fermi level is therefore not a consequence of the quasiperiodicity [1992Hip]. The
electronic specific heat coefficient was also measured for the icosahedral quasicrystalline -2 phase and the
corresponding Frank-Kasper R (-3) phase [1991Miz]. The electronic structure near the Fermi level is
essentially determined by the local atomic structure, which turns to be similar between the -2 phase and the
corresponding Frank-Kasper R (-3) phase [1991Miz]. Low values of the electronic term in the expression
of the specific heat (from 7.0#106 to 1.5#105 J#g1#K2) were found in melt-spun icosahedral -2 and in the
R (-3) phase [1988Wag]. The specific heat of single-grained-icosahedral -2 phase was measured at
low-temperature between 0.25 and 2.7 K [1987Jin], 4 and 80 K [1988Wan], 0.8 to 10 K [1988Bru] and
between 1.5 and 6 K [1989Kim], as well as the electrical resistivity [1987Jin, 1989Kim] and the
magnetoresistance at 1.4, 4.2 and 10 K [1988Bru, 1989Kim].
The understanding of the mechanical properties of the Al-Cu-Li alloys in the Al-Li rich part necessitates the
identification of the GP zones and/or transition phases formed during ageing treatment [1984Bau, 1984Gil,
1984San]. The formation of GP zones on ageing is accompanied by a substantial rise of the electrical
resistivity and strength properties, whilst ductility remains at a reasonable level [1991Kay].
New Series IV/11C2
AlCuLi 9
Miscellaneous
The stable -1 phase was observed to be formed in 9.8Li-0.8Cu-89.4Al (at.%) alloy aged at 190C for times
varying between 10 min and 8 d. Other phases were also formed, which remained unidentified [1985Sai1].
Precipitation of -1 has also been reported to occur heterogeneously either at GP zones in
1.5Li-3.5Cu-95.0Al (mass%) alloys, or at matrix dislocations in 2.0Li-2.5Cu-95.5Al (mass%) alloys
[1972Nob]. The spinodal decomposition of Al rich alloys (2.5Li-0.02Cu-97.48Al, 2.4Li-2.5Cu-95.1Al,
3.0Li-1.0Cu.96.0Al (mass%)) was investigated by high resolution transmission electron microscopy and by
X-ray diffraction in quenched alloys aged for 168 h at room temperature [1989Rad]. Al rich -LiAl3
precipitates (L12 structure) were observed to develop in modulated order/disorder regions of varying Li
content. A critical assessment on the solid-state transformations in Al-Cu-Li alloys was presented by
[1987Flo].
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Landolt-Brnstein
New Series IV/11C2
MSIT
10 AlCuLi
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New Series IV/11C2
AlCuLi 11
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Landolt-Brnstein
New Series IV/11C2
MSIT
12 AlCuLi
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Landolt-Brnstein
New Series IV/11C2
MSIT
14 AlCuLi
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New Series IV/11C2
AlCuLi 15
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New Series IV/11C2
MSIT
16 AlCuLi
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AlCuLi 17
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Landolt-Brnstein
New Series IV/11C2
MSIT
18 AlCuLi
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Mechan. Prop., Morphology, Phase Relations, 13)
[2003Sal] Salem, H.G., Goforth, R.E., Hartwig, K.T., Influence of Intense Plastic Straining on Grain
refinement, Precipitation, and Mechanical Properties of Al-Cu-Li-Based Alloys, Metall.
Mater. Trans. A, 34, 1153-1161 (2003) (Experimental, Mechan. Prop., Morphology, 24)
[2003Yos1] Yoshimura, R., Konno, T.J., Abe, E., Hiraga, K., Transmission Electron Microscopy Study
of the Early Stage of Precipitates in Aged Al-Li-Cu Alloys, Acta Mater., 51, 2891-2903
(2003) (Crys. Structure, Electronic Structure, Experimental, 61)
[2003Yos2] Yoshimura, R., Konno, T.J., Abe, E., Hiraga, K., Transition Electron Microscopy Study of
the Evolution of Precipitates in Aged Al-Li-Cu Alloys: the Q and T1 Phases, Acta Mater.,
51(14), 4251-4266 (2003) (Experimental, Kinetics, Morphology, Phase Relations, 69)
[2004Gro] Groebner, J., Al-Cu (Aluminium-Copper), MSIT Binary Evaluation Program, in MSIT
Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH,
Assessment, 68)
[2006Boc] Bochvar, N., Rokhlin, L., Cu-Li (Copper-Lithium), MSIT Binary Evaluation Program, in
MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services
GmbH, Stuttgart; to be published, (2006) (Crys. Structure, Phase Diagram, Assessment, 12)
New Series IV/11C2
AlCuLi 19
Table 1: Investigations of the Al-Cu-Li Phase Relations, Structure and Thermodynamics

Reference Method/Experimental Technique Temperature/Composition/Phase
Range Studied
[1955Har] Melting in aluminized graphite crucible; annealing, 500, 350C, 0 to 60 mass% Cu,
subsequently quenching in paraffin, optical 0 to 20 mass% Li
microscopy and X-ray powder diffraction
[1961Fri] Microstructure investigation, hardness 200, 500C, 0 to 7 mass% Cu,
measurements 0 to 3 mass% Li
[1960Mik] Microstructural, thermal and wet chemical analysis Eighteen sections at constant atomic
ratios Cu:Li of 1:3, 1:2, 1:1 etc.
As-cast and cooled after DTA alloys
[1963Sha] Microstructural and thermal analysis, powder X-ray As-cast and cooled after DTA alloys
diffraction (6 C/min), 3.0 to 32.8 at.% Cu, 3.0 to
25 at.% Li
[1965Boc] Microstructural, thermal and wet chemical analysis 400C to liquidus, 0 to 6 mass% Cu,
0.25 to 6 mass% Li
[1972Nob] Solution treatment followed by quenching and Al - 3.5 (1.45) mass% (at.%) Cu -1.5
aging. (5.70) mass% (at.%) Li;
Powder X-ray diffraction Al - 2.5 (1.03) mass% (at.%) Cu -2.0
(7.45) mass% (at.%) Li
[1973Sch1] Solution treatment followed by quenching and 4.17 (1.78) mass% (at.%) Cu, 1.01
[1973Sch2] aging. (3.94) mass% (at.%) Li
Powder X-ray diffraction, TEM
[1986Aud] TEM Al rich part of the system; -2--3
phases in unannealed samples
[1986Dub] TEM, HREM, SEM, X-ray diffraction As-cast alloys of composition close to
Al6CuLi3
[1986Mar] Powder X-ray diffraction, TEM, SEM -2, -3 phases
[1987Che] Quantitative DTA, powder X-ray diffraction AlxLi3Cu (4.8 x 6.1)
[1987Dmo] X-ray diffraction -2 and -3 phases
[1987Dub] TEM, HREM, SEM, X-ray diffraction As-cast alloys of composition close to
-2
[1987Hua1] Copper single roller melt-quenching technique, Al-25.8 -18.6Li (mass%)
TEM, powder X-ray diffraction, electrical
resistivity at RT to 600C
[1987Poo] High-resolution 350C, -2, -3 phases
X-ray scattering experiment
[1987Rao] Powder X-ray diffraction, SEM, EPMA Al-25.1Cu-6.9Li (mass%)
Al-27.9Cu-6.1Li (mass%)
Al-27.5Cu-7.2Li (mass%)
[1987She] Synchrotron X-ray powder diffraction 350C, Li33.7Cu10.2Al56.1
[1987Sma] Single crystal X-ray diffraction As-grown alloy Al6CuLi3
[1987Ste] X-ray absorption fine structure (XAFS) -2 phase
[1987Ma] spectroscopy
Landolt-Brnstein
New Series IV/11C2
MSIT
20 AlCuLi

Range Studied
[1988Aud1] Single crystal X-ray and neutron diffraction, SEM -3 (Al5CuLi3) phase
[1988Aud2]
[1988Dor] Commercial alloys homogenized, heat-treated 500 to 600C, 1.96 to 2.67 Li mass%;
subsequently quenched, metallography 2.66 to 2.83 Cu mass%; melting,
solvus
[1988Dub] Thermal analysis, differential scanning calorimetry, > 50 at.% Al, T 500C in the
solution calorimetry vicinity of the ternary compounds -2
and -3, Al--2 section
[1988Els] Single crystal X-ray diffraction -2 phase
[1988Vec1] Optical microscopy, EPMA, 500C, Al-26.9Cu-4.72 Li (mass%);
(wavelength-dispersive X-ray spectrometry), TEM 470C, Al-24.1Cu-9.06Li (mass%),
as cast alloys
[1988Vec3] Single crystal, TEM, convergent beam electron 500C, 49.53Al-27.09Cu-23.42Li
diffraction, EPMA (at.%), -1 phase
[1988Wag] Thermal relaxation method 0.7-10 K, -2 phase
[1988Yu] X-ray and electron diffraction As-cast and as-quenched Al6CuLi3
[1989Dub] Thermal analysis, differential scanning calorimetry, 300 to 600C, Al rich corner of the
solution calorimetry in liquid aluminium, double system, liquidus, isothermal sections
weighting technique in air and silicone oil. at 300, 400, 500, 600 and 750C
Thermodynamic modeling
[1990Ans] Thermodynamic modeling 0 to 60 Cu, 0 to 12 Li mass%;
liquidus surface
[1990Yan] Single crystal X-ray diffraction -1 phase
[1991Boi] Powder and single crystal neutron and X-ray -2 phase
diffraction
[1991Che1] Optical microscopy, electron probe microanalysis, 0 to 50 Cu, 0 to 50 Li at.%;
[1991Che2] X-ray diffraction, scanning electron microscopy, Cu-Li spinodal; isothermal section at
differential thermal and chemical analysis. 500C, liquidus surface
Thermodynamic modeling.
[1991Mat] Powder X-ray diffraction (synchrotron radiation), -2, -3 phase
TEM, inverse photoemission measurement
[1992Sau] Thermodynamic modeling
[1992Tam] HREM Al5CuLi3, Al6CuLi3
[1993Don] TEM, X-ray diffraction Al6Li3Cu - Al5Li3Cu interface
[1997Wan] AC calorimetric method 1 T 6 K, as-cast and annealed
samples of -2 phase
[1998Ans] Thermodynamic assessment
New Series IV/11C2
AlCuLi 21

Range Studied
[2002Kon] HREM -1, -3 phases
[2002Mos] Electromotive force method with salt electrolyte, T = 888 K, xAl/xCu = 9, 0.1 Li at.%
drop, calorimetry, thermodynamic assessment 63.9;
T = 888 K, xAl/xCu = 4, 1.3 Li at.%
81.5;
T = 828 K, xAl/xCu = 7/3, 0.01 Li
at.% 50;
T = 778 K, xAl/xCu = 7/3,
0.32 Li 6.9 (at.%);
T = 986 K, xAl/xLi = 4, 2 Cu 28.5
(at.%);
T = 945 K, xAl/xCu = 6.07,
2.3 Li 26.5 (at.%)
Table 2: Crystallographic Data of Solid Phases

Phase/ Pearson Symbol/ Lattice Parameters Comments/References
Temperature Range Space Group/ [pm]
[C] Prototype
(Al) cF4 a = 404.96 pure Al [Mas2],
< 660.452 Fm3m lattice parameters at
Cu 25C [V-C2], dissolves up to 2.48 at.%
Cu at 548.2C and 14 at.% Li at 596C
(Cu) cF4 a = 361.46 pure Cu [Mas2],
< 1084.62 Fm3m lattice parameters at 25C [V-C2],
Cu dissolves 19.7 at.% Al at 363C and 22
at.% Li at 180C [Mas2]
(Li) cI2 a = 350.96 pure Li [Mas2],
< 180.6 Im3m lattice parameters at 25C [V-C],
W practically no solubility for Al and Cu
, Cu3Al(h) cI2 70.6 to 82 at.% Cu [2004Gro]
Im3m a = 295.4 at 672C in + (Cu) alloy
W
0, Cu1xAlx cI52 - 0.31 x 0.402 [Mas2],
Cu~2Al I43m 0.32 x 0.38 [2004Gro]
1037 - 800 Cu5Zn8
1, Cu9Al4 cP52 62 to 68 at.% Cu [2004Gro];
< 890 P43m a = 870.23 powder and single crystal [2004Gro]
Cu9Al4 a = 870.68 from single crystal [2004Gro]
, Cu1xAlx hR* 0.381 x 0.407 [2004Gro]
< 686 R3m 59.3 to 61.9 at.% Cu
a = 1226 at x = 38.9 [2004Gro]
c = 1511
J1, Cu1-xAlx c** - 0.379 x 0.406
958 - 848 59.4 to 62.1 at.% Cu [2004Gro]
Landolt-Brnstein
New Series IV/11C2
MSIT
22 AlCuLi

[C] Prototype
J2, Cu2xAl hP6 a = 414.6 0.47 x 0.78; 55.0 to 61.1 at.% Cu
850 - 560 P63/mmc c = 506.3 [2004Gro]
Ni2In
, CuAl(h) o*32 a = 408.7 49.8 to 52.4 at.% Cu [2004Gro]
624 - 560 b = 1200
c = 863.5
, CuAl2 tI12 a = 606.7 31.9 to 33.0 at.% Cu [2004Gro]
< 591 I4/mcm c = 487.7
CuAl2
Li9Al4 mC26 a = 1915.51 [2002Gro]
347 - 275 C2/m b = 542.88
Li9Al4 c = 449.88
= 107.671
Li3Al2 hR15 a = 450.8 [2002Gro]
R3m c = 1426
Li3Al2
LiAl cF16 a = 637 at 50 at.% Li, 45 to 55 at.% Li
Fm3m [2002Gro]
NaTl
* -B, LiCu4Al7.5 cF12 a = 583 [1955Har]
< 550 Fm3m a = 583.28 60.0 Al, 32.0 Cu, 8 Li (at.%) [1989Dub]
CaF2 'exp ~ 3.9 g#cm3 [1989Dub, 1991Lud]
* -1, LiCuAl2 hP12 a = 496 Al1.96Cu1.08Li0.96
< 695 P6/mmm c = 935 [1955Har,1963Sha]
LiCuAl2 a = 496 [1987Hua1]
c = 934.5
a = 497 [1988Vec3]
c = 930
a = 497 50.0 Al, 25.0 Cu, 25 Li (at.%)
c = 935 [1989Dub]
a = 495.3 'exp ~ 3.8 g#cm3 [1989Dub]
c = 932.7 [1990Sma]
* -2, Li3CuAl6 quasicrystal a = 505 -3n - = gold number = (1 + 51/2)/2,
n any integer,
point group only m [1989Aud, 1991Leb]
56.0Al-10.8Cu-32.2Li (at.%) [1988Dub]
'exp = 2.47 g#cm3 [1988Dub, 1989Dub]
* -3 cI162 a = 1391.4 [1955Har,1963Che],
< 635 Im3m
Li3CuAl5 Mg32(Zn,Al)49 a = 1390.56 56.4Al-11.6Cu-32.0Li (at.%) [1989Aud]
54.5Al-11.4Cu-34.1Li (at.%) [1987Che]
56.0Al-12.0Cu-32.0Li (at.%) [1988Dub]
'exp = 2.46 g#cm3
[1988Dub,1989Dub] [1986Dub,
1989Aud, 1991Boi, 1993Don]
New Series IV/11C2
AlCuLi 23

[C] Prototype
* -4 - - designated Q in [1955Har]
40 Al, 30Cu, 30 Li (at.%) [1970Ole]
* -5 - - designated P in [1955Har]
Table 3: Invariant Equilibria

Reaction T [C] Type Phase Composition (at.%)
Al Cu Li
L, L, (Cu) ~ 850 c1, critical L, L ~1.5 ~50.5 ~48
point (Cu) ~1.5 ~90 ~8.5
L + J1 1 + J2 836 D1(U) L 44.8 52.0 3.1
J1 39.8 60.2 0
1 36.4 63.5 0
J2 41.9 58.0 0
L -1 693 congruent L, -1 50.0 25.0 25.0
L + 1 + (Cu) 657 U1 L 24.2 50.1 25.7
24.4 75.6 0
1 31.0 69.0 0
(Cu) 21.7 75.8 2.5
L -1 + J 2 655 e2 (max) L 46.6 37.6 15.8
-1 50.0 25.0 25.0
J2 46.0 54.0 0
L + J 2 -1 + 1 654 U2 L 44.8 38.1 17.1
J2 43.2 56.8 0
-1 50.0 25.0 25.0
1 37.5 62.5 0
L -1 + LiAl 649 e3 (max) L 50.0 11.0 39.0
-1 50.0 25.0 25.0
LiAl 50.0 0 50.0
L + LiAl + -1 -3 638 P1 L 56.4 10.9 32.7
LiAl 51.5 0 48.4
-1 50.0 25.0 25.0
-3 55.0 11.7 33.3
L + LiAl + -3 -2 618 P2 L 63.2 8.5 28.3
LiAl 52.6 0 47.4
-3 55.0 11.7 33.3
-2 57.0 11.0 32.0
L + -3 -1 + -2 614 U3 L 63.8 12.1 24.1
-3 55.0 11.7 33.3
-1 50.0 25.0 25.0
-2 57.0 11.0 32.0
Landolt-Brnstein
New Series IV/11C2
MSIT
24 AlCuLi

Al Cu Li
L' + (Cu) L'' + 1 600 U4 L' 23.3 42.2 34.5
L'' 3.2 1.0 95.8
(Cu) 21.1 75.4 3.5
1 31.0 69.0 0
L + J 2 + -1 597 U5 L 59.9 31.9 8.1
J2 45.8 54.2 0
49.0 51.0 0
-1 50.0 25.0 25.0
L + + -1 -B 584 P3 L 61.8 30.7 7.5
49.2 50.8 0
-1 50.0 25.0 25.0
-B 60.0 32.0 8.0
L + + -B 574 U6 L 65.7 29.8 4.5
49.5 50.5 0
67.0 32.9 0
-B 60.0 32.0 8.0
L + LiAl (Al) + -2 564 U7 L 72.9 5.2 21.9
LiAl 53.7 0 46.3
(Al) 85.6 0.3 14.1
-2 57.0 11.0 32.0
L + -2 (Al) + -1 540 U8 L 74.0 11.9 14.1
-2 57.0 11.0 32.0
-1 50.0 25.0 25.0
(Al) 90.1 1.0 8.9
L + (Al) + -B 524 U9 L 76.2 17.6 6.2
67.9 32.1 0
(Al) 94.6 2.2 3.2
-B 60.0 32.0 8.0
L (Al) + -B + -1 522 E1 L 75.0 16.7 8.3
-B 60.0 32.0 8.0
-1 50.0 25.0 25.0
(Al) 93.5 1.9 4.6
L + LiAl -1 + Li3Al2 512 U10 L 25.6 3.2 71.2
LiAl 44.6 0 55.4
-1 50.0 25.0 25.0
Li3Al2 40.0 0 60.0
L, L, -1 ~ 500 c2, critical L, L ~25 ~10 ~65
point -1 50.0 25.0 25.0
L' L'' + 1 + -1 489 E2 L' 26.7 15.0 58.3
L'' 19.0 3.8 77.2
1 33.7 66.3 0
-1 50.0 25.0 25.0
New Series IV/11C2
AlCuLi 25

Al Cu Li
L + Li3Al2 -1 + Li9Al4 334 D2(U) L ~8.8 close to 0 ~91.2
-1 50.0 25.0 25.0
Li3Al2 40.0 0 60.0
Li9Al4 30.8 0 69.2
L + -1 Li9Al4 +1 313 U11 L ~7.2 close to 0 ~92.8
-1 50.0 25.0 25.0
Li9Al4 30.8 0 69.2
1 32.5 67.5 0
L + (Cu) 1 + (Li) 180 D3(U) L close to 0 close to 0 ~100
(Cu) 15.7 83.0 1.3
1 30.7 69.2 0
(Li) 0 0 100
L 1 + Li9Al4 + (Li) 175 D4(E) L ~1.1 close to 0 ~98.9
1 31.0 69.0 0
Li9Al4 30.8 0 69.2
(Li) 0 0 100
Table 4: Investigations of the Al-Cu-Li Materials Properties

Reference Method/Experimental Technique Type of Property Comments
[1959Sil] Powder X-ray diffraction Phase Ageing of supersaturated (Al)
transformation solid solutions
[1960Ter] Tensile Measurement Mechanical 0-1.5 mass% Li, 4.5 mass% Cu
[1973Sch1] X-ray, TEM (transmission electron Precipitation Al alloy 2020
[1973Sch2] microscope) kinetics Aged at 165-275C
[1976Shc] Hardness measurement, TEM-EDP Mechanical Al alloy VAD23
(electron diffraction patterns)
[1984San] TEM, SEM (scanning electron Mechanical Al-4Cu-2Li-0.2Zr
microscope), Tensile measurement Al-2.5Cu-2.5Li-0.2Zr
Al-1.5Cu-3Li-0.5Mn
[1987Jin] Specific heat capacity and Physical 0.25 to 2.7 K, Al6CuLi3 from
electrical resistivity measurements as-cast alloys of similar
composition; -2+-3+(Al)
[1987Lav] Review Physical and 78 references
mechanical
[1988Bru] Specific heat capacity and Physical 0.8 to 10 K, -2
electrical resistivity measurements
[1988Lee] Powder X-ray diffraction, nuclear Physical As-cast and melt-spun ribbons of
magnetic resonance (NMR) composition near Al6CuLi3:
spectroscopy 30 to 34 at.% Li; 9.6 to 13 at.% Cu
[1988She2] Powder X-ray diffraction, TEM, Physical Rapidly solidified LixCu1.0Al5.5,
DSC x = 3.0, 3.25, 3.4, 3.5, 3.7
Landolt-Brnstein
New Series IV/11C2
MSIT
26 AlCuLi

[1988Wan] Powder X-ray diffraction, specific Physical 0.5 to 10 K, quasi-crystalline (-2)
heat capacity measurement dendrites and quasi-crystal of
planar grow casting
[1989Kim] Low-temperature specific heat (1.5 Physical Single crystal
K to 6 K), electrical resistivity (1 K ~Li4CuAl6
to RT), magnetoresistance (1.4,
4.2, 10 K)
[1991Bal] Constant elongation rate technique Physical, stress 2.05 mass% Li
corrosion cracking 2.15 mass% Cu
susceptibility
[1991Kay] TEM, SEM, electrical resistivity, Physical (Al) supersaturated solid solutions
mechanical properties
[1991Miz] Single-roll spinning wheel Electronic, specific -3 phase
apparatus, powder X-ray heat coefficient
diffraction, DSC
[1992Flo] SAXS (small-angle X-ray Physical 8.49 at.% Li, 0.51 at.% Cu
scattering)
[1992Gol] Inelastic-neutron-scattering Physical -2 and -3 single crystals
measurements Mechanical
[1992Hip] Powder X-ray diffraction, pulsed Density of states at Al57Cu10.8Li32.2,
nuclear, magnetic, resonance the Fermi level Al56Cu12Li32
(NMR) spectroscopy
[1992Poo] Review Electronic Quasicrystals
[1993Fuj] Electronic structure modeling Density of states -2, -3 phases
[1993Sta] TEM Physical Quasicrystalline -2
[1993Yu] TEM, HREM (high resolution Physical Quasicrystals
transmission electron microscopy)
HAADF-STEM (high angle
annular detector
dark-field-scanning transmission
electron microscopy)
[1995Yam] Electrical resistivity and Electronic Heat-treated at 823 K and aged at
micro-Vickers measurements, Mechanical 303 to 473 K, alloys;
TEM Al-2.1Li-0.7Cu (mass%);
Al-1.7Li-2.0Cu (mass%);
Al-1.5Li-2.5Cu (mass%)
[1995Yam] Resistivity, microhardness, TEM Physical, 1.5-2.1Li; 0.7-2.5Cu (mass%)
Mechanical
[1997Gil] TEM Mechanical, Al alloys 2020, 2090
Physical
[1997Sem] Compressing measurement Mechanical Quasicrystalline Li3CuAl6,
300-773K, 22-225 MPa
[1997Wan] ac calorimetric method Physical, Cp Quasicrystalline Al6Li3Cu, 1-6 K
New Series IV/11C2
AlCuLi 27

[1997Yu] TEM, electron diffraction contrast Structure defects Quasicrystalline Al6Li3Cu
analysis
[1998Rad] Theoretical model Mechanical, Al alloy 2095
hardness
[2000Cso] TEM, SEM, microhardness and Mechanical, Al alloys AF/C 458, 489
tensile testing microhardness
[2000Dav] Tensile testing, DSC Mechanical, alloy I: 1.7 mass% Li
Elongation alloy II: 1.5 mass% Li
[2001Dut] Microhardness, X-ray, XSAS, Mechanical Al-2.0Cu-3.6Li (mass%)
TEM
[2002Ber] Velocity of sound measurement Physical Al5Li3Cu, Al6Li3Cu,
0-16 K
[2002Dav] TEM, X-ray, DSC, tensile testing Physical, Al alloys 2024, 2219
Mechanical
[2002Gab] TEM, EDS (energy-dispersive Precipitation -1-Al2LiCu, AF/C 458
spectrometer)
[2003Fra] Hardness measurement, TEM Mechanical AF/C 458
[2003Sal] ECAE (equal-channel angular Mechanical, Al alloys 2095, 2195, 9095
extrusion), TEM, EDS, hardness Elongation,
measurement Rockwell hardness
[2003Yos2] TEM, HREM, HAADF-STEM Precipitation 3.2 Cu-1.6 Li, mass%
[2003Yos1] 3.2 Cu-2.4 Li, mass%
Fig. 1: Al-Cu-Li.
Quasibinary section
LiAl - -1
L
700
Temperature, C
L+LiAl
L+1
1+LiAl
600
Li 25.00 30 40 Li 50.00
Cu 25.00 Cu 0.00
Al 50.00 Li, at.% Al 50.00
Landolt-Brnstein
New Series IV/11C2
MSIT
MSIT
28
Al-Li Al-Cu-Li A-B-C Cu-Li Al-Cu
1036 e1
l + (Cu)
1020 p1
01
l + 0
959 p2
01
c1, ~ 850 l + 0 1
850 p3
l + 1 2
836 L + 1 2 + 1 D1(U)
1 + 2 + 1
657 L + 1 + (Cu) U1 L+1+2
L'+L"+(Cu) 655 e2(max)
l 1 + 2
AlCuLi
654 L + 2 1 + 1 U2
649 e3(max)
l LiAl + 1
2 + 1 + 1
638 L + LiAl + 1 3 P1
LiAl + 1 + 3 L+LiAl+3 625 p4

L+1+3 l + 2 1
618 L + LiAl + 3 2 P2
L+3+2 LiAl+3+2
600 L' + (Cu) Li" + 1 U4
614 L + 3 1 + 2 U3
596 e4 3+2+1 597 L' + 2 + 1 U5 596 p5

l (Al) + LiAl l + 1
564 L + LiAl (Al) + 2 U7 2+1+1
L+1+
L+(Al)+2
New Series IV/11C2
LiAl+(Al)+2
Landolt-Brnstein
U10 U8 U8 E2 D3 P3 U6
Fig. 2a: Al-Cu-Li. Reaction scheme, part 1

New Series IV/11C2
Landolt-Brnstein
Al-Li Al-Cu-Li A-B-C Cu-Li Al-Cu
e3 U7 U3 U5 U4
U4 p5
U2
584 L' + + 1 B P3
L+LiAl+2
L'+L"+1
+B+1 L+B+
540 L + 2 1 + (Al) U8 548 e5
544 L + B + U6 l (Al) +
(Al)+2+2
L+1+B +A+ L+B+
L+(Al)+1 524 L + (Al) + B U9

L+(Al)+1
L+(Al)+B +(Al)+B
521 p6
l + LiAl Li3Al2 522 L (Al) + B + 1 E1
AlCuLi
512 L + LiAl 1 + Li3Al2 U10
c2, ~ 500
LLi3Al2+1 L'+L"+1 L+1+1
LiAl+1+ Li3Al2
489 L' L" + 1 + 1 E2
334 p7
334 L+ Li3Al2 Li9Al4+ 1 D2(U)
l + Li3Al2 Li9Al4 L"+1+1
Li3Al2+Li9Al4+1 L+Li9Al4+1
313 L + 1 L9Al4 + 1 U11

180.5 e6
180 L+ (Cu) (Li) + 1 D3(U) L"+(Cu)+1 l (Li) + (Cu)
L+Li9Al4+1
(Cu)+(Li)+1 L+(Li)+1
1+Li9Al4+1
175* e7
175 L+ (Li) + Li9Al4 + 1 D4(E)
l (Li) + Li9Al4
(Li)+Li9Al4+1
*e7 : 175 C - calculated (180C - experimental)
MSIT
Fig. 2b: Al-Cu-Li. Reaction scheme, part 2
29
30 AlCuLi
Al Data / Grid: at.%

Fig. 3a: Al-Cu-Li. Axes: at.%
Liquidus surface
projection
(Al)
e5
20
80
e4 U7 U8
U9
2 E1 U6 p5
B p4
P2
40 U3 P3 60
P1 3 U5
2
LiAl e3 e2 p3
1 D1
U2
60 1
40
p2
1 0
E2'
U10 c2 U1
p6 U'4

80
Li3Al2 20
e1
p7 E2''
c1 (Cu)
U''4
20 40 60 80
Li Cu

Fig. 3b: Al-Cu-Li. Axes: at.%
Liquidus isotherms
projection 650
600
20
80
550
500
40 600
60
650
60 650 40
600
550
650
500 700
80
20
800 750
800
750
850
900 950
1000
20 40 60 80 1050C
Li Cu
New Series IV/11C2
AlCuLi 31

Fig. 3c: Al-Cu-Li. Axes: at.%
Al rich region of the
liquidus projection
10
90
(Al)
e5
20
80
U9
E1
U8
e4 U7

30
70
2 1 B U6 p5
p4
P2
3 U3 P3
40
60
U5
LiAl P1 2
Li 50.00 10 20 30 40 Li 0.00
Cu 0.00 Cu 50.00
Al 50.00 Al 50.00
Li 0.00
Cu 50.00
Al 50.00 Data / Grid: at.%
Fig. 3d: Al-Cu-Li. Axes: at.%
Cu rich region of the
liquidus projection
1
D1
10
40
p2
0
1 p1
20
30
U1
30
20
e1
(Cu)
40
10
L'+L''
Li 50.00 60 70 80 90
Cu
Cu 50.00
Al 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
32 AlCuLi
30
Fig. 3e: Al-Cu-Li. LiAl
Li rich region of the 1 1
liquidus projection U10 E2
25
c2 U1
p6
U4
20
E2
Al, at.%
Li3Al2
15
(Cu)
10
1
p7
miscibility gap
U4
(Cu)
c1
0
Li 0 10 20 30 40 50 60
Cu, at.%
30
Fig. 3f: Al-Cu-Li.
Li rich region of the LiAl U10
liquidus projection,
fragment near the 25
Al-Li side
p6
1
Li3Al2
20
E2
Al, at.%
15
D2
10
p7 miscibility gap
Li9Al4
1
e7 U11,D4
5
U4
(Cu)
0
0 e ,D 1 2 3 4 5
6 3
Cu, at.%
New Series IV/11C2
AlCuLi 33
4.0
(Al) + + B
Fig. 4: Al-Cu-Li.
Partial isothermal
3.6
section at 350C
(Al) + 1+ 2
(Al) + B + 1
3.2
(Al) + 1
(Al) +
2.8
Cu, mass%
2.4
(Al) + B (Al) + 2+LiAl

2.0
(Al) + 2
1.6
1.2
0.8
0.4
(Al) (Al) +LiAl
0
0 0.3 0.6 0.9 1.2 1.5 1.8 2.1 2.4 2.7 3.0
Li, mass%

Fig. 5: Al-Cu-Li. Axes: at.%
Partial isothermal (Al)
section at 400C
10
90
20
80
30
70
(Al)+ B+
40 (Al)+ 2+LiAl (Al)+ 1+ 2 (Al)+ B+ 1 B+ +

60
2 B
2+LiAl
3
3+LiAl 1+ 3+LiAl B + 1+
Li 50.00 1+LiAl 10 20 1 30 40 Li 0.00

Cu 0.00 Cu 50.00
Al 50.00 Al 50.00
Landolt-Brnstein
New Series IV/11C2
MSIT
34 AlCuLi

section at 500C
10
90
20
80
30 (Al)+ + B 70
40 (Al)+ 2+LiAl (Al)+ 1+ 2 (Al)+ 1+ B

60
2 B + B+
3 1+ 3
1+ 3+LiAl 1+ B+
1+LiAl
Li 50.00 10 20 30 40 Li 0.00
Cu 0.00 Cu 50.00
Al 50.00 Al 50.00

section at 555C
10
90
(Al)+L
(Al)+L+ 2
20
80
L+
30
70
L+ + B
L+ 1
L+ 2 L+ B
40 (Al)+LiAl+ 2 + B+
60
2 L+ 1+ 3
L+1+ B
LiAl+ 3 3
LiAl+ 2 LiAl+ 1+ 3 1+ B+
Li 50.00 LiAl+ 1 10 20 1 30 40 Li 0.00

Cu 0.00 Cu 50.00
Al 50.00 Al 50.00
New Series IV/11C2
AlCuLi 35

Fig. 8: Al-Cu-Li. (Al) Axes: at.%
Partial isothermal
section at 615C
10
90
(Al)+L
20
80
L
30
70
L+3
L+LiAl L+ 2 L+
40
60
2
iAl L+ 1
+L L+ 1+ B L+2

L+ 2
3
1+ 3+LiAl L+2+ 1
LiAl
Li 50.00 1+LiAl 10 20 1 30 40 Li 0.00

Cu 0.00 Cu 50.00
Al 50.00 Al 50.00
700
Fig. 9: Al-Cu-Li.
Vertical section at 95 L
mass% Al, plotted in
(Al)+L
at.%
600
L+(Al)+LiAl
(Al)+LiAl 564
(Al)
Temperature, C
500
(Al)+1
(Al)+
(Al)+B
(Al)+LiAl+2 (Al)+2
400
300
200
Li 16.99 15 10 5 Li 0.00
Cu 0.00 Cu 2.19
Al 83.01 Li, at.% Al 97.81
Landolt-Brnstein
New Series IV/11C2
MSIT
36 AlCuLi
700
Fig. 10: Al-Cu-Li.
mass% Cu, plotted in
at.%
(Al)+L
600
540
Temperature, C
564
(Al)
(Al)+2
500
(Al)+1 (Al)+
(Al)+LiAl+2 (Al)+B
400
300
Li 20.28 80 90 Li 0.00
Cu 1.48 Cu 1.74
Al 78.24 Al, at.% Al 98.26
700
Fig. 11: Al-Cu-Li.
at.%
L+(Al)
600
L+(Al)+LiAl
Temperature, C
564
524
L+(Al)+2 540
522
500
(Al)+1 (Al)+
(Al)+2 (Al)+B
400
L+LiAl+2
300
Li 20.48 80 90 Li 0.00
Cu 2.24 Cu 2.64
Al 77.28 Al, at.% Al 97.36
New Series IV/11C2
AlCuLi 37
700
Fig. 12: Al-Cu-Li.
at.%
L+(Al)
600
L+(Al)+LiAl
Temperature, C
564
524
L+(Al)+2 540
522
500
(Al)+1 (Al)+
(Al)+2 (Al)+B
400
L+LiAl+2
300
Li 20.48 80 90 Li 0.00
Cu 2.24 Cu 2.64
Al 77.28 Al, at.% Al 97.36
700
Fig. 13a:Al-Cu-Li.
Vertical section
CuAl2 - -1
L
L+1
L+B+
Temperature, C
600
L+1+ L+
L++
584
L+B L+B+
B++
L+1+B
522 524
500 B+
(Al)+1+B (Al)+B+
Li 25.00 20 10 Li 0.00
Cu 25.00 Cu 33.30
Al 50.00 Li, at.% Al 66.70
Landolt-Brnstein
New Series IV/11C2
MSIT
38 AlCuLi
590
Fig. 13b:Al-Cu-Li.
Vertical section
CuAl2 - -1. Enlarged
L
part separated by
dotted lines in
Fig. 13a
L+1
L+
Temperature, C
585
L++1
584
L+B
L+B+1
580
Li 8.20 8 7 Li 6.20
Cu 30.60 Cu 31.20
Al 61.20 Li, at.% Al 62.60
700
Fig. 14a:Al-Cu-Li.
Vertical section
-1 - Al L
L+1
600
Temperature, C
L+(Al)
L+(Al)+1 522 (Al)

524
500
(Al)+1+B (Al)+
400
Li 25.00 60 70 80 90 (Al)+B Al
Cu 25.00
Al 50.00 Al, at.%
New Series IV/11C2
AlCuLi 39
546
Fig. 14b:Al-Cu-Li.
Vertical section
-1 - Al. Enlarged part
separated by dotted
lines in Fig. 14a
L+(Al)
Temperature, C
(Al)
L+(Al)+1
525
522
524 (Al)+
(Al)+ +B
(Al)+1+B
(Al)+B
506
Li 7.50 90 95 Li 1.50
Cu 7.50 Cu 1.50
Al 85.00 Al, at.% Al 97.00
700
Fig. 15: Al-Cu-Li.
Vertical section
L+LiAl+3
CuAl2 - LiAl L+LiAl
L
638
618
L+LiAl+1 L+3 L+1+3
L+1
Temperature, C
614
L+
600
LiAl+1 L+ +B
LiAl+3 1+2+3 L+
L+1+2
L+B L+ +B
540 + +B
L+1+B
522 524
L+(Al)+1
500
(Al)+B
(Al)+1+2 +B
(Al)+ +B
(Al)+1
(Al)+1+B
Li 50.00 LiAl+1+3 10 20 30 Li 0.00

LiAl+2+3
Cu 0.00 Cu 33.30
Al 50.00 Cu, at.% Al 66.70
Landolt-Brnstein
New Series IV/11C2
MSIT
40 AlCuLi
700
Fig. 16: Al-Cu-Li.
Vertical section L
Al - (Cu:Li = 4:1,
L+LiAl+1
mass%), plotted in
L+1+3
at.%
L+3 L+(Al)
Temperature, C
600
L+2
LiAl+1
L+(Al)+1
L+(Al)+2 (Al)
L+1 L+1+2
L1+ L1+L2+1 LiAl+1+3

(Al)+1
500
L1+1+
(Al)+1+2
L2+1+
1+2+3
L+1+Li3Al2 (Al)+B
Li 50.30 30 40 50 60 70 80 90
(Al)+1+B Al
Cu 21.97 LiAl+1+Li3Al2
Al 27.73 Al, at.%
700
Fig. 17: Al-Cu-Li.
Vertical section
Al - (Cu:Li = 9:1, L
mass%), plotted in
at.%
L+(Al)
Temperature, C
600
L+1
(Al)
L+(Al)+1
500
(Al)+1
(Al)+1+B (Al)+B
Li 24.73 60 70 80 90 (Al)+ Al
Cu 24.33
Al 50.94 Al, at.%
New Series IV/11C2
AlCuLi 41
700
Fig. 18: Al-Cu-Li.
Vertical section
Al - -2 L
L+3
600
L+2 L+(Al)
L+(Al)+2
Temperature, C
(Al)
500
(Al)+1 (Al)+B
(Al)+1+2
400
300
Li 30.00 70 80 90 (Al)+1+B Al
Cu 10.00
Al 60.00 Al, at.%
1000
Fig. 19: Al-Cu-Li.
Vertical section
L
67Li33Cu - Al
L'+L''+(Cu)
750
L+LiAl+1
Temperature, C
L'+L''+1 L+1+3
L1
L2 L+2 (Al)+L
L+(Cu) L+1 (Al)
L+1+2
500
L+1 L+(Al)+2
L+1
LiAl+1 1+2+3
L+Li3Al2+1 LiAl+1+3
L+(Cu)+1
L+1+1 (Al)+1+2 (Al)+1+B
1+1+Li9Al4 1+Li9Al4+Li3Al2 (Al)+1
250
LiAl+Li3Al2+1 (Al)+B
L+1+Li9Al4
Li 67.00 20 40 60 80
Al
Cu 33.00 1+Li9Al4+Li3Al2 1+1+Li3Al2
Al 0.00 Al, at.%
Landolt-Brnstein
New Series IV/11C2
MSIT
42 AlCuLi
Fig. 20a:Al-Cu-Li.
Vertical section
through the critical L L'+L''
points on the
600
miscibility gap (c1-c2)
in the vicinity of c2
point
Temperature, C
L+LiAl
L+1 L'+L''+1
L+1+LiAl
L'+L''+1
500
L+1
L+1+1
L+1+Li3Al2
Li 68.50 10 20 Li 58.50
Cu 3.00 Cu 23.00
Al 28.50 Cu, at.% Al 18.50
Fig. 20b:Al-Cu-Li.
Vertical section
through the critical
L
points on the
miscibility gap (c1-c2)
900
in the vicinity of c1
point
Temperature, C
L'+L'' c1
800
L'+L''+(Cu) L+(Cu)
Li 50.00 50 Li 40.00
Cu 40.00 Cu 60.00
Al 10.00 Cu, at.% Al 0.00
New Series IV/11C2
AlCuRu 43
Aluminium Copper Ruthenium

Viktor Kuznetsov
Introduction
The first work on the system was performed in 1986 [1986Rae], [1986Yan]. Authors presented isothermal
section of the system at 770 K (500C). In addition, the composition region where as cast alloys were clearly
immiscible was delineated. Neither ternary compounds nor any noticeable (>2 at.%) solubility of third
component in binary phases were detected.
The general interest in the system is due to the existence of a stable icosahedral quasicrystalline phase (IQC)
in the Al rich region. This phase was discovered by [1988Tsa] at the composition of Al65Cu20Ru15 both in
conventionally solidified and annealed state. The alloys were obtained by arc melting. Its quasicrystalline
nature was examined by X-ray diffraction, DTA, as well as by optical and transitional electron microscopy
(TEM). [1989Gur] showed that the quasicrystalline order in this phase is one of most perfect among all
known IQC phases. [1989Hir2] found that liquid quenching provides disordered IQC which gets ordered
after a series of transformations.
In addition to IQC, two crystalline phases with X-ray pictures close to the IQC were found [1992Shi1]. Like
the latter, their structures may be represented as projection of high-dimensional hyperlattices into common
3-dimensional space. But contrary to the IQC, this projection is to be done in rational directions (rational
values of tangent of projection angle in the units of hyperlattice constants). Those are called rational
approximants of icosahedral quasicrystals, and may be identified by projection directions.
The phase relations concerning IQC were studied first by [1992Shi1] using samples, obtained by melt
spinning from liquid with subsequent grinding (this technique later became essentially standard for their
preparation). The study of the transformations under DTA conditions revealed the following sequence:
disordered IQC - periodic phases - ordered IQC based on face-centered quasilattice. In addition, a study of
the equilibria at 800C was performed on samples annealed for various time (24 h to a week). Clear DTA
peak at 690 to 710C was ascribed to formation of IQC as stable phase: a conclusion was drawn that the
latter is stable only at high temperatures. Later [1994Gru], [1998Ath] and finally [2004Mi] tracked down
the stability of IQC phase to at least 600C (most probably, it is stable to room temperature). The reaction
at about 700C proved to be a peritectic with participation of IQC [1994Gru], [2004Mi]. The region of
existence of IQC phase was also presented by [1993Shi1] and [1993Was].
[1997Kam] and [2002Guo] found the compositions and cooling regimes which provide single grains of IQC
of millimeter size. The grains obtained had clear morphology of pentagonal dodecahedron.
[1993Ara] found the composition region where IQC forms at liquid quenching to be close to a line with the
valence electrons to atoms ratio e/a 1.75 indicating a possible electronic nature of its stabilization.
The melting region was studied by [1996Log] and [2002Guo], but the results are mutually incompatible and
neither can be considered as quite satisfactory (see below for details). The equilibria with liquid phase still
need further investigation.
[2004Mi] performed very thorough investigation of the phase equilibria in the region of Al compositions
above 50 at.%. Alloys were produced from the constituent elements by levitation induction melting in a
water-cooled copper crucible under an Ar atmosphere. The nominal purity of Al was 99.999%, of Ru 99.9%
and of Cu 99.99%. The ingots were typically of about 5g. The dissolution of Ru in Al being difficult, the
samples were re-melted if after inspection undissolved particles of Ru were detected in the broken ingots.
This procedure was repeated until microscopically homogeneous ingots were obtained. Annealing
temperatures from 600 to 1100C were applied depending on the sample compositions. The phase
morphology of the annealed samples was compared to that of the as-cast samples in order to verify whether
equilibrium had been achieved. Additional annealing was applied if required. At 600C the annealing time
was up to 4392 h, at 680C up to 864 h, at 800C up to 2712 h, at 890C up to 690 h, at 1000C up to 117 h
and at 1100C up to 40 h. The alloys were studied by powder X-ray diffraction (XRD) and scanning electron
microscopy (SEM). The local phase compositions were determined by SEM using energy-dispersive X-ray
Landolt-Brnstein
New Series IV/11C2
MSIT
44 AlCuRu
analysis (EDX) on polished unetched cross sections. The samples were also studied by electron diffraction
in a transmission electron microscope (TEM) operated at 200 kV. The compositions of selected
single-phase samples were examined by inductively coupled plasma optical emission spectroscopy. These
compositions were used to correct the EDX data. The vertices of the tie triangles were determined on the
basis of the EDX measurements of equilibrated three-phase samples. The melting temperatures of the
phases were determined by differential thermal analysis (DTA) at the rate of 20C#min1.
Authors [2004Mi] presented the projection of phase compositions to concentration triangle to indicate the
compositions of all the phases found in the region studied at all the temperatures, and the isothermal sections
at 1100, 1000, 890, 800, 680 and 600C. For constructing the 600C section their results were
complemented by some data from unpublished PhD thesis, performed in the same laboratory. In addition to
the experimental work, a critical analysis of nearly all published data was performed.
The structure of the stable IQC phase was generally established by [1989Gur], [1989Hir1]. [1992Hu] tested
the models of projection from 6-dimensional hyperspace as well as Penrose tiling as models of the structure
of IQC; the former proved to be more adequate. Further refinement of the structure was performed by
[2004Yam], who used synchrotron radiation. Structural data were obtained also by [1997Ham] (posytron
annihilation).
[1993Shi2] suggested the structure of {1/1} approximant phase to be identical to 'AlMnSi. [2000Sad]
studied this phase in more details on a single-crystal sample and found another structure, though close to
'AlMnSi and some other approximant phases. This was confirmed also by [2004Mi].
The structure of the phase considered as {1/0} approximant to IQC was suggested by [1993Ara], [1993Was]
to be of UH3 type (cP32). [1998Sug] re-determined the structure of this phase on a quaternary sample
Al55.1Cu14.6Ru20.2Si10.1, using single-crystal X-ray diffraction, and found that it has its own structural type
instead of the UH3 one. This phase was called (Al-Cu-Ru-Si). Later the same structure was found for {1/0}
approximant phase in the ternary [2004Mi].
The structure of a tetragonal phase found by [1992Shi1] as stable at 500C, was determined by [1993Shi2]
to be of Al7Cu2Fe type (tP40); it is not related to IQC.
As thermodynamics concerns, only heat capacity data seem to exist. [1990Miz] measured heat capacity of
IQC sample Al68Cu17Ru15 at 1.5 to 6K. Low temperature heat capacities of Al61.5Cu25Ru13.5 and
Al65Cu20Ru15 IQC were studied by [1994Nak]; only the values of the electronic specific heat coefficient
el and Debye temperatures are reported. [1996Ina] measured heat capacities of Al65Cu20Ru15 as perfect
quasicrystal and quasicrystal with phason disorder as well as approximant phase with Al70Cu20Ru10
composition, all for 1 to 350 K. Results were presented as the values of el and graphs of temperature
dependence of apparent Debye temperature. Those were used only for comparing electronic contribution to
heat capacity and vibrational spectra for IQC with different structural states; no attempt to extract standard
thermodynamic values was performed. The same data are discussed in more details in [1997Ina].
A number of other physical properties of IQC and related phases was measured, mostly as a tool for the
study of their electronic structure. [1990Miz] studied resistivity of IQC at 4.2 to 300 K, in addition to the
heat capacity, for samples with different degree of quasicrystalline order. Transport properties of
quasicrystalline phase (resistivity and Hall coefficient) were studied by [1995Lal], [1994Nak] and
[1994Tam1, 1994Tam2]; strong dependence on degree of quasicrystalline order was found. [1992Shi2],
[1993Sha], [1994Hil], and [1995Sha] studied IQC using NMR technique. In addition experimental
investigations of the IQC band structure were performed by [1994Sta] and [1996Bel], who used
spectroscopic techniques. Theoretical analysis of resistivity of IQC was made by [2000Mac].
[2002Boz] performed theoretical prediction of distribution of a number of elements, including Cu, between
sublattices of B2 phase RuAl.
[1991Aka], [1998Sad] and [2000Sad] determined volume of IQC under high pressures. Fitting the data to
Murnaghan equation, bulk modulus and its pressure dependence were calculated.
[2001Sur] reviewed the formation of quasicrystals in the processes of mechanical alloying for various
systems.
[2004Gru] presented general review of formation of quasicryslalline phases (not only icosahedral) in Al-3d
metal alloys.
New Series IV/11C2
AlCuRu 45
Details of the experimental investigations of phase relations, crystal structure and thermodynamics are
listed in Table 1.
Binary Systems
For the Al-Cu and Cu-Ru binaries new MSIT evaluations [2004Gro], [2002Du] are accepted. For the Al-Ru
edge the results of recent investigation [2003Mi] are accepted. These were not accounted for by [2004Oka]
but were performed in the same group as most detailed investigation of the ternary Al-Cu-Ru system
[2004Mi].
Solid Phases
Contrary to [1986Yan], Cu solubility in the binary Al-Ru phases is indeed measurable. The Al6Ru phase
dissolves up to 5 at.% Cu and its homogeneity range extends along a constant Ru line. The AlRu takes about
50 at.% Cu with simultaneous increase of Ru content, so its homogeneity range extends towards the 7 phase
of the Al-Cu edge. The solubility of Cu in other Al-Ru phases, as well as of Ru in the Al-Cu phases, is small
(app. 1 to 3 at.%).
The results obtained for ternary phases are in good mutual agreement. In addition to the thermodynamically
stable quasicrystalline phase I, three periodic phases are established. Two of these, namely C, called also
AlCuRu [1993Ara] and having composition around Al58Cu30Ru12, and C1, formed at compositions
between Al71Cu8.5Ru20.5 and Al72Cu6.5Ru21.5 have structures considered as rational approximants to the
quasicrystals, of {1/1} and {1/0} type, respectively. The structure of the third periodic phase called 7 was
identified by [1993Shi2] and confirmed by [2004Mi]; it is not related to the quasicrystals.
For the C1 phase [2002Guo] provides the formation temperature as 1090C based on DTA, but [2004Mi]
found this phase at 1100C, and its formation temperature must be somewhat higher. It decomposes
between 890 and 800C [2004Mi]; DTA study of [2002Guo] give for its decomposition the temperature of
~940C, but its presence on isothermal section at 890C [2004Mi] suggests lower value. The C phase forms
also between 890 and 800C [2004Mi], and the 7 phase melts peritectically at about 730C [2004Mi]. The
quasicrystalline I phase is formed at 1057C; contrary to early observations [1992Shi1], [1993Shi1], it
remains stable to low temperatures [1998Ath], [2004Mi].
For the structure of C phase ({1/1} rational approximant to IQC) we accepted the results of [2000Sug]
confirmed by [2004Mi].
[2004Mi] also identified the structure of C1 ({1/0} approximant phase) with that of (Al-Cu-Ru-Si),
investigated by [1998Sug]. This was also accepted. [1993Shi1], [1993Ara] and [1993Was] suggested other
versions, but those were based on more limited data. In particular, the technique, used by [1993Shi1], who
suggested for this phase a cubic structure with two times smaller a value, may reveal the structure of local
atomic configuration instead of the lattice, as was noted by author himself.
Models of structure of quasicrystalline phase are constructed by [1992Hu] and, in more detail, [2002Hir]
and [2004Yam]. For general review of quasicrystalline structures see [1993Kel].
The structures of disordered and ordered quasicrystals [1989Hir2] are not much different; only the
latter is thermodynamically stable, and transitions found by [1992Shi1] are clearly irreversible. For concept
of phason disorder which prevails in IQC see [1989Gur] (experimental data), [1991Fra] (theory), and
[1992Poo] and [1993Kel] (reviews).
All the phases are presented in Table 2, except for numerous metastable ones of the Al-Cu edge, which do
not influence the ternary equilibria. For the quasicrystalline phase the so-called quasilattice constant aR
is provided, which is calculated by the equation aR = %-/q422222 (- is golden section ratio, q422222 is the
scattering vector for the (422222) plane). It is related to period of modeling 6-dimensional hyperlattice
[1993Ara]; see also [1998Ath] for its treatment in terms of Penrose tiling model.
Only the reactions which are related to the IQC formation were more or less studied, and even for those the
results are still contradicting. Peritectic reaction is definitely established [1996Log], [1998Ath], [2002Guo]
Landolt-Brnstein
New Series IV/11C2
MSIT
46 AlCuRu
for the formation of the IQC phase, but the reported temperatures and participating phases are not in
agreement. In particular, [1996Log] suggests a reaction L + Al13Ru4 + Al2Ru I at ~1200C, whereas
[2002Guo] gives this reaction as L + Al68Cu17Ru15 I (the Al68Cu17Ru15 phase of [2002Guo] was
identified by [2004Mi] with C1 phase) which occurs at 1020C. [1998Ath] and [2004Mi] found for the
peritectic melting of I phase the value of 1057C, which confirms the second version. Peritectic formation
of C phase found by [2002Guo] is also accepted. A shift of the temperature of both peritectic temperatures
for about 25C brings the data of [2002Guo] into agreement with [2004Mi]. We had to reject all the three
reactions, suggested by [1996Log], as being incompatible with the accepted data.
Neither [1996Log] nor [2002Guo] determined the compositions of phases participating in the suggested
reactions, so those can not be tabulated.
Liquidus, Solidus and Solvus Surfaces

The miscibility gap in the liquid phase, which exist in the Cu-Ru binary, extends into the ternary up to
~30 at.% Al [1986Rae], [1986Yan].
The partial liquidus projection suggested by [1996Log] shows a wide field of primary crystallization of
IQC. Contrary to that, [2002Guo] found it to be narrow. The composition sets of alloys which give IQC as
primary crystallizing phase as indicated by [1996Log] and by [2002Guo] are mutually exclusive: e.g., for
the section with 65 at.% Al [1996Log] indicates primary crystallization of IQC up to 12 at.% Ru, whereas
[2002Guo] found an alloy with 4 at.% Ru not to form the IQC as primary phase. The results of [2002Guo]
are also in broad agreement with [1998Ath], where a narrower field is suggested.
In addition, the field of primary crystallization of Al2Ru was found by [2002Guo] to extent down to
4.5 at.% Ru along the section with 62 at.% Ru; this could not be brought into agreement with liquidus
projection of [1996Log]. For reasons given in the previous section and above we accepted the results of
[2002Guo] against [1996Log]. The field of primary crystallization of IQC is at about 30 to 40 at.% Cu,
~4 at.% Ru [2002Guo].
Isothermal Sections
Only the Al rich region (50 at.%) is studied in detail. For the Al poor region, no data seem to exist except
for those from [1986Rae], [1986Yan].
All the sections presented here are taken from [2004Mi], as they are based both on detailed experimental
data and on critical analysis of previous results. Thus, the fragmentary sections suggested by [1992Shi1],
[1993Shi1] are considered to be superseded by those presented here.
We had to make some corrections to the compositions of some binary phases in Figs. 1 to 6 below,
especially those of Al-Cu edge, as they were somewhat misplaced in the original figures of [2004Mi].
Moreover, the binary phases of the Al-Ru edge are given by [2003Mi] without homogeneity ranges,
whereas [2004Mi] indicates for those a variable Ru content. To remove this discrepancy we reduced
homogeneity ranges of the binary phases when approaching Al-Ru binary to zero, though in principle this
point needs experimental clarification.
The partial isothermal section at 1100C is presented in Fig. 1; the sample of gross composition
Al60Cu5Ru35 could not be brought to equilibrium, and this part of section is provisional. The
above-mentioned shift of the temperature of peritectic formation of C phase removes contradiction between
the peritectic temperature from [2002Guo] and appearance of this phase on the 1100C section.
The section at 1000C is given in Fig. 2 and at 890C in Fig. 3.
Figure 4 displays the section at 800C. The compositions of C, I and Al2Ru phases on this section are in
excellent agreement with those measured by [2000Sug] for the same temperature; so does the phase
composition in Al56Cu31Ru13 sample, annealed at this temperature by [1996Fre].
Partial section at 680C, presented in Fig. 5, agrees well with the phase composition of the Al70.3Cu19Ru10.3
alloy, annealed by [1996Fre] at 650C.
Partial section at 600C is presented in Fig. 6. As was noticed above, in its constructing authors of [2004Mi]
complemented their data by some results of unpublished PhD thesis, performed in the same laboratory.
New Series IV/11C2
AlCuRu 47
The schematic isothermal section at 500C, provided by [1986Rae], [1986Yan] can not be accepted, as no
tendency for decomposition of the ternary phases I, 7 or C, stable at 600C with decreasing temperature,
can be seen in the sequence of isothermal sections of [2004Mi].

The main part of the isopleth Al62Cu38xRux (x = 2.5 to 25 at.%), as constructed by [2002Guo], is in drastic
contradiction with the accepted phase equilibria after [2004Mi]. So it can not be accepted, though the
temperatures of formation of both C1 and I phases, if raised for about 25C, are in general agreement with
isothermal sections of [2004Mi].
Thermodynamics
Only the heat capacity data were reported, and no standard thermodynamic functions were ever extracted.
Low-temperature data do not fit to standard equation Cp = elT + CD(/T). The value of electronic specific
heat coefficient el strongly varies on degree of quasicrystalline order, from ~0.05 mJ#mol1#K2 for
perfectly ordered sample to 0.75 mJ#mol1#K2 for sample with phason disorder; the latter value is close to
0.81 mJ#mol1#K2 measured for the sample of approximant C phase of close composition [1996Ina],
[1997Ina]. For high-temperature limit of Debye temperature the extrapolated values of 462, 442 and
428 K are given correspondingly for perfect quasicrystal, disordered quasicrystal and approximant phase
[1997Ina].
Miscellaneous
[1991Aka] found that IQC retains the quasicrystalline structure under pressure up to 30.8 GPa. [1998Sad],
[2000Sad] confirmed this up to 35 GPa, though starting from ~10 GPa some degree of phason disorder
appears. Fitting the pressure-volume data to Murnaghan equation, the latter authors obtained the bulk
modulus at zero pressure B = 128 kbar and its pressure derivative BP = 5.
References
[1986Rae] Raevskaya, M.V., Kovalevskaya (Yanson), I.E., Tatarkina A.L. Phase Diagram of the
Aluminium-Copper-Ruthenium System at 770 K (in Russian), Deposited at VINITI,
No. 8684-V86 from 17.12.1986 (Phase Diagram, Experimental, #, 5)
[1986Yan] Yanson, I.E., Interaction of Ruthenium and Copper with Aluminium and Nickel in the
Cu-Ru-Al and Cu-Ru-Ni Ternaries at 500C (in Russian), Materialy Konferenzii
Molodykh Uchenykh Moskovskogo Universiteta, 25-28 Jan. 1986. Deposited at VINITI,
No. 7573-V86 from 06.11.1986, Part 1, 139-142 (Phase Diagram, Experimental, #, 5)
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Alloys, Jpn. J. Appl. Phys., 27, L1587-1590 (1988) (Phase Diagram, Experimental, *, 11)
[1989Gur] Guryan, C.A., Goldman, A.I., Stephens, P.W., Hiraga, K., Tsai, A.P., Inoue, A.,
Masumoto, T., Al-Cu-Ru: an Icosahedral Alloy without Phason Disorder, Phys. Rev. B,
62, 2409-2412 (1989) (Crys. Structure, Experimental, *, 18)
[1989Hir1] Hiraga, K., Lee, K.H., Hirabayashi, M., Tsai, A.-P., Inoue, A., Masumoto, T., Phason
Strains and Periodicity in Al-Cu-Ru Icosahedral Quasicrystals, Jpn. J. Appl. Phys., 28,
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an Al-Ru-Cu Icosahedral Qusicrystal, Philos. Mag. Lett., 60(5), 201-205 (1989) (Crys.
[1990Miz] Mizutani, U., Sakabe, Y., Shibuya, T., Kishi, K., Kimura, K., Takeuchi, S., Electron
Transport Properties of Thermodynamically Stable Al-Cu-Ru Icosahedral Quasicrystals,
J. Phys.: Condens. Matter, 2, 6169-6178 (1990) (Crys. Structure, Electr. Prop.,
Experimental, 14)
Landolt-Brnstein
New Series IV/11C2
MSIT
48 AlCuRu
[1991Aka] Akahama, Y., Mori, Y., Kobayashi, M., Kawamura, H., Kimura, K., Takeuchi, S.,
Pressure-Induced Phase Transformation of Quasicrystals, J. Phys. Soc. Jpn., 60,
[1991Fra] Fradkin, M.A., Elastic Instability and Phason Disorder in Icosahedral Quasicrystals,
Philos. Mag. Lett., 64, 125-128 (1991) (Crys. Structure, Theory, 17)
[1992Hu] Hu, R., Egami, T., Tsai, A.-P., Inoue, A., Masumoto, T., Atomic Structure of
Quasicrystalline Al65Ru15Cu20, Phys. Rev. B, 46(10), 6105-6114 (1992) (Crys. Structure,
Experimental, 30)
[1992Mat] Matsubara, E., Waseda, Y., Structural Study of Icosahedral Al65Cu20TM15 Alloys
(TM=Fe, Ru and Os) by Anomalous X-ray Scattering Method, Met. Abstr. Light Metals
Alloys, 25, 174 (1992) (Crys. Structure, Abstract, 0)
[1992Poo] Poon, S.J., Electronic Properties of Quasicrystals: an Experimental Review, Adv. Phys.,
41, 303-363 (1992) (Crys. Structure, Phys. Prop., Review, 223)
[1992Shi1] Shield, J.E., Hoppe, C., McCallum, R.W., Goldman, A.I., Kelton, K.F., Gibbons, P.C.,
Icosahedral Phase Stabilities in Al-Cu-Ru Alloys, Phys. Rev. B: Condens. Matter, 45,
2063-2072 (1992) (Phase Diagram, Crys. Structure, Experimental, *, 19)
[1992Shi2] Shinohara, T., Tsai, A.P., Sato, T., Masumoto, T., 27Al-and 63Cu-NMR in Quasicrystal
Al65Cu20TM15 Alloy (TM:Fe, Ru, and Os), J. Mater. Res., 7, 1970-1972 (1992) (Magn.
Prop., Experimental, 9)
[1993Ara] Araki, K., Waseda, A., Kimura, K., Ino, H., Structural Relaxation of the Melt-Spun
Icosahedral Phase and a New Type of Approximant in Al-Cu-Ru Alloys, Philos. Mag.
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Temperature-Dependent NMR Features of the Al65Cu20Ru15 Icosahedral Alloy, Phys.
Rev. B, 49(13), 8615-8620 (1994) (Magn. Prop., Experimental, 42)
[1994Gru] Grushko, B., Lemmerz, U., Freiburg, C., On Reaction Involving Al-Cu-Ru Icosahedral
Phase and Al7Cu2Ru, Philos. Mag. Lett., 70(5), 261-267 (1994) (Crys. Structure,
Experimental, 5)
[1993Kel] Kelton, K.F., Quasicrystals: Structure and Stability, Int. Mater. Rev., 38(3), 105-137
(1993) (Crys. Structure, Review, 424)
[1994Nak] Nakamura, Y., Mizutani, U., Study of the Electronic Structure and Electron Transport
Properties of Al-Cu-Ru Quasicrystals, Mater. Sci. Eng. A, A181/A182, 790-793 (1994)
(Crys. Structure, Experimental, 8)
[1993Sad] Sadoc, A., Berger, C., Calvayrac, Y., Structural Analysis of Quasicrystals and
Approximants in AlCu(Ru,Fe) Systems, Philos. Mag. B, 68(4), 475-485 (1993) (Crys.
[1993Sha] Shastri, A., Borsa, F., Goldman, A.I., Shield, J.E., Torgeson, D.R., NMR Study of the
Electronic Properties of Al-Cu-Fe and Al-Cu-Ru Quasicrystals, J. Non-Cryst. Solids,
153-154, 347-352 (1993) (Crys. Structure, Experimental, 12)
[1993Shi1] Shield, J.E., Mccallum, R.W., Goldman, A.I., Gibbons, P.C., Kelton, K.F., Phase
Stabilities in the Al-Cu-Ru System, J. Non-Cryst. Solids, 153&154, 504-507 (1993) (Phase
Diagram, Experimental, *, 18)
[1993Shi2] Shield, J.E., Chumbley, L.S., McCallum, R.W., Goldman,A.I., An Approximant to the
Al-Cu-Ru Icosahedral Phase, J. Mater. Res., 8(1), 44-48 (1993) (Crys. Structure,
Experimental, *, 23)
[1993Was] Waseda, A., Araki, K., Kimura, K., Ino, H., Quasicrystals and Approximants in the
Al-Co-(Fe, Ru) and Al-Pd-Mn Systems, J. Non-Cryst. Solids, 153-154, 635-639 (1993)
(Crys. Structure, Experimental, Phase Diagram, 19)
[1994Sha] Shastri, A., Borsa, F., Torgeson, D.R., Goldman, A.I., Distribution of Nonequivalent
Aluminium Sites Revealed in Al-Cu-Ru and Al-Cu-Fe Quasicrystals by 27Al NQR, Phys.
Rev. B, 50(6), 4224-4228 (1994) (Crys. Structure, Experimental, 22)
New Series IV/11C2
AlCuRu 49
[1994Sta] Stadnik, Z.M., Zhang, G.W., Tsai, A.-P., Inoue, A., A Resonant Photoemission Study of
the Al65Cu20Ru15 Icosahedral Alloy, J. Phys.: Condens. Matter, 6, 6885-6893 (1994)
(Phys. Prop., Experimental, 42)
[1994Sub] Subramanian, P.R., Cu (Copper), in Phase Diagrams of Binary Copper Alloys,
Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E. (Eds.), ASM International, Materials
Park, OH, 1-3 (1994) (Crys. Structure, Thermodyn., Review, 16)
[1994Tam1] Tamura, R., Waseda, A., Kimura, K., Ino, H., Semiconductor-Like Transport in Highly
Ordered Al-Cu-Ru Quasicrystals, Phys. Rev. B, 50(13), 9640-9643 (1994) (Electr. Prop.,
Experimental, 21)
[1994Tam2] Tamura, R., Waseda, A., Kimura, K., Ino, H., Electrical Conductivity and Hall Effect of
Al-Cu-Ru and Al-Cu-Fe Quasi-Crystals, Mater. Sci. Eng. A, A181/A182, 794-797 (1994)
(Electr. Prop., Experimental, 18)
[1995Lal] Lalla, N.P., Tiwari, R.S., Srivastava, O.N., Investigation on the Synthesis, Characterization
and Electronic Behavior of Al65Cu20+xRu15x (x = 2, 1, 0, and 1) Quasi-Crystalline
Alloys, J. Phys.: Condens. Matter, 7, 2409-2420 (1995) (Electr. Prop., Experimental, 32)
[1995Sha] Shastri, A., Baker, D.B., Conradi, M.S., Borsa, F., Torgeson, D.R., NMR Pressure Study
of 27Al and 65Cu in the Al65Cu20Ru15 Quasicrystal, Phys. Rev. B, 52(17), 12681-12684
(1995) (Magn. Prop., Experimental, 25)
[1996Bel] Belin-Ferre, E., Dankhazi, Z., Sadoc, A., Berger, C., Mueller, H., Kirchmayr, H.,
Electronic Distributions in Quasicrystalline Al65Cu20Ru15 Alloy, J. Phys.: Condens.
Matter, 8, 3513-3523 (1996) (Crys. Structure, Experimental, 34)
[1996Fre] Freiburg, C., Lemmrz, U., Reichert, W., Four Ternary Structures in the Al-Cu-Ru System,
Acta Crystallogr., Sect. A: Found. Crystallogr., A52, C395 (1996) (Crys. Structure,
Experimental, *, 5)
[1996Ina] Inaba, A., Ishida, S., Matsuo, T., Shibata, K., Tsai, A.P., Electronic and Vibrational
Properties of an Al-Cu-Ru Icosahedral Quasicrystal Deduced from Heat Capacities,
Philos. Mag. Lett., 74(5), 381-388 (1996) (Electr. Prop., Thermodyn., Experimental, 15)
[1996Log] Lograsso, T.A., Haines, S.A., Determination of the Liquidus Surface in the
Quasicrystalline Region of the Al-Cu-Ru System, J. Non-Cryst. Solids, 197, 197-204
(1996) (Phase Diagram, Experimental, *, 10)
[1997Ham] Hamada, E., Oshima, N., Suzuki, T., Sato, K., Kanazawa, I., Nakata, M., Takeuchi, S.,
Positron Annihilation Studies of Icosahedral AlCuRu and AlCuFe Alloys, Mater. Sci.
Forum, 255-257, 451-453 (1997) (Crys. Structure, Experimental,16)
[1997Ina] Inaba, A., Tsai, A.-P., Shibata, K., Vibrational Properties of Quasicrystals of Al-Cu-Ru,
Al-Pd-Re and Al-Pd-Mn Deduced from Heat Capacities, Proc. 6th Int. Conf.
Quasicrystals, Tokyo, Takeuchi, S., Fujivara, T. (Eds.), Uto-Print, Singapore, 443-450
(1997) (Thermodyn., Electr. Prop., Experimental, 10)
[1997Kam] Kamo, T., Watanabe, Y., Nanao, S., Formation of Millimeter-Sized Al-Cu-Ru Single
Quasicrystals, Mater. Trans., JIM, 38(12), 1116-1118 (1997) (Crys. Structure,
Experimental, 13)
[1998Ath] Athanasiou, N.S., Spirlet, J.C., Zwirner, S., Baskoutas, S., Investigation of the
Quasicrystalline State of the D-Al67.5Cu17.5Rh15 and I-Al70Cu12Ru18 Alloys, Mod. Phys.
Lett. B, 12(9), 343-353 (1998) (Crys. Structure, Experimental, *, 24)
[1998Sad] Sadoc, A., Itie, J.P., Polian, A., Berger, C., Poon, S.J., High-Pressure X-ray Diffraction of
Icosahedral Al-Cu-Ru and Al-Pd-Re Quasicrystals, Philos. Mag. A, 77(1), 115-128 (1998)
(Crys. Structure, Experimental, *, 30)
[1998Sug] Sugiyama, K., Kato, T., Saito, K., Hiraga, K., The Crystal Structure of a
Gamma-(Al-Cu-Ru-Si) Cubic Phase: a New Approximant Phase for the Al-Cu-Ru
Icosahedral Quasicrystal, Philos. Mag. Lett., 77(3), 165-171 (1998) (Crys. Structure,
Experimental, *, 18)
[2000Mac] Macia, E., Modeling the Electrical Conductivity of Al-Cu-Ru Icosahedral Quasicrystals,
Mater. Sci. Eng. A, 294-296, 592-595 (2000) (Electr. Prop., Theory, 30)
Landolt-Brnstein
New Series IV/11C2
MSIT
50 AlCuRu
[2000Sad] Sadoc, A., Itie, J.P., Polian, A., In Situ High Pressure X-Ray Diffraction and EXAFS
Spectroscopy of Icosahedral Al-Cu-Ru Quasicrystals, Philos. Mag. A, 80(9), 2057-2071
[2000Sug] Sugiyama, K., Kato, K., Ogawa, T., Hiraga, K., Saito, K., Crystal Structure of a New
1/1-Rational Approximant for the Al-Cu-Ru Icosahedral Phase, J. Alloys Compd., 299,
169-174 (2000) (Crys. Structure, Experimental, *, 28)
[2001Sur] Suryanarayana, C., Mechanical Alloying and Milling, Prog. Mater. Sci., 46(1-2), 1-184
(2001) (Crys. Structure, Kinetics, Review, 932)
[2002Boz] Bozzolo, G.H., Noebe, R.D., Amador, C., Site Occupancy of Ternary Additions to B2
Alloys, Intermetallics, 10, 149-159 (2002) (Crys. Structure, Theory, 27)
[2002Du] Du, Y., Cu-Ru (Copper-Ruthenium), MSIT Binary Evaluation Program, in MSIT
Stuttgart; Document ID: 2035126.1.20, (2002) (Crys. Structure, Phase Diagram,
Assessment, 3)
[2002Guo] Guo, J.Q., Hasegawa, H., Tsai, A.P., Takeuchi, S., Single-Crystal Growth of the Al-Cu-Ru
Icosahedral Quasicrystal from the Ternary Melt, J. Cryst. Growth, 236, 477-481 (2002)
(Phase Diagram, Experimental, *, 15)
[2002Hir] Hiraga, K., The Structure of Quasicrystals Studied by Atomic-Scale Observations of
Transmission Electron Microscopy, Adv. Imag. Electr. Phys., 122, 1-86 (2002) (Crys.
Structure, Experimental, Review, 99)
[2003Mi] Mi, S., Balanetskyy, S., Gruchko, B., A Study of the Al Rich Part of the AlRu Alloy
System, Intermetallics, 11, 643-649 (2003) (Phase Diagram, Experimental, #, 18)
[2004Gro] Grbner, J., Aluminum-Copper, MSIT Binary Evaluation Program, in MSIT Workplace,
Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart;
Document ID: 20.11492.1.20, (2004) (Crys. Structure, Phase Diagram, Phase Relations,
Thermodyn., Assessment, 70)
[2004Gru] Grushko, B., Velikanova, T.Ya., Stable and Metastable Quasicrystals in Al-based Alloy
System with Transition Metals, J. Alloys Compd., 367(1-2), 58-63 (2004) (Crys. Structure,
Phase Diagram, Review, 44)
[2004Mi] Mi, S., Grushko, B., Investigation of the High-Al Region of Al-Cu-Ru, Intermetallics,
12(4), 425-435 (2004) (Phase Diagram, Experimental, *, #, 29)
[2004Oka] Okamoto H., Al-Ru (Aluminium-Ruthenium), J. Phase Equilib. Diff., 25, 196 (2004)
(Phase Diagram, Review, 3)
[2004Uch] Uchiyama, H., Takahashi, T., Arinuma, K., Sato, K., Kanazawa, I., Hamada, E., Suzuki, T.,
Kirihara, K., Kimura, K., Positron Annihilation Studies of Icosahedral Quasicrystals and
their Approximants in the Al-Cu-Ru-(Si) Alloy Systems, J. Phys.: Condens. Matter, 16,
[2004Yam] Yamamoto, A., Takakura, H., Tsai, A.P., Refinement of i-Al-Cu-Fe and i-Al-Cu-Ru
Quasicrystal Structures, Ferroelectrics, 305, 279-282 (2004) (Crys. Structure,
Experimental, 6)
Table 1: Investigations of the Al-Cu-Ru Phase Relations, Structure and Thermodynamics

Reference Method/Experimental Technique Temperature/Composition Phase Range
Studied
[1986Rae] Metallography, hardness measurement, 500C, 0 to 100% Cu and Ru
EPMA
[1986Yan] Metallography, hardness measurement, 500C, 0 to 100% Cu and Ru
EPMA
New Series IV/11C2
AlCuRu 51

Studied
[1988Tsa] XRD, DTA, metallography, TEM 700 to 1400 K, 15 to 25 at.% Cu, 10 to 20
at.% Ru
[1989Gur] XRD using usual and synchrotron radiation 850C, Al65Cu20Ru15
[1989Hir1] HREM, electron diffraction Al65Cu20Ru15: as cast, rapid quenched from
liquid and annealed at 750C, 30 min
[1989Hir2] XRD, HREM As cast and annealed at 1118 K,
Al65Cu20Ru15
[1991Aka] XRD and electrical resistivity under high 4 to 270 K (resistivity), 270 K (XRD), 0 to 28
pressure GPa, i-Al-Cu-Ru sample
[1992Hu] Anomalous X-ray powder diffraction Annealing at 1130 K, Al65Cu20Ru15
[1992Mat] Anomalous X-ray powder diffraction Annealing at 1130 K, Al65Cu20Ru15
[1992Shi1] XRD, TEM, DTA 500C, 10 to 27 at.% Cu, 5 to 20 at.% Ru
[1993Ara] XRD and TEM Liquid quenching with subsequent annealing
at 800C, 5 to 27 at.% Cu, 10 to 23 at.% Ru,
app. along the line e/a 1.75
[1993Sad] Extended X-ray absorption fine-structure Al65Cu20Ru15
[1993Shi1] XRD, TEM, DTA 800 and 500C, 10 to 27 at.% Cu, 5 to 20
at.% Ru
[1993Shi2] TEM, converged beam electron diffraction Liquid quenching with subsequent annealing
at 800C for Al60Cu25Ru15 and at 560C for
Al65Cu23Ru12
[1993Was] XRD and TEM Liquid quenching with subsequent annealing
at 800C for 1 h; Al61Cu25Ru14,
Al71Cu11Ru18, and Al71Cu7Ru22
compositions
[1994Sha] Nuclear quadrupole resonance of 27Al at Al70Cu15Ru15 (number of nonequivalent Al
4.2K positions in the structure)
[1994Gru] SEM, XRD and DTA Annealing at 800 and 600C
Al70.3Cu19.4Ru10.3, Al67.8Cu22.3Ru9.9,
Al61.0Cu27.4Ru11.6, and Al65.3Cu19.7Ru11.0
compositions
[1996Log] DTA, powder XRD, metallography, energy Melting region of samples with 27, 30 and 35
dispersive spectroscopy at.% (Cu+Ru), 0 to 20 at.% Ru
[1996Fre] Powder XRD with Rietveld refinement 650C Al70.3Cu17Ru10.3 and 800C
Al56Cu31Ru13 (two-phase samples)
[1996Ina] Adiabatic calorimetry (above 5 K) and 1 to 310K, Al65Cu20Ru15 (two samples:
isoperibolic calorimeter in 3He cryostat perfect and with phason disorder) and
(below 5 K) Al70Cu20Ru10 (all contained 0.2 to 0.3
at.% O)
Landolt-Brnstein
New Series IV/11C2
MSIT
52 AlCuRu

Studied
[1997Ina] Adiabatic calorimetry (above 5 K) and 1 to 310K, Al65Cu20Ru15 (two samples:
isoperibolic calorimeter in 3He cryostat perfect and with phason disorder) and
(below 5 K) Al70Cu20Ru10
[1997Kam] Search for heat treatment for obtaining Al58Cu30.8Ru11.2, and Al61.6Cu24.8Ru13.6
single grains of quasicrystals gross compositions
[1998Ath] XRD, DTA Al70Cu12Ru18
[1998Sad] XRD Al65Cu20Ru15, pressure up to 35 GPa
[2000Sad] XRD, EXAFS Al65Cu20Ru15, pressure up to 24.5 GPa
[2000Sug] Single-crystal XRD, EPMA Annealed between 1073 and 1203 K
Al58Cu30Ru12 gross composition
[2002Guo] DTA; search for conditions of single grains 22.5 to 42.5 at.% Cu, 2.5 to 25 at.% Ru
of quasicrystals
[2004Mi] XRD, SEM using energy-dispersive X-ray 600, 680, 800, 890, 100 and 1100C;
analysis, inductively-coupled optical 90 to 60 at.% Al, 0 to 50 at.% Ru
emission spectroscopy, DTA
[2004Uch] XRD Al62Cu25Ru15

[C] Prototype
(Al) cF4 a = 404.96 at 25C [Mas2]
< 660.452 Fm3m
Cu
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m melting point [1994Sub]
Cu
(Ru) hP2 a = 270.58 at 25C [Mas2]
< 2334 P63/mmc c = 428.16
Mg
, Al2Cu tI12 a = 606.7 31.9 to 33.0 at.% Cu
< 591 I4/mcm c = 487.7 [2004Gro]
1, CuAl(h) oP16 a = 401.5 49.8 to 52.3 at.% Cu
624 - 560 Pban b = 1202 [2004Gro]
c = 865.2
2, CuAl(r) mC20 a = 1206.6 49.8 to 52.3 at.% Cu
< 560 C2/m b = 410.5 [2004Gro]
CuAl(r) c = 691.3
= 55.04
1, ~ Cu4Al3(h) hP42 a = 810 55.2 to 59.8 at.% Cu
590 - 530 P6/mmc c = 1000 (or 1237) [2004Gro]
New Series IV/11C2
AlCuRu 53

[C] Prototype
2 ~ Cu4Al3(r) m*21 a = 707 55.2 to 56.3 at.% Cu
590 - 530 b = 408 [2004Gro]
c = 1002
= 90.63
J1 - - 59.4 to 62.1 at.% Cu
958 - 848 [2004Gro]
J2, Cu2xAl hP6 a = 414.6 0.47 x 0.78
850 - 560 P63/mmc c = 1000 55.0 to 61.1 at.% Cu
Ni2In [2004Gro]
, hR* 38.1 x 40.7
< 686 R3m 59.3 to 61.9 at.% Cu
a = 1226 at x = 38.9 [2004Gro]
c = 1511
0, Cu100xAlx cI52 31 x 40.2 [Mas2]
1037 - 800 I4m a 890 [2004Gro]
Cu5Zn8
1, Cu9Al4 cP52 a = 870.68 [V-C2], [2004Gro]
< 890 P43m
Cu9Al4
, Cu100xAlx cI2 a = 295.64 at 672C in + (Cu) alloy [2004Gro]
1049 - 559 Im3m
W
Al6Ru oC28 a = 748.82 0.04 [2003Mi]
< 734 Cmcm b = 655.59 0.03
MnAl6 c = 896.05 0.05
a = 750.2 0.4 at Al82.0Cu3.6Ru14.4 composition

b = 651.2 0.4 [2004Mi]
c = 890.4 0.5 dissolves to 5 at.% Cu [2004Mi]
Al13Ru4 mC102 a = 1586.2 0.6 [2003Mi]
< 1420 C2/m b = 818.8 0.3 dissolves to 2.5 at.% Cu [2004Mi]
Fe4Al13 c = 1273.6 0.4
= 107.77 0.08
Al5Ru2 oC24 a = 780 [2003Mi]
1492 - 1340 Cmcm b = 660 electron diffraction data
Al5Fe2 c = 420 space group by analogy with Al5Fe2
dissolves to 2 at.% Cu in as cast samples
[2004Mi]
Al2Ru tI6 a = 801.2 0.2 [2003Mi]
< 1805 Fddd b = 417.7 0.1 dissolves to 1.5 at.% Cu [2004Mi]
MoSi2 c = 878.5 0.2
Landolt-Brnstein
New Series IV/11C2
MSIT
54 AlCuRu

[C] Prototype
, AlRu cP2 [2004Oka]
< 2069 Pm3m a = 295 [2003Mi]
CsCl
a = 297.0 at Al50Cu31.5Ru18.5 [2004Mi]
a = 296.3 at Al47Cu42Ru11 [2004Mi]
a = 295.5 at Al44.5Cu50.5Ru5 [2004Mi]

*C cP148 a = 1237.73 0.08 at Al57.3Cu31.4Ru11.3 [2000Sug]
< ~ 84545 Pm3 {1/1} rational approximant to IQC
C (= AlCuRu) in original work the phase is called
AlCuRu after [1993Ara]
* C1 cF368 a = 1551.1 0.4 Al69.5-72Cu6.5-9.5Ru21-21.5 [2004Mi]
(1100) - (~ 84545) Fm3 {1/0} rational approximant to IQC
(Al-Cu-Ru-Si)
* 7, Al7Cu2Ru tP40 a = 643.3 0.2 [2004Mi]
< 730 P4/mnc c = 1489 1
Al7Cu2Fe
*I FCI* aR** = 451 [1993Ara], after annealing
< 1057 aR = 452.87 [1998Ath]
Al61Cu26Ru13 to Al70.5Cu12.5Ru17
[2004Mi]
*
Face-centered icosahedral quasicrystal [1989Gur]. For detailed structural model see [2002Hir], [2004Yam]
**A quasi-lattice constant (see Solid Phases section for details).
New Series IV/11C2
AlCuRu 55

Fig. 1: Al-Cu-Ru. Axes: at.%
Partial isothermal
section at 1100C
10
90
20
80
Ru4Al13
L
C1
30
70
RuAl2
40
Ru2Al3 60
50 +R 50
uAl
2 +L
Ru 60.00 10 20 30 40 50 Ru 0.00
Cu 0.00 Cu 60.00
Al 40.00 Al 40.00

Partial isothermal
section at 1000C
10
90
20
80
Ru4Al13
L
C1
30
70
RuAl2
I
40
60
50
50
Ru 60.00 10 20 30 40 50 Ru 0.00
Cu 0.00 Cu 60.00
Al 40.00 Al 40.00
Landolt-Brnstein
New Series IV/11C2
MSIT
56 AlCuRu

Partial isothermal
section at 890C
10
90
20
80
Ru4Al13
L
30 C1
70
RuAl2
I
40
60
50
50

+1+L
Ru 60.00 10 20 30 40 50 Ru 0.00
Cu 0.00 Cu 60.00
Al 40.00 Al 40.00

Partial isothermal
section at 800C
10
90
20
80
Ru4Al13
L
30
70
RuAl2
I
40
60
50
50
2
Ru 60.00 10 20 30 40 50 Ru 0.00
Cu 0.00 Cu 60.00
Al 40.00 Al 40.00
New Series IV/11C2
AlCuRu 57

Partial isothermal
section at 680C
10
90
RuAl6
L
20
80
Ru4Al13
30 70
40
60
Ru 50.00 10 20 30 40 Ru 0.00
Cu 0.00 Cu 50.00
Al 50.00 Al 50.00

Partial isothermal
section at 600C
10
90
RuAl6 L
20
80
Ru4Al13
30
70
40
60
50
50
1
Ru 55.00 10 20 30 40 50 Ru 0.00
Cu 0.00 Cu 55.00
Al 45.00 Al 45.00
Landolt-Brnstein
New Series IV/11C2
MSIT
58 BeCuMg
Beryllium Copper Magnesium

Lazar Rokhlin, updated by Svitlana Ilyenko
Introduction
[1939Pog] investigated the structure and properties of Cu based alloys containing up to 2.5 mass% Be (15.3
at.% Be) and 0.6 mass% Mg (1.6 at.% Mg). The alloys were annealed at 800C for 3 h, quenched from this
temperature and subsequently aged. According to microscopy observations magnesium and beryllium
decreased the solubility of each other in solid copper. However, the (Cu) solid solution area was not outlined
by [1939Pog].
[1940Gor] investigated crystals, segregated in Be-Cu-Mg alloys during solidification, using chemical
analysis and X-ray diffraction. The composition of the crystals corresponded to the formula Cu4Mg3Be2.
The crystal structure of this phase belongs to the Cu2Mg type, and it was considered to be a Cu2Mg based
solid solution.
[1940Pog] investigated the Be-Cu-Mg alloys in the Cu corner up to 2.5 mass% Be (15.3 at.% Be) and 2.8
mass% Mg (7 at.% Mg). Thermal analysis, microscopic methods and hardness measurement were used to
characterize the samples. The phase equilibria in this part of the system were investigated and five
isothermal sections of the phase diagram at 800, 725, 650, 500 and 250C were constructed in the
investigated concentration range. These sections show the solubility limits of the (Cu) solid solution at
different temperatures and the connected phase areas. [1940Pog] also established the invariant eutectic four-
phase equilibrium in the Cu corner area.
[1956Gla] presented a review on some intermetallic compounds. The solubility of Be in Cu2Mg is
approximately 1 at.% at 400C.
[1967Sta] investigated the structure of an alloy with the composition CuMgBe2 by X-ray diffraction. Two
phases, Cu2Mg, and a ternary compound with the Cu2Mg type structure, were detected in the sample. For
the ternary compound [1967Sta] gave the composition CuMgBe4. The results of [1967Sta] were consistent
with [1940Gor] concerning the existence of a ternary phase with the Cu2Mg type structure; however, a
different composition and lattice parameter were given.
[1945Los] studied the Be-Cu-Mg system in the Mg rich area. Copper and beryllium were both added to
molten magnesium held at 900C. After solidification the alloys were analyzed microscopically and the
results of the observation were used to estimate the beryllium solubility in liquid magnesium in the presence
of copper. Furthermore, [1945Los] used resistivity measurements to determine the beryllium solubility in
solid magnesium alloys containing copper.
In the review [1979Dri] the data of [1940Pog] were reproduced.
Binary Systems
The binary phase diagrams Be-Cu and Cu-Mg are accepted from the MSIT Binary Evaluation Program
[2006Wat] and [2002Iva], respectively.
Solid Phases
Experimental data reported by [1940Gor] and [1967Sta] concerning the CuMgBe4 and CuMg3Be2
compounds with the Cu2Mg type structure do not allow a distinction between whether these compounds are
different ternary phases or correspond to two compositions of a single solid solution. According to
[1945Los] the solubility of beryllium is less than 0.3 at.% in magnesium alloys containing 0.38 and
0.77 at.% Cu and 0.42 at.% in a magnesium alloy with 1.95 at.% Cu. However, the description of the
experiments in [1945Los] does not allow a conclusion to be made about which solid phase contains
beryllium.
Solid phases in the investigated parts of the ternary system are listed in Table 1.
New Series IV/11C2
BeCuMg 59
The only reported ternary invariant equilibrium is of the eutectic type and is located in the Cu corner of the
system [1940Pog]. The equilibrium reaction and compositions of the phases are given in Table 2. The
equilibrium temperature was established roughly as the average of four values within the limits 656-694C,
determined by [1940Pog] for four alloys of different compositions. The composition of the (Cu) solid
solution participating in the equilibrium was estimated from the double saturation points on the isothermal
sections. The Cu2Mg composition was accepted taking into consideration some solubility of Be in this
phase, showed by [1956Gla], and the Cu-Mg binary phase diagram. The compositions of the liquid and
phases could not be estimated reasonably from the existing data.
Liquidus Surface
Figure 1 shows isotherms of the liquidus surface, constructed using thermal analysis data from [1940Pog]
and the binary systems. According to [1945Los] the solubility of beryllium in liquid magnesium increases
with increasing copper content and is smaller than 0.40, 0.55, 1.1 and 3.90 at.% Be at 0.55, 1.35, 1.95 and
4.0 at.% Cu, respectively. The beryllium solubility in liquid magnesium seems to be too high and needs to
be confirmed because of many unsuccessful attempts to make Be-Mg alloys by various methods [1987Nay].
Isothermal Sections
Figures 2 to 5 display isothermal sections of the Be-Cu-Mg phase diagram at 800, 725, 650 and 500C. The
sections were constructed after [1940Pog] with minor corrections to comply with the binary systems. In the
sections at 725 and 800C (Figs. 2 and 3) two supposed fields with the liquid phase are separated by a
dashed line, instead of one solid + liquid field, given by [1940Pog]. The 800C isothermal section is also
slightly corrected to be consistent with other isothermal sections reported by [1940Pog].

Mechanical properties and ageing behavior of Be-Cu-Mg alloys have been studied in [1940Pog]. The
ageing slows down in alloys with 2 and 2.5 mass% Be at Mg content 0.4-0.8 mass%. Alloys containing
2.5Be-0.4Mg (mass%) and 1.8Be and 0.4-0.8 mass% Mg after quenching from 800C and ageing at 350C
have the same hardness as alloys without Mg with 2.5 mass% Be, but have lower impact toughness
comparing with non-magnesium bronzes [1940Pog].
References
[1939Pog] Pogodin, S.A., Abrikosov, N.Ch., Effect of Small Additions of Magnesium and Silicon on
the Properties of the Beryllium Bronze (in Russian), Metallurg, 14(12), 57-65 (1939)
(Experimental, 15)
[1940Gor] Goria, C., Venturrello, O., Structure of a Phase Segregated in the Cu-Mg-Be Ternary
Alloy (in Italian), Metal. Ital., 32(2), 47-53 (1940) (Crys. Structure, Experimental, *, 19)
[1940Pog] Pogodin, S.A., Shumova, I.S., About the Solid Solutions of Beryllium and Magnesium in
Copper (in Russian), Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, (5), 763-774 (1940) (Phase
Diagram, Experimental, #, 16)
[1945Los] Losana, L., Alloys of Magnesium Containing Beryllium (in Italian), Atti Accad. Torino,
81/82, 168-173 (1945) (Phase Diagram, 5).
[1956Gla] Gladyshevsky, E.I., Cherkashin, E.E., Solid Solutions on the Basis of Metallic
Compounds, Russ. J. Inorg. Chem., 1(6), 288-295 (1956), translated from Zh. Neorg.
Khim., 1(6), 1394-1401 (1956) (Crys. Structure, Phase Diagram, Review, 4)
[1967Sta] Stadelmaier, H.H., Hofer, G., Phases with the Diamond Substructure in the Ternary
Beryllium Alloys (in German), Monatsh. Chem., 98(1), 45-48 (1967) (Crys. Structure,
Experimental, *, 3)
Landolt-Brnstein
New Series IV/11C2
MSIT
60 BeCuMg
[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova, E.M., Rokhlin, L.L.,
Turkina, N.I., Be-Cu-Mg in Binary and Multicomponent Copper-Base Systems (in
Russian), Nauka, Moscow, 67 (1979) (Phase Diagram, Review, 1)
[1987Nay] Nayeb-Hashemi, A.A., Clark, J.B., The Be-Mg (Beryllium-Magnesium) System, Bull.
Alloy Phase Diagrams, 8(1), 57-58 (1987) (Review, Phase Diagram, 15)
[2002Iva] Ivanchenko, V., Ansara I., Cu-Mg (Copper - Magnesium), MSIT Binary Evaluation
[2006Wat] Watson, A., Be-Cu (Beryllium-Copper), MSIT Binary Evaluation Program, in MSIT
Stuttgart; to be published, (2006) (Crys. Structure, Phase Diagram, Assessment, 10)

[C] Prototype
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m
Cu
(Mg) hP2 a = 320.94 at 25C [Mas2]
< 650 P63/mmc c = 521.07
Mg
(Be) cI2 a = 255.15 HT, dissolves 17 at.% Cu at 1199C
1289 - 1270 Im3m [2006Wat]
W
(Be) hP2 a = 228.59 LT, at 25C [Mas2]
< 1270 P63/mmc c = 358.45 dissolves 9.5 at.% Cu at 1109C
Mg [2006Wat]
CuMg2 oF48 a = 907 [2002Iva]
< 568 Fddd b = 528.4
CuMg2 c = 1825
a = 905
b = 528.3
c = 1824.7
a = 904.4 0.1
b = 527.5 0.1
c = 1832.8 0.2
Cu2Mg cF24 a = 702.1 64.7 to 69 at.% Cu [2002Iva]
< 797 Fd3m
Cu2Mg
, Cu3Be cI2 a = 280 24.5 to 41.7 at.% Be at 850C
900 - 618 Im3m [2006Wat]
W
, CuBe cP2 a = 270.2 0.3 46.2 to 49 at.% Be at 850C
< 933 Pm3m
CsCl
New Series IV/11C2
BeCuMg 61

[C] Prototype
, Cu1xBe2+x cF24 x varies from 0.071 at 930C
< 1219 Fd3m to 0.455 at 1090C
Cu2Mg a = 595.2 at 66.7 at.% Be
a = 589.9 at 75 at.% Be [2006Wat]
* CuMgBe4 cF24 a = 600.4 [1967Sta]
Fd3m
Cu2Mg
* Cu4Mg3Be2 cF24 a = 687 [1940Gor]
Fd3m
Cu2Mg

Be Cu Mg
L (Cu) + + Cu2Mg ~656 to E L ? ? ?
~694 (Cu) ~9.3 ~86.0 ~4.7
? ? ?
Cu2Mg ~1 ~66 ~33
Cu 80.00
Be 0.00
Mg 20.00 Data / Grid: at.%
Fig. 1: Be-Cu-Mg. Axes: at.%
Isotherms of the
liquidus surface near
the Cu corner
90
10
90
0
C
95
0
10
00
105
0
10
Cu Cu 80.00
Be 20.00
Mg 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
62 BeCuMg
Cu 80.00
Be 0.00
Part of the isothermal
section at 800C near
the Cu corner
90
10
L + (Cu)
L + (Cu) +
(Cu)
(Cu) +
10
Cu Cu 80.00
Be 20.00
Mg 0.00
Cu 80.00
Be 0.00
the Cu corner
90
10
L + (Cu)
L + (Cu) +
(Cu)
(Cu) +
10
Cu Cu 80.00
Be 20.00
Mg 0.00
New Series IV/11C2
BeCuMg 63
Cu 80.00
Be 0.00
the Cu corner
90
10
(Cu) + Cu2Mg
(Cu) + + Cu2Mg
(Cu)
(Cu) +
10
Cu Cu 80.00
Be 20.00
Mg 0.00
Cu 80.00
Be 0.00
the Cu corner
90
10
(Cu) + Cu2Mg
(Cu) + + Cu2Mg
(Cu)
(Cu) +
10
Cu Cu 80.00
Be 20.00
Mg 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
64 BeCuNi
Beryllium Copper Nickel

Andy Watson, Lesley Cornish
Introduction
Few experimental investigations of the phase equilibria of this system exist in the literature. The earliest
study was by [1938Sla] who used thermal analysis and hardness measurements to study Cu rich alloys of
up to 5 mass% Be and 3 mass% Ni producing 4 partial vertical sections. The work of [1941Iwa] was more
comprehensive, studying phase equilibria up to 13 mass% Be by thermal and X-ray analyses, dilatometric
and hardness measurements supplemented by microanalysis. They produced isopleths at 4 and 6 mass% Be,
3, 12 and 30 mass% Ni, plus a partial liquidus surface and a diagram showing the solubility of Be in the
(Ni,Cu) phase. More recently, [1958Chz] reinvestigated the Cu rich corner of the phase diagram. Along
with the quasibinary Cu-NiBe section, they gave solidus isotherms for 10 different temperatures between
850 and 1050C and isopleths for 0.25 and 1 mass% Ni. However, the quasibinary section of [1958Chz] is
in conflict with the liquidus surface of [1941Iwa] in that there is no maximum shown on the monovariant
line corresponding to the L (Ni) + reaction. This conflict is yet to be resolved. The experimental work
has been reviewed in [1973Saa, 1979Cha, 1979Dri]. Details of the experimental studies are given in
Table 1. Studies of the mechanical and physical properties of alloys of the system have been made. Details
are given in Table 4.
Binary Systems
The Be-Cu and Cu-Ni systems are taken from the MSIT evaluation program [2006Wat, 2002Leb], and the
Be-Ni is accepted from [Mas2]. For the purposes of this assessment, the phase designated in the binary
evaluation of Be-Cu [2006Wat] is designated here as .
Solid Phases
No ternary phases have been discovered in this system. Details of the binary and unary phases are given in
Table 2. The CuBe and NiBe phases form a continuous series of solid solutions. The phase was found to
dissolve up to 2 mass% Ni [1941Iwa].
Quasibinary Systems
Following the work of [1958Chz], a quasibinary section exists between pure Cu and NiBe, having a simple
eutectic form. Part of the diagram is shown in Fig. 1 taken [1979Cha]. However, this is not consistent with
the liquidus surface of [1941Iwa] (see below). It is highly desirable that this conflict be resolved.
Only one invariant four-phase reaction has been found in the system. [1941Iwa, 1979Cha] reports a
transition reaction occurring at 868C, just above the (Cu) + L peritectic reaction in the Be-Cu system
(863C). An invariant reaction at 855C was found by [1958Chz], but this is most probably the same
reaction [1979Cha]. The data for the invariant reported by [1941Iwa, 1979Cha] are given in Table 3.
Liquidus Surface
Part of the liquidus surface is given in Fig. 2. This is taken from the review of [1979Cha] based on the work
of [1941Iwa]. Owing to the presence of the Cu-NiBe quasibinary section, a maximum has been added
speculatively where the L (Ni) + monovariant crosses the Cu-NiBe join. There must also be a minimum
on the monovariant at some point to the Ni-side of the maximum. Alterations have been made to ensure
consistency with the binary systems.
New Series IV/11C2
BeCuNi 65
Isothermal Sections
Figures 3-5 show isothermal sections for 915, 820 and 500C, resepectively, taken from [1958Chz]. It was
necessary to adjust the phase boundaries to ensure compatibility with the accepted Be-Cu binary phase
diagram.

Isopleths are shown in Figs. 6-9. They correspond to sections of constant Ni content of 3 and 12 mass%,
and constant Be contents of 4 and 6 mass%. Minor changes have been made to make them consistent with
the accepted binary phase diagrams. Owing to the very narrow width of the L+ phase field in the Be-Cu
binary system at 6 mass% Be (31 at.% Be), the gap between the liquidus and solidus at the right-hand edge
of Fig. 9 (0% Ni) is very small. Also, as the assessed phase composition in the (Cu) + eutectoid at
31.4 at.% Be, this is very close to the locus of the phase boundaries separating the , + , (Ni,Cu) + +
and (Ni,Cu) + phase fields in the vertical section of the ternary (31.05 at.% Be). Making the vertical
section agree with the binary phase diagram to within less than 0.5 at.% Be would have great consequences
on the nature of the Ni rich phase equilibria within this section. Therefore, as the difference in the
composition is so small at the binary edge it was decided not to alter these phase boundaries in the vertical
section.

Be-Cu alloys are used as precipitation hardened high-strength alloys for low-temperature applications
where small magnetic susceptibilities are required; such as in SQUID magnetometers and magnetic
resonance imaging. Ni is added to limit grain growth and enhance mechanical properties further. On the
other hand, Cupronickel has application where good corrosion resistance is required, and ternary
additions improve mechanical properties and can give materials with heat resistant properties where high
electrical conductivity is required.
This has led to much research on the mechanical behavior of Be-Cu-Ni alloys, and these are listed in
Table 4. Of particular interest is the age hardening behavior of the material. [1972Gup] found, through
microstructural and hardness studies of a Cu-30Ni-0.3Be alloy, the precipitation of G.P. zones at around
550C.
[2005Coo] studied the origins of paramagnetism in a 0.4Be-Cu-1.95Ni (mass%) commercial alloy. Using a
Quantum SQUID magnetometer, the magnetic susceptibility was found to follow the Curie-Weiss law
between 4.75 and 300 K. The values for the effect Ni magnetic moments correspond to a lower Ni
concentration for the material, which suggests that some of the Ni forms non-magnetic beryllides spread
uniformly throughout the matrix.
References
[1932Mas] Masing, G., Pocher, W., Technical Properties of the Be-Containing Cu-Ni-Alloys (in
German), Wiss. Veroeff. Siemens-Konzern, 11(2), 93-98 (1932) (Experimental, Mechan.
Prop., 3)
[1938Sla] Slavinsky, M.P., Filin, N.A., Ribalchenko, L.P., Investigation of the Nature and Properties
of the Copper-Berylium-Nickel Alloys (in Russian), Metallurg, 11(107), 7-16 (1938)
(Phase Diagram, Phase Relations, Experimental, Mechan. Prop.)
[1941Iwa] K. Iwase, M. Okamoto, Nippon Kinzoku Gakkai-Si, 5, 82 (1941) as quoted in [1979Cha]
[1958Chz] Czhan, B-Ch, Investigation of the Structure and Properties of the Cu-Ternary Alloys
Cu-Ni-Be (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall., 1, 138-147 (1958)
(Phase Diagram, Experimental, Mechan. Prop., Morphology, 8)
[1960Gla] Glasov, V.M., Stepanova, M.V., Chemical Reaction Between Alloying Components in
Ternary Copper-Base Solid Solutions, Rus. Metall. Fuels, (6), 66-70 (1960) (Phase
Relations, Experimental, Mechan. Prop., 5)
Landolt-Brnstein
New Series IV/11C2
MSIT
66 BeCuNi
[1972Gup] Gupta, S.P., Mukherjee, K., Crystal Structure and Morphology of Precipitate Phases
Associated with Age Hardening in a Cu-30Ni-0.3Be Alloy, Mater. Sci. Eng., 10(1), 43-51
(1972) (Experimental, Mechan. Prop., Morphology, 19)
[1973Saa] Saarivirta, M.J., Be-Cu-Ni (Beryllium-Copper-Nickel), Metals Handbook, 8, 401 (1973)
(Phase Diagram, Review, 2)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Be-Cu-Ni, INCRA Monograph
Series 6 Phase Diagrams and Thermodynamic Properties of Ternary Copper-Metall
Systems, NSRD, Washington, 6, 318-328 (1979) (Phase Diagram, Review, 6)
[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova, Rokhlin, L.L., Turkina,
N.I., Cu-Be-Ni in Binary and Multicomponent Copper-Base Systems (in Russian),
Nauka, Moscow, 87-88 (1979) (Phase Diagram, Review, 1)
[1982Spa] Spaic, S., Klemencic, A., Investigation of Cu-Ni-Be Alloy, Rud.-Met. Zb., 29(4), 309-321
(1982) (Phase Reations, Experimental, Electr. Prop., Mechan. Prop, 7)
[2002Leb] Lebrun, N., Copper-Nickel, MSIT Binary Evaluation Program, in MSIT Workplace,
Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart;
Document ID:20.14832.1.20, (2002) (Crys. Structure, Phase Diagram, Assessment, 51)
[2005Coo] Cooley, J.C., Aronson, M.C., Origins of Paramagnetism in Beryllium-Copper Alloys,
J. Alloys Compd., 228, 195-200 (2005) (Magn. Prop., 11)
Table 1: Investigations of the Be-Cu-Ni Phase Relations, Structures and Thermodynamics

Reference Method/Experimental Technique Temperature/Composition/Phase Range
Studied
[1938Sla] Thermal analysis, microstructural studies Cu rich alloys
and hardness measurements
[1941Iwa] Thermal, X-ray, hardness, dilatometric and Up to 13 mass% Be
microscopic analyses
[1958Chz] Hardness and microstructural studies. Cu rich alloys

[C] Prototype
(Ni1xCux) cF4
Fm3m
Cu
(Ni) a = 352.4 pure Ni at 25C [2002Leb]. Dissolves 15
< 1455 at.% Be at 1150C [Mas2]
(Cu) a = 361.46 dissolves 13.7 at.% Be at 863C
< 1084.62 [2006Wat]
(Be) cI2 a = 255.15 HT, dissolves ~17 at.% Cu at 1199C
1289 - 1270 Im3m [2006Wat], 10 at.% Ni at 1338C
W [Mas2]
(Be) hP2 a = 228.59 LT, at 25C [Mas2] dissolves 9.5 at.%
< 1270 P63/mmc c = 358.45 Cu at 1109C [2006Wat], 4.5 at.% Ni at
Mg 1062C [Mas2]
New Series IV/11C2
BeCuNi 67

[C] Prototype
, (Ni,Cu)Be cP2
Pm3m
NiBe CsCl a = 260.4 25 at.% Ni at 1240C to 51.6 at.% Ni at
< 1605 1150C [Mas2, V-C2]
CuBe a = 270.2 0.3 46.2 to 49 at.% Be at 850C [2006Wat]

< 933
, NiBe5 cI52 a = 1527.6 11.5 at.% Ni at 1338C, 19 at.% Ni at
< 1395 I43m 1240C [Mas2]
Ni5Zn21
, NiBe7 cF416 a = 762.4 LT, 14 to 20 at.% Ni. [Mas2, V-C2]
< 1240 F23
-brass
, Cu1-xBe2+x cF24 x varies from 0.071 at 930C to 0.455 at
< 1219 Fd3m 1090C
CuMg2 a = 595.2 at 66.7 at.% Be
a = 589.9 at 75 at.% Be [2006Wat]
, Cu2Be cI2 a = 281.0 24.5 to 41.7 at.% Be at 850C
< 900 Im3m [2006Wat]. Dissolves ~2 mass% Ni at
W 868C [1979Cha]

Be Cu Ni
L + (Ni,Cu) + 868 U1 L 24.5 74.8 0.7
~51.5 ~14.5 ~34.0
(Ni,Cu) 5.4 93.0 1.6
~29.9 ~68.5 ~1.6
L + (Ni,Cu) 1030 e (max)? L ~9.7 ~80.6 ~9.7
Table 4: Investigations of the Be-Cu-Ni Materials Properties

Reference Method/Experimental Technique Type of Property
[1932Mas] Brinell hardness measurements Mechanical properties with respect to
tempering conditions
[1960Gla] Microhardness measurement Microhardness of solid solution.
[1972Gup] Hardness measurement Tempering properties of Cu-30Ni-0.3Be
(mass%)
[1982Spa] Yield strength and hardness measurement Investigation of how mechanical properties
vary with condition of material, tempering
temperature.
[2005Coo] SQUID magnetometry Magnetic susceptibility of commercial alloy
with composition 4Be-Cu-1.95Ni (mass%)
Landolt-Brnstein
New Series IV/11C2
MSIT
68 BeCuNi
1200
Fig. 1: Be-Cu-Ni.
Part of the
quasibinary section 1100
NiBe - Cu L+(Cu)
1030C
1000
(Ni,Cu)
Temperature, C
900
800
(Ni,Cu)+ '
700
600
500
Ni 7.85 86 90 94 98
Cu
Cu 84.31
Be 7.84 Cu, at.%
Be Data / Grid: at.%

Fig. 2: Be-Cu-Ni. Axes: at.%
Part of the liquidus
surface
20
80
40
60
60
40 p1, 900C
1350
' U1
e1, 1150C 1250 p2, 863C
80
20
1150
950C
1250
(Ni,Cu)
1350 1150 1050
e(max)?
20 40 60 80
Ni Cu
New Series IV/11C2
BeCuNi 69
Ni 0.00
Cu 75.00
Be 25.00 Data / Grid: at.%
Isothermal section at
915C
20
10
10
+NiBe
20
Ni 25.00 80 90
Cu
Cu 75.00
Be 0.00
Ni 0.00
Cu 75.00
820C
20
+
+
Ni
Be +
10
10
20
+NiBe

Ni 25.00 80 90
Cu
Cu 75.00
Be 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
70 BeCuNi
Ni 0.00
Cu 75.00
500C
20
10
+
+ +NiBe
10
20 +NiBe
Ni 25.00 80 90
Cu
Cu 75.00
Be 0.00
1300
Fig. 6: Be-Cu-Ni.
Vertical section
96.76Cu3.24Ni - 1200
48.96Be49.16Cu1.88
L
Ni
L+(Ni,Cu)
1100
Temperature, C
1000
L+(Ni,Cu)+ ' L+ ' L+ + '

900
(Ni,Cu) '
+ '
(Ni,Cu)+ + '
800
700
(Ni,Cu)+ '
600
Ni 3.24 10 20 30 40 Ni 1.88
Cu 96.76 Cu 49.16
Be 0.00 Be, at.% Be 48.96
New Series IV/11C2
BeCuNi 71
1300
Fig. 7: Be-Cu-Ni.
L
Vertical section
87.13Cu12.87Ni - 1200
43.67Be48.29Cu8.04 L+(Ni,Cu)
1100
(Ni,Cu) L+ '
Temperature, C
1000
L+(Ni,Cu)+ '
L+ + '
900
+ '
800
(Ni,Cu)+ + '
(Ni,Cu)+ '
700
600
Ni 12.87 10 20 30 40 Ni 8.04
Cu 87.13 Cu 48.29
Be 0.00 Be, at.% Be 43.67
1300
Fig. 8: Be-Cu-Ni. L
Vertical section
21.35Be78.65Ni - 1200
L+(Ni,Cu)
22.71Be77.29Cu L+ '
1100
L+(Ni,Cu)+ '
Temperature, C
1000
900 L+(Ni,Cu)
L+
(Ni,Cu)+
800
(Ni,Cu)+ + '
(Ni,Cu)+ '
(Ni,Cu)+
700
600
500
Ni 78.65 10 20 30 40 50 60 70 Ni 0.00
Cu 0.00 Cu 77.29
Be 21.35 Cu, at.% Be 22.71
Landolt-Brnstein
New Series IV/11C2
MSIT
72 BeCuNi
1400
Fig. 9: Be-Cu-Ni.
Vertical section L
1300
29.37Be70.63Ni - L+ '
31.04Be68.96Cu
1200
L+(Ni,Cu)+ '
1100
Temperature, C
1000
L+ + '
900
L+
(Ni,Cu)+ '
(Ni,Cu)+ + '
800

+ '
700
600
500
Ni 70.63 10 20 30 40 50 60 Ni 0.00
Cu 0.00 Cu 68.96
Be 29.37 Cu, at.% Be 31.04
New Series IV/11C2
BeCuSi 73
Beryllium Copper Silicon

Nathalie Lebrun
Introduction
Only a few data are available concerning the ternary system Be-Cu-Si. Experimental details are reported in
Table 1.
Two ternary compounds have been reported [1967Hof, 1967Sta]. Only solubility data are available in the
literature. [1938Zak1, 1939Pog, 1939Zak, 1940Vel] reported results of the investigations on joint solubility
of Be and Si in solid (Cu) at temperatures 350-800C. The data of separate works agreed with each other
enough well. [1977Mye] investigated ion implantation of Cu and Si together in Be and behavior of Cu and
Si atoms in solid (Be) then during annealing at 400C using the ion backscattering analysis. Conclusion
about influence of Si on Cu solubility in solid (Be) was made. [1938Zak2] studied the solubility of Be in
Cu5Si and of Si in BeCu along the supposed quasibinary section Cu5Si-CuBe. In this experimental work,
solid state investigations are only available. Since no further complete experimental work had been done, it
cannot be concluded in the present assessment that the section Cu5Bi-CuBe is really quasibinary.
[1979Cha, 1979Dri] undertook a short review of the system Be-Cu-Si.
Binary Systems
The binary systems Cu-Si and Be-Cu are accepted from the MSIT Binary Evaluation Program: Cu-Si from
[2002Leb], Be-Cu from [2006Wat]. The Be-Si phase diagrams is taken from [Mas2].
Solid Phases
All the crystallographic data for the unary, binary and ternary phases are reported in Table 2.
Two ternary compounds have been observed. [1967Hof] detected a ternary compound Cu50Be25Si25 with
a brass structure. [1967Sta] found a ternary Laves phase with a Cu2Mg type structure with a composition
of CuBe2Si. The solubility of Be in Cu5Si is established to be about 1 mass% at 800C and that of Si in
CuBe is less than 0.5 mass% at the same temperature along the section Cu5Si-CuBe [1938Zak2].

Figure 1 shows the solubility of Be and Si in (Cu) at 350 and 800C taken from [1938Zak1] with slight
modifications in accordance with the accepted binary systems. The solubility of Cu in solid (Be) decreases
significantly in presence of Si amounting 2.82 at.% Cu at 400C for at.% Si : at.% Cu = 1.6 [1977Mye].

Only hardness measurements are found in the literature on cast and annealed alloys [1938Zak1, 1939Pog,
1939Zak], see Table 3. Agreement is observed. Increase of the Si content in the Be-Cu-Si alloys leads to an
increase of their hardness which also strongly depends on the annealing and cooling processes [1938Zak1].
References
[1938Zak1] Zakharova, M., Chursanova, A., Investigation of the Cu-Be-Si Alloys (in Russian), Zh.
Tekh. Fiz., 8(24), 2085-2092 (1938) (Phase Diagram, Crys. Structure, Experimental,
Mechan. Prop., 3)
[1938Zak2] Zakharova, M., Shternfeld, A., Investigation of the CuBe-Cu5Si Quasibinary Section (in
Russian), Zh. Tekh. Fiz., 8(24), 2093-2096 (1938) (Crys. Structure, Phase Diagram,
Experimental, 1)
Landolt-Brnstein
New Series IV/11C2
MSIT
74 BeCuSi
[1939Pog] Pogodin, S.A., Abrikosov, N.Ch., Effect of Small Additions of Mg and Si on the Properties
of Berilium-Brass (in Russian), Metallurg, 14(2), 57-65 (1939) (Experimental, Mechan.
Prop., 15)
[1939Zak] Zakharova, M.I., Investigation of the Cu-Si-Be and Cu-Mn-Be Alloys Ennoblement (in
Russian), Metallurg, (2), 80-86 (1989) (Phase Diagram, Experimental, Mechan. Prop., 8)
[1940Vel] Velichko, I.P., Shilkina, L.A., About a Problem on Replacement for Deficient Non-Ferrous
Metals in High-Strength Alloys in Yubileyny Sbornik Nauch. Trudov Moskov. Inst. Tsvet.
Metallov i Zolota (in Russian), Metallurgizdat, Moskow-Leningrad, (9), 546-550 (1940)
(Phase Diagram, Experimental, Mechan. Prop., 0)
[1967Hof] Hofer, G., Stadelmaier, H.H., Co, Ni and Cu Phases of the Ternary MnCu2Al-Type (in
German), Monatsh. Chem., 98, 408-411 (1967) (Crys. Structure, Experimental, 9)
[1967Sta] Stadelmaier, H.H., Hofer, G., Phases with Diamond Substructure in Ternary Be Alloys
(in German), Monatsh. Chem., 98(1), 45-48 (1967) (Crys. Structure, Experimental, 3)
[1977Mye] Myers, S.M., Smugeresky, J.E., Low-Temperature Solubility of Cu in Be, in Be-Al and in
Be-Si Using Ion Beams, Metall. Trans., 8A, 609-616 (1977) (Phase Diagram,
Experimental, 16)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Be-Cu-Si, INCRA Monograph
Systems, NSRD, Washington, 6, 329-331 (1979) (Phase Diagram, Review 7)
Turkina, N.I., Cu-Be-Si in Binary and Multicomponent Copper-Base Systems (in
Russian), Nauka, Moscow, 86-87 (1979) (Phase Diagram, 3)
[1994Cha] Chakrabarti D.J., Laughlin D.E. and Tanner L.E., Be-Cu (Beryllium-Copper), in Phase
Diagrams of Binary Copper Alloys, Subramanian P.R., Chakrabarti, D.J., Laughlin, D.E.
(Eds.), ASM International, Materials Park, OH, 85-98 (1994) (Phase Diagram, Crys.
Structure, Thermodyn., Review, 103)
[2002Leb] Lebrun, N., Cu-Si Copper-Silicon, MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials
Science International Services GmbH, Stuttgart; Document ID: 20.12505.1.20, (2002)
(Crys. Structure, Phase Diagram, Assessment, 23)
Workplace, Effenberg, G. (Ed.), Materials Science International Services, GmbH, Stuttgart;
to be published (2006) (Crys. Structure, Phase Diagram, Assessment, 10)
Table 1: Investigations of the Be-Cu-Si Phase Relations, Structures and Thermodynamics

Reference Method/Experimental Technique Temperature/Composition/Phase Range Studied
[1938Zak1] Microstructure, X-ray diffraction, 350 - 800C / Cu rich alloys with 0.25-1.75
Hardness mass% Be and 0.5 to 5.75 mass% Si
[1938Zak2] Microstructure, X-ray diffraction 87.9 to 90.3 mass% Cu; 0.5 to 8.8 mass% Si; 0.7
to 11.5 mass% Be
[1939Pog] Microstructure, Hardness, Tensile 270 to 350C / Cu rich alloys with 0 to 0.5
properties mass% Si and 1.9 to 2.5 mass% Si
[1939Zak] Microstructure, Hardness 300, 350 and 800C / Cu rich alloys with up to 1
mass% Be and 4 mass% Si
[1940Vel] Hardness 400 and 800C / Cu rich alloys with up to 2
mass% Be and 6 mass% Si
[1967Hof] X-ray diffraction Cu50Be25Si25
New Series IV/11C2
BeCuSi 75

[1967Sta] X-ray diffraction CuBe2Si
[1977Mye] Ion implantation and ion backscattering 320 - 750C / Be-Cu-Si

[C] Prototype
(Be) cI2 a = 255.15 HT, dissolves 17 at.% Cu at 1199C
1289 - 1270 Im3m [Mas2, 1994Cha]
W
(Be) hP2 a = 228.59 LT, at 25C [Mas2]
1275 P63/mmc c = 358.45 dissolves 9.5 at.% Cu at 1109C
Mg [1994Cha]
(Cu) cF4 [Mas2]
< 1084.62 Fm3m a = 361.46 at x = 0 [Mas2]
Cu a = 360.82 at x = 0 [V-C2]
(Si) cF8 a = 543.06 0 to 0.003 at.% Cu [2002Leb]
< 1414 Fd3m
C-diamond
, Cu3Be cI2 a = 281.0 24.5 to 43.5 at.% Be at 850C
< 900 Im3m [1994Cha]
W
, CuBe cP2 a = 270.2 0.3 46.2 to 49 at.% Be [1994Cha, V-C2]
< 933 Pm3m
CsCl
, Cu1xBe2+x cF24 x varies from 0.071 at 930C to 0.455 at
< 1219 Fd3m 1090C
Cu2Mg a = 589.9 at 75 at.% Be [1994Cha]
, Cu7Si hP2 11.05 to 14.5 at.% Si
842 - 552 P63/mmc a = 256.06 at 12.75 at.% Si [2002Leb]
Mg c = 418.46
, ~Cu6Si cI2 14.2 to 16.2 at.% Si
853 - 787 Im3m a = 285.4 at 14.9 at.% Si [2002Leb]
W
, Cu5Si(h) t** a = 881.5 17.6 to 19.6 at.% Si
824 - 711 c = 790.3 Sample was annealed at 700C
[2002Leb]
, Cu5Si(r) cP20 a = 619.8 17.15 to 17.6 at.% Si [2002Leb]
< 729 P4132
Mn
J, Cu15Si4 cI76 a = 961.5 21.2 at.% Si [2002Leb]
< 800 I43d
Cu15Si4
Landolt-Brnstein
New Series IV/11C2
MSIT
76 BeCuSi

[C] Prototype
, Cu3Si(h2) hR* a = 247 23.4 to 24.9 at.% Si [2002Leb]
859 - 558 R3m = 109.74
or a = 726.7 [V-C2]
t** c = 789.2
', Cu3Si(h1) hR* a = 472 23.2 to 25.2 at.% Si [2002Leb]
620 - 647 R3 = 95.72
", Cu3Si(r) o** a = 7676 23.3 to 24.9 at.% Si [2002Leb]
< 570 b = 700
c = 2194
* CuBe2Si c** a = 605 Be2(Cu,Si) Laves phase [1967Sta]
Cu2Mg
* Cu50Be25Si25 c** a = 829 brass structure [1967Hof]
Table 3: Investigations of the Be-Cu-Si Materials Properties

[1938Zak1] Hardness measurements Mechanical properties
[1939Pog] Hardness measurements, Tensile properties Mechanical properties
[1939Zak] Hardness measurements Mechanical properties
[1940Vel] Hardness measurements Mechanical properties
Cu 85.00
Be 0.00
Si 15.00 Data / Grid: at.%
Fig. 1: Be-Cu-Si. Axes: at.%
Solubility range of Be
and Si in (Cu) solid
solution at 350 and
800C
90
10
800C
350C
(Cu)
10
Cu Cu 85.00
Be 15.00
Si 0.00
New Series IV/11C2
CeCuGe 77
Cerium Copper Germanium

Oksana BodakA, Nataliya Bochvar
Introduction
There is much information available on the crystal structure and lattice parameters of the ternary compounds
in the Ce-Cu-Ge system, but only two investigations [1996Sal, 2002Nak] on the phase equilibria. The
experimental studies are summarized in Table 1. [1996Sal] constructed isothermal sections for the
concentration range from 0 to 50 at.% Ge (600C) and from 50 to 100 at.% Ge (400C). Eight ternary
compounds have been found (Fig. 1). Two of them (CeCuGe and CeCu0.6-0.8Ge1.4-1.2) along 33.3 at.% Ce
section have the AlB2 structure. On the other hand, [1969Rie1] found a compound with the AlB2 type
structure in the composition range between CeCuGe and CeCu0.67Ge1.33. This information was obtained on
as-cast samples following arc-melting, and according to [2002Ria], probably corresponds to a high
temperature phase. [1993Ian] annealed samples at 750C for 7 to 10 days and found the AlB2 type structure
at the stoichiometric composition. At the same time, according to [1991Yan, 2004Che], the CeCuGe
compound annealed at 800 or 700C crystallizes with a hexagonal structure with a doubled c axis indicating
an ordered ternary structure of the ZrBeSi type.
[2002Nak] studied the phase equilibria at 800C along the sections Ce(CuxGey)2 with x + y = 1; 0.95 and
0.90 at 0.15 x 0.3. The alloys belong to the sections at 33.3 at.% Ce (1), at 34.5 at.% (0.95) and at 35.6
at.% Ce (0.9); the contents of Cu and Ge correspond to ~10 to 20 and ~55 to 45 at.%, respectively. Two
ternary compounds with the AlB2 and ThSi2 type structures have been established along the section at
34.5 at.% Ce. Moreover, [2002Nak] determined that the compounds at Ce:Cu:Ge = 2:1:3 and 2:1:2 are not
formed. However, [2000Tie] indicated the formation of the Ce2CuGe3 compound with an orthorhombic
structure.
[1997Was] investigated the effect of hydrostatic pressure up to 15 GPa on the crystal structure of the
CeCu2Ge2 compound, and [2002Gil] studied the effect of low temperature on the crystal and magnetic
structure of the CeCu0.86Ge compound.
[2002Ria] summarized and discussed the constitutional data of the Ce-Cu-Ge system, including the crystal
structures of the binary and ternary phases, the phase equilibria observed in this system and some magnetic
and electrical properties.
Binary Systems
The Ce-Ge binary system is taken from [Mas2]. The Ce-Cu and Cu-Ge binary systems are accepted from
[2002Fer] and [2002Per], respectively.
Solid Phases
Crystallographic data of the unary, binary and ternary compounds are listed in Table 2.
Eleven ternary compounds have been found in the Ce-Cu-Ge system. The compound -1 (CeCu2Ge2) with
the ThCr2Si2 (or CeGa2Al2) type structure was reported by [1969Rie2, 1997Kri, 1996Sal]. This phase has
been described as a point compound. The crystal structures of the Ce2CuGe6 (-2) and Ce2Cu3Ge3 (-4)
compounds (having their own structure types) have been found and refined using a powder method
[1988Kon1, 1988Kon2] and more recently confirmed by [1995Sol] for -2 and [1996Sal] for -2 and -4. The
ternary CeCuxGe2 (-3) compound was described by [1990Fra]. It is non-stoichiometric and has a
homogeneity range of 0.86 x 1. The stoichiometric CeCuGe (-5) compound crystallizes with an AlB2
structure [1969Rie1, 1993Ian, 1996Sal] or a ZrBeSi structure [1991Yan, 2004Che] depending on heat
treatment. The ternary compound -6 with the AlB2 structure has a homogeneity range. According to
[1996Sal] it lies in the 33.3 at.% Ce section at Cu contents from 20 to 26 at.% and is described as
CeCu0.6-0.8Ge1.4-1.2. According to [2002Nak], this ternary compound lies along the 34.5 at.% Ce section at
Cu contents from ~17 to ~19 at.% and is described as Ce(CuxGey)2 with (x + y) = 0.95 at 0.25 x 0.275.
Landolt-Brnstein
New Series IV/11C2
MSIT
78 CeCuGe
Additional investigation is required to establish the composition of the -6 compound. Also, [2002Nak]
found the ternary -9 compound in the 34.5 at.% Ce section. This compound was described as Ce(CuxGey)2
with (x + y) = 0.95 at 0.12 x 0.14. Two other ternary compounds, -7 (Ce0.60Cu0.25Ge0.15) and -8
(Ce0.60Cu0.05Ge0.35), were found by [1996Sal] but their crystal structures were not determined. The
compound -10 (Ce2CuGe2) as determined by [2000Tie] is included in the present assessment, although
[2002Nak] indicated that this compound does not exist in the Ce-Cu-Ge system. This needs to be confirmed.
The crystal structure of the ternary compound -11 (Ce3Cu4Ge4) was determined by [2002Zah] after
annealing at 800C for 2 weeks and subsequent quenching into water.
The binary compound CeGe2x dissolves up to 10 at.% Cu at 600C according to [1996Sal].
Liquidus Surface
There is only one reference to the melting temperature of the CeCu2Ge2 compound. Using high temperature
differential thermal analysis [1997Mor] determined the melting temperature of CeCu2Ge2 to be 1384C.
Isothermal Sections
The isothermal section of the Ce-Cu-Ge system at 600C in Ge and Cu corner, and at 400C in the Ce corner
is shown in Fig. 1, taken from [1996Sal]. Locations of the -3 and -4 phases which were interchanged in
[1996Sal] have been corrected in Fig. 1. The phase equilibria shown by dashed lines were introduced
speculatively because of two additional phases at the Cu-Ge side according to the accepted binary phase
diagram from [2002Fer]. The partial isothermal section in the region of the phases with the AlB2 and ThSi2
type structures (phases -6 and -9) at 800C is presented in Fig. 2 taken from [2002Nak].
Thermodynamics
[2000Tie] studied the specific heat and the entropy of Ce2CuGe3. The specific heat of Ce2CuSi3 exhibits a
peak at ~4 K. Since the magnetic entropy between 2 and 4 K is much smaller than 2Rln2, the peak in the
specific heat is unlikely to be related to long-range magnetic ordering. This 4 K peak might be due to a
Schottky anomaly with a spin-glass contribution. The coefficient of the linear temperature dependent term
in the specific heat of Ce2CuGe3 is 249.86 mJ#mol1#K2, which is much larger than that of normal metals
[2000Tie].

Studies of electrical, magnetic and other properties of the Ce-Cu-Ge compounds are summarized in Table 3.
The temperature dependence of the resistivity of CeCu2Ge2 was determined by [1985Rau]. Elastic and
inelastic neutron scattering studies of the Kondo lattice of CeCu2Ge2 were performed by [1989Kno]. At
TN = 4.1 K, an incommensurate magnetic order develops with an ordering wave vector q0 = (0.28, 0.28,
0.54) and an ordered s = 0.74 B [1989Kno]. The temperature dependence of the width of the quasielastic
line for CeCu2Ge2 is characteristic of a heavy-fermion system with a high temperature square root
dependence and a limiting low temperature value, yielding a Kondo temperature TK 10 K [1989Kno]. A
close correlation between the unit cell volume and the 4f-local spin / conduction electron hybridization for
the CeCu2Ge2 compound was demonstrated in [1989Loi]. The width of the quasielastic line of the
Lorentzian component in the magnetic neutron scattering spectrum revealing the magnetic relaxation rate
and the strength of the hybridization between the 4f-and the conduction electrons were determined by
[1989Loi]. The temperature-magnetic field phase diagram of Ce(Cu1xNix)2Ge2 was discussed in
[1990Ste]. The magnetic properties of the CeCuGe compound have been studied by [1991Yan].
Ferromagnetic ordering in CeCuGe has been found below 8.6 K. A TN of 15.8 K and eff of 2.5 B has been
determined for Ce2CuGe6 by [1995Sol]. CeCu2Ge2 orders antiferromagnetically below TN = 4.15 in an
incommensurate sinusoidal amplitude modulated structure [1997Kri]. Enhancement of the superconducting
transition temperature TC is confirmed at around 16 GPa in the pressure-induced superconductor CeCu2Ge2
[1998Kob]. The superconducting HC-TC phase diagrams in low-TC and high-TC pressure regions are
presented in Fig. 3 [1998Kob]. With increasing pressure, the compound CeCu2Ge2 evolves from
New Series IV/11C2
CeCuGe 79
antiferromagnetically ordered Kondo to intermediate valence behavior as the Kondo temperature increases
by about two orders of magnitude [1998Var]. The pressure dependence of the temperatures of magnetic
ordering is presented in Fig. 4 according to [1998Var]. The differential thermopower of Ce2CuGe6 was
investigated in the range 78-380 K [2000Kon]. Below 6 K, Ce2CuGe3 shows spontaneous magnetic
ordering [2000Tie]. The results of heat capacity measurements in the presence of an external magnetic field
and the measurement of resistivity for the compound CeCuxGe2 with x = 0.86 are reported in [2001Raw].
The ordered Ce magnetic moment is 2.05(2)B at the 2d site and 1.10(2)B at the 4e site for Ce3Cu4Ge4
[2002Zah]. Below the Neel temperature of 16.5 K for CeCu0.86Ge2 compound, a collinear
antiferromagnetic ordering is present with the Ce magnetic moment aligned along the c-axis [2002Gil]. The
magnetic structure of the CeCu0.86Ge2 compound does not change over the temperature interval between
1.5 K and the Neel temperature of 16.5 K [2002Gil]. A transition from ferromagnetism to non-magnetic
ordering above 1.8 K is evident during the hydrogenation of CeCuGe [2004Che]. Cu containing alloys
(CeCuxGe2, 0 x 1) order antiferromagnetically at a high temperature (~17 K) and shows strong
metamagnetic behavior as a function of externally applied magnetic field [1992Das].
Miscellaneous
[1997Was] investigated the effect of hydrostatic pressure on the crystal structure of CeCu2Ge2. Up to
pressures of 15 GPa, the lattice parameters and unit cell volume for CeCu2Ge2 compound decrease
continuously, whereas the c/a ratio increases. A comparison of the structural parameters of CeCu2Ge2 under
pressure with those at p = 0 indicates that the 4f-hybridization strength is determined by Ce-Cu
hybridization. Non-hydrostatic pressure has a strong influence on the behavior of the structural parameters.
The ternary germanide CeCuGe absorbs hydrogen in the temperature range 393-473 K [2004Che]. The
structural characteristics of CeCuGeH1.0(1) are shown in Table 2.
References
[1965Gla] Gladyshevsky, E.I., Bodak, O.I., Compounds with Structures of the AlB2 Type in the
System Ce-Ni-Si and in Related Systems (in Russian), Dop. Akad. Nauk Ukr. RSR, 5,
[1969Rie1] Rieger, W., Parth, E. Ternary Alkali-Earth Metal and Rare-Earth Metal Silicides and
Germanides with AlB2 Structure (in German), Monatsh. Chem., 100, 439-443 (1969)
[1969Rie2] Rieger, W., Parthe, E., Ternary Alkaline-Earth Metal and Rare-Earth Metal Silicides and
Germanides with ThCr2Si2 Structure (in German), Monatsh. Chem., 100, 444-454 (1969)
[1985Rau] Rauchschwalbe, U., Gottwich, U., Alheim, U., Mayer, H.M., Steglich, F., Investigation of
New Lanthanum-, Cerium- and Uranium-Based Ternary Intermetallics, J. Less-Common
Met., 111(1-2), 265-275 (1985) (Crys. Structure, Experimental, 31)
[1988Kon1] Konyk, M.B., Salamakha, P.S., Bodak, O.I., Pecharskii, V.K., Crystal Structure of
Ce2CuGe6, Sov. Phys.-Crystallogr., 33(4), 494-495 (1988), translated from
Kristallografiya, 33(4), 838-840 (1988) (Crys. Structure, Experimental, 4)
[1988Kon2] Konyk, M.B, Crystal Structure of Cerium-Copper-Germanium (Ce2Cu3Ge3), Visn. Lviv
Univ. Ser. Khim., 29, 25-28 (1988) (Crys. Structure, Experimental, 1)
[1989Kno] Knopp, G., Loidl, A., Knorr, K., Pawlak, L., Ducsmal, M., Caspary, R., Gottwick, U.,
Spille, H., Steglich, F., Murani, A.P., Magnetic Order in a Kondo Lattice: A Neutron
Scattering Study of CeCu2Ge2, Z. Phys. B, 77B, 95-104 (1989) (Magn. Prop.,
Experimental, 30)
[1989Loi] Loidl, A., Knopp, G., Spille, H., Steglich, F., Murani, A.P., Spin Relaxation Dynamics in
Heavy-Fermion Systems, Physica B (Amsterdam), 156-157, 794-797 (1989) (Crys.
Structure, Magn. Prop., Experimental, 15)
Landolt-Brnstein
New Series IV/11C2
MSIT
80 CeCuGe
[1990Ste] Steglich, F., Geibel, C., Horn, S., Ahlheim, U., Lang, M., Sparn, G., Loidl, A., Krimmel, A.,
Assmus, W., Magnetic Phase Diagrams in Heavy-Fermion Compounds, J. Magn. Magn.
Mater., 90-91, 383-388 (1990) (Magn. Prop., Experimental, 17)
[1990Fra] Francois, M., Venturini, G., Malaman, B., Roques, B., New Isotypes of CeNiSi2 in the
Systems R-M-X (R=La, Lu, M=Metals of the Groups 7 to 11) I: Compositions and Structure
Parameters, J. Less-Common Met., 160(2), 197-213 (1990) (Crys. Structure, Review, 15)
[1991Yan] Yang, F., Kuang, J.P., Li J., Bruek, E., Nakotte, H., de Boer, F.R., Wu, X., Li, Z., Wang, Y.,
Magnetic Properties of CeCuX Compounds, J. Appl. Phys., 69(8), Part II A, 4705-4707
(1991) (Crys. Structure, Experimental, Magn. Prop., 4)
[1992Das] Das, I., Sampathkumaran, E.V., Magnetic-Behavior of the Interstitial Alloys of the Type,
CeMXGe2 (M = Fe, Co, Ni and Cu), J. Solid. State. Com., 83(10), 765-770 (1992) (Crys.
Structure, Magn. Prop., Experimental)
[1993Ian] Iandelli, A., The Structure of Ternary Phases of Rare Earths with RCuGe Composition,
J. Alloys Compd., 198, 141-142 (1993) (Crys. Structure, Experimental, 3)
[1995Sol] Sologub, O., Hiebl, K., Rogl, P., Bodak, O., Formation, Crystal Chemistry and Magnetism
of Compounds RE2TGe6, RE=Rare Earth, T=Pd, Pt, Cu, Ag, and Au, J. Alloys Compd.,
227, 37-39 (1995) (Crys. Structure, Magn. Prop., Experimental, 2)
[1996Sal] Salamakha, P.S., Konyk, M.B, Dzyanyi, R., Sologub, O.L., Bodak, O.I, Systematics of
Rare-Earth-Copper-Gernanium Systems, Polish J. Chem., 70, 270-274 (1996) (Phase
Diagram, Phase Relations, Crys. Structure, Experimental, 16)
[1997Kri] Krimmel, A., Loidl, A., Schober, H., Canfield, P.C., Single-Crystal Neutron Diffraction
Studies on CeCu2Ge2 and CeCu1.9Ni0.1Ge2, Phys. Rev. B, 55(10), 6416-6420 (1997)
(Crys. Structure, Experimental, Magn. Prop., 23)
[1997Mor] Morozkin, A.V., Seropegin, Yu.D., Gribanov, A.V., Barakatova, J.M., Analysis of the
Melting Temperatures of RT2 Compounds (MgCu2 structure) (R=Rare Earth, T=Mn, Fe,
Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) and RT2X2 Compounds (R=La, Ce, Sm, Er; T=Mn, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Pt; X=Si, Ge), J. Alloys Compd., 256, 175-191 (1997) (Crys. Structure,
Thermodyn., Experimental, 74)
[1997Was] Wassilew-Reul, C., Kunz, M., Hanfland, M., Hausermann, D., Geibel, C., Steglich, F., The
Crystal Structure of CeCu2Ge2 under Pressure, Phys. B, 230-232, 310-312 (1997) (Crys.
[1998Kob] Kobayashi, T.C., Miyazu, T., Takeshita, N., Shimizu, K., Amaya, K., Kitaoka, Y., Onuki,
Y., Ehhancement of Superconducting Transition Temperature in CeCu2Ge2 under High
Pressures, J. Phys. Soc. Jpn., 67(3), 996-999 (1998) (Crys. Structure, Electr. Prop.,
Experimental, 11)
[1998Var] Vargoz, E., Jaccard, D., Superconducting and Normal Properties of CeCu2Ge2 at High
Pressure, J. Magn. Magn. Mater., 177-181, 294-295 (1998) (Electr. Prop.,
Experimental, 8)
[2000Tie] Tien, C., Feng, C.H., Wur, C.S., Lu, J.J., Ce2CuGe3: A Nonmagnetic Atom-Disorder Spin
Glass, Phys. Rev. B, 61(18), 12151-12158 (2000) (Electr. Prop., Magn. Prop., Phys. Prop.,
[2000Kon] Konyk, M.B., Romaka, L.P., Gorelenko, Yu.K., Bodak, O.I., Magnetic and Electrical
Properties of R2CuGe6 Compounds (R = Y, Ce, Nd, Gd, Tb, Dy, Ho, Er, Yb), J. Alloys
Compd., 311, 120-123 (2000) (Electr. Prop., Magn. Prop., Experimental, 3)
[2001Raw] Rawat, R., Das, I., Magnetic Transitions in CeCu0.86Ge2 and PrCu0.76Ge2 as Studied by
Magnetocaloric Effect, Phys. Rev. B: Condens. Matter, 64(5), 052407_1-052407_4 (2001)
(Electr. Prop., Magn. Prop., Phys. Prop., Thermodyn., Experimental, 9)
[2002Fer] Ferro, R., Bochvar, N., Sneftel, E., Ding, J.-J., Cu-Ge (Copper-Germanium), MSIT
Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials
Science International Services GmbH, Stuttgart; Document ID: 20.22339.1.20, (2002)
New Series IV/11C2
CeCuGe 81
[2002Gil] Gil, A., Penc, B., Gondek, L., Szytula, A., Hernandez-Velasco, J., Crystal and Magnetic
Structure of CeCu0.86Ge2, J. Alloys Compd., 346(1-2), 43-46 (2002) (Crys. Structure,
Magn. Prop., Experimental, 14)
[2002Nak] Nakamoto, G., Hagiuda, T., Kurisu, M., Formation on AlB2- and ThSi2-Type Structures in
Ce(CuxGey)2 System, Physica B, 312-313, 277-279 (2002) (Crys. Structure,
Experimental, 9)
[2002Per] Perrot, P., Ferro, R., Ce-Cu (Cerium-Copper), MSIT Binary Evaluation Program, in MSIT
Assessment, 25)
[2002Ria] Riani, P., Mazzone, D., Zanicchi, R., Marazza, R., Ferro, R., Ternary Rare Earth
Germanium Systems with Cu and Ag - a Review and a Contribution to Their Assessment,
J. Phase Equilib., 23, 7-28 (2002) (Crys. Structure, Phase Relations, Review, 233)
[2002Zah] Zaharko, O., Keller, L., Ritter, C., Magnetic Ordering in Ce3Cu4Sn4 and Ce3Cu4Ge4,
J. Magn. Magn. Mater., 253, 130-139 (2002) (Crys. Structure, Magn. Prop.,
Experimental, 11)
[2004Che] Chevalier, B., Pasturel, M., Bobet, J.-L., Weil, F., Decourt, R., Etourneau, J., The New
Hydrides CeNiGeH1.6 and CeCuGeH1.0 Crystallizing in the Derivative Hexagonal
ZrBeSi-Tyte Structure, J. Solid State Chem., 177(3), 752-759 (2004) (Crys. Structure,
Table 1: Investigations of the Ce-Cu-Ge Phase Relations, Structures and Thermodynamics

[1965Gla] X-ray diffraction Annealing at 800C/ Ce(Cu,Ge)2/Crystal
structure
[1969Rie1] X-ray powder diffraction As-cast samples after arc melting at room
temperature/CeCuGe and
CeCu0.67Ge1.33/Crystal structure
[1969Rie2] X-ray powder diffraction Annealing at 900C for 100 h
/CeCu2Ge2/Crystal structure
[1985Rau] X-ray diffraction As-cast samples after arc melting
/CeCu2Ge2/Crystal structure
[1988Kon1] X-ray powder diffraction / DRON Annealing at 600C for 720 h/
3.0 / HZG-4a Ce2CuGe6/Crystal structure
[1988Kon2] X-ray powder diffraction / DRON Annealing at 600C / Ce2Cu3Ge3/Crystal
3.0 / HZG-4a structure
[1989Kno] X-ray powder diffraction, neutron As-cast samples after arc melting at room
powder diffraction / multidetector temperature / CeCu2Ge2/Crystal structure
diffractometer
[1990Fra] X-ray powder diffraction, electron Homogenizing at 900C/CeCu0.86Ge2/Lattice
microprobe parameters
[1991Yan] X-ray powder diffraction Annealing at 800C for 1 week
/CeCuGe/Crystal structure
[1993Ian] X-ray diffraction Annealing at 750C for 7 to 10 days
/CeCuGe/Crystal structure
Landolt-Brnstein
New Series IV/11C2
MSIT
82 CeCuGe

[1995Sol] Guinier-Huber X-ray powder Annealing at 600C for 150 h and quenching/
diffraction Ce2CuGe6/Crystal structure
[1996Sal] X-ray powder diffraction / Annealing at 600C and 400C for 2 weeks and
DRON-3.0, HZG-4a quenching / Isothermal sections
[1997Kri] neutron powder diffraction, At room temperature and between 1.5 and 300 K
Czochralsky technique, microprobe /CeCu2Ge2/Lattice parameter and magnetic
analysis, X-ray diffraction / structure
triple-axis spectrometers IN3 at the
high-flux reactor, E7 located at the
BERII reactor
[1997Mor] X-ray diffraction / DRON-3.0, high CeCu2Ge2/Melting point
temperature
differential thermal analysis /
VDTA-8M2
[1997Was] X-ray powder diffraction / ID30, ID9, At pressures up to 15 GPa/CeCu2Ge2/Lattice
Fluorescence method parameters
[2000Tie] X-ray diffraction After melting at room temperature /
Ce2CuGe3/Crystal structure
[2001Raw] X-ray diffraction Homogenizing at 900C for 5 days /
CeCu0.86Ge2/Crystal structure
[2002Nak] X-ray diffraction Heat treatment at 800C for 7days/ Ce(CuxGey)2
x = 0.15 to 0.3, x + y = 1; 0.95; 0.90/ Crystal
structure
[2002Zah] X-ray diffraction, neutron powder Annealing at 800C for 2 weeks and quenching /
diffraction / DMC diffractometer at Ce3Cu4Ge4/Crystal structure
SINQ
[2002Gil] X-ray diffraction, neutron powder Homogenizing at 900C for 6 days /
diffraction / E6 diffractometer CeCu0.86Ge2/Lattice parameters at room and
low temperatures
[2004Che] X-ray powder diffraction / Philips Annealing at 700C for 1 month /
1050-diffractometer, automated CeCuGe/Crystal structure
Sieverts-type apparatus (HERA),
electron microscopy experiments
(JEOL 2000FX)
New Series IV/11C2
CeCuGe 83

[C] Prototype
(Cu) cF4 dissolves up to 12 at.% Ge at 824C
< 1084.62 Fm3m [2002Fer]
Cu and 0.1 at.% Ce at 876C [2002Per]
a = 361.46 at 25C [Mas2]
( Ce) cI2 dissolves up to 0.55 at.% Cu at 708C
798 - 726 Im3m [2002Per]
W a = 412 [2002Per]
(Ce) cF4 dissolves up to 0.37 at.% Cu at 708C
726 - 61 Fm3m [2002Per]
Cu a = 510.10 [2002Per]
(Ce) hP4 a = 308.10 at 24C [2002Per]
61 - (177) P63/mmn c = 1185.7
La
(Ce) cF4 a = 485 at 196C [2002Per]
< 177 Fm3m
Cu
(Ge) cF8 a = 565.74 at 25C [Mas2]
< 938.3 Fd3m
C (diamond)
CeCu oP8 a = 737.0 [2002Per]
< 516 Pnma b = 462.3
FeB c = 564.8
CeCu2 oI12 a = 442.9 [2002Per]
< 817 Imma b = 706.1
KHg2 c = 747.4
CeCu4 oP20 a = 458 [2002Per]
< 796 Pnnm b = 810
CeCu4 c = 935
CeCu5 hP6 a = 514.8 [2002Per]
< 798 P6/mmm c = 410.8
CaCu5
CeCu6 oP28 a = 810.88 at 22C [2002Per]
938 - (43) Pnma b = 510.04
CeCu6 c = 1016.21
a = 810.09 at 23C [2002Per]

b = 509.78
c = 1015.48
Landolt-Brnstein
New Series IV/11C2
MSIT
84 CeCuGe

[C] Prototype
CeCu6 mP28 a = 509.5 at 73C [2002Per]
< 43 P21/c b = 1014.66
LaCu6 c = 809.31
= 90.485
a = 508.92 at 173C [2002Per]

b = 1013.26
c = 807.89
= 91.148
a = 508.41 at 263C [2002Per]

b = 1012.79
c = 807.31
= 91.442
Cu3Ge hP8 a = 417 [V-C2]
< 790 P63/mmc c = 696 [Mas2]
AsNa3
J, ~Cu3Ge(h2) hP8 a = 416.9 at 76 at.% Cu [2002Fer]
747 - 549.5 P63/mmc c = 749.9
AsNa3
J2, ~Cu3Ge(h1) cF16 a = 590.6 at 71.4 at.% Cu
698 - 614 Fm3m (Cu5Ge2) [2002Fer]
BiF3
J1, ~Cu3Ge(r) oP8 74.9 to 76.9 at.% Cu
< 636 Pmmn a = 528 [2002Fer]
Cu3Ti b = 422
c = 454
Cu5Ge hP2 a = 261.2 [V-C2]
P63/mmc c = 423.1
Mg
Ce5Ge3 hP16 [Mas2]
< 1500 P63/mmc a = 890 annealing at 600C [V-C2]
Mn5Si3 c = 663
a = 884 after melting [V-C2]

c = 672
a = 885.9 annealing at 1000C [V-C2]

c = 662.8
Ce4Ge3 cI28 - [Mas2]
< 1293 I43d
Th3P4
New Series IV/11C2
CeCuGe 85

[C] Prototype
Ce5Ge4 oP36 [Mas2]
< 1345 Pnma a = 796 [V-C2]
Sm5Ge4 b = 1521
c = 804
CeGe oP8 [Mas2]
< 1433 Pnma a = 835.4 0.5 [V-C2]
FeB b = 408.2 0.3
c = 603.3 0.3
CeGe2x o* 61.1 to 62.12 [Mas2]
< 560 Imma a = 436 0.1 [V-C2]
CdSi2 b = 426 0.1
c = 1407 0.1
a = 428.2 [V-C2]
b = 419.9
c = 1408.1
CeGe2x tI12 61.1 to 62.12 [Mas2]
1513 - 490 I41/amd a = 421.0 0.2 [V-C2]
ThSi2 c = 1418.2 0.5
a = 426 [V-C2]
c = 1422
* -1, CeCu2Ge2 tI10 a = 417 after melting at room temperature
I4/mmm c = 1021 [1989Kno]
ThCr2Si2
or a = 418.6 [1997Kri]
CeGa2Al2 c = 1027.8
a = 417.2 after annealing at 600C and quenching

c = 1021.2 [1996Sal]
* -2, Ce2CuGe6 oC18 a = 421.52 0.01 after annealing at 600C and quenching
Cmm2 b = 407.56 0.02 [1988Kon1,1996Sal]
Ce2CuGe6 c = 2154.08 0.07
a = 421.16 0.05 after annealing at 600C and quenching

b = 407.25 0.05 [1995Sol]
c = 2158.4 0.4
Landolt-Brnstein
New Series IV/11C2
MSIT
86 CeCuGe

[C] Prototype
* -3, CeCuxGe2 oC16 0.86 x <1 [1990Fra]
Cmcm
CeNiSi2 a = 429.9 0.2 at x = 1, after annealing at 600C and
b = 1732.2 0.6 quenching [1996Sal]
c = 416.4 0.1
a = 427.6 0.4 at x = 0.86, after homogenization at

b = 1729 1 900C [1990Fra]
c = 4145 4
a = 428.67 0.07 at x = 0.86, after homogenization at

b = 1430.20 0.14 900C [2002Gil]
c = 415.17 0.03
a = 425.90 0.11 at x = 0.86 and 1.5 K [2002Gil]

b = 1720.89 0.52
c = 412.58 0.10
a = 426.09 0.11 at x = 0.86 and 5 K [2002Gil]

b = 1721.90 0.50
c = 412.76 0.10
a = 426.33 0.13 at x = 0.86 and 20 K [2002Gil]

b = 1723.05 0.58
c = 412.84 0.12
* -4, Ce2Cu3Ge3 oC16 a = 416.8 after annealing at 600C and quenching
Cm2m b = 1740.9 0.2 [1988Kon1]
Ce2Cu3Ge3 c = 421.1

b = 1740.9 0.2 [1996Sal]
c = 421.08 0.05
New Series IV/11C2
CeCuGe 87

[C] Prototype
* -5, CeCuGe hP3 a = 429.6 [1965Gla]
P6mmm c = 398.8
AlB2
a = 429.6 for as-cast sample [1969Rie2]
c = 398.8
a = 430.8 0.2 after annealing at 750 C [1993Ian]

c = 396.6 0.2

c = 396.7 0.1 [1996Sal]
or
hP6 a = 431.1 after annealing at 800C [1991Yan]

P63/mmc c = 793.3
ZrBeSi
a = 430.2 0.1 annealing at 700C [2004Che]
c = 791.9 0.2
* -6 , hP3 annealing at 600C and quenching
CeCu0.6-0.8Ge1.4-1.2 P6mmm [1996Sal]
or AlB2 for CeCu0.67Ge1.33 after melting
[1969Rie]
Ce(CuxGey)2 a = 421.4 0.2 to at 0.25 x 0.275 and
418.8 0.1 0.675 y 0.70 after annealing at
c = 420.6 0.3 to 800C [2002Nak]
426.4 0.2
a = 419.7 at x = 0.275 and y = 0.675 after

c = 424.5 annealing at 800C [2002Nak]
a = 419.1 at x = 0.25 and y = 0.70 after annealing

c = 423.4
a = 418.3 at 800C [2002Nak]

c = 424.5
* -7 , - - annealing at 600C and quenching
Ce0.60Cu0.25Ge0.15 [1996Sal]
* -8 , - - annealing at 600C and quenching
Ce0.60Cu0.05Ge0.35 [1996Sal]
Landolt-Brnstein
New Series IV/11C2
MSIT
88 CeCuGe

[C] Prototype
* -9, Ce(CuxGey)2 tI12 at 0.175 x 0.20 and
I41/amd 0.75 y 0.775 after annealing at
ThSi2 800C [2002Nak]
a = 424.6 at x = 0.20 and y = 0.75 after annealing

c = 1449.4 800C [2002Nak]
a = 422.1 at x = 0.175 and y = 0.775 after

c = 1438.1 annealing 800C [2002Nak]
* -10, Ce2CuGe3 o* a = 726.2 as-cast samples at room temperature /
b = 459.1 [2000Tie]
c = 423.1
* -11, Ce3Cu4Ge4 oI22 a = 1489.4 0.4 annealing at 800C and quenching
Immm b = 692.3 0.2 [2002Zah]
Gd3Cu4Ge4 c = 453.4 0.1
CeCuGeH1.0(1) hP6 a = 424.4 0.1 [2004Che]
P63/mmc c = 831.1 0.2
ZrBeSi
Table 3: Investigations of the Ce-Cu-Ge Materials Properties

[1985Rau] standard techniques Electrical resistivity, thermoelectric power,
magnetic susceptibility, specific heat for
CeCu2Ge2
[1989Kno] time-of-flight spectrometers IN4 (located Quasielastic line widths in CeCu2Ge2
on a thermal neutron source),
[1989Loi] time-of-flight spectrometers IN4 (located Quasielastic line in CeCu2Ge2
on a thermal neutron source), IN6 (located
on a cold source) / high flux reactor at the
Institute Laue-Langevin (Grenoble)
[1991Yan] standard techniques Magnetic susceptibility, magnetization,
specific heat of CeCuGe
[1995Sol] SQUID magnetometer Magnetic susceptibility of Ce2CuGe6
[1998Kob] Fluorescence method, four probes AC Phase diagram in CeCu2Ge2 under high
method for measurement of resistivity pressure, resistivity at low temperature and
high pressure up to 21 GPa
[1998Var] Bridgman technique Pressure, CeCu2Ge2
[2000Kon] Faraday balance Magnetic susceptibility in the range 84 to
300 K, electrical resistivity in the range 78
to 300 K, differential thermopower for
Ce2CuGe6
New Series IV/11C2
CeCuGe 89

[2000Tie] SQUID magnetometer Magnetic properties of Ce2CuGe3
[2001Raw] four-probe method for the measurement of Resistivity of CeCu2Ge2
electrical resistivity, semiadiabatic heat heat capacity measurements
pulse method
[2002Zah] quantum design physical property DC susceptibility, specific heat of
measurement system (PPMS) Ce3Cu4Ge4
[2004Che] Superconducting Quantum Interference Magnetization measurements, electrical
Device magnetometer, dc four probe resistivity, thermoelectric power of
measurements, dynamic method CeCuGeH11.0(1)
Ge Data / Grid: at.%

Fig. 1: Ce-Cu-Ge. (Ge) Axes: at.%
600C (below 45 at.%
Ce) and 400C (above
45 at.% Ce) 20
80
CeGe2-x 2
40
60
CeGe
Ce Ge
Ce4Ge3 5 4 6 3
60 1 40
Ce5Ge3
4
Ce3Ge 8 5
1,~Cu3Ge
80
20
,Cu5Ge
7
(Cu)
20 40 60 CeCu CeCu4 80CeCu CeCu

Ce (Ce)
CeCu 2 5 6 Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
90 CeCuGe
Ce 30.00
Cu 10.00
Ge 60.00 Data / Grid: at.%
Fig. 2: Ce-Cu-Ge. Axes: at.%
Partial isothermal
section at 800C
Filled circles show 6 phase
Half-filled circles show 9 phase
Square points show multiphase alloys
40
50
Ce 50.00 20 Ce 30.00
Cu 10.00 Cu 30.00
Ge 40.00 Ge 40.00
5.0
Fig. 3: Ce-Cu-Ge.
Phase diagram of
CeCu2Ge3 under
high pressure.
4.0
M - magnetic phase, 30 K
SC - superconducting
phase, FL - the
temperature region
Temperature, K
where the p(T) 3.0

follows
the AT2-law
FL
2.0
M
1.0
SC
0
0 5.0 10.0 15.0 20.0
Pressure,GPa
New Series IV/11C2
CeCuGe 91
Fig. 4: Ce-Cu-Ge.
The pressure CeCu2Ge2
dependence of the
temperatures of
magnetic ordering 100.0
T2max
Temperature, K
10.0
T1max
TM TC
magnetic
phase
1.0
superconducting
phase
0
0 5.0 10.0 15.0 20.0 25.0
Pressure,GPa
Landolt-Brnstein
New Series IV/11C2
MSIT
92 CeCuIn
Cerium Copper Indium

Oksana BodakA, Nataliya Bochvar
Introduction
The Ce-Cu-In ternary system was investigated and isothermal sections were constructed at 600C in the
concentration range from 0 to 33.3 at.% Ce and at 400C in the concentration range from 33.3 to 100 at.%
Ce [1991Bar]. Crystal structures and lattice parameters of the ternary compounds of the Ce-Cu-In system
were determined by [1976Dwi, 1984Kal, 1985Fel, 1988Bar, 1988Kal, 1988Tak1, 1989Sys, 1990Bar,
1990Kal, 1991Bar, 1996Kac, 1998Kam, 1999Tak, 2005Bob]. Almost all investigators prepared alloys
using pure compacted metals, arc-melted under argon or helium. After melting, the samples were sealed in
evacuated silica capsules and annealed at different temperatures for prolonged times followed by quenching
into water or slow cooling in the furnace. [2005Bob] used another method of alloys preparation. Mixtures
of the elements were loaded into evacuated alumina crucibles, which were heated at a temperature of
1100C for 4 h, followed by slow cooling (3 K#h1) to 800C. At this temperature, the molten flux (Cu-In
eutectic) was removed by centrifuge. The recovered product consisted of relatively large and well defined
crystals which were later identified as a ternary compound.
Information concerning investigations of phase relations, structures and thermodynamics in the Ce-Cu-In
system is summarized in Table 1.
[1998Kal, 2005Kal] reviewed literature data and the results of their own experimental investigations of the
R-Cu-In systems and presented the isothermal sections of the Ce-Cu-In system and crystal structures of
ternary Ce-Cu-In compounds. [2003Luk] has reviewed the crystal chemistry, chemical bonding and
physical properties of the tetragonal U3Si2 type compounds, in particular, Ce2Cu2In. A series of works were
devoted to the investigation of the magnetic and electrical characteristics of the different ternary
compounds. This information is summarized in Table 3.
Binary Systems
The Ce-In binary system is accepted from [Mas2]. Cu-In is from [2000Goe], based mainly on [1972Jai].
The Ce-Cu system is accepted from [2002Per].
Solid Phases
Crystallographic data of the binary and ternary compounds that are formed in the ternary Ce-Cu-In system
are shown in Table 2. There are ten ternary compounds [1991Bar, 1998Kal].
[1990Bar] discovered the compound -1 {Ce1x(Cu0.68In0.32)12Cu1y at x = 0.22; y = 0.36} and estimated its
crystal structure in a sample annealed at temperature 600C and subsequently quenched. [1989Sys]
determined the crystal structure of the compound -2 (CeCu5.1In6.9) in as-cast samples. [1991Bar] found the
compounds -3 (CeCu9In2) and -4 (~CeCu4.2In4.8) in the isothermal section for 600C. [1991Bar]
determined the crystal structure of -3 and found that the compound has a homogeneity range from ~16 to
25 at.% In along 8.3 at.% Ce section. The crystallographic characteristics of the -4 compound have not been
determined. [1988Kal] investigated the crystal structure of the compound -5 (CeCu4.38In1.62) and estimated
that this compound crystallizes with the space group Pnnm and belongs to a new structure type derived from
the parent CeCu6 compound through the doubling the a axis of the unit cell. On the other hand, [2005Bob]
carried out detailed structural studies of this compound and showed that it belongs to the orthorhombic
CeCu6 structure type (space group Pnma). [2005Bob] considered that such differences could arise from the
differences in samples production - arc-melting and subsequent annealing [1998Kal] or growth in a Cu-In
flux [2005Bob]. The CeCu6 structural type of the -5 compound was expected by [1995Kas, 1998Kam]. The
-5 compound has a homogeneity range from 13 to 26 at.% In [1991Bar] or from 8 to 29 at.% [1995Kas]
along the 14.3 at.% Ce section. Further investigations are required in order to obtain more exact information
about the crystal structure and the homogeneity range of this compound. The crystal structure of the -6
New Series IV/11C2
CeCuIn 93
(CeCu2In) compound was reported by [1985Fel]. The lattice parameters of -6 were determined by [1985Fel,
1987Lah, 1988Tak1]. The crystal structure of the -7 (CeCuIn) compound was estimated by [1976Dwi] and
the lattice parameters were given by [1991Bar]. The crystal structure of the -8 (CeCu0.5In1.5) was
determined by [1988Bar]. According to [1991Bar], this compound has a homogeneity range from 40 to 55
at.% In along the 33 at.% Ce section. The crystal structures of the -9 (Ce2Cu5.1In6.9) and -10 (CeCu2xIn2y)
compounds were described by [1990Kal] and [1990Bar], respectively. [1990Bar] showed that the
compound -10 is found only after casting but not after subsequent annealing at 600C.
Isothermal Sections
[1991Bar] constructed isothermal sections of the Ce-Cu-In system at 600C in the concentration range 0 to
33.3 at.% Ce and at 400C in the concentration range 33.3 to 100 at.% Ce, on the basis of experimental data.
Information of these sections is also reported in [1998Kal] and [2005Kal]. The isothermal sections of
Ce-Cu-In system shown in Fig. 1 were constructed on the basis of data from [1991Bar] with the addition of
the CeCu4 compound taken from the accepted Ce-Cu binary system [2002Per].
Thermodynamics
Specific heat investigation of the CeCu2In compound (Heusler phase) was reported in [1987Lah, 1988Tak1,
1988Tak2, 1992Sat, 1995Kas]. CeCu2In is a heavy fermion compound. It has a large specific heat
coefficient indicating a large effective mass. According to [1987Lah], no magnetic transition is visible for
CeCu2In, and the C/T variation only shows a broad maximum of 2 J#mol1#K1 near T = 2.5 K. According
to [1988Tak1], the low-temperature specific heat of CeCu2In has an enormous electronic contribution, with
C/T = 1.2 J#mol1#K2 below 1.2 K and shows a broad maximum at around 2.2 K. In [1992Sat], the magnetic
specific heat of the CeCu2In compound and its entropy changes were recorded. Anomalous behavior due to
a dense Kondo effect was observed. This indicates that CeCu2In undergoes an antiferromagnetic phase
transition at TN = 2.3 K. Similar results were obtained by [1988Tak2]: the low temperature specific heat
coefficient C/T shows a maximum at 0.9 K; the maximum value is 1.4 J#mol1#K2. [1995Kas] measured
specific heat vs T for the CeCu6xInx compound at x = 0.5, 1.0, 1.25, 1.5 and 1.75. The specific heat
measurements revealed that the samples with x up to 1.0 did not show any anomaly owing to magnetic
ordering within the temperature range investigated (from 1.7 to 15 K). The specific heat coefficient for
CeCu5In (x = 1.0) was 0.2 J#mol1#K2. However, C(T) curves for the samples with x above 1.0 suggested
the onset of magnetic order: TN is 2.2 K for x = 1.5 and ~1.5 K for x = 1.75.

Measurement of the magnetic and electrical properties of the CeCu2In compound, specifically the
temperature and pressure dependencies of magnetic susceptibility and electrical resistivity were made by
[1985Fel, 1987Lah, 1988Tak1, 1988Tak2, 1989Oom, 1992Oom, 1992Kag, 1996Kac, 2000Sio, 2002Mil].
Information regarding investigations of material properties is summarized in Table 3.
The magnetic behavior of the CeCu2In compound was studied by [1985Fel] over the temperature range
from 2 to 300 K. CeCu2In exhibited normal paramagnetic behavior and adhered closely to the Curie-Weiss
law of over the major portion of the measured temperatures.
[1987Lah] constructed magnetic isotherms for a CeCu2In single crystal along the {100} axis at T = 1.5, 4.2
and 8 K. The magnetization anisotropy was found to be extremely small. The reciprocal susceptibilities for
the CeCu2In were constructed by [1987Lah], also in the temperature range from 1.5 to 100 K. [1988Tak2]
reported that for CeCu2In, the ground state is antiferromagnetic. There exists disordering between the Ce
atoms and the In atoms in the Heusler structure. The order parameter is 0.8. CeCu2In undergoes an
antiferromagnetic phase transition at TN = 2.3 K [1988Tak1].
The thermal expansion coefficient, , of single crystalline CeCu2In has been measured between 4.2 and
300 K [1989Oom]. along the {110} direction is very large at temperatures below 100 K. There is a large
contribution from the 4f electron in CeCu2In.
Landolt-Brnstein
New Series IV/11C2
MSIT
94 CeCuIn
The effect of the magnetic field on the electrical resistivity of CeCu2In at pressures up to 2 GPa was
measured over the temperature range from 2 to 60 K [1992Oom]. The coherent temperature was found to
increase with pressure.
[1992Kag] reported the dependence of the lattice parameters of the CeCu2In compound as a function of
pressure at room temperature. The temperature dependence of electrical resistivity was also determined in
[1992Kag]. It was found that the maximum in the '(T) curve due to Kondo effect disappears at high
pressure.
The magnetic behavior of the Ce2Cu2In and Ce2CuIn3 compounds were shown in [1996Kac] and
[2000Sio], respectively. The magnetic susceptibility of Ce2CuIn3 was measured in [2000Sio]. It shows that
compound does not have any ordering temperature down to 4.2 K and remains paramagnetic. The Ce2Cu2In
compound was found to order antiferromagnetically below TN = 5.5 K [1996Kac]. The temperature
dependence of the electrical resistivity for this compound has a metallic character. [2002Mil] has shown
that hydrogenation weakens the magnetic exchange interactions in Ce2Cu2In, which turns from an
antiferromagnet with TN = 5.5 K, into a paramagnet.
Miscellaneous
[1997Ple] studied the effects of Al, Ga, Sn or Fe, Ni, Pd and Pt doping of the cubic CeCu2In compound. At
least 20% In or 10% Cu can be replaced by respective metalloid or transition metal atoms without changing
the crystal structure. The main influence of the substitutions on the physical properties of CeCu2In is to
change the Kondo temperature and crystalline electric field splitting. Using X-ray diffraction, [1999Tak]
detected residual short-range order in the CeCu2In compound. In spite of the long-range order of this
substance, diffuse scattering exhibiting short-range order was observed at room temperature. [2002Mil]
investigated the interaction of the Ce2Cu2In compound with hydrogen. The synthesis of the hydrides was
performed at a hydrogen pressure of 0.8 bar and temperature of 593 K. The formation of the Ce2Cu2InH1.5
hydride was estimated. It has the structure type Mo2FeB2 (space group P4/mbm) with lattice parameters a
= 780.50 0.20 pm and c = 410.40 0.11 pm.
References
[1941And] Andrews, K.W., Hume-Rothery, W., On the / Brass Type of Equilibrium, Proc. Roy.
Soc. A, 178, 464-473 (1941) (Crys. Structure, Experimental)
[1951Rey] Reynolds, J., Wiseman, W.A., Hume-Rothery, W., The Equilibrium Diagram of the
System Copper-Indium in the Region 25-35 at.% Indium, J. Inst. Met., 80, 637-640
(1951-1952) (Experimental, Crys. Structure, Phase Diagram, Phase Relations)
[1972Jai] Jain, K.C., Ellner, M., Schubert, K., On Existance of Phases near Cu64In36 Composition,
Z. Metallkd., 63(8), 456-461 (1972) (Crys. Structure, Phase Diagram, Experimental, 6)
[1976Dwi] Dwight, A.E., Rare Earth-Au(Cu)-X Compounds with the Fe2P-, CaIn2-, and
MgAgAs-Types, Proc. Rare-Earth Research Conference, Vail, Colorado, II.(1976),
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Experimental, 7)
[1980Vro] Vrolijk, J.W.G.A., Wolff, L.R., Crystallography of Aligned Cu-In Eutectoid, J. Cryst.
Growth, 48, 85-92 (1980) (Phase Diagram, Crys. Structure, Experimental)
[1984Kal] Kalychak, Ya.M., Dmytrakh, O.V., Bodak, O.I., Ogryzlo, M.M., The Crystal Structures of
LaCu2In and LaCu6.5In6.5 (in Russian), Dop. Akad. Nauk Ukr. RSR B, Geol., Khim. Biol.,
[1985Fel] Felner, I., Magnetic and Structural Characteristics of the RInCu2 Compounds inthe
Heusler L21 Structure, Solid State Commun., 56(4), 315-317 (1985) (Crys. Structure,
Experimental, Magn. Proper., 7)
[1987Lah] Lahiouel, R., Pierre, J., Siaud, E., Galera, R.M., Besnus, M.J., Kappler, J.P., Murani, A.P.,
Kondo Lattice and Heavy Fermions in Heusler Phases: CeInAg2xCux, Z. Phys. B, 67B,
185-191 (1987) (Crys. Structure, Magn. Prop., Experimental, 19)
New Series IV/11C2
CeCuIn 95
[1988Tak1] Takagi, S., Kimura, T., Sato, N., Satoh, T., Kasuya, T., Evidence for Magnetic Ordering in
the Heavy-Electron Compound CeCu2In, J. Phys. Soc. Jpn., 57(5), 1562-1565 (1988)
(Crys. Structure, Magn. Prop., Experimental, 15)
[1988Tak2] Takayanagi, S., Woods, S.B., Wada, N., Watanabe, T., Onuki, Y., Kobori, A., Komatsubara,
T., Imai, M., Asano, H., Magnetic and Transport Properties in the Cubic Heavy Fermion
System CeInCu2, J. Magn. Magn. Mater., 76-77, 281-282 (1988) (Crys. Structure, Magn.
[1988Bar] Baranyak, V.M., Dmytrakh, O.V., Kalychak, Ya.M., Zavalii, P.Yu., Ternary Intermetallic
Compounds with AlB2-Type Structure in La(Ce,Pr,Nd,Sm,Eu)-Ni(Cu)-In Systems, Izv.
Akad. Nauk SSSR, Neorg. Mater., 24(5), 739-740 (1988) (Crys. Structure, Experimental, 6)
[1988Kal] Kalychak, Ya.M., Baranyak V.M., Belskii, V.K., Dmytrakh, O.V., Crystal Structure of
CeCu4.38In1.62 Compound and Affinitive Compounds (in Russian), Dop. Akad. Nauk Ukr.
RSR B, Geol., Khim. Biol., (9), 40-44 (1988) (Crys. Structure, Experimental, 5)
[1989Sys] Sysa, L.V., Kalychak, Ya.M., Bakar, A., Baranyak, V.M., Crystal Structures of
TRCu5.1In6.9 (TR = Y, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb), Sov. Phys.
Crystallogr., 34(3), 443-444 (1989), translated from Kristallografiya, 34(3), 744-745
[1989Oom] Oomi, G., Okamoto, A., Onuki, Y., Komatsubara, T., Thermal Expansion Coefficient of a
New Heavy Fermion Substance, CeInCu2, J. Phys. Soc. Jpn., 58(7), 2235-2237 (1989)
(Magn. Prop., Experimental, 13)
[1990Bar] Baranyak, V.M., Kalychak, Ya.M., Zavalii, P.Yu., Belskii, V.K., Crystal Structure of
CeCu2xIn2y (x = y = 0.50) and Ce1x(Cu0.68In0.32)12Cu1y (x = 0.22; y = 0.36), Inorg.
Mater., 26(11), 1985-1987 (1990), translated from Izv. Akad. Nauk SSSR, Neorg. Mater.,
26(11), 2316-2318 (1990) (Crys. Structure, Experimental, 5)
[1990Kal] Kalychak, Ya.M., Zaremba, V.I., Baranyak, V.M., Zavalii, P.Yu., Bruskov, V.A., Sysa,
L.V., Dmytrakh, O.V., Crystal Structure of the Compounds R2Ni2In, R2Ni2-xIn, and
R2Cu2In (R = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu or Y, Inorg. Mater., 26(1),
74-76 (1990), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 26(1), 94-96 (1990)
[1991Kag] Kagayama, T., Oomi, G., Takahashi, H., Mori, N., Onuki, Y., Komatsubara, T., Valence
Transition of Heavy Fermion Compound CeInCu2 at High Pressure, Japan. Inst. Met.,
129-133 (1991) (Magn. Prop., Experimental, 4)
[1991Bar] Baranyak, V.M., Kalychak, Ya. M., The Ce-Cu-In System, Inorg. Mater., 27(6),
1038-1041 (1991), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 27(6), 1235-1238
(1991) (Crys. Structure, Phase Relations, Experimental, 15)
[1992Kag] Kagayama, T., Oomi, G., Takahashi, H., Mori, N., Onuki, Y., Komatsubara, T., Crossover
from Concentrated Kondo to Intermediate Valence State in Cerium-Indium-Copper
(CeInCu2), J. Magn. Magn. Mater., 108, 103-104 (1992) (Magn. Prop., Experimental, 13)
[1992Oom] Oomi, G., Kagayama, T., Onuki, Y., Komatsubara, T., Magnetostriction and
Magnetoresistance of the Heavy Fermion Compounds CeCu6 and CeInCu2, Physica B
(Amsterdam), B 177, 185-189 (1992) (Magn. Prop., Experimental, 16)
[1992Sat] Sato, K., Isikawa, Y., Mori, K., Magnetic Specific Heat of Light Rare Earth Heusler
Compounds RInCu2, (R = La, Ce, Pr, Nd and Sm), J. Magn. Magn. Mater., 104-107,
1435-1436 (1992) (Magn. Prop., Thermodyn., Experimental, 7)
[1994Sub] Subramanian, P.R., Cu-In (Copper-Indium), in Phase Diagrams of Binary Copper
Alloys, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E., (Eds.), ASM International,
Materials Park, OH, 218-229 (1994) (Crys. Structure, Phase Diagram, Thermodyn.,
Review, 50)
[1995Kas] Kasaya, M., Satoh, N., Miyazaki, T., Kumazaki, H., Appearance of a new Coherent Kondo
State by In Substitution for Cu in CeCu6, Physika B, 206-207, 314-316 (1995) (Crys.
Structure, Experimental, Electr. Proper., Magn. Prop., Thermodyn., 10)
Landolt-Brnstein
New Series IV/11C2
MSIT
96 CeCuIn
[1996Kac] Kaczorowski, D., Rogl, P., Hiebl, K., Magnetic Behavior in a Series of Cerium Ternary
Intermetallics Ce2T2In (T=Ni,Cu,Rh,Pd,Pt, and Au), Phys. Rev. B, 54(14), 9891-9902
[1997Ple] Plessis P.D.V., Tran V.H., Influence of Substitutions on the Physical Properties of
CeInCu2, J. Phys.: Condens. Matter, 9, 8527-8537 (1997) (Crys. Structure, Magn. Prop.,
Experimental, 31)
[1998Kal] Kalychak, Ya.M., Isothermal Cross Sections of Phase Diagrams and Crystal Structure of
the Compounds for REM-Cu-In Systems, Russ. Metall., (4), 138-148 (1998), translated
from Metally, (4), 110-118 (1998) (Crys. Structure, Phase Relations, Review,
Experimental, 32)
[1998Kam] Kamiyama, T., Oikawa, K., Izumi, F., Kosaka, M., Onodera, H., Yamaguchi, Y., Kasaya,
M., Kojima, K., TOF Neutron Powder Diffraction Studies on f-Electron Systems,
Physica B (Amsterdam), 241-243, 376-378 (1998) (Crys. Structure, Experimental, 6)
[1999Tak] Takahashi, I., Kagayama, A., Oomi, G., Onuki, Y., Komatsubara, T., Residual
Short-Range Order in the Heavy Fermion Compound CeInCu2, Acta Crystallogr., Sect. B:
Struct. Crystallogr. Crys. Chem., B55, 31-34 (1999) (Crys. Structure, Experimental, 8)
[2000Goe] Goedecke, T., Haalboom, T., Ernst, F., Phase Equilibria of Cu-In-Se. II. The
In-I2Se3-Cu2Se-Cu Subsystem, Z. Metallkd., 91(8), 635-650 (2000) (Experimental, Phase
Relations, 13)
[2000Sio] Siouris, I.M., Semitelou, I.P., Yakinthos, J.K., Susceptibility Measurements of R2CuIn3
Compounds (R = Ce,Pr,Nd,Tb,Dy,Ho,Er), J. Alloys Compd., 297, 26-29 (2000) (Crys.
[2002Mil] Miliyanchuk, Kh.Yu., Bulyk, I.I., Trostianchyn, A.M., Kolomiets, A.V., Galadzhun, Y.V.,
Kalychak, Y.M., Hydrides of R2Cu2In (R=Ce,Gd) Intermetallic Compounds, Abstract,
VII Int. Conf. Crys. Chem. Lviv., 140 (2002) (Crys. Structure, Magn. Prop., Experimental, 1)
Stuttgart; Document ID: 20.16303.1.20, (2003) (Phase Diagram, Assessment, 25)
[2003Luk] Lukachuk, M., Pttgen, R., Intermetallic Compounds with Ordered U3Si2 or Zr3Al2 Type
Structure - Crystal Chemistry, Chemical Bonding and Physical Properties, Z. Kristallogr.,
218, 767-787 (2003) (Crys. Structure, Electr. Prop., Magn. Prop., Review,
Thermodyn., 197)
[2005Kal] Kalychak, Ya.M., Zaremba, V.I., Pttgen, R., Lukachuk, M., Hoffmann, R., Rare
Earth-Transition Metal-Indides in Handbook on the Physics and Chemistry of Rare
Earths, 34, 1-133 (2005) (Crys. Structure, Phys. Prop., Phase Relations, Experimental,
Review, 402)
[2005Bob] Bobev, S., Bauer, E.D., CeCu5xIn1+x {x = 0.17 (1)} with the Orthorhombic CeCu6
Structure, Acta Crystallogr., E61, i89-i90 (2005) (Crys. Structure, Expermental, 8)
Table 1: Investigations of the Ce-Cu-In Phase Relations, Structures and Thermodynamics

Reference Method/Experimental Technique Temperature/Composition/Phase Studied
[1976Dwi] X-ray diffraction Annealing at 800C / CeCuIn/Crystal
Debye-Scherrer method structure and lattice parameter
[1984Kal] X-ray powder diffraction/ Annealing at 800C for 700 h / CeCu2In/
DRON-2.0 Lattice parameters
[1985Fel] X-ray powder diffraction As-cast samples / CeCu2In / Lattice
parameters
New Series IV/11C2
CeCuIn 97

[1987Lah] Specific-heat measurements 1.5-300 K / CeCu2In / Specific heat, lattice
Neutron scattering experiments/ parameters at room temperature
IN4 spectrometer
[1988Tak1] X-ray powder diffraction As-cast samples, 0.22-20 K / CeCu2In /
Specific-heat/adiabatic calorimeters and Specific heat, latter parameters at room
Cu NMR measurements/phase-coherent temperature
NMR spectrometer
[1988Tak2] X-ray powder diffraction As-cast samples / CeCu2In / Crystal
structure and lattice parameters
[1988Bar] X-ray single crystal and powder Annealing at 600C for 750 h /
diffraction/HZG-4A CeCu0.5In1.5 (single crystal) / Crystal
Laues method structure and lattice parameters
Weissenberg method
[1988Kal] X-ray single crystal diffraction/Syntex P1 Annealing at 600C / CeCu4.38In1.62
Laues method (single crystal) / Crystal structure and
Weissenberg method lattice parameters
[1989Sys] X-ray single crystal and powder Annealing at 600C /CeCu5.1In6.9 / Crystal
diffraction/DRON-3.0 structure and lattice parameters
Laues method
Weissenberg method
[1990Bar] X-ray single crystal diffraction/Syntex P1 Annealing at 1030C for 24 h /
Laues method CeCu2xIn2y (x = y = 0.50)
Weissenberg method (single crystal) / Crystal structure and
X-ray powder diffraction/ lattice parameters
DRON-3.0 Annealing at 600C for 750 h /
Ce1x(Cu0.68In0.32)12Cu1y
(x = 0.22; y = 0.36) /
Crystal structure and lattice parameters
[1990Kal] X-ray analysis Annealing at 600C / Ce2Cu2In / Lattice
parameters
[1991Bar] X-ray powder diffraction Annealing at 600C for 750 h and
Debye-Scherrer method/APOC quenching / Ce-Cu-In at 0 to 33.3 at.% Ce/
DRON-2.0, DRON-3.0 Annealing to 400C for 1500 h/ Ce-Cu-In
Microstructural analysis/Neophot-30 at 33.3 to 100 at.% Ce/ Isothermal sections
at 600 and 400C, crystal structure and
lattice parameters
[1992Kag] X-ray diffraction Single crystal (Czochralski method)/
CeCu2In/ Lattice parameters at room
temperature and pressure up to 15 GPa
[1992Sat] Specific-heat measurements Single crystal (Czochralski method)/
Adiabatic standard method CeCu2In/ Specific heat
[1995Kas] X-ray analysis Single crystal and polycrystalline samples/
CeCu6xInx (x =0.5, 1.0, 1.25, 1.38, 1.5,
1.75, 2.0), annealing at 530C for 5 days /
Landolt-Brnstein
New Series IV/11C2
MSIT
98 CeCuIn

[1996Kac] X-ray single crystal/STOE Nicolet Annealing at 650C for 2 weeks /
four-circle diffractometer and powder Ce2Cu2In / Lattice parameters
diffraction/Guinier camera, Siemens
D5000 diffractometer
[1997Ple] X-ray powder diffraction As-cast samples, at room temperature /
CeCu2In / Lattice parameters
[1998Kam] Neutron powder diffraction/TOF versatile Annealing at 530C for 5 days / CeCu5In/
diffractometer Crystal structure and lattice parameters
[1999Tak] X-ray single crystal diffraction/four-circle Single crystal (Czochralski method) /
diffractometer (Photon Factory at the CeCu2In /
National Laboratory for High Energy Crystal structure
Physics) Czochralski crystal-pulling
method
[2000Sio] X-ray analysis Annealing at 480C for 30 days /
Ce2CuIn3 / Lattice parameters
[2002Mil] X-ray powder diffraction/Siemens D500, Annealing at 600C / Ce2Cu2In / Lattice
DRON-4.0, HZG-4a parameters
[2005Bob] X-ray analysis Cooling with 800C/ CeCu5xIn1+x
(0 x 0.75)/

[C] Prototype
(Cu) cF4 dissolves up to ~11 at.% In at 574C
< 1084.62 Fm3m [Mas2]
Cu a = 361.46 at 25C [Mas2]
a = 367.27 for 5.9 at.% In [V-C2]
a = 370.665 for 10 at.% In [V-C2]

( Ce) cI2 dissolves up to 0.55 at.% Cu at 708C
798 - 726 Fm3m [2002Per]
W and ~10 at.% In at 730C [Mas2]
a = 412 [Mas2]
(Ce) cF4 dissolves up to 0.4 at.% Cu at 708C
726 - 61 Fm3m [2002Per]
Cu and 4 at.% In at 650C [Mas2]
a = 510.10 [Mas2]
(Ce) hP4 a = 308.10 at 24C [2002Per]
61 - (177) P63/mm c = 1185.7
La
New Series IV/11C2
CeCuIn 99

[C] Prototype
(Ce) cF4 a = 485 at 196C
< 177 Fm3m [2002Per]
Cu
(In) tI2 a = 324.5 0.6 [Mas2], [V-C2]
< 156.634 I4/mmm c = 494.2 0.6
In
CeCu oP8 a = 737.0 [2002Per]
< 516 Pnma b = 462.3
FeB c = 564.8
CeCu2 oI12 a = 442.9 [2002Per]
< 817 Imma b = 706.1
KHg2 c = 747.4
CeCu4 oP20 a = 458 [2002Per]
< 796 Pnnm b = 810
CeCu4 c = 935
CeCu5 hP6 a = 514.8 [2002Per]
< 798 P6/mmm c = 410.8
CaCu5
CeCu6 oP28 a = 810.88 at 22C [2002Per]
938 - (43) Pnma b = 510.04
CeCu6 c = 1016.21
a = 810.09 at 23C [2002Per]

b = 509.78
c = 1015.48
CeCu6 mP28 a = 509.5 at 73C [2002Per]
< 43 P21/c b = 1014.66
LaCu6 c = 809.31
= 90.485
a = 508.92 at 173C [2002Per]

b = 1013.26
c = 807.89
= 91.148
a = 508.41 at 263C [2002Per]

b = 1012.79
c = 807.31
= 91.442
Ce3In cP4 24 to ~25 at.% In [Mas2]
< 910 Pm3m a = 506.1 [V-C2]
AuCu3
Ce2In hP6 32 to 33.3 at.% In [Mas2]
< 960 P63/mm a = 555.7 [V-C2]
InNi2 c = 690.8
Landolt-Brnstein
New Series IV/11C2
MSIT
100 CeCuIn

[C] Prototype
Ce1+xIn - - 43 to 47 at.% In [Mas2]
< 1140
CeIn1+y - - [Mas2]
~ 1070 - ~ 890
Ce3In5 oC32 60 to 63 at.% In [Mas2]
< 1170 Cmcm a = 1025 [V-C2]
Pd5Pu3 b = 831
c = 1054
CeIn2 oI12 [Mas2]
< 1130 Imma a = 474.0 [V-C2]
CeCu2 b = 761.0
c = 901.8
CeIn3 cP4 [Mas2]
< 1180 Pm3m a = 468.93 0.02 [V-C2]
AuCu3
, Cu4In cI2 a = 301.40 20.50 at.% In at 625C [1994Sub]
710 - 574 Im3m a = 304.61 18.64 at.% In at 672C [1941And]
W
, Cu7In3 aP40 a = 107.1 30.0 at.% In [1980Vro]
< 631 P1 b = 913.1
Cu7In3 c = 672.6
= 90.2
= 90.4
= 106.82
a = 1000 29.6 at.% In [1994Sub]
b = 910
c = 672
= 89.9
= 82.6
= 106.9
, Cu9In4 cP52 a = 925.03 29.6 at.% In at 650C [1951Rey]
684 - 631 P43m
InMn3 or Al4Cu9
1, Cu2In hP6 a = 412.0 [V-C2]
667 - 440 P63/mmc c = 526.3
Ni2In
2, Cu7In4(h2) oP55 a = 2137.5 [1972Jai] superstructure of the Ni2In
480 - 350 ? b = 740.5 type
c = 521.8
450 - 298 ? b = 739.5 type
c = 526.2
New Series IV/11C2
CeCuIn 101

[C] Prototype
4, Cu7In4(r) - - [1972Jai]
< 389
5, Cu15In8 - - [1972Jai]
< 350
* -1 , cF112 x = 0.22; y = 0.36 [1990Bar]
Ce1x(Cu0.68In0.32)12Cu1y Fm3c at 5.8Ce-65.5Cu-28.7In (at.%)
NaZn13 after annealing at 600C
a = 1248.2 0.1 at x = 0.22; y = 0.36 [1990Bar]
after annealing at 600C
a = 1248.3 0.1 at x = 0.22; y = 0.36 [1991Bar]
* -2, CeCu5.1In6.9 tI26 at 7.7Ce-39.2Cu-53.1In (at.%)
I4/mmm a = 926.3 0.2 for as-cast [1989Sys] and annealed at
ThMn12 c = 542.3 0.1 600C samples [1991Bar]
* -3, CeCu9.0-8.0In2.0-3.0 tP24 a = 847.6 to 863.1 after annealing at 600C
P4/mbm 0.2 at 8.3 at.% Ce
YNi9In2 c = 498.8 to 511.7 75.0 to 66.7 at.% Cu
0.2 16.7 to 25 at.% In
[1991Bar]
* -4, ~CeCu4.2In4.8 ? ? after annealing at 600C
[1991Bar, 1998Kal]
* -5, CeCu5.1-4.2In0.9-1.8 oP56 [1988Kal]
Pnnm a = 1716.9 0.6 single crystal, after annealing at
CeCu4.38In1.62 b = 1090.8 0.4 600C for CeCu4.38In1.62
c = 520.2 0.2 at 14.3Ce-62.6Cu-23.1In (at.%)
[1988Kal]
or
a = 1672.0 to after annealing at 600C for
1701.9 CeCu4.38In1.62
b = 1060.0 to at 14.3 at.% Ce,
1080.9 72.8 to 60.1 at.% Cu,
c = 507.4 to 518.9 12.8 to 25.7 at.% In [1991Bar]
oP28 a = 837.605 after annealing at 530C for CeCu5In

Pnma 0.015 at 14.3Ce-71.4Cu-14.3In (at.%)
CeCu6 b = 506.975 [1998Kam]
0.009
c = 1062.490
0.019
a = 840.56 0.07 for CeCu4.83In1.17 at
b = 509.39 0.04 14.3Ce-69.0Cu-16.7In (at.%)
c = 1073.80 0.08 [2005Bob]
Landolt-Brnstein
New Series IV/11C2
MSIT
102 CeCuIn

[C] Prototype
* -6, CeCu2In cF16 a = 678.5 0.1 after annealing at 600C [1984Kal]
Fm3m
MnCu2Al a = 679.8 for as-cast sample [1985Fel]
a = 678.4 for as-cast sample at room
temperature [1987Lah]
a = 679.1 for as-cast sample at room
temperature [1988Tak1]
a = 679.06 for as-cast sample [1988Tak2]
a = 678.9 0.3 for as-cast sample [1997Ple]

* -7, CeCuIn hP9 a = 749 after annealing at 800C
P62m c = 424 [1976Dwi]
ZrNiAl
a = 749.0 0.1 after annealing at 600C [1991Bar,
c = 424.9 0.1 1998Kal]
* -8, CeCu0.8-0.4In1.2-1.6 hP3 a = 481.8 0.1 after annealing at 600C for
P6/mmm c = 389.9 0.1 CeCu0.5In1.5 at
AlB2 33.3Ce-16.7Cu-50.0In (at.%)
[1988Bar]
a = 480.4 to 483.5 after annealing at 600C
0.1 at 33.3 at.% Ce
c = 383.7 to 391.7 26.7 to 13.3 at.% Cu
0.1 40.0 to 53.1 at.% In
[1991Bar, 1998Kal]
a = 482.1 after annealing at 470C for

c = 385.2 CeCu0.5In1.5 at
33.3Ce-16.7Cu-50.0In (at.%)
[2000Sio]
* -9, Ce2Cu2In tP10 a = 773.34 0.17 after annealing at 600C [2002Mil]
P4/mbm c = 392.91 0.01
Mo2FeB2
(ordered U3Si2 a = 773.5 0.3 Polycrystalline sample [1996Kac,
type) c = 392.4 0.2 2003Luk]
a = 773.68 0.06 Single crystal sample [1996Kac]

c = 392.40 0.03
a = 772.8 0.1 after annealing at 600C [1990Kal,

c = 391.6 0.2 1991Bar, 1998Kal, 2003Luk]
* -10, CeCu2xIn2y tP10-2.0 x = 50, y = 0.50,
P4/nmm a = 424.5 0.1 at 25Ce-37.5Cu-37.5In (at.%)
CaBe2Ge2 c = 1055.0 0.2 only in cast alloys [1990Bar,
1991Bar, 1998Kal]
New Series IV/11C2
CeCuIn 103
Table 3: Investigations of the Ce-Cu-In Materials Properties

[1985Fel] Magnetic measurements Magnetization and reciprocal susceptibility
for CeCu2In
[1987Lah] Magnetic and electrical measurements Magnetic susceptibility and magnetic
Neutron scattering experiments/ resistivity / 1.5 - 300 K / CeCu2In
IN4 spectrometer
[1988Tak1] Cu NMR measurements/phase-coherent Magnetization for CeCu2In at low
NMR spectrometer temperatures
[1988Tak2] Magnetic and transport investigations Magnetic susceptibility and electrical
resistivity/
for CeCu2In at low temperatures
[1989Oom] Thermal expansion measurements Thermal expansion coefficient of single
Strain gauge method crystalline CeCu2In at 4.2 to 300 K
[1991Kag] Magnetic investigation CeCu2In
[1992Oom] Magnetostriction and magnetoresistance Magnetostriction of single crystalline of
measurements, thermal expansion and CeCu2In up to 60 K. Magnetoresistance of
electrical resistance measurement CeCu2In at pressure up to 2 GPa and 2 to
Strain gauge method 60 K.
Standard four-probe method
[1992Kag] Electrical measurements Resistivity of CeCu2In at high pressure up
Standard four-probe method to 8 GPa
[1995Kas] Magnetic and electrical measurements Magnetic susceptibility and electrical
resistivity/
for CeCu6xInx at 1.7 to 300 K
[1996Kac] Magnetic and electrical Magnetic susceptibility and electrical
measurements/Quantum Desing MPMS-5 resistivity of Ce2Cu2In at 1.7 to 300 K
superconducting quantum interference
device magnetometer, Lake Shore ac
susceptometer
[2000Sio] Magnetic measurements/SQUID High and low temperature magnetic
magnetometer susceptibility at 4.2 to 160 K for Ce2CuIn3
[2002Mil] Magnetic investigation/SQUID Magnetic susceptibility of Ce2Cu2In at 5 to
magnetometer 300 K
Landolt-Brnstein
New Series IV/11C2
MSIT
104 CeCuIn
In Data / Grid: at.%

Fig. 1: Ce-Cu-In. Axes: at.%
400 (above 33.3 at.%
Ce) and 600C (below
33.3 at.% Ce) 20
80
CeIn3
L
CeIn2
Ce3In5
40
60
2
Ce1+xIn 8
4
60
40
Ce2In
1
1
Ce3In 7
80 6 3
20
5
9
(Cu)
20 40 60 80CeCu CeCu
Ce CeCu CeCu2 CeCu4 5 6 Cu
New Series IV/11C2
CeCuNi 105
Cerium Copper Nickel

Oksana BodakA, Gabriele Cacciamani
Introduction
No complete phase diagram exists for the Ce-Cu-Ni ternary system. Phase relations in this system were
studied by [1981Bod, 1986Kha] by investigating alloy samples prepared by arc melting from >99.99 mass%
pure elements.
Most of the other investigations are concerned with the structural, magnetic and electronic properties of
selected phases, especially CeNixCu1x and Ce(NixCu1x)5, often related to the variable valence of the Ce
atoms.
Hydrogen storage properties and thermoelectric power of the Ce(NixCu1x)5 phase have also been
investigated.
Binary Systems
The Ce-Cu and Cu-Ni binary systems are accepted from the assessments by [2002Per] and [2002Leb],
respectively. The Ce-Ni system is accepted from [Mas2].
Solid Phases
Crystallographic data of all the unary, binary and ternary phases are summarized in Table 1.
The crystal structure of two samples at the CeNi3Cu3 and CeNi4Cu2 compositions has been determined by
[1998Moz1, 1998Moz2], by means of time-of-flight neutron diffraction. Whereas presented as two
independent compounds by [1998Moz1, 1998Moz2], it is here tentatively assumed that the two samples
belong to the same off-stoichiometric phase Ce(Ni3+xCu3x) having the TbCu7 type structure. This should
be a line compound where Cu and Ni atoms replace each other in the 2e dumb-bell site. This phase was not
detected at 400C by [1986Kha].
Lattice parameters of Ce(Cu1xNix)5 have been determined by [1982Pou, 1984Pop] as a function of the
Cu/Ni ratio, by [1984Sin] at Cu/Ni equiatomic ratio, as a function of Ce content, and by [2001Sta] as a
function of pressure.
Lattice parameter of the Ce(Cu1xNix) and Ce(Cu1xNix)2 solid solutions have been studied, as a function
of composition, by [2000Esp] and [1977Olc], respectively.
Isothermal Sections
The Ce-Cu-Ni isothermal section at 600C resulting from the combination of the data by [1977Olc,
1986Kha, 1997Sol, 1998Moz1, 1998Moz2] is sketched in Fig. 1. Main uncertainties, indicated by dashed
lines, are related to the different extent of the solid solutions reported by different authors. Such differences
seem larger than those which could be explained by the different temperature of the investigations
considered.
Thermodynamics
The enthalpy of formation of the Ce(NixCu1x)5 phase has been measured, as a function of composition, by
drop calorimetry [1985Mey]. It follows a linear trend between 16 kJ#mol1 at x = 0.188 and 33 kJ#mol1
at x = 1. The same authors calculated the hydrogenation enthalpy of these alloys.
The enthalpy and entropy for hydrogen removal reach H = 15.6 (kJ#mol1) and S = 72.3 J#K1#mol1 for the
CeNi3Cu2 hydride, and H = 17.3 kJ#mol1 and S = 77.4 J#K1#mol1 for the CeNi2.5Cu2.5 hydride [1982Pou,
1984Ped]. According to [1984Sin] it is H = 20.9 kJ#mol1 and S = 81.7 J#K1#mol1 for the Ce1.1Ni2.5Cu2.5
hydride. All data reported here are relative to a hydrogen capacity of 3 H atoms per formula unit.
Landolt-Brnstein
New Series IV/11C2
MSIT
106 CeCuNi

The Ce(Ni1xCux) phase has been investigated by several authors. [1997Sol] studied the low temperature
magnetic and electric properties. Transition from Pauli paramagnetism to Kondo ferromagnetism and to
antiferromagnetism as a function of Cu concentration was interpreted in terms of RKKY and Kondo
interactions. Further studies performed by the same authors [2000Esp, 2000Sal, 2000Sol] leaded to the
magnetic phase diagram reported in Fig. 2. Specific heat in the 0.2-300 K temperature range was measured
by [2002Mar] and related to the magnetic properties.
Magnetic properties of Ce(NixCu1x)2 have been measured by [1977Olc] for 0 < x < 1. He found that Ni
atoms are in a non-magnetic state and have filled d shells while Ce atoms are always in a trivalent state.
Hydrogen storage properties of Ce(NixCu1x)5 have been studied by several authors. [1982Pou] found that,
at intermediate Ni contents, absorption and desorption are very fast and can be performed at room
temperature and hydrogen pressure lower than 10 atm. Moreover, hydrogenation enthalpy is lower than for
LaNi5. [1984Sin] found that at the Ce1.1(Ni0.5Cu0.5)5 composition the H capacity is about 5.3 atoms per
formula unit and the vapor pressure of the hydride is about 4 atm at room temperature.
[1984Ped] measured the magnetic susceptibility in Ce(NixCu1x)5 alloys and their hydrides in the 4-300 K
temperature range in an applied field of 20 kOe. They found that the phase exhibit Pauli paramagnetism at
high Ni content, while, with Cu additions, the total susceptibility can be regarded as a combination of Pauli
and Curie-Waiss paramagnetism associated with the Ce3+ ions. According to [1998Moz1] the trivalent
character of the Ce atoms increases with Cu concentration.
Low temperature specific heat of Ce(NixCu1x)5 (0 < x < 0.8) has been measured by [1985Ale] and results
have been related to the mixed-valence state of Ce. Thermoelectric power of the same phase in the 4-900 K
temperature range was investigated by [2001Kot] and related to the valence instability of Ce, with special
attention to the transition from ordinary intermediate valence to saturated valence state.
References
[1977Olc] Olcese, G.L., Structural and Magnetic Properties of Ce(Cu,Ni)2 Pseudobinary Phases,
J. Phys. Chem. Solids, 38, 1239-1241 (1977) (Crys. Stucture, Magn. Prop., Experimental, 9)
[1981Bod] Bodak, O.I., Pecharskii, V.K., Kalychak, Ya.M., Kharchenko, O.I., Mokra, I.R., Muratova,
L.A., Some Ternary Systems Containing Rare Earth Metals, Fazovye Ravnovesiya v
Metallicheslikh Splavakh, (3), 57-63 (1981) (Crys. Structure, Phase Diagram, Review,
Experimental, 1)
[1982Pou] Pourarian, F., Wsllace, W.E., Hydrogen Strage in CeNi5xCux, J. Less-Common Met., 87,
275-281 (1982) (Phys. Prop., Experimental, 9)
[1984Pop] Pop, I., Pop, R., Coldea, M., The Crystalline Structure of the Intermetallic Compounds
CeCu5xNix, Stud. Univ. Babes-Bolyai, Phys., 29, 27-30 (1984) (Crys. Structure,
Experimental, 8)
[1984Sin] Sinha, V.K., Wallace, W. E., Hydrogen Sorption by the Hyperstoichiometric
Cerium-Nickel-Copper (Ce1+xNi2.5Cu2.5) Alloys, J. Phys. Chem., 88(1), 105-107 (1984)
(Phys. Prop., Experimental, 11)
[1984Ped] Pedsiwiatr, A.T., Pourarian, F., Wallace, W.E., Magnetic Characteristics of CeNi5xCux
(x = 0,1,2,2.5,3 and 4) Alloys and Their Hydrides, J. Appl. Phys., 55(6), 1987-1989 (1984)
[1985Ale] Alekseev, P.A., Lazukov, V.N., Sadikov, I.P., Effect of a Transition to a Mixed-Valence
State on the Specific Heat of the Compound Ce(Cu1xNix)5, JETP Letters, 41(12), 598-601
(1985) (Phys. Prop., Experimental, 7)
[1985Mey] Meyer-Liautaud, F., Pasturel, A., Allibert, C.H., Colinet, C., Thermodynamic Study of the
Valence State of Cerium and Hydrogen Storage in Ce(Ni1xCux)5 Compounds,
J. Less-Common Met., 110, 119-126 (1985) (Thermodyn., 20)
[1986Kha] Kharchenko, O.I., Kondratiuk, L.M., Rak, M.M., Ternary Systems (Y,Ce)-Ni-Cu, Vestn.
Lvov. Univ. Khim., 27, 50-52 (1986) (Crys. Structure, Phase Diagram, Experimental, 4)
New Series IV/11C2
CeCuNi 107
[1990Vrt] Vrtis, M.L., Jorgensen, J.D., Hinks, D.G., The Structural Phase Transition in the RECu6
Compounds (RE = La, Ce, Pr, Nd), J. Solid State Chem., 84, 93-101 (1990)
[1997Sol] Garsia Soldevilla, J., Gomez Sal, J.C., Rodriguez Fernandez, J., Espero, J.I., Monconduit,
L., Allemand, J., Paccard, D., Magnetic Investigations Competing in CeNi1xCux
Compounds, Physica B (Amsterdam), 230-232, 117-119 (1997) (Crys. Structure,
Experimental, 4)
[1998Moz1] Moze, O., Kockelmann, W.A., Brueck, E., Buschow, K.H.J., Crystal Structure and
Magnetic Properties of the Off-Stoichiometric Compounds CeNi3Cu3 and CeNi4Cu2,
J. Phys.: Condens. Matter, 10, 775-782 (1998) (Crys. Structure, Experimental, 15)
[1998Moz2] Moze, O., Kockelmann, W.A., Brueck, E., Buschow, K.H.J., Site Exchange in Hexagonal
Ce(Ni,Cu)6 Intermetallics, Mater. Sci. Forum, 278-281, 532-536 (1998) (Crys. Structure,
Experimental, 4)
[2000Esp] Espeso, J.I., Garcia Soldevilla, J., Blanco, J.A., Rodriguez Fernandez, J., Gomez Sal, J.C.,
Fernandez Diaz, M.T., Neutron Scattering on the Strongly Correlated Electron CeNi1xCux
System: From Non-Magnetic Behaviour to Long-Range Magnetic Order, Eur. Phys. J. B,
18(4), 625-632 (2000) (Crys. Structure, Phys. Prop., Experimental, 4)
[2000Sol] Soldevilla, J.G., Sal, J.C.G., Blanco, J.A., Espeso, J.I., Fernandes, J.R., Phase Diagram of
the CeNi1xCux Kondo System with Spin-Glass-Like Behavior Favored by Hydridization,
Phys. Rev. B, 61(10), 6821-6825 (2000) (Crys. Structure, Magn. Prop., Phase Relations,
Experimental, 4)
[2000Sal] Sal, J.C.G., Espeso, J.I., Soldevila, J.G., Fernandez, J.R., Blanco, J.A., The Role of
Disorder in the Phase Diagram of the CeNi1xCux System, Physica B (Amsterdam),
281-282, 42-43 (2000) (Crys. Structure, Magn. Prop., Phase Relations, Experimental, 4)
[2001Kot] Koterlyn, M.D., Babych, O.I., Koterlyn, G.M., Dependence of the CeNi5 Thermoelectric
Power on Strong 4f-Electron Instability, J. Alloys Compd., 325, 6-11 (2001) (Phys. Prop.,
Experimental, 3)
[2001Sta] Staub, U., Schulze-Briese, C., Alekseev, P.A., Hanfland, M., Pascarelli, S., Simultaneous
Determination of the Electronic and Chemical Structures in CeNixCu5x at High Pressures,
J. Phys.: Condens. Matter, 13(50), 11511-11519 (2001) (Crys. Structure, Electronic
[2002Mar] Marcano, N., Bartolome, F., Espeso, J.I., Rodriguez Fernandez, J., Gomez Sal, J.C.,
Specific Heat of CeNi1xCux in the 0.2 to 300 K Temperature Range, Physica B, 312-313,
246-247 (2002) (Thermodyn., Experimental, 3)
[2002Leb] Lebrun, N., Ce-Ni (Cerium-Nickel), MSIT Binary Evaluation Program, in MSIT
Workplace, Effenberg, G. (Ed.), Materials Science International Services GmbH, Stuttgart;
Document ID: 20.14832.1.20 (2002) (Phase Diagram, Assessment, Crys. Structure, 51)
Workplace, Effenberg, G. (Ed.), Materials Science International Services GmbH, Stuttgart;
Document ID: 20.16303.1.20 (2002) (Phase Diagram, Assessment, Crys. Structure, 25)
Landolt-Brnstein
New Series IV/11C2
MSIT
108 CeCuNi

[C] Prototype
(NixCu1x) cF4 0 x 1, dissolves up to 0.1 at.% Ce at
Fm3m 876C [2002Per]
Cu a = 356.655 at x = 0.5 [V-C2]
(Ni) a = 352.40 at x = 1, 25C [2002Per]

< 1455
(Cu) a = 361.46 at x = 0, 25C [2002Per]
< 1084.62
( Ce) cI2 a = 412 0 to 0.55 at.%Cu at 708C [2002Per]
798 - 726 Im3m
W
(Ce) cF4 a = 510.10 0 to 0.37 at.% Cu at 708C [2002Per]
726 - 61 Fm3m
Cu
(Ce) hP4 a = 308.10 at 24C [2002Per]
61 - (177) P63/mmc c = 1185.7
La
(Ce) cF4 a = 485 at 196C [2002Per]
< 177 Fm3m
Cu
Ce(NixCu1x) oP8 0 < x < 0.8 [1997Sol, 2000Sol]
Pnma a = 741.5 to 731.6 at 0 x 0.4, T < 10 K.
FeB b = 456.4 to 448.6 Neutron diffraction, Rietveld refinement
c = 564.3 to 564.1 [2000Esp]
CeCu a = 737.0 at x = 0 [2002Per]

< 516 b = 462.3
c = 564.8
Ce(NixCu1x)2 oI12 0 < x < 0.5
Imma a = 443.3 to 434.9 at 0 x 0.5 [1977Olc]
CeCu2 b = 706.4 to 712.4
c = 747.2 to 735.1
CeCu2 a = 442.9 at x = 0 [2002Per]

< 817 b = 706.1
c = 747.4
CeCu4 oP20 a = 458 at x = 0 [2002Per]
< 796 Pnnm b = 810
CeCu4 c = 935
New Series IV/11C2
CeCuNi 109

[C] Prototype
Ce(NixCu1x)5 hP6 0x1
P6/mmm dissolves about 1 at.% Ce at x = 0.5
CaCu5 [1984Sin]
a = 507.6 to 486.0 at 0.2 x 1 (non-linear variation)

c = 407.6 to 399.6 [1982Pou, 1984Ped]
a = 514.6 to 487.4 at 0 x 1 (non-linear variation)

c = 410.8 to 401.1 [1984Pop]
a = 508.6 to 488.2 at 0.188 x 1 (non-linear variation)

c = 409.2 to 400.4 [1985Mey]
a = 493.2 to 460.5 at x = 0.6, p = 0 to 40 GPa (from figure)

c = 403.7 to 385.5 [2001Sta]
CeCu5 a = 514.8 at x = 0 [2002Per]

< 798 c = 410.8
CeNi5 a = 486 at x = 1 [V-C2, Mas2, 1982Pou,

< 1345 c = 399.6 1984Ped]
CeCu6 mP28 a = 810.88 at 22C [1990Vrt]
938-(43) Pnma b = 510.04
CeCu6 c = 1016.21
a = 810.09 at 23 [1990Vrt]
b = 509.78
c = 1015.48
CeCu6 oP28 a = 509.5 at 73 [1990Vrt]
< 43 P21/c b = 1014.66
LaCu6 c = 809.31
= 90.485
a = 508.92 at 173 [1990Vrt]

b = 1013.26
c = 807.89
= 91.148
a = 508.41 at 263 [1990Vrt]

b = 1012.79
c = 807.31
= 91.442
Ce7Ni3 hP20 a = 992.6 [Mas2]
< 505 P63mc c = 631.1
Fe3Th7
Landolt-Brnstein
New Series IV/11C2
MSIT
110 CeCuNi

[C] Prototype
CeNi1xCux oC8 0 < x < 0.15
Cmcm a = 375.4 at x = 0 [Mas2]
CrB b = 1057.5
c = 437.6
CeNi2 F24 a = 722.46 [V-C2, Mas2]
< 830 Fd3m
Cu2Mg
CeNi3 hP24 a = 498 [Mas2]
< 930 P63/mmc c = 1654
CeNi3
Ce2Ni7 hP36 a = 490.5 [V-C2, Mas2]
< 1065 P63/mmc c = 2438
Ce2Ni7
* -1, Ce(Ni1xCux)6 hP8 0.33 < x < 0.5
P6/mmm a = 496.57 at x =0.5
TbCu7 c = 406.69
a = 491.21 at x = 0.33
c = 405.68 Neutron diffraction, Rietveld refinement
[1998Moz1, 1998Moz2]
Cu Data / Grid: at.%

Fig. 1: Ce-Cu-Ni. Axes: at.%
600C CeCu6
CeCu5
20
CeCu4 80
CeCu2
40
60
NixCu1-x
CeCu
60
40
80
20
20 40 60
Ce (Ce) Ce7Ni3 CeNi CeNi2 CeNi3 80 CeNi5 Ni
Ce2Ni7
New Series IV/11C2
CeCuNi 111
8.0
Fig. 2: Ce-Cu-Ni.
Paramagnetic
Magnetic phase
1.0
diagram for the 7.0
CeNi1xCux vertical
section as a function Spin Glass
6.0
T.J1
of the Cu 0.5
concentration. Inset:
Van Hemman FM
5.0
Temperature, K
classical phase
II
Unexplored
diagram 0 CrB
4.0 J0.J1 1.0 0.5
FeB
Ni content
3.0
Paramagnetic Spin
Glass
2.0
AFM
1.0
FM
0
CeCu 1.0 0.8 0.6 0.4 0.2 0 CeNi
x
Landolt-Brnstein
New Series IV/11C2
MSIT
112 CeCuSi
Cerium Copper Silicon

Oksana BodakA, Peter Rogl
Introduction
Although phase relations in the ternary system have been established in form of isothermal sections by
several research groups [1965Gla, 1966Bod, 1967Ram, 1969Rie, 1974Bod], the discovery of CeCu2Si2 as
the first superconducting heavy fermion system [1979Ste], made the Ce-Cu-Si system and particularly
CeCu2Si2 the subject of intensive experimental and theoretical investigations because of the unusual
interplay between superconducting and magnetic interactions at low temperature [1980Ste]. A summary of
the physical properties is given below in section Notes on Materials Properties and Applications. Most
of the ternary compounds in the Ce-Cu-Si system are now well characterized with respect to region of
existence and their crystal structures [1965Gla, 1966Bod, 1967Ram, 1969Rie, 1974Bod, 1983Jar, 1983Ian,
1983Kle, 1985Bra, 1985Neu, 1986Gig, 1986Spa, 1987Boe, 1988Neu, 1992Lev, 1996Hwa, 2004Ish].
Information on phase relations, structures and thermodynamics is summarized in Table 1.
Binary Systems
The Ce-Si system was adopted from a recent investigation by [2002Bul]. There is no doubt about the
formation of the phase, Ce2Si3x(CeSi1.34), for which crystal and magnetic structures were determined by
[1993Sch]. The Ce-Cu system is accepted from [1994Sub] and [2002Per]. The Cu-Si binary is taken from
a recent MSIT assessment [2002Leb]. Crystallographic and melting data pertinent to the compounds of the
Ce-Cu-Si system are given in Table 2.
Solid Phases
Crystallographic data of the binary and ternary compounds are listed in Table 2. Of all compounds the heavy
fermion superconductor, CeCu2Si2 with the ThCr2Si2 structure type, has attracted most attention. Although
unnoticed in earlier studies, it was found to exhibit a small homogeneity range at 750C, which extends for
about 3 at.% in the Cu/Si direction, CeCu2xSi2+x [1985Bra]. However, the ground state in CeCu2Si2
depends very delicately on the actual composition. Thus, Cu rich samples exhibit only superconductivity,
Si rich show a magnetically ordered phase called A phase, while in stoichiometric samples (A/S type) a
complex interaction between superconductivity (S) and magnetic order occurs [2001Ste].
Single-crystals of CeCu2Si2 have been investigated by [1983Jar]. The temperature dependence of lattice
parameters for CeCu2Si2 was studied by [1985Neu] and pressure dependence of lattice parameters for
CeCu2Si2 was reported by [1985Neu, 1986Spa] and for CeCu1.8Si2 by [1986Spa]. Two samples of
CeCuxSi2 with x = 1.8 (non superconducting) and x = 2.2 (superconducting) have been investigated by
neutron powder diffraction [1988Neu]. A crystallographic investigation of two CeCuxSi2 samples with
x = 1.8 and x = 2.2 shows that the CeCu2Si2 structure is formed in both cases but with some differences in
the degree of disorder of Cu and Si as well as in the composition of the impurity phases. [1992Lev]
emphasized that CeCu2xSi2+x is a compound of variable composition with lattice parameters and electronic
structure depending on Cu and Si content. Anisotropic vibration is detected for the Cu and Si atoms in both
phases showing that the lattice degrees of freedom are important in CeCu2Si2 [1988Neu]. [2000Lou] found
that the local atomic structure for a superconducting sample with x = 0.33 is fundamentally different from
a nonsuperconducting sample with x = 0.08, and that superconducting, magnetic and
non-Fermi-liquid-like ground states evolve in CeCu2+xSi2 with small changes in the Ce/Cu ratio that leave
the average crystal structure unchanged. The CeCu2Si2 compound has 4f2 final-state amplitudes with
formally 4f1 initial state configurations [1981Bia]. A valence transition would presumably result from
transfer of the 4f1 electron to a conduction band state. The proximity of the f-electron to the Fermi level is
consistent with the normal and superconducting properties [1986Spa]. The tetragonal ambient pressure
New Series IV/11C2
CeCuSi 113
phase was at room temperature found to be stable up to 60 GPa: from the equation of state data a bulk
modulus of 112.0(5.1) GPa was derived for CeCu2Si2 [2005Tsu].
The energy band structures and Fermi surfaces are calculated for CeCu6 in [1992Har]. 4f-electrons of Ce in
CeCu2Si2 are well localized and do not affect the Fermi surface significantly in an applied magnetic field
[1992Har].
[2004Ish] synthesized a new ternary compound Ce2Cu3Si5 (with orthorhombic U2Co3Si5 structure type),
which was not included in the phase triangulation of [1974Bod] at 600C.
The phases -2 and -3 show a close crystallographic relationship: although unit cell, crystal symmetry and
atom sites are identical, both compounds differ with respect to atom occupation. As a consequence the two
structures may be considered as type (-3-CeCuSi2) and inverse type (-2-CeCu2Si). It shall be noted that both
compounds are not in equilibrium but separated by foreign two phase regions. A similar situation is met
with the phases -4 and -5, which both adopt the AlB2 type structure separated by a two-phase field between
the two phases. In this case a miscibility gap is conceivable suggesting a critical point at higher
temperatures.
Liquidus Surface
[2000Nue1, 2000Nue2] performed a systematic investigation to determine the primary solidification area
of the heavy fermion system CeCu2Si2 examining the liquidus surface by differential scanning calorimetric
analysis in a special crucible system. Using the Nacken-Kyropoulos technique crystal growth experiments
from a levitated melt within the primary solidification area yielded high quality single crystals of CeCu2Si2
with dimensions up to 7 mm [2000Nue2].
The phase CeCu2Si2 with the ThCr2Si2 structure type forms peritectically at (1545 15)C without
evidence for a high temperature polymorphic transformation: L + Ce2CuSi3 + CeSi2 CeCu2Si2 [1984Bra,
1985Bra].
Isothermal Sections
The isothermal section of the Ce-Cu-Si system at 600C, as shown in Fig. 1, is based on an early
investigation by [1974Bod, 1985Bra] with amendments to comply with the accepted binary systems as well
as with the findings concerning the extension of the homogeneity region for CeCu2Si2 (see details in Fig. 2).
The location of the ternary compound Ce2Cu3Si5 found by [2004Ish] is indicated by a filled circle. It may
be a high temperature phase. Cerium solubility in copper silicides is generally below ca. 1 at.% Ce. Mutual
solubility among cerium silicides and cerium copper phases, however, is significant. The essentially random
substitution of the almost equally sized atom species copper and silicon is also reflected in extended
homogeneous regions for some ternary compounds such as for -4-Ce(PtxSi1x)2 and -5-Ce(Pt1xSix)2.
Thermodynamics
[1985Bre, 1998Geg] studied the low temperature specific heat and the entropy changes for CeCuxSi2,
x = 1.9, 2.0, 2.2.

Physical property data are known for CeCu2Si2, CeCuSi, CeCu0.5Si1.5, CeCu0.24Si1.76, Ce2Cu3Si5 and are
discussed below.
CeCu2Si2:
Since the observation of superconductivity in CeCu2Si2 [1979Ste], much work has been devoted to
understand the unusual properties of this prototypical heavy-fermion superconductor. Particularly the
unusual type of magnetic order in the so-called A phase [1994Bru], discovered about ten years after the
superconductivity by NMR [1988Nak] and muon spin rotation (mSR) [1989Uem], has attracted much
Landolt-Brnstein
New Series IV/11C2
MSIT
114 CeCuSi
interest. From thermodynamic and transport measurements a complex magnetic (B,T) phase diagram was
constructed with superconducting and magnetically ordered phases and a ground state depending very
delicately on the actual stoichiometry [1994Bru]. The ground state was claimed to be (i) the A phase,
sometimes coexisting with superconductivity, A+S where superconductivity expels the A phase, or (ii) the
superconducting S phase [2001Ste]. Doping experiments (Ge substituting for Si) as well as experiments
under hydrostatic pressure indicated that CeCu2Si2 is near a quantum critical point in line with the
disappearance of the A phase. In the vicinity of the quantum critical point Non-Fermi-liquid behavior (in the
specific heat and the electrical resistivity) was reported. A detailed investigation of the A phase in order to
detect magnetic order by neutron diffraction failed, but measurements of the electrical resistivity revealed
a spin-density wave (SDW), with an opening of a gap below the ordering temperature in certain directions
[1998Geg], and SR experiments gave a rough estimation of the ordered moment of ~0.1 B [1989Uem].
Below TN ~0.8 K the A phase exhibits long-range antiferromagnetic order derived from neutron diffraction
experiments on a magnetically ordered CeCu2Si2 single crystal (see also Fig. 3) [2004Sto]. The propagation
vector, T = (0.215 0.215 0.530) at T = 50 mK, of the magnetic order appears to be determined by the
topology of the Fermi surface of heavy quasiparticles as indicated by renormalized band-structure
calculations. The absence of magnetic Bragg peaks in the superconducting phase gives evidence that
antiferromagnetism and superconductivity seem to exclude each other on a microscopic scale. The observed
instability of the Fermi liquid was reported to be related to the fact that the Fermi surface exhibits parallel
flat parts separated by the measured propagation vector. These results suggest that a spin-density-wave
instability is the origin of the quantum critical point observed in CeCu2Si2. However, the discrepancy
between the small ordered moment and the observed large anomalies in the thermal expansion as well as
the elastic constants [1994Bru] demand further examination. The existence of long-range incommensurate
antiferromagnetic order in the A phase suggests that the origin of the quantum critical point arises from a
spin-density-wave instability. The strong electron correlations in CeCu2Si2 show up e.g. in a huge linear
coefficient to the electronic specific heat at low temperatures, = C/T ~1 J#mol1#K2, indicative of a
largely enhanced effective electron mass (heavy-fermion system).
The description of the physical behavior of CeCu2Si2 given above is rather short. For detailed information
the reader may be transferred to a series of reviews on the subject given in [1980Ste, 1984Bra, 1998Geg,
2001Ish, 2001Ste, 2002Kit, 2004Sto, 2005Ste1, 2005Ste2, 2005Ste3, 2005Sto].
CeCuSi:
CeCuSi exhibits a ferromagnetic ordering below Tc = 15.5 K, with a magnetic moment of 1.25 B at 2.5 K,
perpendicular to the c-axis [1983Kid, 1986Gig]. Neutron scattering measurements on the heavy fermion
system CeCu0.24Si1.76 confirm a phase transition to ferromagnetic order below Tc = 8 K. The ordered
moment = 0.62 0.05 B [1987Boe].
CeCu0.5Si1.5:
Temperature dependences of specific heat, electrical resistivity and magnetic susceptibility of CeCu0.5Si1.5
with AlB2 structure type are reported on polycrystalline samples [1996Hwa] as well as on single crystals
[2000Nak] revealing complex magnetic properties with strong anisotropy. CeCu0.5Si1.5 orders
antiferromagnetically at 2.1 K. The magnetic susceptibility exhibits a maximum at 2 K only along the
hexagonal c-axis at low magnetic fields [2000Nak]. Electrical resistivity shows the typical behavior of a
Kondo compound with crystalline electric field effect [1996Hwa].
Ce2Cu3Si5:
Magnetization measurements up to 30 T at 1.5 K in the temperature range from 2.0 to 300 K showed that
Ce2Cu3Si5 undergoes a transition to the antiferromagnetic state at TN = 4.4 K. The highest magnetization
values per Ce atom of Ce2Cu3Si5 is 0.92 B at B = 30 T [2004Ish].
Microhardness was reported for CeCu2Si2 (394), CeCu1.6Si1.4 (464), CeCuSi2 (613), CeCu1.19-1.10Si0.8-0.90
(446), and for CeCu0.78-0.44Si1.24-1.56 (634 kg#mm2) [1974Bod].
New Series IV/11C2
CeCuSi 115
References
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Landolt-Brnstein
New Series IV/11C2
MSIT
116 CeCuSi
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Melting Temperatures of RT2 Compounds (MgCu2 Structure) (R=Rare Earth, T=Mn, Fe,
New Series IV/11C2
CeCuSi 117
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Horn, R., Donnevert, L., Link, A., Assmus, W., Breakup of Heavy Fermions on the Brink
of Phase A in CeCu2Si2, Phys. Rev. Lett., 81(7), 1501-1504 (1998) (Thermodyn.,
Experimental, 27)
[1998Koy] Koyama, T., Sumiyama, A., Nakagawa, M., Oda, Y., Supercurrent through Thick Cu Layer
between Nb and Heavy-Fermion Superconductors: CeCu2.2Si2 and UPd2Al3, J. Phys.
Soc. Jpn., 67(5), 1797-1798 (1998) (Experimental, 6)
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Steglich, F., Evolution from Magnetism to Unconventional Superconductivity in a Series
of CexCu2Si2 Compounds Probed by NQR, Phys. Rev. Lett., 82(26), 5353-5356 (1999)
(Experimental, Phase Relations, 23)
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Kwei, G.H., Atomic Disorder in the Heavy Fermion Superconductor CeCu2+xSi2, Phys.
Rev. B, 61(22), R14940-R14943 (2000) (Crys. Structure, Magn. Prop., Superconduct.,
Experimental, 28)
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Ce2CuSi3 Single Crystal, Physica B (Amsterdam), 281-282, 76-78 (2000) (Crys. Structure,
Electr. Prop., Magn. Prop., Experimental, 4)
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Primary Crystallisation Field, Physica B (Amsterdam), 281-282, 979-980 (2000) (Crys.
Structure, Phase Relations, Experimental, 5)
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Matter., 12(22), 4807-4815 (2000)
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International, Materials Park, OH, 2000 (Experimental, Phase Diagram)
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and Superconductivity of CeCu2Si2, J. Phys.: Condens. Matter, 13, L25-L31 (2001)
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Steglich, F., Exotic Superconducting Phase in CeCu2Si2 Close to Antiferromagnetism:
a Cu-NQR Study under Hydrostatic Pressure, Phys. Rev. B: Condens. Matter, 63(14),
140501-1-4 (2001) (Magn. Prop., Superconduct., Experimental, 19)
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Heavy-Fermion Metals, J. Magn. Magn. Mater., 226, 1-4 Part 1, SI (2001) (Review, 38)
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Cerium-Silicon System, J. Alloys Compd., 345, 110-115 (2002) (Crys. Structure,
Experimental, Phase Relations, 17)
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Ferromagnetic Interaction and Superconductivity of CeCu2Si2, J. Phys. Chem. Solids,
63(6-8), 1165-1169 (2002) (Electr. Prop., Phys. Prop., Superconduct., Thermodyn.,
Experimental, 17)
[2002Kit] Kitaoka, Y., Kawasaki, Y., Mito, T., Kawasaki, S., Zheng, G.Q., Ishida, K., Aoki, D., Haga,
Y., Settai, R., Onuki, Y., Geibel, C., Steglich, F., Coexistence of Antiferromagnetism and
Superconductivity in Heavy-Fermion Systems, J. Phys. Chem. Solids, 63(6-8), 1141-1146
(2002) (Experimental, Magn. Prop., 18)
Landolt-Brnstein
New Series IV/11C2
MSIT
118 CeCuSi
[2002Leb] Lebrun, N., Cu-Si (Copper-Silicon), MSIT Binary Evaluation Program, in MSIT
Workplace, Effenberg G. (Ed.), MSI, Materials Science International Services GmbH,
Stuttgart; Document ID: 20.12505.1.20 (2002) (Crys. Structure, Phase Diagram,
Assessment, 23)
[2002Per] Perrot P., Ferro R., Ce-Cu (Cerium-Copper), MSIT Binary Evaluation Program, in MSIT
Stuttgart; Document ID: 20.16303.1.20 MSIT (2002) (Crys. Structure, Phase Diagram,
Assessment, 25)
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Magnetization Studies of the Heavy-Fermion Superconductor CeCu2Si2 at very Low
Temperatures and in High Magnetic Fields, Phys. Rev. B: Condens. Matter, 67(21),
214504-1-214504-8 (2003) (Magn. Prop., Experimental, 37)
[2004Ish] Ishii, Y., Kosaka, M., Abe, H., Kitazawa, H., Kido, G., Uwatoko, Y., High-Field
Magnetization and other Physical Properties of Ce2T3X5 Compounds (T=Pd, Rh and Cu;
X=Si and Al), J. Magn. Magn. Mater., 277(1-2), 60-63 (2004) (Crys. Structure, Electr.
Prop., Magn. Prop., Phase Relations, Thermodyn., Experimental, 1)
[2004Sto] Stockert, O., Faulhaber, E., Zwicknagl, G., Stusser, N., Jeevan, H.S., Deppe, M., Borth, R.,
Kuchler, R., Loewenhaupt, M., Geibel, C., Steglich, F., Nature of the A Phase in
CeCu2Si2, Phys. Rev. Lett., 92 (13), Art. No. 136401 (2004) (Experimental, Magn.
Prop. 19)
[2005Ste1] Steglich, F., Quantum Criticality and Superconductivity in Heavy-electron Metals, Phys.
Status Solidi B, 242(2), 392-397 (2005) (Review, Magn. Prop., 35)
[2005Ste2] Steglich, F., Superconductivity and Magnetism in Heavy-Fermion Compounds, J. Phys.
Soc. Jpn., 74(1), 167-177 (2005) (Review, Magn. Prop., 76)
[2005Ste3] Steglich, F., Twenty-five Years of Heavy-fermion Superconductivity, Phys. B: Cond.
Matter., 359, 326-332 (2005) (Review, 96)
[2005Sto] Stockert, O., Faulhaber, W., Schmidt, M., Enderle, K., Schmalzl, D., Andreica, A., Armato,
M.M., Koza, A., Hiess, N., Bernhoeft, A., Murani, Jeevan, H.S., Deppe, Loewenhaupt, M.,
Geibel, C., Steglich, F., Magnetism and Superconductivity in Heavy-Fermion Systems
Close to Quantum Criticality, Paper presented at the Joint Workshop on
NQP-Skutterudites and NPM in Multi-Approach, Tokyo Metropolitan University, Nov. 21st
- 24th 2005 (Review, Magn. Prop.)
[2005Tsu] Tsuduki, S., Onodera, A., Ishida, K., Kitaoka, Y., Onuki, A., Ishimatsu, N., Shimomura, O.,
Synchrotron X-ray Diffraction and Absorption Studies of CeM2X2 (M = Cu, Ni and
X = Si, Ge) at High Pressure, Solid State Commun., 134(11), 747-751 (2005)
(Experimental, Crys. Structure, 31)
Table 1: Investigations of the Ce-Cu-Si Phase Relations, Structures and Thermodynamics

[1965Gla] X-ray diffraction (XPD) formation, structure of AlB2 type Ce(Cu,Si)2 at
800C
[1966Bod] XPD formation, structure of CeCu2Si2
[1967Ram] XPD formation, structure of AlB2 type Ce2CuSi3,
Ce2Cu3Si
[1969Rie] XPD formation, structure of CeCu0.67Si1.33, CeCuSi,
CeCu0.5Si1.5, CeCu1.5Si0.5
[1974Bod] XPD; X-ray single crystal photographs formation, structure of CeCu1.6Si1.4, CeCuSi2,
CeCu0.78-0.44Si1.24-1.56
New Series IV/11C2
CeCuSi 119

[1981Bia] synchrotron radiation formation, structure of -Ce, CeCu2Si2
[1983Jar] X-ray single-crystal four-circle data structure of CeCu2Si2
[1983Kid] XPD formation, structure of CeCuSi
[1983Kle] Bridgman single-crystal growth, XPD, structure of CeCu2Si2
X-ray single crystal photographs
[1983Ian] XPD formation, structure of CeCuSi
[1984Kit] nuclear quadrupole resonance CeCu2Si2
[1984Onu] Czochralski single-crystal growth, structure of CeCu2Si2
XPD, X-ray single crystal photographs
[1985Neu] XPD formation, structure of CeCu2Si2
[1985Bra] XPD, metallography and differential partial isothermal section
thermal analysis (DTA),
microprobe analysis (EMPA)
[1986Gig] neutron powder diffraction structure of CeCuSi
[1986Spa] XPD formation, structure of CeCu2Si2, CeCu1.8Si2
[1986Lev] XPD formation, structure of CeCu2Si2
[1987Boe] neutron powder diffraction structure of CeCu0.24Si1.76
[1988Neu] neutron powder diffraction structure of CeCuxSi2; x = 1.8, 2.2
[1992Lev] XPD formation, structure of CeCu2xSi2+x at 1000 K;
x = -0.20, -0.15, -0.10, -0.05, 0.005, 0.10, 0.15,
0.20
[1996Hwa] XPD formation, structure of Ce2CuSi3
[1997Mor] XPD, DTA formation, structure of CeCu2Si2
[1997Nue] Nacken Kyropoulos technique, CeCu2Si2

microscopy
[1998Koy] scattering technique 900C; CeCu2.2Si2
[1999Ish] XPD formation, structure of CeCu2.05Si2,
Ce1.025Cu2Si2, Ce0.99Cu2.02Si2, Ce0.975Cu2Si2
[2000Nue1] DSC measurements, Nacken partial isothermal section
[2000Nue2] Kyropoulos technique, scanning
electron microscopy (SEM), X-ray
analysis (EDX), XPD, metallography
[2000Nak] Czochralski single-crystal growth, formation, structure of Ce2CuSi3, 800C
XPD, X-ray single crystal photographs
[2000Lou] neutron pair density function analysis, formation, structure of CeCu2+xSi2 at 900C,
(GLAD) of the Intense pulsed neutron x = 0.33, 0.08
source (IPNS), powder diffractometer
(GPPD) of IPNS, Rietveld refinement
method
[2001Kaw] Cu-NQR measurements, EPMA Ce0.99Cu2.02Si2, CeCu2.05Si2
Landolt-Brnstein
New Series IV/11C2
MSIT
120 CeCuSi

[2001Ish] XPD 750C; samples with 20 different compositions
near CeCu2Si2compound
[2002Ish] XPD 750C; samples with 20 different compositions
near CeCu2Si2compound
[2003Tay] X-ray diffraction formation, structure of CeCu2Si2
[2004Ish] XPD formation, structure of Ce2Cu3Si5 at 900C

[C] Prototype
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m 0 to 11.3 at.% Si [Mas2]
Cu
( Ce) cI2 a = 412 0 to 0.55 at.% Cu at 708C [1994Sub]
798 - 726 Im3m 0 to 2.5 at.% Al at 720C [2000Oka]
W
(Ce) cF4 a = 516.10 0 to 0.37 at.% Cu at 708C [1994Sub]
726 - 61 Fm3m
Cu
(Ce) hP4 a = 308.10 at 24C [1994Sub]
61 -(177) P63/mm c = 1185.7
La
(Ce) cF4 a = 485 at 196C [1994Sub]
< 177 Fm3m
Cu
(Si) cF8 a = 543.09 [V-C2]
< 1414 Fd3m 0-0.002 at.% Cu [Mas2]
Cdiam.
CeCu oP8 a = 737.0 [1994Sub], [2002Per]
< 516 Pnma b = 462.3
FeB c = 564.8
CeCu2xSix oI12 a = 442.9 0 < x < 0.15
Imma b = 706.1
CeCu2 KHg2 (CeCu2) c = 747.4 at x = 0 [1994Sub], [2002Per]
< 817
CeCu4 oP20 a = 458 [1994Sub], [2002Per]
< 796 Pnnm b = 810
CeCu4 c = 935
CeCu5xSix hP6 a = 514.8 0 < x < 0.54
P6/mmm c = 410.8
CeCu5 CaCu5 [Mas2, 1994Sub]
< 798
New Series IV/11C2
CeCuSi 121

[C] Prototype
CeCu6 oP28 a = 810.88 at 22C [1990Vrt]
938 - (43) Pnma b = 510.04
CeCu6 c = 1016.21
a = 810.09 at 23C [1990Vrt]
b = 509.78
c = 1015.48 [1994Sub], [2002Per]
CeCu6 mP28 a = 509.5 at 73C [1990Vrt]
< 43 P21/c b = 1014.66
LaCu6 c = 809.31
= 90.485
a = 508.92 at 173C [1990Vrt]

b = 1013.26
c = 807.89
= 91.148
a = 508.41 at 263C [1990Vrt]

b = 1012.79
c = 807.31 [1994Sub], [2002Per]
= 91.442
Cu7Si (K) hP2 a = 256.05 at 730C, 12.75 at.% Si [Mas2]
842 - 552 P63/mmc c = 418.46 11.05 to 14.5 at.% Si [1994Ole]
Mg
Cu6Si () cI2 14.2 to 16.2 at.% Si [1994Ole]
853 - 787 Im3m a = 285.4 at 14.9 at.% Si [1994Ole]
W
Cu5Si () cP20 a = 619.8 17.15 to 17.6 at.% Si [1994Ole]
< 729 P4132
Mn
Cu5Si ( ) t** 17.6 to 19.6 at.% Si [1994Ole]
824 - 711
a = 881.5 sample annealed at 700C [V-C2]
c = 790.3
Cu15Si4 (J) cI76 a = 961.5 21.2 at.% Si [1994Ole, V-C2]
< 800 I43d
Cu15Si4
Cu3Si () hR* a = 247 23.4 to 24.9 at.% Si [1994Ole]
859 - 558 R3m = 109.74
or a = 726.7 [V-C2, Mas2]

t** c = 789.0
Cu3Si () hR* a = 472 23.2 to 25.2 at.% Si [1994Ole]
620 - 467 R3 = 95.72
Landolt-Brnstein
New Series IV/11C2
MSIT
122 CeCuSi

[C] Prototype
Cu3Si () o** a = 676 23.3 to 24.9 at.% Si [1994Ole]
< 570 b = 700
c = 2194
Ce5Si3 tI32 a = 789 [2002Bul]
< 1260 I4/mcm c = 1377
Cr5B3
a = 786.8 [V-C2]
c = 1373
Ce3Si2 tP10 a = 778.0 [2002Bul]
< 1335 P4/mbm c = 436.7
U3Si2
Ce5Si4 tP36 a = 793.6 [2002Bul]
< 1500 P41212 c = 1502.9
Zr5Si4
CeSi oP8 a = 828.8 [2002Bul]
< 1630 Pnma b = 396.4
FeB c = 595.2
CeSi1.34 oC20 x a = 440.35 [1993Sch]

Cmcm b = 2483.89
V2B3 (Nd2Si3x) c = 395.17
CeSi1.67 oI12 a = 411.3 [2002Bul]

< 1725 Imma b = 419.0
GdSi2x c = 1390.6
a = 410.0 [V-C2]
b = 418.0
c = 1382.0
CeSi2yCuy tI12 a = 417.1 0 < y < 0.27 [V-C2]
I41/amd c = 1394 at y = 0.24; [1987Boe]
ThSi2
a = 415.4 at x = 0.214
c = 1382.2
CeSi2x a = 419.2 at x = 0 [2002Bul]

< 1575 c = 1391.3
New Series IV/11C2
CeCuSi 123

[C] Prototype
* -1, CeCu2Si2 tI10 a = 419.3 [1966Bod]
I4/mmm c = 998.6
ThCr2Si2 a = 409.4 0.1 [1983Jar]
(CeGa2Al2) or c = 993.0 0.2
BaAl4
a = 411.0 0.1 [1983Kle]
c = 994.8 0.1
a = 411.2 [1983Kle]
c = 994.6 single crystal with an excess of 21.5
mass% Cu
a = 409.7 [1984Onu]
c = 991.8
a = 410.0 0.1 - [1985Bra]

410.8 0.3
c = 992.1 0.3 -
993.1 0.6
for CeCu1.8Si2
a = 408.63 0.01 at 1.5 K [1988Neu]

c = 991.15 0.01
a = 408.64 0.01 at 10 K [1988Neu]

c = 991.15 0.01
a = 408.91 0.01 at 100 K [1988Neu]

c = 991.16 0.01
for CeCu2.2Si2 at
a = 408.25 0.01 at 1.5 K [1988Neu]

c = 991.03 0.01
a = 408.26 0.01 at 10 K [1988Neu]

c = 991.00 0.02
a = 408.56 0.01 at 100 K [1988Neu]

c = 991.01 0.02
Landolt-Brnstein
New Series IV/11C2
MSIT
124 CeCuSi

[C] Prototype
CeCu2xSi2+x a = 409.8 0.1 at 1000 K x = 0.20 [1992Lev]
c = 987.2 0.3
a = 409.4 0.2 at 1000 K x = 0.15 [1992Lev]

c = 986.8 0.6
a = 409.6 0.2 at 1000 K x = 0.10 [1992Lev]

c = 989.0 0.4
a = 410.0 0.1 at 1000 K x = 0.05 [1992Lev]

c = 991.8 0.3
a = 409.3 0.1 at 1000 K x = 0.005 [1992Lev]

c = 990.3 0.3
a = 409.6 0.1 at 1000 K x = 0.10 [1992Lev]

c = 991.2 0.3
a = 409.5 0.1 at 1000 K x = 0.15 [1992Lev]

c = 990.8 0.3
a = 409.6 0.3 at 1000 K x = 0.20 [1992Lev]

c = 990.9 0.3
a = 408.599 CeCu1.92Si2 at 20 K [2000Lou]

0.013
c = 991.49 0.03
a = 408.441 CeCu2.23Si2 at 13 K [2000Lou]

0.013
c = 990.99 0.07
a = 410.6 0.1 CeCu2Si2 [1997Nue]

c = 993.6 0.9
* -2, CeCu2xSi1+x oS16 a = 416 at x = 0.4 [1974Bod]
Cmcm b = 1721
invers CeNiSi2 c = 417
* -3, CeCu1+xSi2x oS16 a = 412 at x = 0 [1974Bod]
Cmcm b = 1648
CeNiSi2 c = 416
New Series IV/11C2
CeCuSi 125

[C] Prototype
* -4, Ce(Cu1xSix)2 hP3 a = 423.1 to 423.8 0.405 < x < 0.45 [1974Bod]
P6/mmm c = 398.9 to 403.0
AlB2 a = 423.8 at x = 0.25 [1967Ram]
c = 403.0
hP6 a = 423.3 at x = 0.50; 750C [1986Gig]

P63/mmc c = 798.1
Ni2In
a = 423.9 0.2 for x = 0.50 [1983Ian]
c = 798.0 0.4
* -5, Ce(CuxSi1x)2 hP3 a = 410.3 to 407.0 0.22 < x < 0.38 [1974Bod]
P6mmm c = 424.4 to 429.1
AlB2
a = 405.9 0.2 [1996Hwa]
c = 429.4 0.5
a = 406.5 CeCu0.5Si1.5 [1967Ram] Si rich

c = 430.2
a = 413.6 CeCu0.5Si1.5 [1967Ram] Cu rich

c = 423.7
a = 412.4 at x = 0.50 [1969Rie]

c = 421.4
a = 407.5 at x = 0.333 [1969Rie]

c = 428.0
a = 407.7 for Ce(Cu,Si)2 [1965Gla]

c = 431.4
Ce2Cu3Si5 oI40 a = 997.4 900C [2004Ish]
Ibam b = 1158
U2Co3Si5 c = 584.4
Landolt-Brnstein
New Series IV/11C2
MSIT
126 CeCuSi
Si Data / Grid: at.%

Fig. 1: Ce-Cu-Si. Axes: at.%
600C (0 - 33.3 1 - CeCu2Si2
at.% Ce) and 400C 2 - CeCu2-xSi1+x
(> 33.3 at.% Ce) 20 3 - CeCu1+xSi2-x
80
4 - Ce(Cu1-xSix)2
5 - Ce(CuxSi1-x)2
CeSi
CeSi2-x 2
40
CeSi1.34 60
CeSi
3 Ce2Cu3Si5
Ce5Si4
4
Ce3Si260 1
40
2
Ce5Si3
5 , Cu3Si
Cu15Si4
80
20
Cu5Si
, Cu5Si
(Cu)
Ce ( Ce)
20 40
CeCu 60
CeCu2 CeCu4 80CeCu CeCu6 Cu
5
Ce 19.50
Cu 39.00
Fig. 2: Ce-Cu-Si. Axes: at.%
Phase relations
around -1 at about
600C
20
1+ 3 1+(Si)+ 3
1+4+CeSi2
1+(Si)+
1+4 40
1
1+
1+ 2+ 4
1+Cu15Si4+
1+Cu15Si4+Cu
1+ 2 1+(Cu)+
1+Cu5Si+
1+ 2+CeCu5
1+(Cu)
Ce 40
22.00 1+CeCu5+(Cu) Ce 19.50
Cu 39.00 Cu 41.50
Si 39.00 Si 39.00
New Series IV/11C2
CeCuSi 127
Fig. 3: Ce-Cu-Si.
Schematic magnetic
(B,T) phase diagram B
of CeCu2Si2 with
different magnetically
ordered phase
(A-,B-phase)
paramagnetic region
PM, and the PM
superconducting
phase SC
B, T
SC
Temperature, K
Landolt-Brnstein
New Series IV/11C2
MSIT
128 CeCuSn
Cerium Copper Tin

Kostyantyn Korniyenko
Introduction
The ternary R-T-X alloys formed by rare earths elements (R) with a transition element (T) and an element
X of the p-block of the Periodic Table have often been described as promising materials, in particular, due
to their specific electrical and magnetic properties. Therefore the attention of investigators of the ternary
system formed by the rare-earth element cerium with the transition metal copper and p-element tin was
concentrated mainly on these aspects besides crystal structures of the ternary compounds [1968Rie,
1976Dwi, 1982Sko, 1983Kom, 1984Kom, 1985Cor, 1988Kom, 1989Goe, 1990Fra, 1994Nak, 1994Sle,
1996Guz, 1996Lid, 1997For, 1997Ria1, 1997Ria2, 1997Sko, 1998For, 1998Ria, 2000Isn, 2000Sin,
2001Sin, 2002Zah, 2005Cha]. The publications about phase equilibria belong to 1996 year and later
[1996Mar, 1997Din, 1997Ria1, 1997Ria2, 1998Ria, 2001Sin]. Isothermal section at 400C [1996Mar,
1997Din, 1997Ria2, 1998Ria], partial liquidus surface projection [1997Ria1, 1998Ria] as well as reaction
scheme [1998Ria] are presented in these works. Critical assessment of the available data about crystal
structures and phase relations was carried out by [1998Ria]. Table 1 gives an overview on the experimental
methods and the temperature / concentration regimes studied in the above works. The knowledge about the
phase equilibria in the Ce-Cu-Sn system, however, is still incomplete. In particular, data concerning solidus
and solvus surfaces as well as temperature-composition sections are lacking. Information on the liquidus
surface and the isothermal sections at 400C are confined to the Ce rich region. Thermodynamic properties
of several phases in the Ce-Cu-Sn system were studied at very low temperatures to indicate magnetic
transformations [2000Sin, 2001Sin, 2002Zah]. Such kind of information can not be applied to Calphad-type
assessment.
Binary Systems
Data concerning the Ce-Cu system were evalated by [2002Per]. The Ce-Sn system (Fig. 1) is accepted
mainly from [1998Ria] who compiled phase diagram information based on experimental works of
[1988Fra1] and [1988Fra2]. The 5,Ce2Sn3 compound was determined by [2003For] and is incorportaed
into the present phase diagram, Fig. 1. The invariant lines coresponding to the polymorphic transformations
in cerium are incorportaed as well, shown as dashed lines at 61C and 13C. For the temperature of the
eutectoid reaction ( Ce) + (Ce) a balanced mean value was adopted between [1988Fra1] and
[1998Ria] which is now consistent with the ternary invariant reaction U4 (see Invariant Equilibria
section). The Cu-Sn system is accepted as given by [Mas2].
Solid Phases
Crystallographic data for unary, binary and ternary phases are listed in Table 2. The solid solubilities of
copper and tin in cerium as well as those of cerium and copper in tin are negligible. All the binary phases
in the Ce-Cu system have very small homogeneity ranges. The same is valid for the Ce-Sn system with
exception of ) phase. According to available experimental data, the majority of binary phases in the above
mentioned systems do not dissolve third component. Exceptions are the CeCu6 and ) phases at 400C (see
chapter Isothermal Sections). Noticable solubilities of cerium in the binary Cu-Sn phases were not found
so far. Information about existence of ten ternary phases is available in literature. High-temperature stability
limits were reported only for the -7 and -10 phases (Table 2), both phases are formed by peritectic reactions
[2001Sin]. Among all the ternary phases extended homogeneity regions were reported only for the -4 and
-5 phase. [1984Kom] found that the -10, CeCu9.4Sn3.6 phase has a cubic structure (NaZn13 type) at 500C,
while [1997Ria2] found a phase of the CeCu9Sn4 composition (labelled as -7) with the same structure.
However, later investigation of [2001Sin] showed that the phase CeCu9.4Sn3.6 has cubic structure NaZn13,
while the phase CeCu9Sn4 possesses a tetragonal LaFe9Si4 structure being an ordered derivative of the
New Series IV/11C2
CeCuSn 129
cubic NaZn13 structure. [2001Sin] also declared that the formation of cubic or tetragonal structures is
related to the alloy composition rather than to the annealing temperature. No structural changes were
observed by [2001Sin] in the samples of the CeCu9Sn4 composition after re-annealing at 500C. It was
noted by [2001Sin] that results of [1998Ria] are in contradiction with results of their investigation and
[1984Kom] data. The reason of disagreement could be the uncertainty of composition determined by
[1998Ria] or that equilibrium was not reached by [1998Ria] when executing the experiment. Both groups
of authors [1997Ria2, 1998Ria] and [2001Sin] used induction melting for sample preparation, but the
specimens obtained by [2001Sin] were annealed at higher temperatures during longer times (500 and
680C, 720-1200 h) comparing with [1997Ria2, 1998Ria] (400 and 630C, 250-720 h). This makes us
assume that equilibrium conditions were better reached in the experiments of [2001Sin].
Quasibinary Systems
The e1(max) point on the liquidus curve E1U2 corresponds to the maximum temperature of ~800C and the
composition belonging to -2(CeCuSn)-CeCu2 section, i.e. approximately 33.3 at.% Ce, 63.5 at.% Cu and
3.2 at.% Sn. [1998Ria] and coworkers assumed that the CeCu2-CeCuSn section probably is a quasibinary
system, where the point e1(max) is a eutectic point and micrographs of alloys close to its composition reveal
a eutectic structure.
The partial Scheil reaction scheme is shown in Fig. 2. It is based on the [1997Ria1, 1998Ria] data obtained
by differential scanning calorimetry by heating annealed samples. It should be mentioned that there is an
inconsistency in the reaction scheme presented by [1998Ria]. This inconsistency is between the temperature
of the binary eutectoid reaction e5 and the temperature of the invariant reaction U4. The type of the U4
reaction was determined by [1997Ria1] as transitional, but its temperature is lower than that of e5. We
accepted the type and the temperature of the U4 reaction and decreased the temperature of the e5 reaction
in the binary system within the experimental uncertainty limit given there (see section Binary Systems).
Invariant reactions were studied in the composition range adjacent to the Ce-Cu binary system, up to 70 at.%
Cu where eight four-phase and one three-phase invariant reactions were detected. The temperatures of the
invariant points and the corresponding compositions of the liquid phase are listed in Table 3.

The partial liquidus surface is shown in Fig. 3. It is based on [1997Ria1] and [1998Ria] data. Slight
corrections of the isotherms positions according to the accepted binary systems are made. The resulting
liquidus surface shows large extensions of primary fields related to the crystallization of the and Ce5Sn3
phases. Small primary regions are associated with the ( Ce), (Ce), and phases. According to the
assumption of [1998Ria], this may be related to the highly exothermic character of these alloys in
comparison with the Ce-Cu and Cu-Sn systems. These characteristics appear to be dominant and
substantially unaffected by the formation of ternary phases.
Data about solidus and solvus surfaces are lacking.
Isothermal Sections
Figure 4 presents an isothermal section at 400C for the whole range of compositions composed from to the
data of [1996Mar, 1997Ria2] and [1998Ria] with some corrections according to the accepted binary
systems. For the binary Ce-Sn system these are in fact the data compiled by [1988Fra1] and [1988Fra2]
while the composition of Sn rich liquid was plotted from data of [1997Ria2]. The L / L + 3 border was
plotted at about 96 at.% Sn, but according to the data of [1988Fra2] this position is closer to the Sn apex).
It should be mentioned that the phase 5, Ce2Sn3, is not shown in Fig. 4 because equilibria with participation
of this phase in the ternary system have not been verified, [1997Ria2, 1998Ria]. The 1 (Ce-Cu) phase found
by [1984All] was also observed by [1998Ria] in equilibrium conditions though they assume that this phase
is actually metastable, but stabilized by impurities [1998Ria]. According to the Ce-Cu binary phase diagram
Landolt-Brnstein
New Series IV/11C2
MSIT
130 CeCuSn
accepted in the present work the 1 phase is not stable, that is why equilibrium with this phase is not shown
in Fig. 4. Composition of the -10 phase is marked. This phase at the temperature of 400C should be stable
along with the -7 phase according to the data of [2001Sin]. However, it is not possible to conclude the
character of phase equilibria involving the -10 phase from the available experimental information. The
nature of the phase equilibria between (Cu), -3, -6 and -8 phases is uncertain. In this respect equilibria
information reported by [1998Ria] are in disagreement and the corresponding place in Fig. 4 is marked by
the symbol ?.

Electrical and magnetic properties of the Ce-Cu-Sn alloys were investigated widely. The applied
experimental techniques and studied types of properties are listed in Table 4.
The magnetic properties of the -2, CeCuSn phase were studied by [1983Kom, 1994Nak, 2005Cha]. Electric
resistivity of -2 phase was measured between 4.2 and 300 K by [1994Nak]. Antiferromagnetic ordering was
observed in this phase at 8.6 K according to the data of [1994Nak]. In contrast to these results showing broad
features at 8-10 K, the onset of antiferromagnetic order was observed at about 12 K by [2005Cha] with an
inflection in the temperature dependence of the magnetic intensities at about 8 K. Temperature dependence
(between 1.3 and 15 K) of the specific heat of -2, CeCuSn phase in various applied magnetic fields
(0 to 5 T) (Fig. 5) was established by [1994Nak]. [1983Kom] noted that magnetic susceptibility of the -2,
CeCuSn phase changes according to the Curie-Weiss law, with paramagnetic Curie temperature of 13 K.
The negative value of it indicates the possibility of antiferromagnetic ordering. In the B-T diagram of this
phase (Fig. 6) [1994Nak] three different antiferromagnetic phase structures were detected. They are labelled
as AF1 (exists between 7.35 and 8.6 K for magnetic fields below 1.5 T), AF2 (forms from AF1 below 7.35
K) and AF3 (forms at lower temperatures at magnetic field more than 2.5 T).
The specific heat, magnetic susceptibility and magnetisation of -3, Ce3Cu4Sn4 phase, were measured by
[2000Sin] and [2002Zah]. Using these data and data on neutron diffraction [2002Zah] reports on the
microscopic picture of magnetic ordering. The data on specific heat Cp at low temperatures for the -3,
Ce3Cu4Sn4 phase measured by [2000Sin, 2002Zah] are in a good agreement with each other. According to
[2000Sin] it exhibits three peaks at 10.2, 7.8 and 2.5 K. According to [2002Zha] there are peaks at TN = 10.3
(Neel temperature), T2 = 7.3 K and the beginning of upturn due to the transition at T3 = 2.6 K. The
temperature dependence of heat capacity of the -3, Ce3Cu4Sn4 phase below 30 K is presented in Fig. 7
according to [2002Zah]. Upturn at 2.6 K is shown as a peak similar to [2000Sin]. The magnetic entropy S -
temperature dependence for this phase obtained by [2002Zah] is presented in Fig. 8. A significant magnetic
contribution to the entropy persists up to at least 30 K, revealing an existence of magnetic fluctuations far
above TN. The temperature dependence of electric resistivity of -3, Ce3Cu4Sn4 phase was constructed by
[2000Sin]. There is a rapid decrease of resistivity below ~40 K which is precursor to the magnetic transition
occuring at ~10.4 K. The inverse susceptibility versus temperature dependences for this phase were
established by [2000Sin] and [2002Zah]. The obtained values of paramagnetic Curie temperature were
12.5 and 11.6 K, respectively. The curves shape is similar.
The temperature dependence of magnetic susceptibility of the -5, CeCu1xSn2y phase determined on the
CeCu0.52Sn1.83 alloy corresponds to the Curie-Weiss law [1988Kom]. Magnetic properties of the -6,
CeCu2Sn2 phase were studied by [1982Sko] at 78-293 K using Faraday technique and by [1996Guz] at
1.5 -100 K using inelastic neutron scattering spectra. Temperature dependences of the inverse susceptibility
were presented in both studies. Several other properties were reported for -6. Electrical resistivity at low
temperature for -6 was measured by [1985Rau], 119Sn Mssbauer spectra of between 4.2 and 300 K was
studied by [1989Goe] and thermal expansion data at low temperature was obtained by [1994Sle].
Temperature dependences of the heat capacity of the -7, CeCu9Sn4 and -10, CeCu9.4Sn3.6 phases obtained
by [2001Sin] are presented in Figs. 9 and 10, respectively. For the -7 phase the heat capacity curve shows
peak at 5.5 K, and, in opinion of the authors, such anomalies typically arise due to the transition from the
paramagnetic to the magnetically ordered state. The heat capacity data thus confirm the occurence of
magnetic transitions. For the -10 phase the heat capacity data show upturn below 3 K and indicate the
occurence of magnetic transition below 1.5 K. The inverse susceptibilities of -7 and -10 phases versus
New Series IV/11C2
CeCuSn 131
temperature dependences were constructed by [2001Sin]. The obtained values of paramagnetic Curie
temperature are 14.5 and 1 K, respectively. Electrical resistivity and magnetization were also investigated.
[1984Kom] obtained the Curie temperature value for CeCu9.4Sn3.6 similar to the data of [2001Sin]: 0 K.
According to the results of [1997Sko], the -9, CeCu5Sn phase electrical resistivity curve is similar to that
of heavy fermion compounds, but the maximum on it is much lower than that of the CeCu6 heavy fermion
system. The magnetic susceptibility 3of CeCu5Sn follows the Curie-Weiss law, however the 3 (T) function
becomes almost independent of the temperature below 10 K, may be due to a long range antiferromagnetic
ordering below 10 K. [2000Isn] established that CeCu5.25Sn0.75 and CeCu5Sn alloys order
antiferromagnetically at TN = 4 and 10 K, respectively. Magnetoresistance, reciprocal magnetic
susceptibility and thermopower were studies by them for the CeCu6xSnx alloys (x = 0, 0.25, 0.75 and 1).
It was noted in review of [2004Wu] that additions of cerium and lanthanum to the Sn-0.7Cu (mass%)
increase its tensile strength, improve its wettability and decrease ductility and creep strain (substantially for
the last property). The authors consider that the Pb free solder alloys doped with rare earth elements (the
Sn-0.7Cu + Ce + La) alloy is among of them are now ready for reliability studies such as thermal shock and
electromigration to prove their feasibility as working solders.
Miscellaneous
[1996Sle] have obtained the valence band and 3d core-level X-ray photoemission spectra (XPS) of the
CeCu2Sn2 compound. An analysis of these spectra was carried out using the Gunnarsson-Schoenhammer
model. A large hybridization of the f orbitals with a conduction band was found as characteristic for this
compound. The XPS valence band was compared with self-consistent band structure calculations of the
linear muffin-tin orbital (LMTO) type, and were discussed. The Ce LIII X-ray absorption spectra of the
CeCu6xSnx (x = 0, 0.25, 0.75 and 1) solid solutions have been studied by [2000Isn]. A trivalent state of
cerium in the alloys containing Sn was shown.
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New Series IV/11C2
MSIT
132 CeCuSn
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New Series IV/11C2
CeCuSn 133
[1982Bor] Borzone, G., Borsese, A., Ferro, R., On the Alloying Behaviour of Cerium with Tin,
J. Less-Common Met., 85(2), 195-203 (1982) (Crys. Structure, Phase Diagram,
[1982Sko] Skolozdra, R.V., Komarovskaya, L.P., Crystal Structure and Magnetic Properties of the
RCu2Sn2 Compounds (in Russian), Ukrain. Fiz. Zhur., 27(12), 1834-1838 (1982) (Crys.
Structure, Experimental, Magn. Prop., 4)
[1983Kom] Komarovskaya, L.P., Skolosdra, R.V., Filatova, I.V., Crystal Structure and Magnetic
Susceptibility of RCuSn Compounds (in Ukrainian), Dop. Akad. Nauk Ukr. RSR, Ser. A,
Fiz-Mat. Tekh. Nauki, 45(1), 81-83 (1983) (Crys. Structure, Experimental, Magn. Prop., 4)
[1983Kuw] Kuwano, N., Wayman, C.M., Precipitation Processes in a -Phase Cu-15 at.% Sn Shape
Memory Alloy, Trans. Jpn. Inst. Met., 24(8), 561-573 (1983) (Crys. Structure,
Experimental, 22)
[1983Wat] Watanabe, Y., Fujinaga, Y., Iwasaki, H., Lattice Modulation in the Long Period
Superstructure of Cu3Sn, Acta Crystallogr., Sect. B., 39, 306-311 (1983) (Phase Relations,
Crys. Structure, Experimental) as quoted by [1994Sau]
[1984All] Allibert, C., Wong-Ng, W., Nyburg, S.C., CeCu3.6 Disordered Variant of Gd14Ag51
Type, Acta Crystallogr., Sect. C., 40, 211-214 (1984) (Crys. Structure, Experimental) as
quoted by [1998Ria]
[1984Kom] Komarovskaya, L.P., Skolozdra, R.V., Crystal Structure and Magnetic Susceptibility of
the RCu9.4Sn3.6 (R = La, Ce, Pr, Nd) Compounds (in Russian), Dokl. AN USSR, Ser. B.,
Geol., Khim., Biol. Nauki, 8, 40-42 (1984) (Crys. Structure, Experimental, Magn. Prop., 3)
[1984Sau] Saunders, N., Ph. D. Thesis, Phase Formation CoDeposited Alloy Thin Films, Univ.
Surrey, U.K. (1984) (Phase Relations, Crys. Structure, Experimental) as quoted by
[1994Sau]
[1985Cor] Cordier, G., Czech, E., Schaefer, H., Woll, P., Structural Characterization of New Ternary
Compounds of Uranium and Cerium, J. Less-Common Met., 110(1-2), 327-330 (1985)
[1985Gir] Girodin, D., Allibert, C.H., Givord, F., Lemaire, R., Phase Equilibria in the CeCo5-CeCu5
System and Structural Characterization of the Ce(Co1xCux)5 Phases, J. Less-Common
Met., 110, 149-158 (1985) (Crys. Structure, Phase Diagram, Experimental, Magn.
Prop., 13)
[1985Rau] Rauchschwalbe, U, Gottwick, U., Ahlheim, U., Mayer, H.M., Steglich, F, Investigation of
New Lanthanum-, Cerium- and Uranium-based ternery Intermetallics, J. Less-Common
Met., 111, 265-275 (1985) (Crys. Structure, Experimental, 31)
[1986Vrt] Vrtis, M.L., Jorgensen, J.D., Hinks, D.G., Structural Phase Transition in CeCu6,
Physica, B/C, 136B, 489-492 (1986) (Crys. Structure, Experimental) as quoted by
[1998Ria]
[1988Fra1] Franceschi, E.A., Costa, G.A., The Phase Diagram of the Ce-Cu System up to 50 at.% Sn,
J. Therm. Anal., 34, 451-456 (1988) (Crys. Structure, Phase Diagram, Experimental) as
quoted by [1998Ria]
[1988Fra2] Franceschi, E.A., Costa, G.A., Phase Equilibria in the Ce-Sn System: the Partial
Equilibrium Diagram from 50 at.% Sn to Sn, Lanthanide Actinide Res., 2, 407-413 (1988)
(Crys. Structure, Phase Diagram, Experimental, Mechan. Prop., *, 8)
[1988Kom] Komarovskaya, L.P., Sadykov, S.A., Skolozdra, R.V., Magnetic and Electrical Properties
of New Stannides RCu1xSn2y (R = La, Ce, Pr, Nd) with the Defective Structure
(in Russian), Ukrain. Fiz. Zhur., 33(8), 1249-1251 (1988) (Crys. Structure, Experimental,
Electr. Prop., Magn. Prop., 4)
[1989Goe] Goerlich, E.A., Latka, K., Moser, J., Structural and Magnetic Properties of RET2Sn2
Compounds (RE = La, Ce, Sm; T = Ni, Cu), Hyperfine Interact., 50, 723-728 (1989) (Crys.
Systems R-M-X (R = La, Lu, M = Metals of the Groups 7 to 11 and X = Ge, Sn).
Landolt-Brnstein
New Series IV/11C2
MSIT
134 CeCuSn
I. Compositions and Structure Parameters (in French), J. Less-Common Met., 160(2),

Structure, Phase Relations, Experimental, 26)
[1994Nak] Nakotte, H., Brueck, E., Prokes, K., Brabers, J.H.V.J., de Boer, F.R., Havela, L., Buschow,
K.H.J., Fu-ming, Y., Complex Antiferromagnetic Order of Ce-Cu-Sn, J. Alloys Compd.,
207/208, 245-248 (1994) (Crys. Structure, Thermodyn., Experimental, Electr. Prop., Magn.
Prop., 9)
[1994Sau] Saunders, N., Miodownik, A.P., Cu-Sn (Copper-Tin), in Phase Diagrams of Binary
Copper Alloys, Subramanian, S.R., Chakrabarti, D.J., Laughlin, D.E. (Eds.), ASM
International, Materials Park, OH, 412-418 (1994) (Phase Diagram, Crys. Structure,
Thermodyn., Review, #, 55)
[1994Sle] Slebarski, A., Kaczmarska, K., Pierre, J., Structural properties of REM2Sn2 (Re = La, Ce
and M = Ni, Cu), Acta Phys. Pol. A, 85(2), 267-270 (1994) (Crys. Structure,
Experimental, 4)
[1994Sub1] Subramanian, P.R., Cu (Copper), in Phase Diagrams of Binary Copper Alloys,
Park, OH, 1-3 (1994) (Crys. Structure, Review, Thermodyn., 16)
[1994Sub2] Subramanian, P.R., Laughlin, D.E., Ce-Cu (Cerium-Copper), in Phase Diagrams of
International, Materials Park, OH, 127-133 (1994) (Crys. Structure, Phase Diagram,
Thermodyn., Review, #, 29)
[1996Guz] Guzik, A., Kaczmarska, K., Pierre, J., Murani, A.P., Spin Dynamics in Some Cerium
Ternary Stannides and Antimonides, J. Magn. Magn. Mater., 161, 103-110 (1996) (Crys.
[1996Lid] Lidstroem, E., Ghandour, A.M., Haeggstroem, L., Andersson, Y., X-Ray Diffraction and
Moessbauer Studies of CeT2Sn2 (T = Cu, Pd and Pt), J. Alloys Compd., 232, 95-100 (1996)
[1996Mar] Marazza, R., Riani, P., Mazzone, D., Zanicchi, G., Ferro, R., The Isothermal Section at
400C of the Phase Diagram Ce-Cu-Sn in the Region Between CeCu2-Ce3Sn7-Ce,
Intermetallics, 4, 131-138 (1996) (Crys. Structure, Morphology, Phase Diagram, Phase
Relations, Experimental, Review, #, 26)
[1996Poe] Poettgen, R., Kotzyba, G., Structure Refinement and Magnetic Properties of DyCuSn,
J. Alloys Compd., 235, L9-L12 (1996) (Crys. Structure, Experimental, Magn. Prop., 17)
[1996Pol] Polyakova, V.P., Shelimova, L.E., Ce-Cu. Cerium-Copper, in Phase Diagrams of
Binary Metallic Systems (in Russian), Lyakishev, N.P. (Ed.), Vol. 1, Mashinostroenie,
Moscow, 898-900 (1996) (Crys. Structure, Phase Diagram, Review, *, 7)
[1996Sle] Slebarski, A., Jezierski, A., Zygmunt, A., Neumann, M., Maehl, S., Borstel, G.,
The Crystallographic, Magnetic and Electronic Properties of RM2X2 (R = La, Ce, Pr;
M = Cu, Ni; X = Sn, Sb), J. Magn. Magn. Mater., 159, 179-191 (1996) (Crys. Structure,
Calculation, Experimental, Electronic Structure, Magn. Prop., 41)
[1997Boc] Bochvar, N.R., Cu-Sn. Copper-Tin, in Phase Diagrams of Binary Metallic Systems
(in Russian), Lyakishev, N.P. (Ed.), Vol. 2, Mashinostroenie, Moscow, 323-326 (1997)
(Crys. Structure, Phase Diagram, Review, *, 10)
[1997Din] Dinsdale, A.T., Summary of the Proceedings of the Calphad XXV Meeting, Calphad,
21(1), 105-135 (1997) (Crys. Structure, Phase Relations, Thermodyn., Abstract,
Calculation, Experimental, Review, Phys. Prop., Superconduct., *, 154)
[1997For] Fornasini, M.L., Marazza, R., Mazzone, D., Riani, P., Zanicchi, G., Ferro, R., New Phases
in the R-Cu-Sn Systems (R = Rare Earth), 12th Intern. Conf. Solid Compounds Trans.
Elements, P-C02 (1997) (Crys. Structure, Experimental, 6)
New Series IV/11C2
CeCuSn 135
[1997Ria1] Riani, P., Mazzone, D., Marazza, R., Ferro, R., Faudot, F., Harmelin, M., Ce-Cu-Sn
System: Experimental Determination of the Liquidus Surface in the Ce rich Corner,
J. Chem. Phys., 94, 1081-1086 (1997) (Crys. Structure, Morphology, Phase Diagram, Phase
Relations, Experimental, #, 9)
[1997Ria2] Riani, P., Mazzone, D., Zanicchi, G., Marazza, R., Ferro, R., The Isothermal section at
400C of the Ce-Cu-Sn Ternary System, Intermetallics, 5, 507-514 (1997) (Crys.
Structure, Morphology, Phase Diagram, Experimental, #, 25)
[1997Sko] Skolozdra, R.V., Romaka, L.P., Akselrud, L.G., Pierre, J., The New Phases RCu5Sn with
the CeCu6 Structure Type, 12th Intern. Conf. Solid Compounds Trans. Elements, P-C08
(1997) (Crys. Structure, Experimental, Electr. Prop., Magn. Prop.)
[1998For] Fornasini, M.L., Marazza, R., Mazzone, D., Riani, P., Zanicchi, G., New Phases RCu5Sn
(R = La, Ce, Pr, Nd, Sm, Gd) and Ce2Cu9Sn2.65, Z. Kristallogr., 213, 108-111 (1998)
[1998Ria] Riani, P., Mazzone, G., Zanicchi, G., Marazza, R., Ferro, R., Faudot, F., Harmelin, M.,
On the Ce-Cu-Sn System, J. Phase Equilib., 19(3), 239-251 (1998) (Crys. Structure,
Phase Diagram, Experimental, Assessment, #, 53)
[2000Isn] Isnard, O., Pierre, J., Fruchart, D., Romaka, L.P., Skolozdra, R.V., Crossover from Kondo
Lattice to Antiferromagnetic Ordering in the CeCu6-xSnx Phase, Solid State Commun.,
113, 335-340 (2000) (Crys. Structure, Experimental, Electronic Structure, Electr. Prop.,
Magn. Prop., 20)
[2000Sin] Singh, S., Dhar, S.K., Manfrinetti, P., Palenzona, A., Magnetic Properties of R3Cu4Sn4
(R = Ce, Gd and Y), J. Alloys Compd., 298, 68-72 (2000) (Crys. Structure, Thermodyn.,
Experimental, Magn. Prop., 7)
[2001Sin] Singh, S., Fornasini, M.L., Manfrinetti, P., Palenzona, A., Dhar, S.K., Paulose, P.L.,
Crystallographic and Magnetic Behaviour of RCu9Sn4 and RCu9.4Sn3.6 (R = La to Nd)
Compounds, J. Alloys Compd., 317-318, 560-566 (2001) (Crys. Structure, Phase
Relations, Thermodyn., Experimental, Magn. Prop., *, 17)
Stuttgart, ID: 20.16303.1.20 (2002) (Crys. Structure, Phase Diagram, Phase Relations,
Assessment, #, 25)
[2002Zah] Zaharko, O., Keller, L., Ritter, C., Magnetic Ordering in Ce3Cu4Sn4 and Ce3Cu4Ge4,
J. Magn. Magn. Mater., 253, 130-139 (2002) (Crys. Structure, Thermodyn., Experimental,
Magn. Prop., 11)
[2003For] Fornasini, M.L., Manfrinetti, P., Palenzona, A., Dhar, S.K., R2Sn3 (R = La-Nd, Sm):
A Family of Intermetallic Compounds with their Own Triclinic Structure, Z. Naturforsch.,
58B, 521-527 (2003) (Crys. Structure, Experimental, Magn. Prop., 25)
[2004Szy] Szytula, A., Wawrzynska, E., Penc, B., Stuesser, N., Tomkowicz, Z., Zygmunt, A.,
Magnetic Properties and Electronic Structure of R3T4X4 (R: La-Nd, Gd-Er; T: Mn, Cu; X:
Ge, Sn) Compounds, J. Alloys Compd., 367(1-2), 224-229 (2004) (Crys. Structure,
Electronic Structure, Experimental, Magn. Prop., Phase Relations, 17)
[2004Wu] Wu, C.M.L., Yu, D.Q., Law, C.M.T., Wang, L., Properties of Lead Free Solder Alloys with
Rare Earth Element Additions, Mater. Sci. Eng. R, 44, 1-44 (2004) (Morphology, Review,
Interface Phenomena, Mechan. Prop., 100)
[2005Cha] Chang, S., Janssen, Yu., Garlea, V.O., Zarestky, J., Nakotte, H., McQueeney, R.J.,
Magnetic Structure of the Local-Moment Antiferromagnetic CeCuSn, J. Appl. Phys., 97,
10A913(1-3) (2005) (Crys. Structure, Experimental, Magn. Prop., 11)
Landolt-Brnstein
New Series IV/11C2
MSIT
136 CeCuSn
Table 1: Investigations of the Ce-Cu-Sn Phase Relations, Structures and Thermodynamics

Studied
[1968Rie] X-ray diffraction Ce5CuSn3
[1976Dwi] X-ray Debye-Scherrer powder diffraction CeCuSn
[1982Sko] X-ray diffraction CeCu2Sn2
[1983Kom] X-ray Debye-Scherrer diffraction CeCuSn
[1984Kom] X-ray Debye-Scherrer diffraction CeCu9.4Sn3.6
[1985Cor] X-ray single crystal diffractometry CeCu2Sn1.9
[1988Kom] X-ray powder diffraction 25 to 32 at.% Ce at 18 to 30 at.% Cu
[1989Goe] X-ray diffraction; 119
Sn Moessbauer CeCu2Sn2
measurements
[1990Fra] X-ray Guinier powder diffraction CeCu0.5Sn2
[1994Nak] X-ray polycrystal diffraction CeCuSn
[1994Sle] X-ray powder diffraction < 27C, CeCu2Sn2
[1996Guz] Inelastic neutron scattering diffraction CeCu2Sn2
[1996Lid] X-ray Guinier powder diffraction; CeCu2Sn2
Moessbauer studies
[1996Mar] X-ray diffraction; optical microscopy; 400C, the region between CeCu2-Ce3Sn7-Ce
EMPA
[1997Din] Preparatory and anaytical techniques 400C, whole range of compositions
[1997For] X-ray diffraction CeCu5Sn, Ce2Cu9Sn2.65
[1997Ria1] Differential scanning calorimetry; SEM; < 800C,. the Ce rich part
energy dispersive spectrometry
[1997Ria2] X-ray diffraction; optical microscopy; 400C, whole range of compositions
SEM; EMPA
[1997Sko] X-ray powder diffraction CeCu5Sn
[1998For] X-ray single crystal diffractometry CeCu5Sn, Ce2Cu9Sn2.65, Ce3Cu4Sn4
[1998Ria] X-ray diffraction; differential scanning 1300C, whole range of compositions
calorimetry; optical microscopy; SEM;
EMPA
[2000Isn] X-ray powder diffraction 500C, 14.3 at.% Ce at 71.4 to 85.7 at.% Cu
[2000Sin] X-ray Guinier powder diffraction Ce3Cu4Sn4
[2001Sin] X-ray Guinier powder diffraction; DTA CeCu9Sn4, CeCu9.4Sn3.6
[2002Zah] X-ray powder diffraction; Ce3Cu4Sn4
neutron diffraction
[2005Cha] Single crystal neutron diffraction CeCuSn
New Series IV/11C2
CeCuSn 137

[C] Prototype
( Ce) cI2 a = 412 at 757C [1994Sub2]
798 - 726 Im3m x = 0, 0 x ~0.02, 729C [1994Sub2]
Ce1xyCuxSny W y = 0, 0 x ~0.077, 708C [1994Sub2]
(Ce) cF4 a = 516.10 [1994Sub2]
726 - 61 Fm3m y = 0, 0 x ~0.0037, 708C [1994Sub2]
Ce1xyCuxSny Cu
(Ce) hP4 a = 368.10 at 24C [1994Sub2]
61- (177) P63/mmc c = 1185.7
La
(Ce) cF4 a = 485 at 196C [1994Sub2]
< -177 Fm3m
Cu
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m at x = 0, 0 y 0.077, 798C [1944Ray,
CexCu1xySny Cu 1994Sau]
at x = 0, 0 y 0.087, 700C [1970Tok,
1997Boc]
at x = 0, 0 y 0.057, 250C [1970Tok,
1997Boc]
at x = 0, 0 y 0.007, 200C [1944Ray,
1994Sau]
at y = 0, 0 x 0.001, 876C [1994Sub1]
a = 361.46 to 370.46 at x = 0, 0 y 0.091 [1994Sau]

a = 361.8 at x = 0.001, y = 0.001, 400C [1997Ria2]
a = 367.6 at x = 0.002, y = 0.07, 400C [1997Ria2]
(Sn) tI4 a = 583.18 at 25C [Mas2]
231.9681 - 13 I41/amd c = 318.18 at x = 0, 0 y 0.0001, [1939Hom,
CexCuySn1xy Sn 1994Sau]
(Sn) cF8 a = 648.92 at 25C [Mas2]
< 13 Fd3m
C (diamond)
,CeCu oP8 a = 730 [1961Lar2]
< 516 Pnma b = 430
FeB c = 636
a = 719 [1965Wal, 1998Ria]

b = 430
c = 623
a = 737 [1965Dwi, 1994Sub2]

b = 462.3
c = 564.8
Landolt-Brnstein
New Series IV/11C2
MSIT
138 CeCuSn

[C] Prototype
,CeCu2 oI12 dissolves ~1.4 at.% Sn at 1400C
< 817 Imma [1997Ria2]
CeCu2 a = 443 at 0 at.% Sn [1961Lar1]
b = 705
c = 745
a = 442.5 at 0 at.% Sn [1963Sto]

b = 705.7
c = 747.5
a = 442.9 at 0 at.% Sn [1994Sub2]

b = 706.1
c = 747.4
a = 444.1 at 33.5 at.% Ce, 0.1 at.% Sn, 400C

b = 707.7 [1997Ria2]
c = 745.9
a = 444.1 at 33.8 at.% Ce, 1.4 at.% Sn, 400C

b = 707.7 [1997Ria2]
c = 745.9
,CeCu4 oP20 a = 454 [1964Rhi, 1998Ria]
< 796 Pnnm b = 810
CeCu4 c = 919
,CeCu5 hP6 a = 514.8 [Mas2]
< 798 P6/mmm c = 410.8
CaCu5
a = 514 [1964Rhi, 1996Pol]
c = 411
a = 513.4 [1985Gir]
c = 410.5
New Series IV/11C2
CeCuSn 139

[C] Prototype
CeCu6 oP28 dissolves ~7 at.% Sn at 400C [1997Ria2]
938 - (-43) Pnma a = 811.2 [1960Cro]
CeCu6 b = 510.2
c = 1016.2
a = 810.9 [1986Vrt, 1998Ria]

b = 510.0
c = 1016.2
a = 810.88 at 22C [1990Vrt]

b = 510.04
c = 1016.21
a = 810.09 at 23C [1990Vrt]

b = 509.78
c = 1015.48
a = 811.0 [1994Sub2]
b = 510.2
c = 1016.1
a = 810.0 at 15.3 at.% Ce, 4.3 at.% Sn, 400C

b = 510.3 [1997Ria2]
c = 1018
a = 805 at 14.0 at.% Ce, 7 at.% Sn, 400C

b = 504 [1997Ria2]
c = 1018
CeCu6 mP28 a = 509.5 at 73C [1990Vrt]
< 43 P21/c b = 1014.66
LaCu6 c = 809.31
= 90.485
a = 508.41 at 263C [1990Vrt]

b = 1012.79
c = 807.31
= 91.442
1 (Ce-Cu) hP68 a = 1185.8 at 0 at.% Cu, 78.46 at.% Cu, labelled as
Gd14Ag51 c = 910.7 Ce14Cu51.
Metastable, impurity stabilized(?)
[1984All, 1998Ria]
, Ce3Sn cP4 a = 492.9 [S]
< 940 Pm3m a = 493 to 494 [1982Bor]
AuCu3 a = 492.7 [1988Fra1, 1998Ria]
a = 492.3 at 400C [1997Ria2]
Landolt-Brnstein
New Series IV/11C2
MSIT
140 CeCuSn

[C] Prototype
Ce5Sn3 hP16 a = 933 [1982Bor]
1505 - 940 P63/mcm c = 681
Mn5Si3
Ce5Sn3 tI32 a = 1259.1 [1979Fra]
< 940 I4/mcm c = 617.4
W5Si3 a = 1260 [1982Bor]
c = 617
a = 1259.9 [1988Fra1, 1998Ria]
c = 617.9
a = 1258 at 400C [1996Mar]
c = 615.3
', Ce5Sn4 oP36 a = 833.7 [1971For, 1998Ria]
< 1515 Pnma b = 1605
Sm5Ge4 c = 848.0
a = 834.8 [1988Fra1, 1998Ria]
b = 1603
c = 849.2
a = 836 at 400C [1996Mar]
b = 1607
c = 848.4
), Ce11Sn10 tI84 dissolves 5 at.% Cu at 400C [1997Ria2]
< 1375 I4/mmm a = 1220 [1988Fra1, 1998Ria]
Ho11Ge10 c = 1790
a = 1197 [1982Bor]
c = 1782
a = 1206 to 1212 [1998Ria]
c = 1761 to 1795
5, Ce2Sn3 aP20 a = 644.4 [2003For]
P1 b = 851.0
Nd2Sn3 c = 1119.5
= 107.36
= 96.78
= 99.42
!, Ce3Sn5 oC32 a = 1025 [1982Bor]
< 1180 Cmcm b = 822
Pu3Pd5 c = 1058
a = 1024.3 at 400C [1996Mar]
b = 821.4
c = 1065.2
%, Ce3Sn7 oC20 a = 452.4 [1988Fra2]
< 1135 Cmmm b = 2574.2
Ce3Sn7 c = 461.0
New Series IV/11C2
CeCuSn 141

[C] Prototype
Q, Ce2Sn5 oC28 a = 455.9 [1988Fra2]
< 1145 Cmmm b = 3501.4
Ce2Sn5 c = 461.9
a = 459.0 at 400C [1997Ria2]

b = 3514
c = 466.2
3, CeSn3 cP4 a = 472.2 [S]
< 1170 Pm3m a = 472.1 [1988Fra2]
AuCu3 a = 472.4 at 400C [1997Ria2]
,CexCu1xySny cI2 a = 297.81 to 298.71 x = 0, 0.131 y 0.165 [1994Sau]
798 - 586 Im3m a = 298.1 to 299.1 x = 0, 0.134 y 0.157 [1994Sau]
W x = 0, 0.152 y 0.172 [1939Isa, 1994Sau]
, Cu3Sn cF16 15.5 - 27.5 at.% Sn [1994Sau]
755 - 520 Fm3m a = 606.05 to 611.76 16.6-25.0 at.% Sn, 710C [1994Sau]
BiF3 a = 611.6 0.06 at 25 at.% Sn, 700C [1957Kno]
, Cu41Sn11 cF416 20 - 21 at.% Sn [1994Sau]
590 - ~350 F43m labelled as Cu31Sn8 [1979Cha]
Cu41Sn11 a = 1798.0 at 20.5 at.% Sn, 560C [1977Boo]
, Cu10Sn3 hP26 20.3 - 22.5 at.% Sn
640 - 582 P63 a = 733.0 at 23.1 at.% Sn [1975Bra]
Cu10Sn3 c = 786.4
J, Cu3Sn oC80 24.5 - 25.9 at.% Sn
< 676 Cmcm a = 552.9 at 25 at.% Sn [1983Wat, 1994Sau]
Cu3Sn b = 477.5
c = 432.3
, Cu6Sn5(h) hP4 43.5 - 45.5 at.% Sn
415 - 186 P63/mmc a = 419.0 at 45.45 at.% Sn, 0 at.% Ce [1994Sau]
NiAs c = 508.6
a = 419.2 0.2 at 45.45 at.% Sn, 0 at.% Ce, 210C

c = 503.7 0.2 [1973Gan]
', Cu6Sn5(r) h* ~45.45 at.% Sn
< 186 Superlattice based on NiAs-type structure
[1994Sau]
a = 2087.0 [1973Gan]
c = 2508.1
Landolt-Brnstein
New Series IV/11C2
MSIT
142 CeCuSn

[C] Prototype
' (Cu-Sn) hP2 metastable
P63/mmc ~8 - 11.5 at.% Sn [1963Der, 1967Deb,
Mg 1994Sau]
a = 2087.0 at ~8 at.% Sn, [1963Der]
c = 2508.1
a = 2087.0 at 11.5 at.% Sn, [1984Sau, 1994Sau]

c = 2508.1 in the alloy with 16.5 at.% Sn heated to
570C for 10 min, and then aged at 100C
and 130C. Labelled as [1973Van]
7(Cu-Sn) hP12 metastable
15 - 16 at.% Sn [1973Van, 1980Zak]
a = 421 at 15.5 at.% Sn, 700C [1980Zak]
c = 1110
X (Cu-Sn) hP9 metastable
on tempering of a quenched single phase
alloy [1932Isa, 1934Bug, 1957Bag]
a = 728 at ~15 at.% Sn, [1932Isa, 1957Bag]
c = 258
a = 740 at 15 at.% Sn, 100C.

c = 260 Labelled as L [1983Kuw]
2 (Cu-Sn) ordered rhombic metastable
a = 1273 in a 15.5 at.% Sn, alloy quenched from
b = 424 700C and aged during 15 years [1980Zak]
c = 600
(Cu-Sn) ordered cubic metastable
a = 899 in a 19.5 at.% Sn alloy, vapor quenched,
below 200C [1984Sau, 1994Sau]
* -1, Ce5CuSn3 hP18 a = 947.4 [1968Rie]
P63/mcm c = 669.9
Ti5Ga4
a = 948.3 at 400C [1996Mar]
c = 673.5
a = 948.6 [1998Ria]
c = 671.2
New Series IV/11C2
CeCuSn 143

[C] Prototype
* -2, CeCuSn hP6 a = 458 [1976Dwi]
P63/mmc c = 791
CaIn2a) a = 457.0 [1983Kom]
c = 790.3
a = 459.1 at 400C [1996Mar]
c = 793.5
a = 458.8 [1998Ria]
c = 791.9
hP6 a = 459 ordered structure, single crystal data

P63mc c = 790 [2005Cha]
GaGeLi
* -3, Ce3Cu4Sn4 oI22 a = 1510.8 at 400C [1996Mar]
Immm b = 702.6
Gd3Cu4Ge4 c = 456.0
a = 1509.8 [2000Sin]
b = 702.2
c = 459.7
a = 1490.3 at 264C (11.5 K) [2002Zah]

b = 692.5
c = 454.2
* -4, (Ce-Cu-Sn) hP3 31.5 to 36 at.% Ce at 21 to 7 at.% Cu, 400C
P6/mmm [1997Ria2]
AlB2 a = 452 at 33 at.% Ce, 21 at.% Cu, 400C
c = 429 [1997Ria2]
a = 439.5 at 36 at.% Ce, 7 at.% Cu, 400C [1997Ria2]

c = 450
* -5, CeCu1xSn2y oC16 27.5 to 30 at.% Ce at 16 to 9 at.% Cu, 400C
Cmcm [1997Ria2]
CeNiSi2 a = 449.2 at 397C [1988Kom]
b = 1785
c = 443.9
a = 449.4 CeCu0.5Sn2 [1990Fra]

b = 1799
c = 444.5
a = 450 at 28 at.% Ce, 16 at.% Cu, 400C

b 1785 [1997Ria2]
c = 445
a = 450 at 30 at.% Ce, 9 at.% Cu, 400C [1997Ria2]

b 1780
c = 444
Landolt-Brnstein
New Series IV/11C2
MSIT
144 CeCuSn

[C] Prototype
* -6, CeCu2Sn2 tP10 a = 445.6 [1982Sko]
P4/nmm c = 1047.5
CaBe2Ge2
a = 442.9 CeCu2Sn1.9 single crystal [1985Cor]
c = 1042.6
a = 445.8 [1989Goe]
c = 1048.4
a = 445 after annealing between 600 and 700C

c = 1035 [1996Guz]
a = 445.79 at 900C [1996Lid]

c = 1047.35
a = 445.3 at 400C [1997Ria2]

c = 1047
* -7, CeCu9Sn4 tI56 a = 862.6 [2001Sin]
< 745 I4/mcm c = 1238.2
LaFe9Si4
* -8, Ce2Cu9Sn2.65 oP56-1.4 labelled as Ce3Cu13Sn4 [1997Ria2]
Pnnm a = 1066.9 [1997For, 1998For]
Ce2Cu9In3 b = 1673.4
c = 506.6
* -9, CeCu5Sn oP28 a = 834.18 [1997Sko]
Pnma b = 506.88
CeCu6 c = 1065.1
a = 831.7 at 500C [2001Sin]

b = 506.6
c = 1059.1
a = 832.3 [1997For, 1998For]

b = 506.4 The CeAuCu5-prototype - a ternary
c = 1059.7 derivative of the CeCu6 structure
* -10, CeCu9.4Sn3.6 cF112 a = 1215.3 at 500C [1984Kom]
< 800 Fm3c a = 1217.7 [2001Sin]
NaZn13
a)
Possibly, according to the assumption of [1998Ria], the -2 phase structure is of the ordered hP6 P63mc
NdPtSb type according to single-crystal data obtained from other RECuSn compounds [1996Poe]. Later the
ordered P63mc GaGeLi type was attributed by [2005Cha] to the structure of this phase (as a results of
antiferromagnetic ordering experimental investigation)
New Series IV/11C2
CeCuSn 145

Ce Cu Sn
L -2 + ~800 e1 L ~33 ~63.8 ~3.2
L + -2 + 780 U1 L 23 75 2
L + -2 -1 + 775 U2 L 41 56 3
L + -1 (Ce5Sn3) + 760 U3 L 42.5 54.5 3
L + + -2 740 E1 L 25 73 ~2
L + ( Ce) + (Ce) 699 U4 L 91 5 4
L + Ce5Sn3 + 530 U5 L 56 42 2
L++ 510 U6 L 59.5 39.5 1
L + + (Ce) 420 E2 L 71 27.5 1.5
Table 4: Investigations of the Ce-Cu-Sn Materials Properties

[1982Sko] Faraday method Magnetic susceptibility of the CeCu2Sn2
compound
[1983Kom] Faraday method Magnetic susceptibility of the CeCuSn
compound
[1984Kom] Faraday method Magnetic susceptibility of the CeCu9.4Sn3.6
compound
[1988Kom] Faraday method Magnetic susceptibility of the CeCu0.52Sn1.83
compound
[1989Goe] 119
Sn Moessbauer measurements Isomer shift, recoil free fraction of the
CeCu2Sn2 compound
[1994Nak] Four-point probe method; SQUID Electrical resistivity, magnetization of the
pendulum magnetometer measurements; CeCuSn
standard semi-adiabatic specific heat
measurements
[1996Guz] Magnetic susceptibility measurements Reciprocal magnetic susceptibility of the
CeCu2Sn2 single crystal
[1997Sko] Electrical and magnetic properties Electrical resistivity, thermopower, magnetic
measurements susceptivbility of the CeCu6xSn1+x (x = 0,
0.25, 0.50, 0.75 and 1) alloys
[2000Isn] Extraction method; ac current four probes Electrical resistivity, magnetoresistance,
method; direct comparison of a copper- reciprocal magnetic susceptibility,
sample-copper chain to a standard thermopower of the CeCu6xSnx (x = 0, 0.25,
thermocouple 0.75 and 1)
Landolt-Brnstein
New Series IV/11C2
MSIT
146 CeCuSn

[2000Sin] Ac current four probes method; SQUID Inverse susceptibility, magnetization,
magnetometer measurements; semi- electrical resistivity of the Ce3Cu4Sn4
adiabatic, heat pulse method of heat compound
capacity measurements
[2001Sin] Ac current four probes method; SQUID Inverse susceptibility, magnetization,
magnetometer measurements; semi- electrical resistivity of the CeCu9Sn4 and
adiabatic, heat pulse method of heat CeCu9.4Sn3.6 compounds
capacity measurements;
[2002Zah] Quantum design physical property Magnetic susceptibility, magnetization of the
measurement system (PPMS) technique; Ce3Cu4Sn4 compound
specific heat measurements using a
quantum design physical property
measurement system (PPMS)
[2004Szy] SQUID magnetometer technique Magnetic susceptibility of the Ce3Cu4Sn4
compound
[2004Wu] Mechanical properties measurements Tensile strength, ductility, creep strain,
wettability
[2005Cha] Single crystal neutron diffraction Antiferromagnetic behavior of the CeCuSn
studies compound
Fig. 1: Ce-Cu-Sn. 1515

1500 1505
The Ce-Sn phase L
diagram 1375
1250
1180 1170
Ce5Sn3
1155 1130 1145
1135
Temperature, C
1000
940
( Ce)
798C ,Ce2Sn3
750 729
726C
696 ,Ce3Sn5
,Ce3Sn
,Ce3Sn7
500
Ce5Sn3 ,Ce2Sn5
(Ce)
,Ce11Sn10 ,CeSn3
250 231.9681C
225
,Ce5Sn4 ( Sn)
( Ce) 61 13
0 ( Sn)
Ce 20 40 60 80
Sn
Sn, at.%
New Series IV/11C2
CeCuSn 147
Ce-Cu Ce-Cu-Sn A-B-C Ce-Sn

1505 p1
l+ Ce5Sn3
1375 p2
l+
940 p3
L+1+2 l + Ce5Sn3
~800 e1(max)
L 2 + L++2
796 p4
l+
780 L + 2 + U1
+2+
775 L + 2 1 + U2
L+Ce5Sn3+1
2+1+ L+1+
L+2+
760 L+ 1 Ce5Sn3 + U3
1+Ce5Sn3+
756 e2
l+ L+Ce5Sn3+
740 L + + 2 E1 729 e3
l (Ce) +
++2
708 e4
(Ce) l +(Ce)
699 L+(Ce)+(Ce) U4
ca. 696 e5
(Ce) (Ce)+
530 L + Ce5Sn3 + U5
L++(Ce)
516 p5 L++ Ce5Sn3++
l +
510 L+ + U6
424 e6 L++ ++
l + (Ce)
420 L + + (Ce) E2
++(Ce)
Fig. 2: Ce-Cu-Sn: Partial reaction scheme
Landolt-Brnstein
New Series IV/11C2
MSIT
148 CeCuSn
Sn Data / Grid: at.%

Fig. 3: Ce-Cu-Sn. Axes: at.%
Liquidus surface
projection in the
Ce rich region
20
80
40
60
p2,1375
60
40
p1,1505
CeSn3
80
20
p3,940 1
2
e3,729

U4 700 600 500 U6 U U3 U2
e1(max) E
1
U1
750C 5
(Ce)
e4,708 20 E2 e ,424 40 p ,516 60
Ce ( Ce) 6
5 e2,756 80 Cu
p4,796

Fig. 4: Ce-Cu-Sn. Axes: at.%
Isothermal section at L
400C L+
20
80

L+ + 7

L++ 7
4 + + 40 60
5
4
++ 2

60
+ 4+ 2 6
Ce5Sn3 40
3
Ce5Sn3+ 1+ + 7+
1 7
1+ 2+ 2
Ce5Sn3+ + ? ?
8 10
80
20
6++(Cu)
9 8+ 9+(Cu)
+( Ce)+ + + (Cu)
2+ +
20 40 60 80
Ce ( Ce) CeCu6 Cu
New Series IV/11C2
CeCuSn 149
1.0
Fig. 5: Ce-Cu-Sn.
Temperature
dependence of the 0.5
specific heat of 0.0 T
CeCuSn in various
magnetic fields 0.5 T
0.0
1.0 T
0.0
1.5 T
Cp, J.K2.mol1
0.0
1.8 T
2.0 T
0.0
2.2 T
0.0
0.0
2.5 T
3.0 T
0.0
4.0 T
0.0
0.0 5.0 T
0.0
0
0 5.0 10.0 15.0
Temperature, K
6.0
Fig. 6: Ce-Cu-Sn.
Magnetic phase
diagram of CeCuSn ferro
4.0
AF3
B, T
2.0
AF2
para
AF1
0
0 2.0 4.0 6.0 8.0 10.0
Temperature, K
Landolt-Brnstein
New Series IV/11C2
MSIT
150 CeCuSn
20.0
Fig. 7: Ce-Cu-Sn.
The heat capacity of
Ce3Cu4Sn4 below
30 K
15.0
CP, J.molR1.K1
10.0
5.0
0
0 10.0 20.0 30.0
Temperature, K
Fig. 8: Ce-Cu-Sn. 12.0

Temperature
dependence of the
magnetic entropy in
10.0
Ce3Cu4Sn4 below
30 K
8.0
S, J.molCe1.K1
6.0
4.0
5.0
0
0 5.0 10.0 15.0 20.0 25.0 30.0
Temperature, K
New Series IV/11C2
CeCuSn 151
40
Fig. 9: Ce-Cu-Sn.
8.0
S, J.mol1.K1
CeCu9Sn4
4.0
30 0
0 5.0 10.0 15.0 20 25
Temperature, K
C, J.mol1.K1
20
10.0
0
0 5.0 10.0 15.0 20 25
Temperature, K
12.0
Fig. 10: Ce-Cu-Sn.
CeCu9.4Sn3.6
9.0
C, J.mol1.K1
6.0
6.0
0
0 5.0 10.0 15.0
Temperature, K
Landolt-Brnstein
New Series IV/11C2
MSIT
152 CeCuZn
Cerium Copper Zinc

Oksana BodakA, Paola Riani
Introduction
In a series of consecutive investigations of the Ce-Cu-Zn ternary system [2004Pav1, 2004Pav2, 2005Pav]
determined the isothermal section at 200C. A number (not specified in the papers) of samples prepared by
arc melting the elements (purity better than 99.9 mass%) was subsequently heat treated at 200C for 600 h.
Previous investigations of this system were directed to study thermal properties of CeCuxZn1x single
crystals and their crystallochemical transition [2002Ish, 1989Uwa, 1988Fuj, 1988Uwa], crystalline electric
fields (CEF) and magnetic structures in the Ce(CuxZn1x)2 system [1992Mor, 1992Gig1, 1992Gig2] and
mechanical behavior of cerium-modified - brass at high temperatures was investigated by [1976Cha].
The crystal structure of CeCuZn equiatomic compound was refined by [2000For]. [2004Jia] investigated
the Fermi-liquid behavior in CeCu6xMx (M = Ni, Zn) systems.
Experimental details of the phase diagram studies are summarized in Table 1.
Binary Systems
The assessed version of the Ce-Cu and Cu-Zn systems reported by [2002Per] and [2006Leb], respectively,
are here accepted as edge boundary systems; the Ce-Zn binary system is accepted from [Mas2].
Solid Phases
Crystallographic data of all the unary, binary and ternary compounds are listed in Table 2. Notice that for
the Ce2Zn17 composition two structures have been reported in literature: Th2Ni17 type [1967Ian] and
Th2Zn17 type [1987Sie]. It is not known, however, if both of them are stable and, eventually, their
temperature and composition ranges of stability. In the Ce-Zn binary system reported by [Mas2] only the
Th2Zn17 type structure is cited. The crystal structure of the new ternary compound Ce2Cu5-5.7Zn2-1.3 (-1)
was determined by single crystal method [2005Pav]. It crystallizes in the Ce2Ni5Zn2 structure type.
[2000For] studied the crystal structures of a series of RECuZn equiatomic ternary compounds including
CeCuZn. However, [2005Pav] tends to interpret CeCuZn as being the terminal composition of the
CeCu2-1Zn0-1 solid solution. This interpretation is supported by the fact that the binary CeCu2 and the
ternary CeCuZn compounds have the same structure type.
Isothermal Sections
The isothermal section of the Ce-Cu-Zn ternary system at 200C was investigated in the whole
concentration range by [2005Pav]. Being the only experimental work available on phase equilibria in this
system, it is reported in Fig. 1. However more experimental details should be given in order to evaluate its
reliability. Presently, the following facts raise doubts concerning the results of [2004Pav1, 2004Pav2,
2005Pav]: the weight losses of Zn samples during arc-melting are not reported and annealing times of 600 h
at 200C seem to be rather short for samples close to the Ce-Cu axis. Also it is not clear how many samples
were investigated to conclude the isothermal section.

For the Ce(CuxZn1x)2 system the CEF (crystalline electric field) was measured by [1992Mor]. For the
CeZn2 two excitation transfers were identified at 15.7 and 37.5 meV (10 K). With increase of Cu content
the energy transfers and intensities become weaker. For the CeCu2 there is only one transfer at 150 K of
14 meV intensity. [2002Ish] stated that for CeCuxZn1x at x = 0.2 and 0.4 an antiferromagnetic ordering
takes place, while at x = 0.6 - ferromagnetic order is observed (Fig. 2). Moreover, the ground level of 4f
configuration of Ce also changed from quartet (x = 0.2) to doublet (x = 0.6).
New Series IV/11C2
CeCuZn 153
References
[1967Ian] Iandelli, A., Palenzona, A., Zinc-Rich Phases of the Rare-Earth-Rinc Phases, J. Less
Common Met., 12, 333-343 (1967)
[1976Cha] Chandra, T., Jonas, J.J., Taplin, D.M.R., The Mechanical Behaviour of Ce-Modified ,
Brass at High Temperatures, J. Mater. Sci., 11, 1843 (1976) (Phys. Prop., Morphology,
Experimental, 17)
[1988Fuj] Fujii, H., Yagasaki, K., Uwatako, Y., Kawanaka, H., Inoue, T., Neutron Diffraction
Studies of Cerium-Zinc-Copper CeZn1xCux Single Crystal, Kyoto Daigaku Genshiro
Jikkensho Gakujutsu Koenkai Koen Yoshishu, TR 321, 54 (1988) (Crys. Structure,
Experimental, 0)
[1988Uwa] Uwatoko, Y., Fujii, H., Nishi, M., Motoya, K., Ito, Y., Neutron Diffraction Studies of
Cerium-Zinc-Copper CeZn1-xCux Single Crystal, J. Magn. Magn. Met., 76(7), 411-412
(1988) (Crys. Structure, Phase Relations, Experimental, 8)
[1987Sie] Siegrist, T., Le Page, Y., Crystal Chemistry of some Th2Zn17-Type Rare Earth-Zinc
Phases, J. Less Common Met., 127, 189-197 (1987)
[1989Uwa] Uwatoko, Y., Fujii, H., Nishi, M., Motoya, K., Ito, Y., A New Crystallographic Phase
Transition in the CsCl-Type CeZn1xCux Compounds, Solid State Commun., 72(9),
941-943 (1989) (Experimental, Crys. Structure, 8)
[1992Gig1] Gignoux, D., Morin, P., Voiron, J., Burlet, P., Field-Induced Magnetic Structures in the
Ce(Zn1xCux)2 System (x < 0.2), J. Magn. Magn. Met., 104, 1262-1264 (1992)
(Experimental, Magn. Prop., 6)
[1992Gig2] Gignoux, D., Morin, P., Voiron, J., Burlet, P., Magnetic Phase Diagrams and
Metamagnetic Processes in Ising Systemsthe Case of CeZn2, Phys. Rev. B, 46(14),
8877-8885 (1992) (Crys. Structure, Experimental, Magn. Prop., Thermodyn., 15)
[1992Mor] Morin, P., Gignoux, D., Voiron, J., Murani, A.P., Crystalline Electric Field in the
Ce(Zn1xCux)2 System, Physica B (Amsterdam), 180-181A, 173-175 (1991) (Phys. Prop.,
Experimental, 6)
[1994Sub] Subramanian, P.R., Laughlin, D.E., Ce-Cu (Cerium-Copper), in Phase Diagrams of
International, Metals Park, OH, 10, 127-133 (1994) (Phase Diagam, Rewiew, 9)
[2000For] Fornasini, M.L., Iandelli, A., Merlo, F., Pani, M., Crystal Structure of the RCuZn, RAgZn
and RAgAl Intermetallic Compounds (R = Rare Earth Metals), Intermetallics, 8, 239-246
[2002Ish] Ishii, Y., Ohshjma, Sh., Kosaka, M., Uwatoko, Y., Thermal Properties of Single Crystals
of CeZn(1x)Cux, Physica B, 312-313, 267-268 (2002) (Thermodyn., Experimental, 2)
[2002Per] Perrot P., Ferro R., Ce-Cu (Cerium-Copper), MSIT Binary Evaluation Program, in MSIT
Stuttgart; Document ID: 20.16303.1.20 MSIT (2002) (Crys. Structure, Phase Diagram,
Assessment, 25)
[2004Jia] Jiang, L.X., Meng, J.B., Xia, Z.Y., Chen, Z.J., Luo, J.L., Wang, N.L., Low-temperature
Specific Heat and Resistance for the Heavy-electron Metals CeCu6xMx (M=Ni,Zn),
Chinese Physics, 13(12), 2130-2135 (2004) (Phys. Prop., Experimental, 12)
[2004Pav1] Pavlyuk, V.V., Marciniak, B., Rozycka-Sokolowska, E., Zelinska, O.Ya., Solokha, P.G.,
Solubility of Zinc in the CeCu6 Intermetallic Compound, Intermetallics, 12(6), 665-669
(2004) (Crys. Structure, Morphology, Phase Diagam, Experimental, *, 1)
Landolt-Brnstein
New Series IV/11C2
MSIT
154 CeCuZn
[2004Pav2] Pavlyuk, V., Rozycka-Sokolowska, E., Marciniak, B., Prochwicz, W., Solokha, P.,
Dzierzanowski, P., Structural Study of the Pseudobinary CeCu5-CeZn5 System, J. Alloys
Compd., 373(1-2), 137-141 (2004) (Crys. Structure, Morphology, Phase Relations,
Experimental, *, 1)
[2006Leb] Lebrun, N., V., Cu-Zn (Copper-Zinc), MSIT Binary Evaluation Program, in MSIT
[2005Pav] Pavlyuk, V., Prochwich, W., Solokha, P., Interaction of the Components in the Ce-Cu-Zn
Ternary System at 200C, J. Alloys Compd., in press (Experimental, Phase Diagram, 7)
Table 1: Investigation of the Ce-Cu-Zn Phase Relations, Structures and Thermodynamics

[1976Cha] Mechanical investigation, 475C T 675C, Ce0.07Cu61.33Zn38.6 (in
X-ray line broadening measurements mass%)
[1988Fuj] Neutron diffraction CeCu1xZnx at 0 x 1
[1989Uwa] Neutron diffraction 263C T 123C (from figure),
CeCu1xZnx at 0 x 1
[1992Mor] Neutron spectroscopy, magnetic 268C T 27C, Ce(CuxZn1x)2
measurements at 0 x 1
[2000For] X-ray analysis T = 750C, CeCuZn
[2002Ish] X-ray analysis, calorimetry 271C T 27C, CeCu1xZnx,
at x = 0.2, 0.4, 0.6
[2004Pav1] X-ray analysis, WDS, EPMA T = 200C, Ce(Cu1xZnx)5, at 0 x 1
[2004Pav2] X-ray analysis, WDS, EPMA T = 200C, CeCu6xZnx, at 0 x 0.84
[2005Pav] X-ray analysis, WDS, EPMA T = 200C, Ce-Cu-Zn, whole concentration
range

[C] Prototype
(Cu1xZnx) cF4 0 x 0.383 at 454C
Fm3m a = 369.612 at 35.84 at.% Zn and 300C [V-C2]
Cu
(Cu) a = 361.46 at 25C [Mas2]
< 1084.62
( Ce) cI2 a = 412 0 to 0.55 at.% Cu at 708C [2002Per]
798 - 726 Fm3m
W
(Ce) cF4 a = 510.10 0 to 0.37 at.% Cu at 708C [1994Sub]
726 - 61 Fm3m
Cu
(Ce) hP4 a = 308.10 at 24C [2002Per]
61 - (177) P63/mmc c = 1185.7
La
New Series IV/11C2
CeCuZn 155

[C] Prototype
(Ce) cF4 a = 485 at 196C [2002Per]
< 177 Fm3m
Cu
(Zn) hP2 dissolves up to 1.5 at.% Cu at 424C
< 419.6 P63/mmc [2006Leb]
Mg a = 266.5 at 25C [Mas2]
c = 494.70
Ce(Cu1xZnx) oP8 0 x 0.3
Pnma a =737 at x = 0.3 from figure [2005Pav]
FeB b = 447
c = 642
CeCu a = 719 at x = 0 [2002Per]

< 516 b = 430
c = 623
Ce(Cu1xZnx)2 oI12 0 x 0.5
Imma a = 454.1 at x = 0.5 [2000For]
CeCu2 b = 722.9
c = 758.1
CeCu2 a = 442.9 at x = 0 [2002Per]

< 817 b = 706.1
c = 747.4
CeCu4 oP20 a = 458 at x = 0 [2002Per]
< 796 Pnnm b = 810
CeCu4 c = 935
Ce(Cu1xZnx)5 hP6 0 x 0.63
P6/mmm a = 522.6 at x = 0.63 [2004Pav1]
CaCu5 c = 417.2
CeCu5 a = 514.8 at x = 0 [Mas2, 1994Sub]

< 798 c = 410.8
Ce(Cu1xZnx)6 oP28 0 x 0.14
Pnma a = 810.88 at x = 0, 22C [1990Vrt]
CeCu6 b = 510.04
c = 1016.21
a = 815.4 at x = 0.14 [2004Pav2]

b = 505.6
c = 1018.5
CeCu6 a = 810.09 at x = 0, 23[1990Vrt]

938 - (43) b = 509.78
c = 1015.48
Landolt-Brnstein
New Series IV/11C2
MSIT
156 CeCuZn

[C] Prototype
CeCu6 oP28 a = 509.5 at 73C [1990Vrt]
< 43 P21/c b = 1014.66
LaCu6 c = 809.31
= 90.485
a = 508.92 at 173C [1990Vrt]

b = 1013.26
c = 807.89
= 91.148
a = 508.41 at 263C [1990Vrt]

b = 1012.79
c = 807.31
= 91.442
, CuZn cI2 36.1 to 55.8 at.% Zn, [Mas2, V-C2]
903 - 454 Im3m a = 295.39 at 47.5 at.% Zn
W
, CuZn cP2 44.8 to 50.0 at.% Zn, [Mas2]
< 468 Pm3m a = 295.9 at 49.5 at.% Zn
CsCl
, Cu5Zn8 cI52 a = 886.9 57.0 to 70.0 at.% Zn, [Mas2, V-C2]
< 835 I43m
Cu5Zn8
, CuZn3 hP3 a = 427.5 72.45 to 76.0 at.% Zn, [Mas2, V-C2]
665 - 548 P6 c = 259.0
CuZn3
J, CuZn4 hP2 a = 274.2 78.0 to 88.0 at.% Zn, [Mas2]
< 574 P63/mmc b = 429.4
Mg
Ce(CuxZn1x) cP2 0 x 0.5
Pm3m a = 390.5 at x = 0.5 from figure [2005Pav]
CsCl
CeZn a = 369.7 at x = 0 [V-C2]
< 825
Ce(CuxZn1x)2 oI12 a = 462.0 at x = 0.6 [2005Pav]
Imma b = 748.2
CeCu2 c = 752.0
CeZn2 a = 463.9 at x = 0 [V-C2]

< 875 b = 755.2
c = 751.0
CeZn3 oP16 a = 664.0 [V-C2]
< 820 Pnma b = 462.0
YZn3 c = 1044.0
New Series IV/11C2
CeCuZn 157

[C] Prototype
Ce3Zn11 oI28 a = 451.9 [V-C2]
< 840 Immm b = 1344.4
La3Al11 c = 888.3
Ce13Zn58 hP142 a = 1460.0 [V-C2]
< 870 P63/mmc c = 1411.0
Gd13Cd58
Ce(CuxZn1-x)5 hP6 a = 540 at x = 1 [2005Pav]
P6/mmm c = 424
CaCu5
CeZn5 a = 541.63 at x = 0 [V-C2]
< 885 c = 426.47
Ce3Zn22 tI100 a = 894 [V-C2]
< 960 I41/amd c = 2133
Pu3Zn22
CeZn11 tI48 a = 1066.2 [V-C2]
< 795 I41/amd c = 685.5
BaCd11
Ce2Zn17 see comments in section Solid Phase
< 980 hP38 a = 908.8 [V-C2]
P63/mmc c = 885.6
Th2Ni17
or
hR57 a = 909.07 [V-C2] single crystal data

R3m c = 1328.47
Th2Zn17
* -1, Ce2(Cu5+xZn2x) hR54 a = 499.8 to 507.8 0 x 0.7
R3m c = 3692.4 to 3698.7 [2005Pav] Single crystal refinement
Ce2Ni5Zn2
Landolt-Brnstein
New Series IV/11C2
MSIT
158 CeCuZn
Zn Data / Grid: at.%

Fig. 1: Ce-Cu-Zn. (Zn) Axes: at.%
CeZn
Isothermal section at Ce Zn 11
200C Ce3Zn22 2 17
Ce Zn CeZn5
13 58
20
Ce3Zn11 80
CeZn3
CeZn2

40
60
CeZn

60
40
80
20
1
(Cu)
20 40 CeCu 60 CeCu CeCu3 80CeCu CeCu

Ce 2 4 5 Cu
Fig. 2: Ce-Cu-Zn.
50
Specific heat Cp as a
function of
temperature for TN
CeZn1-xCux. The 40
inset is a
magnification around
anomalies
Cp, arb. unit
Cp, J.mol.K1
30
TN
TC
20
x=0.2
x=0.4
x=0.6 TC
10
0 10 20 30 40 50
Temperature, K
0
0 50 100 150 200 250 300
Temperature, K
New Series IV/11C2
CoCuSi 159
Cobalt Copper Silicon

Lesley Cornish, Andy Watson
Introduction
Copper alloys are of general interest to the electrical industry because of coppers very high electrical and
thermal conductivity. The Co-Cu-Si system has been under study since the late 1920s through the so called
Corson Alloys. Cu rich compositions can be strengthened considerably through the precipitation of Co2Si
within the Cu rich matrix following a suitable aging treatment [1927Cor1, 1927Cor2, 1930Cor1,
1930Cor2]. This feature of Cu rich alloys of this system raised the prospect of the fabrication of stronger
cabling wire. However, there has been surprisingly little study of the phase diagram. Initial studies were
carried out by [1927Cor1, 1927Cor2, 1930Cor1, 1930Cor2] which were confined to the Cu rich part of the
diagram, although the presence of a Cu-Co2Si quasibinary section was speculated. Later, [1968Gro]
presented two isopleths for 1 and 2.5 mass% Co, respectively, but again, only for Cu rich alloys.
[1975Rev1] presented Cu rich isothermal sections for 700, 900 and 1000C. They used 67 different alloys
which had been prepared by vacuum induction melting followed by hot working and cold drawing into
wires. The wires were sealed in evacuated silica ampoules before annealing and subsequent examination by
optical microscopy, X-ray analysis and mechanical and electrical property measurement. This work was
also reported by [1979Dri, 1979Cha, 1988Las]. More recently, [1985Alb1] used in situ resistivity
measurements to determine the solubility of Co2Si in the Cu-Co2Si quasibinary system; the results being in
good agreement with [1975Rev1]. The majority of investigations of this system however, relate to the
precipitation of the Co2Si phase and its strengthening properties [1927Cor1, 1927Cor2, 1930Cor1,
1930Cor2, 1933Wil, 1975Tep, 1985Alb2, 1988Len, 2001Don, 2002Var, 2003Var1, 2003Var2].
Mechanical property measurement [1933Wil], TEM [1975Tep, 1988Len] and DSC measurements were
used to study the precipitation kinetics.
Overview of the works related to phase realtions and crystal structure is given in Table 1.
Binary Systems
The binary systems are taken from [2006Ans] (Co-Cu), [2002Leb] (Cu-Si), and [Mas2] (Co-Si).
Solid Phases
The solid phases of the system are listed in Table 2. No ternary phases were reported by [1979Cha] in their
review of the system. [1988Las] reported that Co2Si precipitated after aging selected alloys at 400-500C,
in agreement with much earlier work [1927Cor2, 1930Cor2].
[1985Alb2] studied precipitation in high Cu content alloys, and found it to begin between 400C and 600C,
with Co being formed first, clustering and acting as a nucleation site for Si, followed by formation of Co2Si.
The reaction rates were found to be faster with increasing Si content of the alloy, with excess Si remaining
in the (Cu) solid solution.
Quasibinary Systems
There is a quasibinary section between Cu and Co2Si [1930Cor3,1975Rev1]. The solubility of Co2Si in
(Cu) in this section was given as 2.35 mass% at 1050C, 1.9 mass% at 1000C, 1.1 mass% at 900C, 0.55
mass% at 800C and 0.3 mass% at 700C. The work of [1985Alb1] is in good agreement.

[2002Zab] calculated the liquidus surface using thermodynamic parameters for the accepted constituent
binary phase diagrams. As this was prepared by extrapolation from the binary systems using no ternary
equilibrium data, the surface is not reproduced here.
Landolt-Brnstein
New Series IV/11C2
MSIT
160 CoCuSi
Isothermal Sections
[1975Rev1] prepared isothermal sections for Cu contents greater than 95 mass% for 700C (Fig. 1), 900C
(Fig. 2) and 1000C (Fig. 3), observing three-phase fields between: (Cu) + Co2Si + CoSi and
(Cu) + (Co) + Co2Si at 700C; L + (Cu) + CoSi; (Cu) + Co2Si + CoSi and (Cu) + (Co) + Co2Si at 900C;
L + (Cu) + Co2Si and (Cu) + (Co) + Co2Si at 1000C. These results at 700C were in agreement with
[1988Las], and at 900C in agreement with [1979Dri]. The sections at 900 and 1000C (Figs. 2 and 3) have
been modified slightly to maintain consistency with the accepted binary phase diagrams.

[1968Gro] produced temperature-composition sections at 1 and 2.5 mass% Co. However, as there are
contraventions with the phase rule (as pointed out by [1979Cha]) they are not reproduced here.
Thermodynamics
In order to try and understand the hardening mechanism, the kinetics of the precipitation of Co2Si were
calculated in the quasibinary section: Cu - 0.65 at.% Co - 0.33 at.% Si (Cu - 1 at.% Co2Si) [2002Var]. The
results from enthalpimetric calculations agreed with the DSC experiments: Co atoms cluster, followed by
Si preciptation, to finally form Co2Si. This agreed with the results of [1975Rev2, 1985Alb2, 1988Len]. The
effective activation energy of both Co and Si precipitation was found as ~1.5eV. [2001Don] subsequently
showed the Co and Co2Si precipitations to be two overlapping exothermic reactions. The enthalpies of the
reactions were proportional to the precipitate volume fractions.

Copper alloys are of interest for the effect of various alloying additions on their electrical properties. This
system, amongst others, is beneficial because there is a strengtheing mechanism (precipitation of Co2Si)
which allowed for stronger electrical alloys. The Corson process was a heat treatment and quenching
schedule which optimised the precipitation for specific alloys [1927Cor2], as well as retaining reasonable
electrical properties [1927Cor1]. This was achieved by using the Cu-Co2Si quasibinary section [1930Cor2],
and undertaking various heat treatments and quenching, e.g. from 400-600C. More age hardening studies
were carried out by [1933Wil]. Using TEM, [1975Tep] showed that at maximum strength, the Co2Si
particles have an orthorhombic lattice.
[1998Shi] observed in-plane four-fold symmetry in the magnetisation and magnetoresistance in Co/Cu
multilayers electrodeposited on Si(001) substrates covered in a thin evaporated Cu seed layer. This could
be of relevance for electronic devices.
[1992Var] measured fatigue crack propagation rates in Cu - 0.67 at.% Co - 1.1 at.% Si and Cu - 0.34 at.%
Co - 0.95 at.% Si alloys, to investigate the influence of precipitation processes and the mechanisms of crack
propagation.
Details of materials properties studies in Co-Cu-Si alloys are given in Table 3.
Miscellaneous
[1992Dau] observed a decagonal phase in (Al,Si)65Co20Cu15 alloys.
References
[1927Cor1] Corson, M.G., Copper Hardened by New Method. What the Corson Alloys Are - Stronger
Cable Wire Possible - Many Uses Suggested - Silicon-Aluminum and Silver-Silicon
Alloys, Trans. Amer. Inst. Min. Metall. Pet. Eng., Inst. Met. Div., 421-424 (1927)
(Experimental, Phase Diagram)
[1927Cor2] Corson, M.G., The Hardening of Copper Following a New Procedure (in German),
Z. Metallkd., 19(9), 370-371 (1927) (Experimental, Phase Diagram, 2)
New Series IV/11C2
CoCuSi 161
[1930Cor1] Corson, M.G., Copper Alloy Systems with Phase and Variable Limits and their
Application for the Copper Hardening (in French), Rev. Metall., 27, 194-213 (1930)
(Experimental, Phase Diagram, 6)
Application for the Copper Hardening, Fourth Part (in French), Rev. Metall., 27, 265-281
(1930) (Experimental, Phase Diagram, 4)
[1933Wil] Wilson, C.L., Silliman, H.F., Little, E.C., The Rate of Precipitation of Nickel Silcide and
Cobalt Silcide in the Hardenable Cu-Ni-Si and Cu-Co-Si Alloys, Trans, AIME, 104,
131-132 (1933) (Experimental, Kinetics, 1)
[1968Gro] Gronostajski, J., Partial Equilibrium Diagram of the Copper-Silicon-Cobalt System, Rudy
Met. Niezela., 13(4), 164-167 (1968) (Experimental, Phase Diagram, 7)
[1975Rev1] Revina, N.L., Nikolayv, A.K., Rozenberg, V.M., The Constitution Diagram of
Copper-Rich Cu-Co-Si Alloys, Russ. Metall., (1), 182-185 (1975) (Electr. Prop., Mechan.
Prop., Phase Diagram, #, 6)
[1975Rev2] Revina.,N.I., Nikolaev, A.K., Rozenberg, V.M., Effect of Cr on the Kinetics of Phase
Transformations in Alloys of Cu with the Silicides of Ni and Co (in Russian), Nauchn. Tr.
Nauchno-Issled. Proektn. Inst. Splavov Obrab. Tsvetn. Met., (48), 61-70 (1975)
(Experimental, Kinetics, Phase Diagram, 9)
[1975Tep] Teplitskii, M.D., Nikolaev, A.K., Revina, N.I., Rozenberg, V.M., Investigation of the
Dispersed Particles in Ageing Alloys of Cu-Ni-Si and Cu-Co-Si, Phys. Met. Metallogr.,
40(6), 99-103 (1975) (Experimental, Kinetics, 9)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Co-Cu-Si, INCRA Monograph
Systems, NSRD, Washington, 6, 433-434 (1979) (Review, Crys. Structure, 5)
Turkina, N.I., Cu-Co-Si (in Russian), in Binary and Multicomponent Copper - Base
Systems, Nauka, Moscow, 145-146 (1979) (Phase Diagram, Review, 5)
[1985Alb1] Albert, B., Solubility and Precipitation Processes in Cu-Co-Si Alloys. I.-Determination of
Solubility by In Situ Resistance Measurements (in German), Z. Metallkd., 76(7), 475-478
(1985) (Experimental, Phase Diagram, Thermodyn., 8)
[1985Alb2] Bela, A., Solubility and Precipitation Processes In Cu-Co-Si Alloys. II. Analysis of
Precipitiation Processes, Z. Metallkd., 76(8), 528-531 (1985) (Experimental,
Thermodyn., 14)
[1988Las] Laska, J., The Co2Si Phase in Cobalt-Silicon Bronzes. Pr. Nauk. Inst. Materialozn. Mech.
Tech. Politech Wroc. Stud., 47(27), 69-85 (1988) (Experimental, Crys. Structure, 19)
[1988Len] Lendvai, J., Ungar, T., Kovacs, I., Albert, B., Precipitation Processes in Cu-Co-Si Alloys,
J. Mater. Sci., 23(11), 4059-4065 (1988) (Crys. Structure, Electr. Prop., Experimental,
Mechan. Prop., Thermodyn., Transport Phenomena, 15)
[1992Dau] Daulton, T.L., Kelton, K.F., The Decagonal Phase in (Al,Si)65Co20Cul5 Alloys, Philos.
Mag. B, 66(1), 37-61 (1992) (Crys. Structure, Experimental, 26)
[1992Var] Varschavsky, A., Donoso, E., A Microcalorimetric Study of Fatigue Crack-propagation in
Precipitation-hardened Cu-Co-Si Alloys, Mater. Lett., 15(3), 207-211 (1992) as quoted in
[2003Var2]
[1998Shi] Shima, M., Salamanca-Riba, L., Moffat, T.P., McMichael, R.D., Swartzendruber, L.J.,
Structural and Magnetic Fourfold Symmetry of Co/Cu Multilayers Electrodeposited on
Si(001) Substrates, J. Appl. Phys., 84(3), 1504-1507 (1998) (Experimental, Magn. Prop.)
[2001Don] Donoso, E., Calorimetric Evaluation of Precipitation in Cu Rich, Cu-Co-Si (in Spanish),
Rev. Metall. (Madrid), 37(4), 492-498 (2001) (Experimental, Kinetics, Thermodyn., 32)
Landolt-Brnstein
New Series IV/11C2
MSIT
162 CoCuSi
[2002Leb] Lebrun, N., Dobatkina, T., Kuznetsov, V., Li, C., Cu-Si (Copper - Silicon), MSIT Binary
Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science
International Services GmbH, Stuttgart; Document ID: 20.12505.1.20, (2002) (Crys.
Structure, Phase Diagram, Thermodyn., Assessment, 23)
[2002Var] Varschavsky, A., Donoso E., Energetic and Kinetic Evaluations Conducted in a
Quasi-Binary Cu-1 at.% Co2Si Alloy through DSC, J. Therm. Anal. Calorim., 68, 231-241
(2002) (Experimental, Kinetics, Phase Relations, Thermodyn., 21)
[2002Zab] Zabdyr, L., Calculation of the Liquidus Surface in Ternary Co-Cu-Si System, Arch.
Metall., 47(3), 321-334 (2002) (Phase Diagram, Thermodyn., Assessment)
[2003Var1] Varschavsky, A.; Donoso E., DSC Study of Precipitation Processes in Cu-Co-Si Alloys,
J. Therm. Anal. Calorim., 74(1), 41-56 (2003) (Calculation, Experimental, Thermodyn., 29)
[2003Var2] Varschavsky, A., Donoso, E., Energetic and Kinetic Evaluations in a Quasi-Binary
Cu-1 at.% Co2Si Alloy, Mater. Lett, 57(7), 1266-1271 (2003) (Experimental, Kinetics,
Phase Relations, Thermodyn., 19)
[2006Ans] Ansara, I., Ivanchenko, V., Turchanin, M., Agraval, P., Co-Cu (Cobalt - Copper), MSIT
Binary Evaluation Program in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials
Science International Services GmbH, Stuttgart; to be published (2006) (Crys. Structure,
Phase Diagram, Thermodyn., Assessment, 19)
Table 1: Investigations of the Co-Cu-Si Phase Relations, Structures and Thermodynamics

Reference Method Experimental Technique Temperature/Composition/Phase Range
Studied
[1927Cor1, Metallography Various
1927Cor2,
1930Cor1,
1930Cor2]
[1968Gro] Metallography, chemical analysis, X-ray Various; > 90 mass% Cu
diffraction, dilatometry.
[1975Rev1] Metallography, kinetics 400-1000C; Cu-1.62 % Co- 0.38 % Si
[1975Rev2] Metallography, X-ray diffraction, 700C, 900C and 1000C; > 95 mass% Cu
mechanical properties and electrical
resistance.
[1975Tep] TEM, X-ray diffraction Cu-1.73 Co - 0.85% Si (at.%)
[1979Dri] Metallography, X-ray analysis. 900C; > 95 mass% Cu
[1985Alb1, Electrical resistance and thermoelectric < 1000C; Cu - 0.3 - 1.75 at.% Co - 0.05 - 1.9
1985Alb2] force measurements. at.% Si
[1988Las] Metallography, X-ray analysis, X-ray 700C; > 95 mass% Cu; Ageing at 400C,
diffraction. 450C and 500C.
[1988Len] Electrical resistivity, thermoelectric 400-600C; Cu - 0.63 - 0.56 at.%
power, mechanical testing, TEM, DSC. Co - 0.27 - 1.91 at.% Si
[2001Don] DSC, Kissinger calculations Cu - 0.5 - 1.0 at.% Co2Si
New Series IV/11C2
CoCuSi 163

[C] Prototype
(Co) cF4 a = 356.88 at 520C [V-C2]
Fm3m a = 354.47 Dissolves ~17 at.% Cu at ~1360C
Cu [2006Ans], 16.5 at.% Si at 1250C
[Mas2]
(JCo) hP2 a = 250.71 at 25C [Mas2]
< 422 P63/mmc c = 406.86
Mg
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m Melting point [1994Sub]. Dissolves 11.1
Cu at.% Si at 853C [2002Leb], 9.1 at.%
Co at 1113.3 [2006Ans].
(Si) cF8 a = 543.06 [Mas2]. Dissolves 0.003 at.% Cu
< 1414 Fd3m [2002Leb], negligible Co [Mas2]
Diamond
Co3Si hP8 a = 497.6 0.2 [Mas2, V-C2]
1214 - 1193 P63/mmc b = 406.9 0.6
Mg3Cd
Co2Si oP12 a = 491.9 [Mas2, V-C2]
1320 Pnma b = 372.5
Co2Si
Co2Si - - [Mas2]
1334 - 1238
CoSi cP8 a = 445.0 [V-C2]
< 1460 P213
FeSi
CoSi2 cF12 a = 535.3 [V-C2]
< 1326 Fm3m
CaF2
, Cu7Si hP2 11.05 to 14.5 at.% Si.
842 - 552 P63/mmc a = 256.05 at 12.75 at.% Si [2002Leb]
Mg c = 418.46
, ~Cu6Si cI12 14.2 to 16.2 at.% Si
853 - 787 Im3m a = 285.4 at 14.9 at.% Si. [2002Leb]
W
, Cu5Si(h) t** 17.6 to 19.6 at.% Si [2002Leb]
824 - 711 a = 881.5 sample was annealed at 700 C
c = 790.3 [2002Leb]
< 729 P4132
Mn
Landolt-Brnstein
New Series IV/11C2
MSIT
164 CoCuSi

[C] Prototype
< 800 I43d
Cu15Si4
859 - 558 R3m = 109.74
or a = 726.7 [V-C2]
c = 789.2
620 - 467 R3 = 95.72
'', Cu3Si(r) o** a = 7676 23.3 to 24.9 at.% Si [2002Leb]
< 570 b = 700
c = 2194
~Cu5Si t** a = 647 at 17 at.% Si
c = 873 metastable
[2002Leb]
Table 3: Investigations of the Co-Cu-Si Materials Properties

[1927Cor1] Resistivity measurements Electrical resistivity
[1930Cor1] Hardness and tensile tests Hardness and tensile test data
[1930Cor2] Corrosion tests, resistivity measurements, Corrosion rates, electrical resistivity from
hardness tests 400C, 500C and 600C, hardesses
[1975Rev1] Resistivity measurements and tensile tests Electrical resistance and tensile yield stress
[1975Tep] Tensile tests UTS and proof stress
[1988Len] Electrical resistivity, thermoelectric power, Electrical resistivity, thermoelectric power,
simultaneous tortion and extension tortional yeild stress
[1992Var] Fatigue Fatigue crack propagation rates
[1998Shi] XRD, TEM Magnetoresistance
[2003Var1, DSC Thermodynamics (heat contents), kinetics,
2003Var2, order of preciptation events
2002Var]
New Series IV/11C2
CoCuSi 165
Co 0.00
Cu 90.00
Fig. 1: Co-Cu-Si. Axes: at.%
Partial isothermal
section at 700C
(Cu)+CoSi
(Cu)+
Co S
2 i+C
oSi
(Cu)+Co2Si
(Cu)+(Co)+Co Si
2 (Cu)
Co 10.00 (Cu)+(Co)
Cu
Cu 90.00
Si 0.00
Co 0.00
Cu 90.00
Partial isothermal L+(Cu)
section at 900C
L+(Cu)+CoSi
(Cu)+CoSi
(Cu)+
CoSi+
Co Si
2
(Cu)+Co2Si
(Cu)+(Co)+Co Si
2 (Cu)
Co 10.00 (Cu)+(Co) Cu
Cu 90.00
Si 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
166 CoCuSi
Co 0.00
Cu 90.00
Partial isothermal L
section at 1000C
L+(Cu)
L+(C
u)+C
o2 Si
(Cu)
(Cu)+Co 2Si
(Cu)+(C
o)+Co
2 Si
Co 10.00 (Cu)+(Co) Cu
Cu 90.00
Si 0.00
New Series IV/11C2
CoCuSm 167
Cobalt Copper Samarium

Oksana BodakA, Olga Fabrichnaya
Introduction
Since the discovery of hard magnetic properties in the SmCo5 phase, the following investigations were
conducted to improve the magnetic characteristics using the various methods of synthesis, doping with other
elements, etc. The interest in the Co-Cu-Sm alloys is due to excellent hard magnetic properties that can be
obtained in copper-containing alloys lying between the SmCo5 and Sm2Co17 compounds. In spite of this,
practically all investigations were performed in the Sm concentration range up to 20 at.% in this system.
The studies of this system have been conducted mainly in two directions - phase and structural
characterizations and investigations of magnetic properties (Curie temperature, coercive force, etc.).
The phase, structural and microstructural characterization of the ternary alloys in the Co-Cu-Sm system are
presented in [1973Kam, 1974Nis, 1976Zak, 1976Oes, 1976Mel, 1977Mel, 1977Per, 1979Gla, 1979Arb,
1979Mag, 1979Oes, 1981Ter, 1981Gla, 1982Arb1, 1983Arb, 1987Mey, 1989Tur, 1989Der, 1998Tel,
1999Zai, 1999Est1, 1999Est2, 2000Alo, 2000Che, 2002Ven, 2003Gop, 2003Luo, 2005Gjo]. Investigations
of magnetic properties have been made by [1973Kam, 1973Sav, 1976Oes, 1976Nag, 1978Nag, 1979Arb,
1979Mag, 1979Oes, 1982Arb2, 1983Arb, 1986Lhy, 1998Tel, 1999Zai, 1999Est1, 1999Est2, 2000Alo,
2000Che, 2002Ven, 2003Gop, 2003Luo, 2003Zha, 2005Gjo]. An extended discussion of recent
investigations has been made in [2005Sta] including a detailed review of the permanent magnet alloys based
on the Sm2Co17 phase.
Some works are devoted to the thermodynamic properties of alloys. [1987Mey] investigated the crystal
structures and enthalpies of formation of alloys with compositions Sm(Co1xCux)5 (0.2 x 0.8).
[1989Tur] calculated the integral enthalpies of mixing of the Co-Cu-Sm system by an isopotential method.
[1981Gla] studied the solidification path of a Sm10Co70Cu20 alloy using electron probe microanalysis
(EPMA) on cross-sections made along the quenched interface. The results are discussed using the ternary
phase diagram and a simple theoretical analysis based on the Scheil equation. This approach is a powerful
tool for the prediction of microsegregation in complex alloys. Microsegregation leads to the formation of
Cu rich zones which are detrimental to the magnetic properties and need to be eliminated by a
homogenization heat treatment.
During the last decade, many investigations were conducted on the study of alloys obtained by new methods
of synthesis. [2000Che] studied the crystal structure and magnetic properties of a milled
Sm2(Co0.98Cu0.02)17 alloy, [2002Ven] investigated the phase composition and magnetic properties of a
SmCo6.7Cu0.3 alloy sintered by different methods (arc-melting, milling). The ball-milled alloy shows a
greater coercive force. [2003Gop] studied a mechanically milled Sm(Co0.9Cu0.1)4.8 alloy. It has been
established that milling decreases the coercivity. [2003Zha] studied the effect of Cu substitution on
microstructure and magnetic properties of SmCo7xCux (0 x 4.5) ribbons.
Information relating to investigations of phase relations, structures and thermodynamics is summarized in
Table 1.
Binary Systems
The Cu-Sm binary system has been taken from [1996Zhu, 1998Oka]. The phase diagram given in [Mas2]
is based on thermodynamic calculations carried out by [1988Sub]. However, it disagrees with several
experimental data and therefore is not accepted here. It should be mentioned that experimental studies in
the ternary system [1979Gla] indicated narrow homogeneity ranges for the SmCu5 and SmCu6 phases. The
phase diagram for the Co-Sm system is accepted from [1995Oka]. It is based on experimental data from
[1993Ge]. The accepted diagram is different from [Mas2]. The major differences are: a) an absence of
polymorphic transformations in the phases Sm2Co17, SmCo5, Sm5Co19 and Sm2Co7, b) Sm5Co19 is stable
over a wide temperature range, c) SmCo5 melts incongruently. The thermodynamic assessment of [1998Su]
reproduces the phase diagram given by [1995Oka] very well. However, it is not accepted here because the
Landolt-Brnstein
New Series IV/11C2
MSIT
168 CoCuSm
homogeneity ranges of the Sm2Co17 and Co5Sm phases are not taken into account by [1998Su]. The Co-Cu
system is accepted from [2006Ans].
Solid Phases
Crystallographic data of the unary, binary and ternary phases of the Co-Cu-Sm system are listed in Table 2.
The formation and range of solid solutions based on the binary phases, the existence of the ternary
compounds and the crystal structures of the phases is strongly dependent on the synthesis method and
annealing temperature. The ternary phase X, SmCo3.3Cu1.7 (CaCu5 type) was reported to be stable at 900C
by [1981Ter]. However, later investigations did not confirm the stability of this phase and thus its existence
is doubtful. The ternary phase Sm(Co1xCux)7 (TbCu7 type), stable at 0.114 x 0.57 and 600C, was
reported by [2003Luo]. A phase with the same structure was reported by [2000Alo] at 0 x 0.1 and by
[2002Ven] at 0 x 0.043. In both studies, [2000Alo] and [2002Ven], at x = 0, the SmCo7 phase formed
together with Sm2Co17. It was shown by [2002Ven] that Sm(Co1xCux)7 decomposed into a two-phase
mixture of Sm(Co1xCux)5 and Sm2(Co1xCux)17 after annealing. Probably the solid solutions obtained by
[2000Alo] were metastable. According to [2000Alo], the Sm(Co1xCux)7 phase cannot be formed at x > 0.1
contradicting the data of [2003Luo]. Other investigations indicated only solid solutions based on binary
phases. [1974Nis] studied the Sm(Co1xCux)5 (0 x 0.8) alloys at 800C and discovered the formation
of solid solutions with the CaCu5 structure. At T > 800C, [1974Nis] observed the separation of the
Sm2(Co,Cu)17 phase. This result is in conflict with later investigations. For example, [1977Per] found that
Sm(Co1xCux)5 decomposed at temperatures below 730C at x = 0.1 and below 615C at x = 0.2. According
to [1976Zak], the Sm(Co,Cu)5 alloys (24.9-36.4 at.% Cu) are single-phase at 1100C and decompose at
600C into two phases. [1979Gla] found a complete mutual solubility between the SmCo5 and SmCu5
phases at 850C. [1979Arb] investigated the crystal structure of the Sm(Co0.81Cu0.19)5.5 alloy. It has been
established that this alloy contains two phases: Sm2(Co1xCux)17 (Th2Ni17 or Th2Zn17 type) and
Sm(Co1xCux)5 (CaCu5 type). The annealing of the alloy was in the range 900 to 1200C. [1979Mag] also
studied an alloy of composition Sm(Co0.65Cu0.35)5.6 at different annealing temperatures and found a
three-phase mixture, coherently bonded on (0001) planes. [1989Der] indicated that the
Sm1s(Co1xCux)5+2s phase is stable up to x = 0.98 at 850C. However, this statement contradicts the binary
Cu-Sm diagram and the data for the ternary system from [1979Gla] (see more details in the section
Isothermal Sections). The Sm2Cu9 phase found by [1989Der] was not confirmed by any other investigations
and is therefore doubtful. [1989Der] measured lattice parameters for Sm(Co1xCux)5 alloys and showed that
they do not deviate from Vegards law. At Sm deficient compositions, the a parameter increases and c
decreases with increasing x. [1999Zai] investigated the Sm(Co1xCux)2 alloys and established that the solid
solubility limits for Cu in SmCo2 and Co in SmCu2 are 14 and 11%, respectively. [2003Luo] investigated
the structural stability of Sm(Co1xCux)7 alloys. According to the results obtained, Cu doping can stabilize
the TbCu7 type structure in Sm(Co1xCux)7 alloys at Cu contents ranging from 0.114 x 0.571 at 600C.
[1979Gla] presented details of some transformations in the ternary system. These are given in Table 3.
Liquidus Surface
The liquidus surface of the Co-Cu-Sm phase diagram presented in Fig. 1 is taken from [1979Gla] with slight
modifications made to ensure correct intersection angle between the monovariant lines in the U1 point.
Isothermal Sections
Isothermal sections of the Co-Cu-Sm system (up to 20 at.% Sm) were studied experimentally at different
temperatures by [1977Per] at 1200C and 800C, by [1979Gla] at 850C and by [1981Ter] at 900C. The
data of these investigations are slightly different in relation to the homogeneity ranges of the solid solutions
based on the binary phases. The results of [1989Der] for 850C disagree with the accepted Cu-Sm binary
diagram and the data of [1979Gla] for the ternary system. According to accepted binary diagram, the SmCu5
New Series IV/11C2
CoCuSm 169
phase should be stable at 850C and there is no phase Sm2Cu9. The tie lines obtained by [1979Gla] at 850C
are different from those of [1989Der]. For example, the three-phase equilibrium (Co)+(Cu)+SmCu6 was
indicated by [1979Gla], whilst [1989Der] indicated equilibrium between (Co), (Cu) and Sm(Co1xCux)5
solid solutions. The tie lines obtained by [1979Gla] at 850C agree with the data of [1981Ter] and [1977Per]
obtained at 900 and 800C, respectively. That is why the isothermal section of [1979Gla] for 850C is
accepted. It is presented in Fig. 2 after modifications made to ensure agreement with the accepted binary
diagrams. Namely: homogeneity ranges of Sm(Co,Cu)5, Sm2Co17, SmCu6, (Co) and (Cu) phases have
been reduced, violation of the Schreinmaker rule has been eliminated at the Sm2Co17 triangle-tip of the
(Co) + Sm2Co17 + Sm(Co,Cu)5 tie triangle.

Isoplethal sections at 10.5 and 16.7 at.% Sm are shown in Figs. 3 and 4, respectively [1979Gla]. The
liquidus at 10 and 30 at.% Cu was also determined by [1979Gla]. Some limited data for isopleths at 10 and
20 at.% Cu were obtained by [1977Per].
Thermodynamics
[1987Mey] determined the heat of dissolution in liquid tin for pure elements and compounds in a
Tian-Calvet calorimeter at 900C and deduced the enthalpies of formation of alloys with compositions
Sm(Co1xCux)5 (0.2 x 0.8) at 25C for the measured values. The enthalpies of formations of
Sm(Co1xCux)5 alloys are presented in Table 4. The x dependences of enthalpies of formation and lattice
parameters indicate an ideal behavior for the mixing of SmCo5 and SmCu5. [1989Tur] calculated the
integral enthalpies of mixing of Co-Cu-Sm system by isopotential method. These are reproduced in Fig. 5.

[1973Kat] studied magneto-crystalline anisotropy in Sm(Co1xCux)5 alloys. It was shown that the
magneto-crystalline anisotropy constant decreases monotonically with increasing x. A characteristic feature
of the high-coercivity Sm(Co,Cu)5 compound is the magnetic after-effect. It was studied in a SmCo3.5Cu1.5
alloy by [1973Sav]. [1976Oes] investigated the saturation moments (at 4.2 K) and coercive force for a
Sm0.167Co0.683Cu0.15 alloy. The measured value of the saturation moment is 0.75 B and the coercive force
is IHC=12.5kOe. [1976Mel] found a correlation between the observed microstructure and the corresponding
magnetic parameters for alloys of compositions Sm(Co0.65Cu0.35)5.6, Sm(Co0.84Cu0.16)6.9 and studied the
effect of aging on the microstructure. [1977Mel] used electron microscopy to study Sm(Co0.87Cu0.13)z
(7.5 z 7.8) aged at 400 and 800C. It was shown that the coercivity of these materials with the Sm2Co17
structure is due to the presence of very fine precipitates of the Sm(Co1xCux)5 phase. [1976Nag, 1978Nag]
investigated the hard-magnetic properties of Sm(Co,Cu)z alloys at composition ratios of the rare-earth to the
transition metal of 1:5 and 2:17 with copper contents up to 35% of the transition metal fraction. The
coercivity IHC showed a maximum along a tie line from the off-stoichiometric Sm(Co0.65Cu0.35)5.6 to the
Sm2Co17 phase. The investigations showed that alloys have useful hard-magnetic properties in the bulk
form. Coercivity and microhardness were measured for Sm2(Co1xCux)17 alloys by [1986Lhy]. It was
shown that the hardness maximum corresponds to the peak of coercivity. [1982Mag] studied the coercive
force of Sm(Co0.65Cu0.35)z with z = 4.5, 5.6, 6 and found that eutectoid decomposition does not contribute
to the rise in the coercive force very much, while the main process responsible for its rise is the
decomposition of the supersaturated solid solution with the formation of a non-equilibrium
Sm2(Co1xCux)17 phase. [1979Arb] investigated the coercive force of a Sm(Co0.81Cu0.19)5.5 alloy.
Annealing the alloy from 900 to 1200C increases the coercive force. [1979Oes] studied the magnetic
properties of Sm(Co1xCux)5 (0.3 x 0.9) alloys and showed that the coercivity is intrinsic in nature, and
not dependent on pinning by second phases. [1986Mit] studied magnetic properties, microstructure and
domain structure of a cast and annealed alloy of SmCo3.25Cu1.75 using magnetometry, the Kerr
magneto-optic effect, SEM and EPMA. The magnetic properties, in particular the mechanism of
magnetization reversal, were found to be related to the microstructure and domain structure. [1999Est1]
Landolt-Brnstein
New Series IV/11C2
MSIT
170 CoCuSm
performed microstructural studies of Sm(Co1xCux)5 (0 x 0.5), determined the crystal structures of the
alloys and measured magnetic properties. Coercivity increased with Cu content, while the Curie
temperature decreased. The highest pinning field is observed in the Sm(Co0.5Cu0.5)5 alloy. [1999Est2]
performed a more detailed investigation of Sm(Co0.5Cu0.5)5. The as-cast state showed long elongated
regions with a solidification texture. The sample annealed at 1000C showed a more homogeneous
composition. Two slightly different regions were observed. The pinning mechanism is associated with
structural disorder introduced by an excess of Sm in the otherwise CaCu5 type structure. [2000Alo]
investigated the structural and magnetic properties of Sm(Co1xCux)7 alloys. These samples have uniaxial
anisotropy. The maximum value of TC is 852C. [2000Che] studied the crystal structure and magnetic
properties of milled Sm2(Co0.98Cu0.02)17 alloy. The coercive force IHC measured by [2000Che] is 9.0 kOe.
The coercive force of the permanent magnet Sm(Co1xCux)7 was studied by [1982Arb2] as a function of
the heat treatment program. Magnetization variation during recovery was measured for a
Sm(Co0.84Cu0.16)6.9 alloy in a low and a high-coercivity state by [1989Lil]. [2003Luo] investigated the
structural stability and magnetic properties of Sm(Co,Cu)7 alloys. It was shown that Sm(Co1xCux)7
exhibits ferromagnetic order. A strong uniaxial anisotropy at fields higher than 20 T is obtained with
x = 0.114 at 5 K. Saturation magnetization and Curie temperature decrease with increasing Cu content.
[2003Zha] studied the effect of Cu substitution on the microstructure and magnetic properties of
Sm(Co1xCux)7 (0 x 0.643) ribbons. Cu substitution is helpful to enhance the degree of preferred
orientation of the c-axis of the columnar dendrite grains parallel to the longitudinal direction of the ribbons.
[2005Gjo] studied the structure and magnetic properties of Sm(Co1xCux)5 alloys and established that the
Curie temperature decreases with increasing Cu content.
The information relating to the investigations of materials properties is summarized in Table 5.
Miscellaneous
The coercivity mechanism of magnetic materials in Co-Cu-Sm system was discussed in a number of works
[1973Kat, 1976Per, 1977Mel, 1978Nag, 1980Laz, 1983Arb, 1986Mit, 2004Yam]. [1973Kat] presented
evidence of spinodal decomposition. [1983Arb] found a mixture of two macroscopic phases (one with an
ordered Th2Zn17, another with the CaCu5 structure). [1986Mit] revealed the existence of two phases;
SmCo5 rich and SmCu5 rich. Theoretical interpretation of the hard-magnetic properties of Sm(Co,Cu)z
compounds with 5 < z < 8.5 was presented in [1976Per]. [1980Laz] evaluated critical fields for the pinning
of a narrow domain wall in materials with high magnetocrystalline anisotropy, such as Sm(Co,Cu)z
compounds, with 5 < z < 6. [2004Yam] calculated the crystal field parameter at each Sm site using a point
charge model. The temperature dependence of the coercivity in SmCo3.5Cu1.5 at low temperatures was
interpreted in terms of a physical model in the framework of the quantum regime by [1991Su]. [1999Zai]
investigated the effect of hydrogenation on phase composition and magnetic properties of Sm(Co1xCux)2
alloys. First-principle calculations [2005Gab] demonstrated that Sm(Co1xCux)5 alloys are unstable with
respect to decomposition into two phases of the same structure with different x values. The calculations also
suggest that the magnetic state of the alloys affects the stable x values and the Cu atomic site preferences.
SEM and thermomagnetic studies confirmed the two-phase structure of the as-cast Sm(Co1xCux)5 alloys.
High-temperature homogenization eliminates the chemical microsegregation and slightly increases the
coercivity of the alloys.
References
[1973Kam] Kamino, K., Kimura, Y., Suzuki, T., Itayama, Y., Variation of the Magnetic Properties of
Sm(Co,Cu)5 Alloys with Temperature, Trans. Jap. Inst. Met., 14(2), 135-139 (1973)
(Phase Diagram, Magn. Prop., Phase Relations, Experimental, #, 11)
[1973Kat] Katayama, T., Shibata, T., Magneto-Crystalline Anisotropy Constant in Sm(Co,Cu)5 Base
Alloy, Japan. J. Appl. Phys., 12(5), 762-764 (1973) (Magn. Prop., Experimental, 5)
[1973Sav] Savina, E.A., Mishin, D.D., Grechishkin, R.M., Lagutin, A.E., The Magnetic Aftereffect
in Alloys of Samarium with Cobalt and Copper, Izv. Vyss. Uchebn. Zaved., Fiz., (9),
New Series IV/11C2
CoCuSm 171
[1974Nis] Nishida, L., Ushara, M., Study of the Crystal Structure and Stability of Pseudobinary
Compounds SmCo5xCux, J. Less-Common Met., 34, 285-291 (1974) (Crys. Structure,
Experimental, 13)
[1976Zak] Zakharova, M.I., Gladyshev, S.N., Khatanova, N.A., Tulupov, I.F., Vereshnikov, E.E.,
Balzhinev, S.A., Phase Composition and Structure of RCo5 Type Alloys with Additional
Elements (Cu, Al, Mn, Nb, Ni), Russ. Metall., 3, 156-159 (1976) (Crys. Structure,
Experimental, 3)
[1976Mel] Melton, K.N., Perkins, R.S., Magnetic Properties of Sm:(Co, Cu) Alloys. I. Electron
Microscopy, J. Appl. Phys., 47(6), 2671-2678 (1976) (Crys. Structure, Magn. Prop.,
Morphology, Phase Relations, Thermodyn., Experimental, 20)
[1976Nag] Nagel, H., Perry, A.J., Menth, A., Hard-Magnetic Properties and Microstructure of
Sm(Co,Cu)z Compounds, J. Appl. Phys., 47(6), 2662-2670 (1976) (Magn. Prop.,
Morphology, Experimental, 33)
[1976Oes] sterreicher, H., McNeely, D., Low-Temperature Magnetic Studies of Various Substituted
Rare Earth (R)-Transition Metal (T) Compounds RT5, J. Less-Common Met., 45, 111-116
(1976) (Crys. Structure, Magn. Prop., Experimental, 6)
[1976Per] Perkins, R.C., Bernasconi, J., Wiesmann, H.J., Magnetic Properties of Sm(Co,Cu) Alloys.
2. Coecivity Mechanism, J. Appl. Phys., 47(6), 2679-2687 (1976) (Magn. Prop.,
Theory, 23)
[1977Mel] Melton, K.N., Nagel H., An Electron Microscope Study of Sm-Co-Cu-Based Magnetic
Materials with the Sm2Co17 Structure, J. Appl. Phys., 48(6), 2608-2611 (1977) (Magn.
Prop., Morphology, Experimental, 18)
[1977Per] Perry, A.J., The Constitution of Copper-Hardened Samarium-Cobalt Permanent Magnets,
J. Less-Common Met., 51, 153-162 (1977) (Phase Diagram, Experimental, #, 34)
[1978Nag] Nagel, H., Menth, A., Influence of Cu-Content on the Hard Magnetic Properties of
Sm(Co,Cu) 2:17 Compounds, IEEE Trans. Magn., 14(5), 671-673 (1978) (Magn. Prop.,
[1979Arb] Arbuzov, M.P., Pavlykov, A.A., Golub, N.S., X-Ray Investigation of the Structure of
(Co0,81Cu0,19)5,5Sm Alloys (in Russian), Poroshk. Metall., 11, 66-68 (1979) (Crys.
[1979Gla] Glardon, R., Kurz, W., The Cobalt-Samarium-Copper Phase Diagram, Z. Metallkd.,
70(6), 386-391 (1979) (Morphology, Phase Diagram, Phase Relations, Experimental, #, 21)
[1979Mag] Magat, L.M., Khrabrov, V.I., Crystal Geometry of Cast High-Coercivity Alloy
Sm(Co0.65Cu0.35)5.6, Phys. Met. Metallogr., 48(6), 178-181 (1979) (Crys. Structure,
Experimental, 7)
[1979Oes] sterreicher, H., Parker, F.T., Mizroch, M., Giant Intrinsic Magnetic Hardness in
SmCo5xCux, J. Appl. Phys., 50(6), 4273-4278 (1979) (Magn. Prop., Mechan. Prop.,
Experimental, 29)
[1980Laz] Lazar, D.P., Coercivity Mechanism of Sm(Co,Cu) Alloys, IEEE Trans. Magn. 16(1),
154-156 (1980) (Magn. Prop., Theory, 9)
[1981Gla] Glardon, R., Kurz, W., Solidification Path and Phase Diagram of Directionally Solidified
Co-Sm-Cu Alloys, J. Cryst. Growth, 51(2), 283-291 (1981) (Morphology, Phase Diagram,
Phase Relations, Experimental, 8)
[1981Ter] Terekhova, V.F., Markova, I.A., Torchinova, R.S., Shkatova, T.M., Mordovin, V.P.,
Alloys of Rare-Earth Metals, in Physics and Chemistry of Rare Metals (in Russian),
Savitskii, E.M. (Ed.), Nauka, Moscow, 138-153 (1981) (Phase Diagram, Magn. Prop.,
Experimental, #, 42)
[1982Arb1] Arbuzov, M.P., Pavlyukov, A.A., Opanasenko, O.S., Golub, N.S., Structural Changes in
Alloy Sm(Co0.86Cu0.14)7 During Heat Treatment, Phys. Met. Metall., 53(2), 187-189
(1982), translated from Fiz. Metal. Metalloved. 53(2), 400-402, (1982) (Crys. Structure,
Experimental, 4)
Landolt-Brnstein
New Series IV/11C2
MSIT
172 CoCuSm
[1982Arb2] Arbuzov, M.P., Pavlyukov, A.A., Boroday, N.G., Features of Phase Transformations
During Heat Treatment of Permanent Sm(Co,Cu,Fe)7 Magnets, Phys. Met. Metallogr.,
53(5), 97-100 (1982) (Magn. Prop., Experimental, 8)
[1982Mag] Magat, L.M., Khrabrov, V.I., Lapina, T.P., Makarova, G.M., Gaviko, V.S., Concerning the
Influence of the Saturated Solid Solution and Eutectoid Decomposition on the Coercive
Force of Sm(Co,Cu)5 Alloys, Phys. Met. Metallogr., 53(5), 189-191 (1982) (Magn. Prop.,
Experimental, 3)
[1983Arb] Arbuzov, M.P., Pavlyukov, A.A., The Structural Mechanism of Formation of the
High-Coercivity State in Sm-Co-Cu Alloys, Phys. Met. Metallogr, 56(5), 78-83 (1983),
translated from Fiz. Met. Metalloved., 56(5), 918-923 (1983) (Crys. Structure,
Experimental, 12)
[1986Lhy] Lhymn, C., Coercivity and Microhardness of Cast Sm2(Co,Cu)17 Magnets,
Metallography, 19(3), 327-334 (1986) (Mechan. Prop., Magn. Prop., Morphology, Phase
Relations, Experimental, 7)
[1986Mit] Mitchell, R.K., McCurrie, R.A., Magnetic Properties, Microstructure, and Domain
Structure of SmCo3.25Cu1.75, J. Appl. Phys., 59(12), 4113-4122 (1986) (Magn. Prop.,
[1987Mey] Meyer-Liautaud, F., Derkaoui, S., Allibert, C.H., Castanet, R., Structural and
Thermodynamic Data on the Pseudobinary Phases R(Co1xCux)5 with R = Sm, Y, Ce,
J. Less-Common Met., 127, 231-242 (1987) (Crys. Structure, Thermodyn.,
Experimental, 33)
[1988Sub] Subramanian, P.R., Laughlin, D.E., The Cu-Sm (Copper-Samarium) System, Bull. Alloy
Phase Diagrams, 9, 382-389 (1988) (Review, Phase Diagram, 20)
[1989Der] Derkaoui, S., Allibert, C.H., Redetermination of the Phase Equilibria in the System
Sm-Co-Cu for Sm Content 0.20 at.% at 850C, J. Less-Common Met., 154(2), 309-315
(1989) (Phase Diagram, Experimental, #, 16)
[1989Lil] Lileev, A.S., Melnikov, S.A., Menushenkov, V.P., Study of Recovery in Alloys Based on
Sm-Co-Cu, Izv. Akad. Nauk SSSR, Met., (3) 143-145 (1989) (Magn. Prop.,
Experimental, 7)
[1989Tur] Turchanin, M.A., Nikolaenko, I.V., Heats of Formation of Co-Cu Liquid Alloys and
Calculation of Mixing Enthalpies in the System Co-Cu-Sm (in Russian), Rasplavy, (5),
80-82 (1989) (Thermodyn., #, 10)
[1991Su] Su, G., Liu, H., Li, F.-S., Ge, M.-L., Theoretical Interpretation of the Anomalous
Temperature Dependence of Coercivity at Low Temperatures in Some Pseudobinary
Intermetallics, Phys. Status Solidi A, 126, 459-468 (1991) (Thermodyn., Experimental, 10)
[1993Ge] Ge, W.Q., Wu, C.H., Chung Y.C., Reinvestigation of the Sm-Co Binary System,
Z. Metallkd., 84, 165-169 (1993) (Phase Diagram, Experimental, 34)
[1995Oka] Okamoto, H., Comment on Co-Sm (Cobalt-Samarium), J. Phase Equilib., 16, 367-368
(1995) (Phase Diagram, 7)
[1996Zhu] Zhuang, W., Qiao, Z.-Y., Wei, S., Shen, J., Thermodynamic Evaluation of the Cu-R (R:
Ce, Pr, Nd, Sm) Binary Systems, J. Phase Equilib., 17, 508-521 (1996) (Phase Diagram,
Thermodyn., 42)
[1998Oka] Okamoto, H., Cu-Sm (Copper-Samarium), J. Phase Equilib., 19, 183 (1998) (Phase
Diagram, 3)
[1998Su] Su, X., Zhang, W., Liu, G., Du, Z., A Thermodynamic Assessment of the Co-Sm System,
J. Alloys Compd., 267, 149-153 (1998) (Phase Diagram, Thermodyn., 22)
[1998Tel] Tellez-Blanco, J.C., Groessinger, R., Sato Turtelli, R., Structure and Magnetic Properties
of SmCo5xCux Alloys, J. Alloys Compd., 281, 1-5 (1998) (Crys. Structure, Magn. Prop.,
Experimental, 15)
[1999Est1] Estevez-Rams, E., Penton, A., Novo, S., Fidler, J., Tellez-Blanco, J.C., Groessinger, R.,
Microstructural Evolution of Sm(Co1xCux)5 (0 < x < 0.5) Alloys, J. Alloys Compd., 283,
289-295 (1999) (Crys. Structure, Magn. Prop., Experimental, 18)
New Series IV/11C2
CoCuSm 173
[1999Est2] Estevez-Rams, E., Fidler, J., Penton, A., Valor-Reed, A., Tellez-Blanco, J.C., Sato Turtelli,
R., Groessinger, R., Microstructural Study of High Coercivity Sm(Co,Cu)5 Alloy,
J. Magn. Magn. Mater., 195, 595-600 (1999) (Crys. Structure, Magn. Prop.,
Experimental, 9)
[1999Zai] Zaikov, N.K., Mushnikov, N.V., Ermakov, A.E., Shtolz, A.K., Korolev, A.V., The Effect
of Hydrogenation on the Phase Composition and Magnetic Properties of Sm(Co1xCux)2
Alloys, Phys. Met. Metallogr. (Engl. Transl.), 88(6), 547-554 (1999) (Crys. Structure,
[2000Alo] Al-Omari, I.A., Yeshurun, Y., Zhou, J., Sellmyer, D.J., Magnetic and Structural Properties
of SmCo7xCux Alloys, J. Appl. Phys., 87(9), 6710-6712 (2000) (Crys. Structure, Magn.
[2000Che] Chen, Z., Meng-Burany, X., Okumura, H., Hadjipanayis, G.C., Magnetic Properties and
Microstructure of Mechanically Milled Sm2(Co,M)17-Based Powders with M = Zr, Hf, Nb,
V, Ti, Cr, Cu, Fe, J. Appl. Phys., 87(9), 3409-3414 (2000) (Crys. Structure, Magn. Prop.,
Experimental, 18)
[2000Oka] Okamoto, H. (Ed.), Phase Diagrams for Binary Alloys, ASM Intl., Materals Park, OH
(2000) (Phase Diagram)
[2002Ven] Venkatesan, M., Jiang, C., Coey, J.M.D., 1:7-type Magnets Produced by Mechanical
Milling, J. Magn. Magn. Mater., 242-245, 1350-1352 (2002) (Phase Relations, Magn.
[2003Gop] Gopalan, R., Suresh, K., Singh, A.K., Chandrasekaran, V., Metallurgical and Magnetic
Characterisation of Mechanically Milled Sm(Co0,9xFexCu0,1)4.8 Alloys, Scr. Mater.,
48(11), 1555-1559 (2003) (Crys. Structure, Magn. Prop., Morphology, Phase Relations,
Experimental, 14)
[2003Luo] Luo, J., Liang, J.K., Guo, Y.Q., Liu, Q.L., Yang, L.T., Liu, F.S., Rao, G.H., Li, W., Effects
of Cu on Crystallographic and Magnetic Properties of Sm(Co, Cu)7, J. Phys.: Condens.
Matter, 15(32), 5621-5628 (2003) (Crys. Structure, Phase Relations, Magn. Prop.,
Experimental, 21)
[2003Zha] Zhang, W.Y., Zhang, X.D., Yang, Y.C., Shen, B.G., Effect of Cu Substitution on Structure
and Magnetic Properties of Anisotropic SmCo Ribbons, J. Alloys Compd., 353(1-2),
274-277 (2003) (Morphology, Magn. Prop., Experimental, 25)
[2004Yam] Yamashita, O., Coercivity Mechanism of Sm(Co,Cu)5, J. Phys. Chem. Solids, 65(5),
907-912 (2004) (Magn. Prop., Theory, 31)
[2005Gab] Gabay, A.M., Larson, P., Mazin, I.I., Hadjipanayis, G.C., Magnetic States and Structural
Transformations in Sm(C,Cu)5 and Sm(Co,Fe,Cu)5 Permanent Magnets, J. Phys. D: App.
Phys., 38(9), 1337-1341 (2005) (Theory, Experimental, Magn. Prop., 16)
[2005Gjo] Gjoka, M., Panagiotopoulos, I., Niarchos, D., Structure and Magnetic Properties of
Sm(Co1xMx)5 (M = Cu, Ag) Alloys, J. Mater. Proc. Tech., 161(1-2), 173-175 (2005)
[2005Sta] Stadelmaier, H.H., Goll, D., Kronmueller, H., Permanent Magnet Alloys Based on
Sm2Co17; Phase Evolution in the Quinary System Sm-Zr-Fe-Co-Cu, Z. Metallkd., 96(1),
17-23 (2005) (Crys. Structure, Phase Relations, Review, 32)
[2006Ans] Ansara, I., Ivanchenko, V., Turchanin, M., Agraval, P., Co-Cu (Cobalt-Copper), MSIT
Science International Services GmbH, Stuttgart; to be published (2006) (Crys. Structure,
Phase Diagram, Thermodyn., Assessment, 19)
Landolt-Brnstein
New Series IV/11C2
MSIT
174 CoCuSm
Table 1: Investigations of the Co-Cu-Sm Phase Relations, Structures and Thermodynamics

[1973Kam] DTA 920C/Sm(Co,Cu)5 16-66 at.% Cu/ hypothetical
isothermal section
[1974Nis] X-ray analysis, X-ray microanalysis, 800-1000C / Sm(Co1xCux)5, 0 x 0.8
metallographic examination / X-ray
powder diffractometer
[1976Zak] X-ray diffraction, optical microscopy / 500, 700, 1100C / SmCo5xCux: SmCo4.4Cu0.6,
Debye camera SmCo4Cu0.8, SmCo4Cu, SmCo3.5Cu1.5
[1976Oes] X-ray analysis / Debye-Scherrer Sm0.167Co0.683Cu0.15
[1976Mel] X-ray analysis, Electron microscopy / 400-800C / Sm(Co0.65Cu0.35)5.6,
Siemens powder diffractometer, Phillips Sm(Co0.84Cu0.16)6.9
EM300 electron microscope
[1977Per] DTA, metallographic examination, EPMA 800, 1200C / SmCo5-Sm2Co17 up to 20 at.%
Cu / partial isothermal section
[1979Gla] DTA, metallographic examination, 850C / isothermal section, liquidus surface
EPMA / ARL, SEMQ microanalyser
[1979Arb] X-ray analysis 400-1000C / Sm(Co0.81Cu0.19)5.5
[1979Mag] X-ray analysis / RKU-114M, RKV-86 420-1100C / Sm(Co0.65Cu0.35)5.6
[1979Oes] X-ray analysis / GE XRD-5 diffractometer 800C / Sm(Co1xCux)5, 0.3 x 0.9
[1981Ter] X-ray analysis, metallography, EPMA Phase relations
[1981Gla] EPMA Solidification path
[1982Arb1] X-ray analysis 800-1220C / Sm(Co0.86Cu0.14)7
[1983Arb] X-ray analysis 500-1250C / Sm(Co0.8Cu0.2)5,
Sm(Co0.7Cu0.3)5 / phase composition
[1987Mey] X-ray analysis, calorimetric 400, 950C / Sm(Co1xCux)5, 0.2 x 0.8
measurements / X-ray focusing camera,
Tian-Calvet calorimeter
[1989Tur] Calculation of enthalpies of mixing by Co-Cu-Sm
isopotential method
[1989Der] X-ray analysis, EPMA, DTA 850C / 0-20 at.% Sm / partial isothermal
section
[1998Tel] X-ray analysis / X-ray powder 1000C / Sm(Co1xCux), x = 0.2, 0.3, 0.4, 0.5,
diffractometer 0.6, 0.8
[1999Zai] X-ray analysis / DRON-4U, DRON-2 800C / Sm(Co1xCux)2, x = 0, 0.2, 0.4, 0.6,
powder diffractometers 0.8, 1
[1999Est1] X-ray analysis, metallographic 1000C / Sm(Co1xCux)5, x = 0.0, 0.2, 0.3, 0.4,
microscopy, SEM / X-ray powder 0.5
diffractometer, polar Kerr microscopy,
SEM
New Series IV/11C2
CoCuSm 175

[1999Est2] X-ray analysis, metallographic 1000C / Sm(Co0.5Cu0.5)5
microscopy, SEM / X-ray powder
diffractometer, polar Kerr microscopy,
SEM
[2000Alo] X-ray analysis / X-ray powder Sm(Co1xCux)7, x = 0, 0.014, 0.029, 0.0429,
diffractometer 0.057, 0.071, 0.1
[2000Che] X-ray analysis, TEM / Phillips X-ray Milling, 500-900C / Sm2(Co0.98Cu0.02)17
powder diffractometer, JEOL
JEM-2000FX
[2002Ven] X-ray analysis / X-ray powder 1150, 800C, as-milling / Sm(Co0.957Cu0.043)7
diffractometer
[2003Gop] X-ray analysis, optical microscopy, SEM, Milling, 700C / Sm(Co0.9Cu0.1)4.8
EPMA, DSC / Phillips PW3020 X-ray
powder diffractometer, Leo 440i SEM,
CAMECA analyser
[2003Luo] X-ray analysis / Rigaku D/max 2500 600C / Sm(Co1xCux)7, x = 0.114-0.571
diffractometer
[2005Gjo] X-ray analysis / X-ray powder Sm(Co1xCux)5
diffractometer

[C] Prototype
(Co) cF4 a = 356.88 at 520C [V-C2]
1495 - 422 Fm3m a = 354.47 [Mas2]
Cu
(JCo) hP2 a = 250.71 at 25C [Mas2]
< 422 P63/mm c = 406.86
Mg
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m
Cu
(Sm) hR9 a = 362.90 at 25C [Mas2]
< 734 R3m c = 2620.7
Sm
(Sm) hP2 a = 366.30 [Mas2]
922 - 734 P63/mm c = 584.48
Mg
(Sm) cI2 - [Mas2]
1074 - 922 Im3m
W
Landolt-Brnstein
New Series IV/11C2
MSIT
176 CoCuSm

[C] Prototype
( Sm) hP4 a = 361.8 at 25C, 4.0 GPa [Mas2]
P63/mm c = 1166
La
Sm2(Co1xCux)17 hR57 a = 842.0 10.5-12.5 at.% Sm at x = 0
< 1347 R3m c = 1221.0 [Mas2], [V-C2], [2000Oka]
Th2Zn17 0 x 0.1 at 850C [1979Gla]
Sm5Co19 hR72 a = 503.5 [Mas2], [V-C2], [2000Oka]
< 1270 R3m c = 4845
Ce5Co19
Sm2(Co1xCux)7 hR54 a = 504.52 [V-C2], [1995Oka]
< 1241 R3m c = 3648.6 0.2 x 0.35 at 800C [1977Per]
Er2Co7
SmCo3 hR36 a = 505 [Mas2] [V-C2]
< 1200 R3m c = 2459
Be3Nb
Sm(Co1xCux)2 cF24 a = 726.4 to 727.6 at 800C, 0 x 0.14, [1999Zai],
< 1070 Fd3m [Mas2]
Cu2Mg
Sm9Co4 o*52 a = 1115 2 [Mas2] [V-C2]
< 613 b = 946.1 0.8
c = 917.3 0.9
Sm3Co oP16 a = 706 [Mas2] [V-C2]
700 Pnma b = 960
Fe3C c = 634
Sm(Cu1xCox)6 oP28 a = 806.0 [Mas2], [V-C2], [2000Oka]
< 967 Pnma b = 503.4 maximal 0.17 x 0.24 [1979Gla]
CeCu6 c = 1004.9
SmCu4 oP20 a = 442 [1988Sub]
< 880 Pnnm b = 801
CeCu4 c = 901
Sm(CoxCu1x)2 oI12 a = 435.2 to 433.8 at 800C, 0 x 0.11, [1999Zai],
< 855 Imma b = 692.3 to 690.5 [Mas2]
CeCu2 c = 737.7 to 736.3
SmCu cP2 a = 353.4 [1988Sub]
< 785 Pm3m
CsCl
New Series IV/11C2
CoCuSm 177

[C] Prototype
Sm(Co1xCux)5 hP6 a = 503 to 505 0.12 x 0.3 at 1100-700C [1976Zak]
P63/mmm c = 399 to 401
CaCu5
a = 500.1 x = 0.18 [1976Oes]
c = 399.7
a = 500.7 to 505.2 at 800C, 0.3 x 0.9, [1979Oes]

c = 399.0 to 407.7
a = 500.6 - 504.8 at 950C, 0.2 x 0.8, [1987Mey]

c = 399.9 - 406.6
a = 500.83 0.02 at 1000C, 0.2 x 0.8, [1998Tel]

to 504.10 0.09
c = 399.24 0.02
to 405.4 0.1
a = 504.8 at 900C, x = 0.34 [1981Ter]

c = 400.9
a =497.8 to 500.5 at 1000C, 0 x 0.3 [2005Gjo]

c = 398.4 to 401.5
a = 499.0 Sm(Co0.65Cu0.35)5.6 at 400C

c = 403.8 [1976Mel]
a = 503.8 Sm(Co0.65Cu0.35)5.6 at 800C [1976Mel]

c = 402.7
SmCo5 a = 500.2 0.5 at x = 0 [Mas2] [V-C2], homogeneity

1322 - 810 c = 396.4 0.5 range at x = 0 is 15 - 17.5 at.% Sm
SmCu5 a = 507 at x = 1 [Mas2] [V-C2], homogeneity

< 923 c = 410.4 range at x = 1 is 16 - 17 at.% Sm
[1979Gla]
Sm(Co1xCux)7 hP8 probably metastable
P63/mmm a = 493.5 to 498.1 0 x 0.1, [2000Alo]
TbCu7 c = 401.0 to 401.1
a = 493.48 0.01 at 600C, 0.114 x 0.571, [2003Luo]

to 497.36 0.02
c = 403.51 0.01
to 406.74 0.01
Landolt-Brnstein
New Series IV/11C2
MSIT
178 CoCuSm
Reaction T [C] Type Phase Composition (at.%)*

Co Cu Sm
L + Sm2(Co,Cu)17 (Co) + ~1130 U1 L 17.9 69.8 12.3
Sm(Co,Cu)5 Sm2(Co,Cu)17 65.1 23 11.9
(Co) 92.9 6.16 0.94
Sm(Co,Cu)5 51.3 34.6 14.1
L + (Co) + Sm(Co,Cu)5 ~995 P - - - -
Sm(Co,Cu)6
L + (Co) Sm(Co, Cu)6 + (Cu) ~910 U2 - - - -
* - as digitized from Fig. 1.
Table 4: Thermodynamic Data
Reaction or Transformation Temperature Quantity per Reaction Comment

[C] [J, mol, K]
1/5Sm + (1x)Co + xCu = 25 fH = 7400 Sm0.166Co0.669Cu0.165
1/5Sm(Co1xCux)5 fH = 8700 Sm0.174Co0.492Cu0.334
fH = 10400 Sm0.163Co0.33Cu0.507
fH = 11000 Sm0.168Co0.285Cu0.547
fH = 12200 Sm0.167Co0.167Cu0.666
Table 5: Investigations of the Co-Cu-Sm Materials Properties

[1973Kam] Magnetic measurements Magnetic properties
[1973Kat] Magnetic measurements / Vibrating sample Saturation magnetization, anisotropy field
magnetometer
[1973Sav] Magnetic measurements, Kerr effect Magnetic after-affect
[1976Oes] Magnetic measurements / Foner magnetometer Saturation moments, coercive force
[1976Nag], Bulk-magnetic measurements / Vibrating Hard-magnetic properties
[1978Nag] sample magnetometer, optical metallography
[1979Arb] Magnetic measurements Coercive force
[1979Mag], Magnetic measurements Coercive force
[1982Mag]
[1979Oes] Magnetic measurements / Vibrating sample Magnetic properties
magnetometer
[1982Arb1] Magnetic measurements Coercive force
[1982Arb2]
[1983Arb] Magnetic measurements Coercive force
[1986Lhy] Magnetic and microhardness measurements / Coercive force, microhardness
vibrating sample magnetometer
New Series IV/11C2
CoCuSm 179

[1986Mit] Magnetometer, Kerr magneto-optic effect Demagnetization
[1998Tel] Magnetic measurements / pulsed-field ac susceptibility, coercive force
magnetometer
[1999Zai] Magnetic measurements / vibrating-sample Magnetic properties of hydrogenated
magnetometer, MPMS-5XL SQUID samples Sm(Co1xCux)2 x = 0, 0.2, 0.4,
magnetometer 0.6, 0.8, 1
[1999Est1] Magnetic measurements / vibrational Curie temperature, coercive force
magnetometer VSM
[1999Est2] Magnetic measurements / vibrational Curie temperature, coercive force
magnetometer VSM
[2000Alo] Magnetic measurements / SQUID Magnetization, Curie temperature
magnetometer, vibrating-sample magnetometer
VSM
[2000Che] Magnetic measurements / vibrating-sample Magnetization, Curie temperature
magnetometer Oxford VSM
[2002Ven] Magnetic measurements / SQUID Magnetization, Curie temperature
magnetometer, vibrating-sample magnetometer
VSM
[2003Gop] Magnetic measurements / vibrating-sample Coercivity
magnetometer (Digital Measurements Systems)
[2003Luo] Magnetic measurements / SQUID Magnetization, Curie temperature
magnetometer
[2003Zha] Magnetic measurements Magnetic properties
[2005Gab] Magnetic measurements /MPMS and vibrating Coercivity
sample magnetometer (VSM)
Microstructure/SEM
[2005Gjo] Magnetic measurements / vibrating sample Magnetic properties
magnetometer
Landolt-Brnstein
New Series IV/11C2
MSIT
180 CoCuSm

Fig. 1: Co-Cu-Sm. Axes: at.%
Partial liquidus
surface
20
80
U1
~1130C
40
60
60
40
Sm(Co,Cu)5 ( Co)
80
20
Sm2(Co,Cu)17
20 40 60 80 e, 1327C
Sm p, 1322C Co

Fig. 2: Co-Cu-Sm. (Cu) Axes: at.%
(Cu)+SmCu6
Partial isothermal
section at 850C SmCu6
SmCu5
20
80
(Co)+(Cu)+SmCu6
(Co)+SmCu6
40 SmCu5+SmCu6
60
( Co)+(Cu)
( Co)+SmCo5
(Co)+SmCu6+SmCu5
60
40
80
20
(Co)+Sm2Co17+SmCo5
Sm2Co17+SmCo5
(Co)+Sm2Co17
20 40 60 80
Sm SmCo5 Sm2Co17 Co
New Series IV/11C2
CoCuSm 181
1400
Fig. 3: Co-Cu-Sm.
L+Sm2Co17
Partial isopleth at 10.5
at.% Sm
1300
L+(Co)
L+(Co)+Sm2Co17
1200
Temperature, C
L+(Co)+SmCo5
Sm2Co17
1100
1000
(Co)+Sm2Co17+SmCo5 (Co)+SmCo5
900
800
Sm 10.50 10 20 30 Sm 10.50
Co 89.50 Co 57.50
Cu 0.00 Cu, at.% Cu 32.00
1400
Fig. 4: Co-Cu-Sm.
Schematic isopleth at
L+Sm2Co17 L
16.7 at.% Sm
1300
1200
L+Sm(Co,Cu)5
Temperature, C
L+Sm2Co17+SmCo5
1100
Possible congruent melting
1000
L+SmCu6
Sm(Co,Cu)5
L+SmCu6+SmCu5
900
800
Sm 16.70 20 40 60 80 Sm 16.70
Co 83.30 Co 0.00
Cu 0.00 Cu, at.% Cu 83.30
Landolt-Brnstein
New Series IV/11C2
MSIT
182 CoCuSm

Fig. 5: Co-Cu-Sm. Axes: at.%
Calculated integral
enthalpies of mixing
of liquid alloys, in
kJ#mol1 20
80
40
60
-14
60
-13
40
0
-12
-5
-11
-11 -10
-10
80
20
-8
-5 -12
20 40 60 80
Sm Co
New Series IV/11C2
CrCuFe 183
Chromium Copper Iron

Tamara Velikanova, Mikhail Turchanin
Introduction
Phase equilibria in the Cr-Cu-Fe alloys are of importance both for the development of Cr-Cu-Fe alloys and
for their possible use in recycling processes in metallurgy. The Cr-Cu-Fe system is of interest for ferrous
and nonferrous metallurgy and for development of Cu based composites with favorable mechanical and
electrical properties. The Cu rich alloys of the system are promising as new cost effective, high strength,
high conductivity copper alloys. Copper has widely been used as an alloying element in ferrous metallurgy
to improve strength of steels under aging, their corrosion resistance and antifriction properties. On the other
hand, the presence of copper in ferrous alloys has negative aspects as well. It is known that a small amount
of residual Cu in steel scrap, which is difficult to remove by conventional steelmaking process, is a reason
of surface fissures during hot rolling process. The solubility of Cu in solid Fe, and therefore the influence
of Cr on the solubility, and liquid-solid wettability are considered as important factors affecting surface
fissures formation. Features of phase relations in the Cr-Cu-Fe alloys appeared to help solving the problem
of Cu separation from steel scrap, which is important for both metallurgical processing difficulties and
environmental problems. All these aspects stimulated intensive investigation of the Cr-Cu-Fe alloy phase
diagram. The main works are listed in Table 1.
Seven temperature-composition sections in the Fe rich corner of the diagram, three at constant chromium
and four at constant copper content, were reported by [1939Mor]. It is worth noting that the alloys
investigated below the solidus were contaminated with carbon up to 0.1 mass%. Additional information on
vertical sections at 2 and 4 mass% Cu in a high Fe content composition range was reported by [1970Ahm,
1974Zap] on alloys obtained by powder-metallurgical process and later the sections were calculated by
[1998Mie]. The calculated temperature-composition sections at 1 and 4 mass% Cu in the whole
concentration range were reported by [2004Wan] on the basis of own experimental data. The phase
equilibria were studied in a wide composition range, and a number of isothermal sections were constructed
in the temperature range from 800 to 1300C by [1967Sal, 1993Hao, 1997Oht, 2001Fer1, 2002Wan]. The
effect of Cr on the solubility of Cu in iron was investigated by [1967Sal] using alloys based on mild steel.
All the available experimental data on the phase equilibria in the ternary Cr-Cu-Fe system generally well
agree. Miscibility gap in liquid of the system was studied by [2004Wan].
The results of investigations of physical, chemical and mechanical properties of Cr-Cu-Fe alloys obtained
by both conventional and powder metallurgical methods were presented by [1967Sal, 1970Ahm, 1974Zap,
1971Yam, 2001Les, 2001Fer1, 2001Fer2, 2001Fer3, 2001Son, 2002Kim].
The Cr-Cu-Fe system was first critically assessed by [1979Cha]. This assessment was mainly based on the
results of [1939Mor, 1970Ahm, 1974Zap]. The same data set was used for modeling thermodynamic
properties of (Cu), and phases of the system in the framework of development of approximate
thermodynamic solution phase data for steels [1998Mie]. The thermodynamic parameters of the ternary
system were evaluated by [1997Oht] on the basis of own experimental results for the solubility ranges of
phases in the temperature interval 1100-1300C, and an isothermal section of the system at 1200C was
presented. The thermodynamic assessment of the phase equilibria in the Cr-Cu-Fe system was carried out
by [2002Wan] on the base of own experimental results and data of [1997Oht] taking into account data of
previous works, excluding [1967Sal] who investigated the Cr-Cu-mild steel alloys instead of Cr-Cu-Fe as
mentioned above. The results of calculation agree well enough with the experimental data available. The
optimized and consistent thermodynamic description of the Cr-Cu-Fe system of [2002Wan] was used for
calculation of the majority of figures on phase relations and reaction scheme presented in this assessment.
Binary Systems
The assessments of the Cr-Fe system by [1987And], of the Cr-Cu system by [1990Ham] and of the Cu-Fe
system by [1995Che] are accepted. These works are in good consent with [2002Ans, 2006Tur, Mas2]. The
Landolt-Brnstein
New Series IV/11C2
MSIT
184 CrCuFe
thermodynamic data sets of [1987And, 1990Ham, 1995Che] were used by [2002Wan] for thermodynamic
assessment of the ternary Cr-Cu-Fe system.
Solid Phases
Table 2 summarizes the crystallographic data on the Cr-Cu-Fe phases and their temperature and
concentration ranges of stability. The (Cu), and phases have marked homogeneity ranges in the ternary
system.
Cr and Fe decrease the solubility of each other in (Cu). The solubility of Cr in the (Cu) phase is not
significantly decreased by addition up to 0.3 mass% Fe after [2001Fer]. The solubility of Fe in the (Cu)
phase is significantly reduced due to the presence of Cr. At 750C and below this tendency becomes less
brightly expressed. This indicates that at lower aging temperatures less precipitation occurs during sample
quenching.
An increase in the Cr solubility in the phase with increasing Cu concentration and a decrease in the Cu
solubility in the phase with increasing Cr concentration was found by [1939Mor, 1967Sal, 1970Ahm,
1974Zap, 1993Hao, 1997Oht, 2002Wan] to be general tendencies. The minimum of Cu solubility in
austenite of mild steel with 5-7 mass% Cr reached in equilibrium with liquid at 1250C was reported by
[1967Sal]. It was not confirmed by the experimental investigations of [1993Hao, 1997Oht, 2002Wan] and
the thermodynamic calculations of [1997Oht, 2002Wan] for the ternary Cr-Cu-Fe alloys. According to our
calculation based on the thermodynamic models of [2002Wan], the phase homogeneity range penetrates
down to ~80 at.% Fe at 1100 to 1300C in the ternary system.
The calculated maximal saturation of the phase by copper is about 8 at.% Cu at 1380C. This value
correlates well with the experimental results of [1993Hao, 1997Oht].
The (Cu), and phases were treated as ternary solid solution phases in the thermodynamic assessment of
[2002Wan]. For the ) phase the homogeneity range only in the binary system was taken into account in the
calculation.
The data on the invariant equilibria given in Table 3 follow from the thermodynamic calculation carried out
in the present assessment. The reaction scheme after the calculation is given in Fig. 1. The existence of the
miscibility gap of the liquid phase in the ternary system despite its absence in the boundary binary systems
is an interesting peculiarity of the ternary. The existence of the point corresponding to the cupola top of the
miscibility gap of liquid, c1, and of two critical invariant points, c2 and c3, corresponding to the origin of
the three-phase monovariant equilibria of the and phases with two liquid phases rich in Fe or Cu given
in Table 3, reflects such a specific interaction of the components in the ternary. Invariant four-phase
monotectic equilibrium of the transition type, U1, and invariant equilibrium of the transition type, U2, are
shown. The calculated temperature of the U2 equilibrium, 1088C, agrees perfectly with that measured
experimentally by [1939Mor], 1084C. The calculated and experimental compositions of the and phases
are also close.
Liquidus and Solidus Surfaces

A liquidus projection is given in Fig. 2a (in the whole composition range) and in Fig. 2b (enlarged part near
the Cu corner) according to the thermodynamic calculation performed in this assessment. A wide two-phase
L' + L'' region exists in the ternary system over a large composition range. Addition of Cr to the Cu-Fe alloys
decreases the liquidus temperature of the phase as well as addition of Fe to the Cr-Cu alloys decreases the
liquidus of Cr-Cu alloys (liquidus of -phase) down to the monotectic valleys L' L'' + and L' L'' + ,
respectively. The above mentioned feature gives rise to the minimum fold on the liquidus surface of the
phase in the ternary system. The fold extends from the point of the temperature minimum in the
solid-liquid equilibrium region of the binary Cr-Fe up to the invariant e1(min) point at the monovariant
monotectic L' L'' + line in the ternary system. Accordingly, the tie lines L'L'' in the equilibria L' + L'' +
, which radiate from the Cu corner torwards the Cr-Fe side, go from the c2 and c3 critical points to meet
New Series IV/11C2
CrCuFe 185
one another at the minimal temperature on the ruled surface L'L'' at 1362C. The composition range of the
primary crystallisation surface of (Cu) is shown to be very restricted in agreement with the data for the
binary Cr-Cu and Cu-Fe phase diagrams.
The calculated solidus surface projection is given in Fig. 3. The narrow + + (Cu) three-phase region
shifted to the Cu-Fe edge separates the two-phase + (Cu) and + (Cu) regions. A very slight decrease in
solidus temperature from the Cu-Fe to Cr-Cu boundary systems is observed. According to the calculation,
the solubility of Cu in the (Fe) and (Fe) phases at solidus decreases from 5.8 and 6.9 at.% in the binary
Cu-Fe after [2006Tur] down to 3.9 at 18.3 at.% Cr and 5.7 at.% at 14.7 at.% Cr at 1088C, respectively. The
content of Cr in (Cu) solid solution is rather small being of 0.3 at.% at 3.4 at.% Fe.
Miscibility Gap Surface

The calculated miscibility gap of the liquid phase in the ternary system in the stable and metastable ranges
is given in Fig. 4. The isotherms at 1127 to 1477C are taken from [2004Wan]. The set of the vertical
sections of the miscibility gap parallel to the Cu-Fe edge is given in Fig. 5. The curve at 4 mass% Cr is taken
from [2004Wan]. The others are shown after the present calculation. Figures 4 and 5 show that additions of
Cr to Cu-Fe alloys and Fe to Cr-Cu increase the critical temperature of the miscibility gap (metastable in
the binaries Cu-Fe and Cr-Cu). Above 1.7 at.% Cr addition to Cu-Fe (critical point c3 at 1431C) the stable
miscibility gap appears. The minimal addition of Fe to Cr-Cu alloys to stabilize the miscibility gap is 9.7
at.% (critical point c2 at 1516C). One can see that the stable miscibility gap exists in a wide composition
region in the ternary system, forming the rather flat cupola with maximum at 1523C.
Isothermal Sections
Isothermal sections at 1500, 1250, 1050, and 800C are given in Figs. 6 to 9 according to the
thermodynamic calculations. The calculated isothermal sections at 1000, 1100 and 1300C were reported
by [2002Wan]. Additionally the isothermal sections at 1600, 1500, 1400, 1250, 1200, 1050, 900 and 800C
were calculated in the present assessment using the thermodynamic models of [2002Wan]. The results of
the calculations correlate well with the experimental investigations of [1993Hao, 1997Oht, 2001Fer1,
2002Wan].
No experimental data on phase equilibria at temperatures above 1300C are published. Strong bend of the
L / L + boundary towards the Cr-Fe edge giving a minimum Cu content at about 20 at.% Fe is seen in the
calculated section at 1500C, Fig. 6. This feature agrees with the location of the invariant minimum at
1513C and 21 at.% Cr in the boundary Cr-Fe system.
The composition of the equilibrium phases (Cu) / (Fe) at 800C, (Cu) / (Fe) at 900, 1000C and L /(Fe)
at 1200C were reported by [2002Wan] for the Fe rich alloys of the Cr-Cu-Fe system. The alloys were
prepared by melting and subsequently hot-rolled at 900C, solution-treated at 900C for 24 h, heat-treated
at 800 to 1000C for 336-1680 h and then quenched in iced water. It was tested and confirmed that the
specimens had reached an equilibrium state. The equilibrium compositions were determined up to a Cr
content of 10.1, 10.79, 10.85 mass% in the Fe based phases and 0.22, 0.21, 0.49 mass% in the (Cu) phase
at 800, 900 and 1000C, respectively. The (Fe) solid solution of the composition 9.20Cr-3.38Cu (mass%)
was found to be in equilibrium with liquid of the composition of 0.12Cr-97.77Cu (mass%). The equilibrium
compositions of the solid and liquid phases at 1100, 1200 and 1300C were measured by [1997Oht] using
solid-liquid diffusion couples held at the above mentioned temperatures for 24-48 h and subsequently
quenched in iced brine. The average composition of the frozen solid and liquid at the interphase boundaries
of the diffusion couples were obtained up to a Cr content of 28.81, 15.33, 16.40 mass% in solid and of 0.52,
0.47, and 0.80 mass% in liquid at 1100, 1200 and 1300C, respectively. It was shown that the addition of
Cr decreases the solubility of Cu in the Fe based phases. This tendency becomes remarkable with increasing
temperature. Being obtained using diffusion couples technique the experimental data of [1997Oht] might
be less reliable than those of [2002Wan] who used conventional metallurgical methods and well
equilibrated alloys. However, the data of both [1997Oht] and [2002Wan] perfectly agree, and good
agreement was achieved between the calculated locations of the phase boundaries and the experimental
results. The isotermal sections at 1200C constructed by [1997Oht] is cited in the review by [2002Rag].
Landolt-Brnstein
New Series IV/11C2
MSIT
186 CrCuFe
The Cr effect on the solubility of Cu in austenite of mild steel at 900, 1100 and 1250C was studied by
[1967Sal]. The measured solubility of Cu in Fe based phases is slightly lower compared with the results of
[1997Oht, 2002Wan], and a slight minimum of the solubility upon addition of about 5-6 mass% Cr was
found. The minimum point of Cu solubility in Fe based solid solution, reported by [1967Sal], was not
confirmed by the calculation for the Cr-Cu-Fe system.
The calculated sections at 1300, 1250,1200 and 1100C demonstrate the equilibria of the , and liquid
(very rich in Cu) phases and differ from each other in the equilibrium compositions of phases only. The
phase equilibria at 1250C are shown in Fig. 7. The equilibrium composition of phases at this and the above
mentioned temperatures are given in Table 4. The calculated isothermal section at 1050C is given in Fig. 8.
The same feature of the phase equilibria formed by , and (Cu) phases is shown in the calculated
isothermal sections at 1000 and 900C. Only the compositions of equilibrium phases differ. They are given
in Table 5. The isothermal section at 1000C, reported by [1993Hao], shows slightly elevated Cu content
in the and phases in equilibrium with (Cu) phase comparing with the data of [2002Wan]. [1993Hao]
based on own study of three ternary diffusion couples annealed for 150 h with subsequent quenching in
water. The (Cu) / (Cu) + boundary at 1050C after the calculation is shown in Fig. 8. It agrees well with
the experimental results of [2001Fer1] obtained using WDS method. One can see in Fig. 8, that Fe decreases
the solubility of Cr in (Cu) at 1050C, and the solubility of Cr reduces more markedly with increasing Fe
content. Similar tendency was found by [2001Fer1] for lower temperatures (down to 500C) using
resistivity measurements on aged and subsequently quenched in water alloys. However, the values of the
solubility measured by this method at 1050C were found to be noticeably lower than those after WDS
method. Consequently, the isotherms at 1025, 1000, 950, 850, 750, 650 and 500C reported by [2001Fer1]
cannot be considered for description of the equilibria at the indicated temperatures.
The calculated isothermal section at 800C is shown in Fig. 9. The (Cu) + (Fe) / (Fe) phase boundary
shown in Fig. 9 agrees with that of [2002Wan] obtained up to about 10 mass% Cr. There are no
experimental data on a possible Cu solubility in the ) phase. It is assumed to be small taking into account
the size of the Cu atomic radii on one hand, and Cr and Fe radii, on the other hand. Isothermal sections in
the temperature interval 831 to 510C, where the ) phase is stable in the Cr-Fe binary system, have to differ
in the ) + (Cu) and neighboring + (Cu) + ) regions only.

The calculated vertical sections are shown in Figs. 10 to 24. The section at 1 mass% Cr is taken from
[2004Wan], and the others are given after the calculation performed in the present assessment
corresponding to [2002Wan, 2004Wan]. Satisfactory agreement of the published calculations [1997Oht,
2002Wan, 2004Wan] in a wide temperature range including the region of the equilibria with liquid phase
and the available experimental data of [1939Mor, 1970Ahm, 1974Zap, 1997Oht, 2002Wan, 2004Wan] was
achieved as mentioned above. Thus one should believe that the thermodynamic models evaluated by
[1997Oht, 2002Wan] fit well to the thermodynamic description of the vertical sections in the whole
composition range at the temperatures under consideration, and the calculated vertical sections are reliable.
The first detailed experimental investigation of the temperature-composition sections of the Cr-Cu-Fe
system was carried by [1939Mor]. Contamination with 0.04 to 0.11 mass% carbon was reported for the
alloys used in the study of phase equilibria in the solid state. Seven partial vertical sections for the Fe rich
part of the system were presented: at 2 mass% Cr (up to about 20 mass% Cu), at 5 and 14 mass% Cr (up to
40 mass% Cu), and at 1, 2, 4 and 5 mass% Cu (up to 20 mass% Cr). The results of the later works of
[1970Ahm, 1974Zap, 1993Hao, 1997Oht, 2002Wan] concerning the mutual solubility of Cr and Cu in the
phase and the solidus temperatures generally agree with the presented vertical sections. [1939Mor] found
that the phase homogeneity range is enlarged by addition of copper so that the / + boundary lies
between 14 mass% Cr at 5 mass% Cu and 19 mass% Cr at 4 mass% Cu at about 1084C. With increasing
Cr content, the solubility of Cu in the phase and the Cu content at eutectoid composition at first decrease
and then increase, while the eutectoid temperature changes slighly. [1970Ahm, 1974Zap] studied the
influence of Cr on phase relations in the Fe rich alloys along the sections at 2 and 4 mass% Cu up to 18 and
15 mass% Cr in the temperature range from the solidus down to 700 and 1100C, respectively.
New Series IV/11C2
CrCuFe 187
The calculated vertical sections at 2 and 5 mass% Cr given in Figs. 11 and 13, at 1 and 4 mass% Cr
[2004Wan] given in Figs. 10 and 12, as well as at 1, 2, 4 and 6 mass% Cu, Figs. 18 to 21, confirm the above
mentioned a peculiarity of the ternary system, namely, the widening of the phase homogeneity range in
the equilibria with the phase when Cu is added. The miscibility gap of the liquid phase is shown in the
sections parallel to the Cu-Fe edge at 2 mass% Cr and more (including the highest content of Cr up to 40
at.%), Figs. 11 to 17. The same is seen in the sections parallel to the Cr-Fe edge at 2 mass% Cu and more
given in Figs. 19 to 22. The isothermal line at 1395.5C, corresponding to the monotectic invariant
equilibrium U1, appears in the sections at 4 and 5 mass% Cr as well as at 20 at.% Cu additionally to the
L' + L'' region, as shown in Figs. 12, 13 and 22a, 22b. The isothermal plane of the invariant four-phase
equilibria corresponding to the + + (Cu) three-phase alloys solidification is intersected by the vertical
sections at 1, 2, 4, 5 and 14 mass% Cr, Figs. 10 to 14.
The minimum on the liquidus surface in the sections at 1, 2, 4 and 6 mass% Cu, Figs. 18, 19a, 20 and 21,
near 20 at.% Cr at the temperature close to 1500C is associated with the invariant minimum on the
liquidus/solidus of the Cr-Fe binary system at 21 at.% Cu and 1513C.
The very narrow L' + L'' + and L' + L'' + ranges spearing the L + and L + fields, respectively, as
shown in the sections at 2, 4 and 6 mass% Cu, Figs. 19a, 20 and 21, seem to be very unusual. At higher Cu
content, a minimum at 1362C within the curves separating the L' + L'', L' + L'' + and L + phase regions
appears, Figs. 22a, b. It corresponds to the intersection of the degenerated into the line L' + L'' + tie triangle
with the plane of this vertical section.
Thermodynamics
There are no experimental data about thermodynamic properties of ternary solution phases in the system.
In [1974Sig] and [1988Uen] the thermodynamic properties of liquid alloys in the ternary system were
modeled on the basis of theoretical ideas and equations for interaction parameters in ternary solution were
developed. In [1997Oht, 1998Mie, 2002Wan] thermodynamic properties of the ternary solution phases, L,
(Cu), and , were modeled on the base of data on phase equilibria between these phases. All the results
of the calculation, both theoretical modeling and thermodynamic optimization of phase equilibria,
demonstrate strong positive deviations of the thermodynamic properties of the solution phases from the
ideality. In all cases when ternary interaction parameters were taken into account they have highly positive
values. Thus, positive deviations from the ideality, inherent in phases of the boundary Cr-Cu and Cu-Fe
binary systems, become more significant in the ternary. As a result, the miscibility gap in the liquid phase,
which is metastable in the binary Cr-Cu and Cu-Fe melts, appears in the ternary system.
The thermodynamic assessment of the Cr-Cu-Fe system was carried out by [2002Wan] using the
CALPHAD approach. Binary interaction parameters for the Cr-Cu, Cr-Fe and Cu-Fe systems were taken
from previous works of [1987And, 1990Ham, 1995Che]. Thermodynamic descriptions for the liquid, (Cu)
and phases were taken from [1997Oht]. Thermodynamic description for the phase was obtained by
[2002Wan] on the basis of the experimental data of [1997Oht, 2002Wan]. The ternary parameter for liquid
phase was equal to zero. The excess thermodynamic properties of solid solution phases took into account
the mixing enthalpy and the mixing entropy of components.
Due to the lack of experimental information, the solubility of ) phase in the ternary system is not considered
in [2002Wan]. The thermodynamic assessment was carried out for temperatures above 900C.

The experimental works devoted to study of materials properties in the Cr-Cu-Fe system are listed in
Table 6.
New cost effective, high-strength, high-conductivity and resistant to softening copper rich Cr-Cu-Fe alloys
were developed and their properties were investigated by [2001Fer1, 2001Fer2, 2001Fer3]. Determination
of the temperature dependence of the solid solubility of Fe and Cr in copper at 500 to 1050C for alloys
containing 0 to 1 mass% Cr and 0 to 1 mass% Fe was undertaken by [2001Fer1] to help interpreting the
observed mechanical and electrical properties of alloys. The linear relationship between resistivity and
chromium and iron concentrations in the Cu based solid solution was found by [2001Fer1]. Similarly, the
Landolt-Brnstein
New Series IV/11C2
MSIT
188 CrCuFe
relationship between the resistivity and composition of alloys was also approximately linear after the solid
solubility limit of (Cu) phase has been exceeded. Using these data the limit composition of (Cu) solid
solution was determined in aged and subsequently quenched alloys.
The evident difference in the compositions of the (Cu) solid solution coexisting with (or ) phase was
observed depending on experimental technique, namely WDS method or electrical resistivity
measurements. The lower solubility observed by the resistivity measurements was explained by the partial
(Cu) solid solution decomposition accompanied by small secondary precipitations under quenching
experiments. The WDS method gives an average signal including concentration of the above mentioned
precipitations. The method based on resistivity measurements gives only composition of (Cu) solid solution
remaining under quenching. Thus the curves shown in Fig. 23 by thin lines are not isotherms of solubility
at given temperatures. They correspond to unknown lower temperatures.
The mechanical properties of the Cu -0.7 mass% Cr - 0.3 mass% Fe alloy which indicated large precipitation
hardening response combined with the ability to stabilize cold worked microstructures to high temperatures
with a high electrical conductivity remaining were reported by [2001Fer2]. The age hardening response of
the Cu - 0.7 mass% Cr - 2.0 mass% Fe alloy was minimal, but the resistance to softening was superior to
that reported for any commercial high-strength, high-conductivity copper alloy with comparable
mechanical and electrical properties. For example, an excess of 85% of the original hardness of the 40 %
cold worked alloy is retained after holding at 700C for 1 h, whereas commercial high-strength,
high-conductivity Cu-Fe-P alloys have been reported to soften significantly after 1 h exposure below
500C. The Cu - 0.7 mass% Cr - 2.0 mass% Fe alloy was expected to be more suitable for applications with
a significant risk of exposure to elevated temperatures. Optical microscope examination of cold worked and
aged microstructures confirmed the high resistance to recrystallization for Cu - 0.7 mass% Cr - 2.0 mass%
Fe. The Zener-Smith drag term, predicting the pinning effect of second phase particles on dislocations in
cold worked microstructures, was calculated using the precipitate characteristics obtained from TEM, WDS
and resistivity measurements [2001Fer2, 2001Fer3]. The pinning effect of the precipitate dispersions in the
peak-aged condition was determined to be essentially equivalent for the Cu - 0.7 mass% Cr - 0.3 mass% Fe
and Cu - 0.7 mass% Cr - 2.0 mass% Fe alloys. A lower recrystallization temperature in the Cu - 0.7 mass%
Cr - 0.3 mass% Fe alloy was therefore attributed to faster coarsening kinetics of the secondary precipitates
resulting from a higher Cr concentration in the precipitates at a lower iron content [2001Fer3].
The microstructure and mechanical properties of the deformation processed Cr-Cu-Fe microcomposite
wires combined with intermediate heat treatments have been investigated by [2001Son, 2002Kim]. The
investigations were performed using samples of the Cu-1.2Cr-9Fe (mass%) composition. The primary and
secondary dendrite arms were aligned along the deformation axis and elongated into filaments during cold
drawing. It was shown that Cr atoms were mostly located in the Fe based filaments and the copper matrix
was almost free of Cr atoms in agreement with the partition coefficient of Cr between the (Cu) and or (Cu)
and phases according to the alloy phase diagram. The filaments in Cr-Cu-Fe microcomposites were
strengthened by the addition of Cr atoms and their refinement is relatively difficult due to the strengthening
of filaments by Cr. Thermo-mechanical treatments have been employed by [2002Kim] to optimize the
strength and conductivity of Cr-Cu-Fe microcomposites. The ultimate tensile strength and the conductivity
of the Cu-1.2Cr-9Fe (mass%) wires drawn to the cold drawing strain = 4.8 without intermediate heat
treatments were observed to be 920 MPa and 33.8% IACS, respectively, and those with heat treatments
were 891 MPa and 41% IACS. Further drawing wires to the cold drawing strain = 6.3 after an additional
heat treatment increased the conductivity from 43.1 to 53.3% IACS with a slight increase in hardness. The
precipitation of impurities and alloying elements during intermediate heat treatments is thought to increase
the conductivity due to reduced impurity scattering. Fig. 24 shows the variations of the strength and the
ductility as a function of heat treatment temperature. The activation volumes for deformation increased from
138b3 in the as-drawn wire to 230b3 in the wire annealed at 500C. Numerous particles were observed in
Cu matrix, and the spacing between these particles was found to be slightly smaller than the activation
length (138b = 35 nm). The most probable rate controlling mechanism of Cr-Cu-Fe microcomposites is
suggested to be the interaction between dislocations and precipitates in Cu matrix.
The processes of sintering of Cr-Cu-Fe alloys with 2 to 18 mass% Cr and 2 and 4 mass% Cu using iron,
copper and chromium or ferrochromium polvers as starting materials were studied by [1970Ahm,
New Series IV/11C2
CrCuFe 189
1974Zap]. A notable homogenization degree of the alloys during the sintering process was reached at
1300C after 12 h holding only. Examination of the diffusion phenomena and corrosion tests in nitric acid
and magnesium chloride solution were carried out. While diffusion of Cr in Fe was found to slightly
increase with Cu addition, microhardness and corrosion resistance increased with Cr addition markedly.
The obtained diffusion coefficients of chromium in the and phases as well as the corresponding
activation energies are listed in Table 7.
The diffusion coefficients of copper and chromium in liquid Cr-Cu-Fe alloys at 1550C were determined
by [1975Wan], and the following values were obtained: DCu,Cu = (5.5 0.1)105 cm2s1,
DCu,Cr = (0.1 0.03)105 cm2s1, DCr,Cr = (3.1 0.2)105 cm2s1, DCr,Cu = (2.5 0.8)105 cm2s1.
Composite materials constituted of a Cu rich phase with a high electric conductivity and of a Fe rich phase
with a high strength have an obvious advantage in terms of various properties. The preparation of such
composite materials, however, is not easy by the powder metallurgical process because of diffusion
problems, poor wetting between Cu and Fe [2001Les] and the high cost for fabrication. The formation of
the core-type macroscopic morphology of as-cast Cr-Cu-Fe alloys due to the stable miscibility gap of the
liquid phase is considered as useful peculiarity of the system for development of easy process of
manufacture of the natural composites on the base of the conventional casting process [2004Wan].
Miscellaneous
The problem of hot shortness (cracking) of steels, induced by subscale enrichment of alloying elements
during reheating before hot working, stimulated the investigation of the Cr effect on the Cu solubility in
austenite and on the penetration of liquid copper rich phase down austenite grain boundaries. A slight
decrease in the Cu solubility in austenite of mild steel when Cr content increased with a slight solubility
minimum at 5 to 6 mass% Cr was found by [1967Sal] as mentioned above. Although the Cu solubility
increased at higher Cr additions, but, with 9.38 mass% Cr, at 1250C, it was still lower than that with no
additions. Thus, the effect of Cr appears to be nearly neutral. However, because of a slight negative effect
observed particularly over the critical temperature range at about 1100C, Cr may be classified as a
detrimental rather than beneficial addition.
The dihedral angle of the copper rich phase at the phase grain boundaries was measured by [1967Sal] to
assess the effect of temperature on the penetration of the liquid copper rich phase into grain boundaries. The
alloys containing more than 3 mass% chromium display a sharp decrease in the dihedral angle at about
1100C. Minimum dihedral angle values, giving rise to maximum grain boundary penetration and probably
maximum susceptibility of the steel to hot shortness are between 1075C and 1175C.
The multilayers Fe-X/Cu-8/Fe-Y/Cr/Fe-Y/Cu-8 show an inverse giant magnetoresistance [2001Mil]. The
electrical conductivity of such multilayers decreases with the applied magnetic field. The electronic band
contribution to the giant magnetoresistance for Fe-3/Cu-4/Fe/Cr/Fe/Cu-4 and Fe-3/Cu-4 multilayers was
calculated within the semiclassical approximation. The results show a large change in the giant
magnetoresistance behavior when one layer of Cr is introduced within the Fe layers. The dependence of
impurity vs band effects in the appearance of inverse giant magnetoresistance in Cu/Fe superlattices with
Cr was studied by [2002Mil]. The calculated giant magnetoresistance ratios have been compared with the
experimental results, and it was concluded that the experimental data can only be explained by taking into
account Cr bands.
Laser surface remelting/resolidifying treatment on a powder metallurgically manufactured Cr-Cu-Fe
contact material was studied by [2000Gen]. A compact remelting/resolidifying layer was obtained with
appropriate laser treatment conditions and a suitable surface absorption coating. After the treatment, the
Cr-Cu-Fe microstructure of alloy on surface was greatly refined and the phase was uniformly dispersed
in the Cu rich matrix with a fine spherical or near spherical form. Improved compactness and microstructure
of the laser remelted Cr-Cu-Fe material yielded increased hardness (up to 80%), wear resistance, and a
reduced friction coefficient compared with the base material. The mechanism of laser strengthening was
concerned with the microstructural features of the Cr-Cu-Fe material.
Landolt-Brnstein
New Series IV/11C2
MSIT
190 CrCuFe
References
[1939Mor] Moriwaki, K., The Equilibrium Diagram of the Ternary System, Iron-Chromium-Copper,
Tetsu to Hagane, 25, 396-403 (1939) (Phase Diagram, Experimental, 3)
[1967Sal] Salter, W.J.M., Effect of Chromium on Solubility of Copper in Meld Steel, J. Iron Steel
Inst. Jpn., 205, 1156-1160 (1967) (Phase Diagram, Experimental, 30)
[1970Ahm] Ahmed, M., Thuemmler, F., Zapf, G., Metallographic Investigations of the Fe-Cr-Cu
Alloys Prepared by Powder Metallurgical Methods, Arch. Eisenhuettenwes., 41, 797-803
(1970) (Phase Diagram, Mechan. Prop., Experimental, 25)
[1971Yam] Yamaguchi, M., Ymakoshi, Y., Mima G., Miscibility Gap in the Iron-Chromium-Metal
(X=Copper, Manganese, Molybdenum, Nickel, Vanadium, Silicon and Aluminium)
System, Proc. Int. Conf. Sci. Technol. Iron Steel, Tokyo, 2, 1015-1019 (1971) (Phase
[1974Sig] Sigworth, G.K., Elliott, J.F., The Thermodynamics of Liquid Dilute Iron Alloys, Met.
Sci., 8, 298-310 (1974) (Thermodyn., Review, 249)
[1974Zap] Zapf, G., Ahmed, M., Research Report of the State of Noth Rhine-Westphalia, No. 2430:
Investigations on the Sinter Alloying of the Binary Iron-Chromium System and the Ternary
Iron-Chromium-Copper System (Forschungsbericht Des Landes Nordrheim),
Westdeutscher Verlag, Opladen, Germany, 149 pp (1974) (Phase Diagram, Mechan.
Properties, Experimental, 88)
[1975Wan] Wanibe, Y., Takagi, T., Sakao, H., Coupling Phenomenon in the Ternary Isothermal
Diffusion of Liquid Iron-Chromium-Copper Alloys, Arch. Eisenhuettenwes., 46(9),
561-565 (1975) (Transport Phenomena, Experimental, 7)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Cr-Cu-Fe, INCRA Monograph
Series 6. Phase Diagrams and Thermodynamic Properties of Ternary Copper-Metall
Systems, NSRD, Washington, 439-446 (1979) (Phase Diagram, Review, 6)
[1987And] Anderson, J.O., Sundman, B., Thermodynamic Properties of the Cr-Fe System, Calphad,
11, 83-92 (1987) (Calculation, Phase Diagram, Thermodyn., Assessment) as cited in
[2002Wan]
[1988Uen] Ueno, S., Waseda, Y., Jacob, K.T., Tamaki, S., Theoretical Treatment of Interaction
Parameters in Multicomponent Metallic Solutions, Steel Res., 59(11), 474-483 (1988)
(Thermodyn., Theory, Calculation, 44)
[1990Ham] Haemaelainen, M., Jaaskelainen, K., Luoma, R., Nuotio, M., Taskinen, P., Teppo, O.A.,
Thermodynamic Analysis of the Binary Alloy Systems Cu-Cr, Cu-Nb and Cu-V,
Calphad, 14(2), 125-137 (1990) (Calculation, Phase Diagram, Thermodyn.,
Assessment, 52)
[1993Hao] Hao, S.M., Jiang, M., Cr-Cu-Fe, Proc. 7th Nat. Symp. Phase Diagrams, Chinese Phys.
Soc., Shanghai, 11-13 (1993) (Phase Diagram, Experimental, 0)
[1995Che] Chen, Q., Jin, Z., The Fe-Cu System: a Thermodynamic Evaluation, Metal. Mater. Trans.
A, 26A(2), 417-426 (1995) (Calculation, Phase Diagram, Thermodyn., Assessment, 55)
[1997Oht] Ohtani, H., Suda, H., Ishida, K., Solid/Liquid Equilibria in Fe-Cu Based Ternary Systems,
ISIJ Int., 37(3), 207-216 (1997) (Experimental, Calculation, Phase Relations, Review,
Thermodyn., 47)
[1998Mie] Miettinen, J., Approximate Thermodynamic Solution Phase Data for Steels, Calphad,
22(2), 275-300 (1998) (Review, Calculation, 83)
[2000Gen] Geng, H.R., Liu, Y., Chen, C.Z., Sun, M.H., Gao, Y.Q., Laser Surface Remelting of
Cu-Cr-Fe Contact Material, Mater. Sci. Technol., 16(5), 564-567 (2000) (Experimental,
Morphology, Mechan. Prop., Electr. Prop.) cited from abstract
[2001Fer1] Fernee, H., Nairn, J., Atrens, A., Cu-Rich Corner of the Cu-Fe-Cr Phase Diagram,
J. Mater. Sci. Lett., 20, 2213-2215 (2001) (Experimental, Electr. Prop., Phase Relations, 6)
[2001Fer2] Fernee, H., Nairn, J., Atrens, A., Cold Worked Cu-Fe-Cr Alloys, J. Mater. Sci., 36(22),
5497-5510 (2001) (Electr. Prop., Mechan. Prop., Experimental, 19)
New Series IV/11C2
CrCuFe 191
[2001Fer3] Fernee, H., Nairn, J., Atrens, A., Precepitation Hardening of Cu-Fe-Cr Alloys - Part 1 -
Mechanical and Electrical Properties, J. Mater. Sci., 36(11), 2711-2719 (2001)
(Experimental, Electr. Prop., Mechan. Prop., 19)
[2001Les] Lesnik, N.D., Minakova, R.V., Khomenko, E.V., Chromium-Copper System: Adhesion
Characteristics, Doping, the Structure of Phase Boundary and Composites, Powder Metall.
Met. Ceram., 40(7-8), 432-440 (2001) (Experimental, Morphology, Phys. Prop., Interface
Phenomena, 12)
[2001Mil] Milano, J. Llois, A.M., From Direct to Inverse GMR: Introduction of Cr in Fe/Cu
Superlattices, J. Mag. Mag. Mater., 226, 1755-1757 (2001) (Calculation, Magn. Prop.)
cited from abstract
[2001Son] Song, J.S., Hong, S.I., Kim, H.S., Heavily Drawn Cu-Fe-Ag and Cu-Fe-Cr
Microcomposites, J. Mat. Proc. Tech., 113(1-3), 610-616 (2001) (Experimental, Mechan.
Prop., Morphology, 21)
[2002Ans] Ansara, I., Ivanchenko, V., Cr - Cu (Chromium - Copper), MSIT Binary Evaluation
[2002Kim] Kim, Y.S., Song, J.S., Hong, S.I., Thermo-Mechanical Properties of Cu-Fe-Cr
Microcomposites, J. Mat. Proc. Tech., 130, 278-282 (2002) (Experimental, Mechan. Prop.,
Morphology, 23)
[2002Mil] Milano, J., Llois, A.M., Steren, L.B., Combined Impurity and Band Effects on the
Appearance of Inverse Giant Magnetoresistance in Cu/Fe Multilayers with Cr, Phys.
Rev. B, 66(13), Art. No. 134405 (2002) (Calculation, Magn. Prop.) cited from abstract
[2002Rag] Raghavan, V., Cr-Cu-Fe (Chromium-Copper-Iron), J. Phase Equilib., 23(3), 257-258
(2002) (Review, Phase Relations, 5)
[2002Wan] Wang, C.P., Liu, X.J., Ohnuma, I., Kainuma, R., Ishida, K., Phase Equilibria in Fe-Cu-X
(X: Co, Cr, Si, V) Ternary Systems, J. Phase Equilib., 23(3), 236-245 (2002)
(Experimental, Calculation, Phase Diagram, Thermodyn., #, 38)
[2004Wan] Wang, C.P., Liu, X.J., Takaku, Y., Ohnuma, I., Kainuma, R., Ishida, K., Formation of
Core-Type Macroscopic Morphologies in Cu-Fe Base Alloys with Liquid Miscibility Gap,
Metall. Mater. Trans. A, 35A(4), 1243-1253 (2004) (Experimental, Calculation,
Morphology, Phase Diagram, Thermodyn., 31)
[2006Tur] Turchanin, M., Agraval P., Cu - Fe (Copper - Iron), MSIT Binary Evaluation Program, in
MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services
GmbH, Stuttgart; to be published (2006) (Crys. Structure, Phase Diagram, Thermodyn.,
Assessment, 36)
Landolt-Brnstein
New Series IV/11C2
MSIT
192 CrCuFe
Table 1: Investigations of the Cr-Cu-Fe Phase Relations and Structures

[1939Mor] DTA, dilatometric measurements, Temperature-composition sections:
optical microscopy at 2 mass% Cr and 0 to 20 mass% Cu;
at 5 mass% Cr and 0 to 40 mass% Cu;
at 14 mass% Cr and 0 to 40 mass% Cu;
at 1 mass% Cu and 4 to 20 mass% Cr;
at 6 mass% Cu and 4 to 20 mass% Cr
[1967Sal] Optical microscopy, EPMA, Partial isothermal sections:
Cr-Cu-mild steel alloys at 900C ((Cu)/ phase boundaries);
at 1100 and 1250C ((L)/ phase boundaries)
[1970Ahm, Optical microscopy, dilatometric Temperature-composition sections:
1974Zap] measurements, DTA, X-ray at 2 mass% Cu and 2 to 18 mass% Cr;
analysis at 4 mass% Cu and 2 to 18 mass% Cr
/ phase boundaries
[1971Yam] Optical microscopy, DTA Influence of Cu additions on the miscibility gap in the
-phase
[1993Hao] Diffusion couples technique, Isothermal section at 1000C, (Cu)/, (Cu)/ and /
optical microscopy, EPMA phase boundaries
[1997Oht] Solid-liquid diffusion couples Partial isothermal sections at 1100, 1200, 1300C,
technique, SEM-Electron (L)/ and (L)/ phase boundaries
Dispersive X-ray analysis
[2001Fer1] Wavelength dispersive Partial isothermal section at 1050C, (Cu)-phase
spectroscopy, resistivity
measurements
[2002Wan] SEM-Electron Dispersive X-ray Partial isothermal sections:
analysis at 800C, (Cu)/ phase boundaries;
at 900C, (Cu)/ phase boundaries;
at 1000C, (Cu)/ phase boundaries;
at 1200C, (L)/ phase boundaries
[2004Wan] Optical microscopy 49 to 65 mass% Cu, 34 to 49.5 mass% Fe, 2 to 7.2
mass% Cr, miscibility gap in liquid phase
New Series IV/11C2
CrCuFe 193

[C] Prototype
(Cu), CrxCuyFe1xy cF4 at x = 0 and 1096C, 0.955 y 1
< 1084.62 Fm3m [1995Che]
Cu at x + y = 1 and 1075C, 0.9992 y 1
[1990Ham]
a = 361.46 at x = 0, y = 1 and 25C [V-C2, Mas2]
, CrxCuyFe1xy cF4 at x = 0, 0 y 0.13 [1995Che]
1486 - 849 Fm3m at y = 0 and 977C, 0 x 0.12
Cu [1987And]
(Fe) a = 364.68
1394 - 912 at x = 0, y = 0 and 912C [V-C2, Mas2]
, CrxCuyFe1xy cI2 at x = 0 and 1486C, 0 y 0.063
< 1863 Im3m at x = 0 and 849C, 0 y 0.017
W [1995Che]
at y = 0, 0 x 1 [1987And]
at x + y = 1 and 1557C, 0 y 0.0034
[1990Ham]
(Cr) a = 288.48 at x = 1, y = 0 and 25C [V-C2, Mas2]
< 1863
( Fe) a = 293.15 at x = 0, y = 0 and 1394C [V-C2, Mas2]
1538 - 1394
(Fe) a = 293.22 at x = 0, y = 0 and 25C [V-C2, Mas2]
< 912
), CrxFe1x tP30 at 831C, x = 0.45
831 - 510 P42/mnm at 510C, x = 0.51
CrFe at 700C, 0.44 x 0.5 [1987And]
a = 879.66 at 650 - 790C and x = 0.495 [V-C2]
c = 455.82

Cu Cr Fe
L, L', L'' 1523 c1(critical) L 48.0 33.0 19.0
L', L'', 1516 c2(critical) L', L'' 48.8 41.5 9.7
1.0 84.4 14.6
L', L'', 1431 c3(critical) L', L'' 53.4 1.7 44.9
14.0 2.1 83.9
L' + L'' + 1396 U1 L' 25.1 9.7 65.2
11.1 8.6 80.3
L'' 77.0 2.9 20.1
8.6 10.2 81.2
Landolt-Brnstein
New Series IV/11C2
MSIT
194 CrCuFe

Cu Cr Fe
L' L'' + 1362 e1(min) L' 18.8 25.7 55.5
L'' 84.2 5.7 10.1
6.3 29.7 64.0
L + + (Cu) 1088 U2 L 96.7 0.7 2.6
5.7 14.7 79.6
3.9 18.3 77.8
(Cu) 96.3 0.3 3.4
Table 4: Equilibrium Compositions of the , and Liquid Phases in the Three-Phase Region
T [C] Phase Composition (at.%)
Cu Cr Fe
1300 L 89.7 1.8 8.5
7.1 13.4 79.5
9.5 11.3 79.3
1250 L 92.2 1.6 6.2
6.3 14.9 78.8
8.5 12.3 79.2
1200 L 94.1 1.2 4.7
5.5 16.1 78.4
7.6 13.2 79.2
1100 L 96.5 0.8 2.7
4.0 18.2 77.8
5.9 14.5 79.6
Table 5: Equilibrium Compositions of the , and (Cu) Phases in the Three-Phase Region
T [C] Phase Composition (at.%)
Cu Cr Fe
1050 (Cu) 96.9 0.2 2.9
3.3 18.6 78.1
4.9 14.8 80.3
1000 (Cu) 97.5 0.2 2.3
2.6 18.8 78.6
3.9 15.0 81.1
900 (Cu) 98.5 0.1 1.4
1.6 17.8 80.6
2.5 14.4 83.1
850 (Cu) 98.8 0.1 1.1
1.2 15.8 83.0
2.0 13.3 84.7
New Series IV/11C2
CrCuFe 195
Table 6: Investigations of the Cr-Cu-Fe Materials Properties

[1967Sal] Optical microscopy Dihedral angle measurements at 1 to 15 mass% Cu, 0
to 9.38 mass% Cr and at 900 to 1250C
[1970Ahm, Diffusion couple method Homogenization degree of sintered of Cr-Cu-Fe
1974Zap] alloys with 2 to 18 mass% Cr and 2 to 4 mass% Cu at
1050 to 1410C, diffusion coefficient and activation
energy of diffusion of Cr in and phases.
Corrosion tests, micro-hardness tests Microhardness and corrosion resistance
[1975Wan] Diffusion couple method Diffusion coefficients of copper and chromium in
liquid Cr-Cu-Fe alloys at 1550C
[2000Gen] Optical microscopy, friction tests, Mechanical and electrical properties of laser surface
resistance tests, hardness tests remelting/resolidifying processed Cr-Cu-Fe contact
material manufactured by powder metallurgy
[2001Fer1] Resistivity measurements Temperature dependence of resistivity of Cu rich
alloys at < 1 mass% Fe, < 0.6 mass% Cr and at 500 to
1050C
[2001Fer2] Electrical conductivity Microstructure, electrical and mechanical properties
measurements, optical microscopy, of Cu - 0.7 mass% Cr - 0.3 mass% Fe, Cu - 0.7 mass%
TEM, WDS, hardness tests Cr - 0.8 mass% Fe and Cu - 0.7 mass% Cr - 2.0
mass% Fe alloys
[2001Fer3] TEM, WDS, hardness tests, Microstructure, electrical and mechanical properties
resistivity measurements of Cu - 0.7 mass% Cr - 2.0 mass% Fe cold-worked
alloy
[2001Les] Stationary-drop method tests of Adhesive characteristics and formation of phase
wettability, optical microscopy, boundaries in Cu rich composite materials
electron microscopy, EPMA manufactured by powder metallurgical process at
1100-1300C
[2001Son] Mechanical properties tests using Microstructure, mechanical and electrical properties
extensometer, optical microscopy, of deformation processed Cu - 1.2 mass% Cr - 9
SEM, resistivity tests using mass% Fe microcomposite wires
four-probe technique
[2002Kim] Mechanical strength tests using Ultimate tensile strength and the conductivity of
machine equipped with deformation processed Cu - 1.2 mass% Cr - 9 mass%
extensometer, Vickers Fe microcomposite wires
micro-hardness tests, image
analysis, TEM
[2004Wan] Optical microscopy Core type macroscopic morphologies
Landolt-Brnstein
New Series IV/11C2
MSIT
196 CrCuFe
Table 7: Diffusion Coefficient and Activation Energy of Diffusion of Cr in and Phases

Diffusion Couple Diffusion Coefficient [cm2#s1] at Sintering Temperature Q Q
[kJ#g-atom 1] [kJ#g-atom1]
1410C 1250C 1050C
D D D D D
(Fe-Cr)/Fe 1.7107 3.2108 4.61010 1.9109 4.21011 239.3248 212.1288
7 8 9 10 10
(Fe-Cr + 2%Cu)/ 2.210 2.810 1.710 8.210 1.710 298.7376 194.9744
Fe
(Fe-Cr)/ 1.2107 1.3108 4.21010 3.01010 3.01011 308.7792 233.0488
(Fe + 2%Cu)
(Fe-Cr + 2%Cu)/ 1.5107 2.8108 5.01010 1.4109 6.51011 251.8768 176.9832
(Fe + 2%Cu)
(Fe-Cr + 4%Cu)/ 2.2107 4.2108 3.6109 3.0109 3.91010 227.6096 195.3928
Fe
(Fe-Cr)/ 1.5107 2.7108 8.51010 1.4109 9.41011 256.0608 187.4432
(Fe + 4%Cu)
(FeCr + 4%Cu)/ 1.5107 1.6108 8.01010 3.11010 6.51011 329.6992 216.7312
(Fe + 4%Cu)
(FeCr)/Cu/Fe - 1.5108 3.8109 - - 239.3248 212.1288
Cu-Fe Cr-Cu-Fe A-B-C Cr-Cu
c2, 1516
c3, 1431
1487 p1
l+ L'+L"+
1395 L' + L" + U1

L'+L"+
L'+L"+
1362 e1(min)
L' + L" L"++
1095 p2
l+
1088 L + + (Cu) U2
++(Cu) 1075 e2
L++(Cu)
l + (Cu)
Fig. 1: Cr-Cu-Fe. Reaction scheme
New Series IV/11C2
CrCuFe 197

Fig. 2a: Cr-Cu-Fe. e2 (Cu) Axes: at.%
Calculated liquidus U2 p2
projection 1200C
130
0
e1''
14
00
20
80
U1''
1431
40 1500
60
L'+L''
c3
c2
c1
60
40
1362C
1516
1600 U1'
80

20
e1' 1400
1700 p1
1800C 1431
20 40 60 80
Cr Fe

Fig. 2b: Cr-Cu-Fe. Axes: at.%
Enlarged part of the
e2 (Cu)
liquidus projection
p2
U2
10
90

e1''
20
80
L'+L''
U1''
Cr 25.00 10 20 Cr 0.00
Fe 0.00 Fe 25.00
Cu 75.00 Cu 75.00
Landolt-Brnstein
New Series IV/11C2
MSIT
198 CrCuFe

Fig. 3: Cr-Cu-Fe. (Cu) Axes: at.%
Solidus surface
projection
20
80
40
60
+(Cu)
60
40
+(Cu)+ (Cu)+
80 1085C 20

20 40 60 80
Cr Fe

Fig. 4: Cr-Cu-Fe. Axes: at.%
Calculated isotherms
of the cupola of stable
and metastable
miscibility gap of the 20
80
liquid phase. Dashed
lines are the tie lines
at 1127C.
40
60
60
40
L'+L''
1477
80 1427
20
1327
1227
1127C
20 40 60 80
Cr Fe
New Series IV/11C2
CrCuFe 199
1600
Fig. 5: Cr-Cu-Fe.
Calculated vertical
20 at.% Cr 33 at.% Cr
sections of the 1500
miscibility gap.
Solid lines 10 at.% Cr
correspond to the
1400
stable range and
dashed lines 4 mass% Cr 1.7 at.% Cr
Temperature, C
correspond to the
1300
metastable range,
section at 4 mass%
Cr is taken from
[2004Wan] 1200
1100
1000
900
Fe 20 40 60 80 Cu
Cu, at.%

Calculated isothermal
section at 1500C
20
80
40
60
L'+L''
60
40
L'+L''+
80
20

20 40 60 80
Cr Fe
Landolt-Brnstein
New Series IV/11C2
MSIT
200 CrCuFe

Calculated isothermal L
section at 1250C
20
80
40
60
L++
60
40
80
20

20 40 60 80
Cr Fe

section at 1050C
20
80
40
60
+ +(Cu)
60
40
80
20

20 40 60 80
Cr Fe
New Series IV/11C2
CrCuFe 201

section at 800C
20
80
40
60
+(Cu)+
60
40
80 +(Cu)+
20
20 40 60 80
Cr Fe
1600
Fig. 10: Cr-Cu-Fe.
Calculated 1500
temperature-
composition section
1400
at 1 mass% Cr,
plotted in at.%
1300
Temperature, C
L+ +
1200
L+(Cu)+ U2
1100
L+(Cu)+
1000
(Cu)+ (Cu)+ +
900
800

(Cu)+
700
(Cu)+ (Cu)+ +
600
Cr 1.07 10 20 30 40 50 60 70 80 90 Cr 1.22
Fe 98.93 Fe 0.00
Cu 0.00 Cu, at.% Cu 98.78
Landolt-Brnstein
New Series IV/11C2
MSIT
202 CrCuFe
1600
Fig. 11: Cr-Cu-Fe. L
Calculated 1500
temperature- L'+L'''
composition section
1400
at 2 mass% Cr, L'+L''+
plotted in at.%
1300
L''+ +
Temperature, C
1200
U2
1100
L''+(Cu)+
L''+(Cu)+
1000
(Cu)+ (Cu)+ +
900
(Cu)+ +
800

700
(Cu)+
600
Cr 2.15 10 20 30 40 50 60 70 80 90 Cr 2.43
Fe 97.85 Fe 0.00
Cu 0.00 Cu, at.% Cu 97.57
1600
Calculated 1500
temperature-
composition section L'+L''
1400
at 4 mass% Cr, L'+L''+
U1
plotted in at.%
1300
Temperature, C
1200
L'+ +
L''+(Cu)+
1100
L''+(Cu)+ U2
1000
900
800
(Cu)+ +
700
(Cu)+ +
600
Cr 4.28 10 20 30 40 50 60 70 80 90 Cr 4.85
Fe 95.72 Fe 0.00
Cu 0.00 Cu, at.% Cu 95.15
New Series IV/11C2
CrCuFe 203
1600
Calculated 1500
temperature-
L'+L''
composition section
1400
at 5 mass% Cr, L'+L''+ U1
plotted in at.%
1300
Temperature, C
1200
L'+ +
U2 L''+(Cu)+
1100
1000
900
800

(Cu)+ +
700
600
Cr 5.35 10 20 30 40 50 60 70 80 90 Cr 6.04
Fe 94.65 Fe 0.00
Cu 0.00 Cu, at.% Cu 93.96
1600
Fig. 14: Cr-Cu-Fe.
L
Calculated 1500
temperature-
L'+L''
composition section
1400
at 14 mass% Cr,
plotted in at.% L'+L''+
1300
Temperature, C
1200
L''+ + L''+(Cu)+
1100
+
U2
1000
(Cu)+ +
900
(Cu)+
800
700
(Cu)+ +
600
Cr 14.88 10 20 30 40 50 60 70 80 Cr 16.60
Fe 85.12 Fe 0.00
Cu 0.00 Cu, at.% Cu 83.40
Landolt-Brnstein
New Series IV/11C2
MSIT
204 CrCuFe
1600
Calculated 1500
temperature-
L'+L''
composition section
1400
at 20 at.% Cr
L'+L''+
1300
Temperature, C
1200
L''+(Cu)+
1100
1000
900
(Cu)+
800
700
(Cu)+ +
600
Cr 20.00 10 20 30 40 50 60 70 Cr 20.00
Fe 80.00 Fe 0.00
Cu 0.00 Cu, at.% Cu 80.00
1600
Fig. 16: Cr-Cu-Fe.
L
Calculated 1500
temperature-
composition section L'+L''
1400
at 30 at.% Cr L'+L''+

1300
Temperature, C
1200
L''+(Cu)+
1100
1000
900
800
(Cu)+
700
+ (Cu)+ +
600
Cr 30.00 10 20 30 40 50 60 Cr 30.00
Fe 70.00 Fe 0.00
Cu 0.00 Cu, at.% Cu 70.00
New Series IV/11C2
CrCuFe 205
1600
Fig. 17: Cr-Cu-Fe.
L
Calculated 1500
temperature- L'+L''
composition section L'+L''+
1400
at 40 at.% Cr

1300
Temperature, C
1200
L''+(Cu)+
1100
1000
900
800
+
(Cu)+
700
(Cu)+ +
600
Cr 40.00 10 20 30 40 50 Cr 40.00
Fe 60.00 Fe 0.00
Cu 0.00 Cu, at.% Cu 60.00
2000
Fig. 18: Cr-Cu-Fe.
Calculated
temperature-
composition section 1750
L
at 1 mass% Cu, L+
plotted in at.%
1500
Temperature, C

1250
L+(Cu)+

1000
(Cu)+
(Cu)+
750
(Cu)+ +
Cr 99.18 10 20 30 40 50 60 70 80 90 Cr 0.00
Fe 0.00 Fe 99.12
Cu 0.82 Fe, at.% Cu 0.88
Landolt-Brnstein
New Series IV/11C2
MSIT
206 CrCuFe
2000
Fig. 19a:Cr-Cu-Fe.
Calculated 1900
L
temperature- 1800
composition section
at 2 mass% Cu, 1700
L+
plotted in at.% 1600
L'+L''+
1500
Temperature, C
1400

1300
1200
L+(Cu)+
1100

1000
900
(Cu)+
(Cu)+
800
700
(Cu)+ +
600
Cr 98.36 10 20 30 40 50 60 70 80 90 Cr 0.00
Fe 0.00 Fe 98.24
Cu 1.64 Fe, at.% Cu 1.76
840
Fig. 19b: Cr-Cu-Fe.
Enlarged part of the +
calculated
temperature-
at 2 mass% Cu,
plotted in at.% (Cu)++
Temperature, C
+
820
(Cu)++
810
(Cu)+
(Cu)+
800
Cr 19.13 80 85 90 95 Cr 3.22
Fe 79.13 Fe 95.02
Cu 1.74 Fe, at.% Cu 1.76
New Series IV/11C2
CrCuFe 207
2000
Fig. 20: Cr-Cu-Fe.
Calculated 1900
L
temperature- 1800
composition section
at 4 mass% Cu, 1700
L+
1500
Temperature, C
1400
L'+L''+
1300

1200
L+(Cu)+
1100

1000
(Cu)+
900
(Cu)+ (Cu)+
800
(Cu)+ +
700
(Cu)+ +
600
Cr 96.70 10 20 30 40 50 60 70 80 90 Cr 0.00
Fe 0.00 Fe 96.47
Cu 3.30 Fe, at.% Cu 3.53
2000
Fig. 21: Cr-Cu-Fe.
Calculated 1900
L
temperature- 1800
composition section
at 6 mass% Cu, 1700
L+
1500
Temperature, C
1400
L'+L''+
1300
1200
L+(Cu)+ L+ +
1100
U2
1000
L+(Cu) (Cu)+ + (Cu)+
900
(Cu)+
800
700
(Cu)+ +
(Cu)+ +
600
Cr 95.04 10 20 30 40 50 60 70 80 90 Cr 0.00
Fe 0.00 Fe 94.69
Cu 4.96 Fe, at.% Cu 5.31
Landolt-Brnstein
New Series IV/11C2
MSIT
208 CrCuFe
1800
Fig. 22a:Cr-Cu-Fe.
Calculated 1700
L
temperature-
at 20 at.% Cu
1500
L'+L''
1400
L'+L''+ U1
Temperature, C
L'+
1300
1200
L+ L+(Cu)+ L''+ + L'+
1100
U2 L'+(Cu)+
1000
(Cu)+ (Cu)+
900
800
(Cu)+ +
700
(Cu)+
(Cu)+ +
600
Cr 80.00 70 60 50 40 30 20 10 Cr 0.00
Fe 0.00 Fe 80.00
Cu 20.00 Cr, at.% Cu 20.00
1600
Fig. 22b:Cr-Cu-Fe.
Enlarged part of the
calculated
temperature- L
composition section
at 20 at.% Cu
Temperature, C
1500
L''+
L'+L''+
L'+L''+
L'+ +
L'+
1400
L'+L''+ U1
L+
L'+L'' L'+
L''+ +
Cr 80.00 10 20 30 40 50 60 70 Cr 0.00
Fe 0.00 Fe 80.00
Cu 20.00 Fe, at.% Cu 20.00
New Series IV/11C2
CrCuFe 209

Composition of (Cu)
solid solution in
alloys quenched from 600
values on the curves denote aging temperature
aging temperature
after resistivity 650
measurements
[2001Fer1]
750
850
950
1000
1025
1050
isotherm at 1050C
Cr 1.00 Cr 0.00
Fe 0.00 Fe 1.00
Cu 99.00 Cu 99.00
21
Fig. 24: Cr-Cu-Fe. 900
Variations of
ultimate tensile 18
strength (U.T.S.) 800
and ductility of Cu
1.2 mass% Cr 9 700
15
mass% Fe wires as a
function of heat
U.T.S., MPa
600
Ductility, %
treatment
12
temperature
500
[2002Kim]
400 9
300
6
U.T.S.
200 Ductility
3
100
0 0
0 100 200 300 400 500
Landolt-Brnstein
New Series IV/11C2
MSIT
210 CrCuNi
Chromium Copper Nickel

Gautam Ghosh
Introduction
A summary of experimental studies of phase equilibria is given in Table 1. [1909Jae] measured the melting
point of a ternary alloy. [1923Sie] carried out extensive thermal analysis and reported a liquidus surface.
[1955Mei1] reported an isothermal section at 930C showing a miscibility gap island in the , (Cr,Ni,Cu)
field. Since then a large number of studies have been carried out to understand the phase separation
mechanism in ternary alloys, and the associated structure-property relationships. In addition, solubility of
Cr in ,(Ni,Cu) alloys as a function of temperature has also been reported [1939Ale, 1948Hib, 1967Zak].
Phase relations in the Cr-Cu-Ni system have been reviewed by [1949Jae, 1979Cha, 1979Dri, 1985Gup].
Binary Systems
The Cr-Cu binary phase diagram is accepted from [1993Cha1, 2002Ans]. The Cr-Ni binary phase diagram
is accepted from [Mas2]. The Cu-Ni binary system is accepted from [2002Leb].
Solid Phases
The crystallographic data of the solid phases are listed in Table 2.
The solid solubility isotherms of Cr and Ni in (Cu) were investigated by [1967Zak] at 840, 910, 980, 1030
and 1070C by means of X-ray diffraction and resistivity, and their results are shown in Fig. 1.
In the Cu-Ni system, the critical temperature of the miscibility gap is 354.5C [1993Cha2]. With the
addition of Cr phase separation in phase is thermodynamically favored, as a result the miscibility gap
widens and the critical temperature increases significantly. Above 354.5C, the miscibility gap is
considered as an island as it does not extend up to the Cu-Ni binary edge. The locus of the miscibility gap
island at a temperature other than 930C is not known. The decomposition of Cu and Ni rich solid
solutions, containing up to 16 mass% Cr, has been studied extensively in the temperature range of 500 to
850C, as they undergo spinodal decomposition [1958Man, 1960Bad, 1973Kre, 1977Wu, 1978Cho,
1978Sau, 1978Wu, 1980Bow, 1983Rao, 1986Jia, 1986Rao, 1987Rao, 1991Abe, 1991Rao, 1992Fin,
1993Fin1, 1993Fin2, 1993Fin3, 1993Fin4, 1994Bha1, 1994Bha2, 1994Bha3, 1994Rag, 2001Lop,
2002Fin]. [1986Rao] reported that the coherent spinodal temperature for a Cu-26.7Ni-1.9Cr (mass%) alloy
is 673C. On the other hand, [1973Kni] observed that a Cu-29.45Ni-1.2Cr (mass%) alloy does not undergo
spinodal decomposition in the temperature range of 500 to 750C, rather the phase separation takes place
by nucleation and growth mechanisms. Similarly, [1980Bow] found that the phase separation in a
Cu-9Ni-2.5Cr (mass%) alloy also takes place by nucleation and growth processes in the temperature range
of 550 to 850C. [2001Lop] determined the composition of phases by analytical electron microscopy in
two alloys that were aged at 800C for more than 250 h. The compositions of Cu and Ni rich phases are
listed in Table 3, and thus define only partly the locus of miscibility gap island at 800C.

The liquidus surface [1993Fin1] is shown in Fig. 2 along with selected isotherms. An earlier version of the
liquidus by [1923Sie], accepted by [1985Gup], is thought to be unreliable, as it is based on a Cr-Cu phase
diagram that is different from the one presently accepted. The drawbacks of experimental results of
[1929Sei] and associated uncertainties of the Cr-Cu phase diagram have been discussed in detail
[1993Cha1]. Specifically, the reported monotectic reaction L1 + L2 at 1467C in Cr-Cu system
[1923Sie] could not be verified in subsequent investigations [1993Cha1]. [1985Gup] proposed a possible
reaction scheme of the ternary system that includes the monotectic reaction. [1993Fin1] examined the
as-solidified microstructures of four ternary alloys, Cu-31.7Ni-2.7Cr, Cu-28.5Ni-4.9Cr, Cu-44.2Ni-10.1Cr
and Cu-45.1Ni-15.2Cr, and found primary dendrites of Ni rich phase and the eutectic mixture of and
New Series IV/11C2
CrCuNi 211
Cu rich phases in the interdendritic region. These results clearly demonstrate that the eutectic reaction
originating from the Cr-Ni binary feeds directly into the eutectic in the Cr-Cu system, as shown in Fig. 2.
Isothermal Sections
Figure 3 shows the calculated isothermal section at 1200C [1995Xia]. An isothermal section at 930C
[1955Mei1] is shown in Fig. 4, where minor adjustments are made along Cr-Ni edge to comply with the
corresponding accepted phase diagram. It is characterized by the presence of a miscibility gap (1+2)
island and a three-phase field (+1+2). This feature was confirmed by [1993Fin3]. However, phase
compositions in the tie-triangle, which were determined by SEM and TEM X-ray energy-depressive
analyses by [1993Fin3], differ by up to 4% compared to those by [1955Mei1]. In [1993Fin3] a conclusion
was made that there were possibilities to be slightly wrong in the microanalysis.
The locus of the miscibility gap island at a temperature other than 930C is not known. However, [2001Lop]
determined the composition of phases by analytical electron microscopy in two alloys that were aged at
800C for more than 250 h. The compositions of Cu and Ni rich phases are listed in Table 3, and thus define
only partly the locus of miscibility gap island at 800C.

Polythermal sections were reported by [1939Ale] and [1967Zak]. [1939Ale] determined the solubility of Cr
in Cu-Ni alloys at a constant mass ratio of Cu:Ni as 70:30 and Cu:Ni as 80:20. Their results are shown in
Figs. 5 and 6. In addition, [1948Hib] determined the solubility of Cr in Cu-10 mass% Ni, Cu-20 mass% Ni
and Cu-30 mass% Ni, and the solubilities in these three alloys were reported to be 0.55 mass% Cr at 1065C,
0.58 mass% Cr at 1075C and 0.88 mass% Cr at 1120C, respectively.
A polythermal section in the Cu corner was reported by [1967Zak], and it is shown in Fig. 7.
Thermodynamics
There is no experimental thermodynamic data of ternary alloys. However, since the discovery of phase
separation of the phase [1955Mei1], thermodynamic modeling has been carried out to understand phase
equilibria and phase separation mechanism [1955Mei2, 1957Mei, 1973Ans, 1981Gal, 1995Xia].
[1955Mei2, 1957Mei] used a regular solution model and calculated the isothermal section at 927 and 930C
that showed a remarkable agreement with the experimental isothermal section [1955Mei1]. In particular,
both the three-phase field (+1+2) and the miscibility gap (1+2) were reproduced, whereas a simple
graphical interpolation method did not yield any of the these results [1955Mei2, 1957Mei].

A summary of experimental investigation of properties is given in Table 4. There has been a considerable
interest in understanding the origin of strengthening mechanism in spinodally decomposed microstructures
of ternary alloys. It has been shown that the increase in strength is proportional to the strain amplitude and
independent of the wavelength of composition modulation [1986Rao, 1987Rao, 1992Fin, 1993Fin4].
Furthermore, prior deformation accelerates the spinodal decomposition kinetics, and also leads to a
substantial increase in strength [1973Kre, 1994Rag]. The fatigue properties of ternary alloys, with and
without spinodally decomposed microstructure, have also been reported [1992Wan, 1993Wan1,
1993Wan2, 1993Wan3, 1994Bom, 1994Wan]. Alloys with spinodally decomposed microstructures have
higher fatigue strength [1992Wan].
The Cr impurity contribution to the resistivity and magnetoresistance was studied by [1972Eag]. These
properties show a marked dependence on the Ni content, and the impurity contribution is proportional to
the Cr content only in the alloys containing 23 at.% Ni. The results are consistent with the concept of
spin-flip-scattering process.
Other properties investigated include corrosion and wear [1973And, 1988Qin, 1990Elb, 1990Sof],
weldability [1969Pet], wettability [1995Xia, 2001Les], and oxidation [2003Cao1, 2003Cao2].
Ternary alloys have been used for decorative purposes by an electrodeposition process [1980Sri].
Landolt-Brnstein
New Series IV/11C2
MSIT
212 CrCuNi
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New Series IV/11C2
CrCuNi 213
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Corrosion-Resistance of Cu-Ni-Cr Alloys, Mater. Lett., 7(4), 149-151 (1988)
(Experimental, 4)
[1990Elb] Elboujdaini, M., Ghali, E., Angers, R., Electrochemical-Behavior of Microcrystal
Cu-Ni-Cr Alloys in Chloride Solution, J. Appl. Electrochem., 20(5), 848-854 (1990)
(Experimental, 6)
[1990Sof] Sofronkov, A.N., Pervy, E.N., Zhurlova, R.V., The Electrochemical Properties of the
Ternary Alloys of Ni-Cr-Cu (in Russian), Ukr. Khim. Zh., 56(4), 387-389 (1990)
(Experimental, 4)
[1991Abe] Abe, T., Brenner, S.S., Soffa, W.A., Decomposition of a Cu-Ni-Cr Ternary Alloy, Surf.
Sci., 246, 266-271 (1991) (Experimental, Phase Relations, 13)
[1991Rao] Rao, P.P., Agrawal, B.K., Rao, A.M., Comparative Study of Spinodal Decomposition in
Symmetric and Asymmetric Cu-Ni-Cr Alloys, J. Mater. Sci., 26(6), 1485-1496 (1991)
(Crys. Structure, Electronic Structure, Experimental, Kinetics, Mechan. Prop., 30)
[1992Fin] Findik, F., Flower, H.M, Microstructure and Hardness Development in Cu-30Ni-(2-5)Cr
and Cu-45Ni-10Cr Spinodal Alloys, Mater. Sci. Tech., 8(3), 197-205 (1992)
Landolt-Brnstein
New Series IV/11C2
MSIT
214 CrCuNi
[1992Wan] Wang, G.X., Schwalbe, K.H., Bomas, H., Mayr, P., Fatique Behaviour of
Cu-35%Ni-3,5%Cr after Different Heat Treatments (in German), Mat-Wiss. Werkstoff, 23,
133-138 (1992) (Experimental, Mechan. Prop., 6)
[1993Cha1] Chakraborty, D.J., Laughlin, D.E., Cr-Cu (Chromium-Copper), in Phase Diagrams of
Binary Copper Alloys, Subramanian, P.R, Chakrabarty, D.J., Laughlin, D.E., (Eds.), ASM
International, Materials Park, OH, 144-152 (1993), (Crys. Structure, Phase Diagram,
Review, #, *, 38)
[1993Cha2] Chakraborty, D.J., Laughlin, D.E., Chen, S.W., Chang, Y.A., Cu-Ni (Copper-Nickel), in
Phase Diagrams of Binary Copper Alloys, Subramanian, P.R, Chakrabarty, D.J.,
Laughlin, D.E., (Eds.), ASM International, Materials Park, OH, 266-270 (1993), (Crys.
Structure, Phase Diagram, Review, #, *, 85)
[1993Fin1] Findik F., Side-Band in Spinodal Cu-Ni-Cr Alloys and Lattice-Parameters Inquiries,
J. Mater. Sci. Lett., 12(5), 338-342 (1993) (Experimental, Phase Relations, 21)
[1993Fin2] Findik F., As-Cast Structures and Liquidus Projection in Some Spinodal Cu-Ni-Cr
Alloys, J. Mater. Sci. Lett., 12(7), 505-508 (1993) (Experimental, Phase Relations, 9)
[1993Fin3] Findik, F., Observations on Particle Size/Spacing Relationships and Phase Equilibria in the
Cu-Ni-Cr System, J. Mater. Sci., 28, 5056-5059 (1993) (Experimental, Optical Prop.,
Phase Diagram, 10)
[1993Fin4] Findik, F., Flower, H.M, Morphological-changes and Hardness Evolution in Cu-30Ni-5Cr
and Cu-45Ni-15Cr Spinodal Alloys, Mater. Sci. Tech., 9(5), 408-416 (1993)
(Experimental, Phase Relations, Phase Diagram, 29)
[1993Wan1] Wang, G.X., Schwalbe, K.H., Bomas, H., Mayr, P., Small Crack-Propagation and Lifetime
of the Alloy Cu-33.8% Ni-3.4% Cr in Different Environments (in German), Mat.-Wiss.
Werkstoff, 24(12), 432-439 (1993) (Experimental, Mechan. Prop., 13)
[1993Wan2] Wang, G.X., Schwalbe, K.H., A Study of the Transition from Intercrystalline to
Transcrystalline Fatigue Crack-Propagation in Different Aging Conditions of the Alloy
Cu-35% Ni-3.5% Cr, Int. J. Fatigue, 15(1), 3-8 (1993) (Experimental, Mechan. Prop., 8)
[1993Wan3] Wang, G.X., Bomas, H., Boschen, R., Mayr, P., Cyclic Deformation of the Alloy Cu-35%
Ni-3.5% Cr in the Homogenized Condition, Int. J. Fatigue, 15(5), 423-428 (1993)
(Experimental, Mechan. Prop., 14)
[1994Bha1] Bhat, R.R., Rao, P.P., Effect of Preaging on the Transformation Behavior of
Thermomechanically Treated Spinodal Cu-Ni-Cr Alloy, Trans. Indian Inst. Met., 47(4),
239-249 (1994) (Experimental, Phase Relations, 30)
[1994Bha2] Bhat, R.R., Rao, P.P., Kamath, S.L., Effect of Thermomechanical Treatment on the
Phase-Transformation in Cu-44Ni-5Cr Alloy, J. Mater. Sci., 29, 4808-4818 (1994)
[1994Bha3] Bhat, R.R., Rao, P.P., Kamath, S.L., High-Strength Cu-Ni-Cr Alloys by
Thermomechanical Treatment, Indian J. Eng. Mater. Sci., 1(1), 41-47 (1994)
[1994Bom] Bomas, H., Golos, K., Linkewitz, T., Mayr, P., Block Loading Sequence Effects on Fatigue
in the Copper Alloy Cu-35% Ni-3.5% Cr, Int. J. Fatigue, 16(2), 147-150 (1994)
[1994Rag] Raghavendra, R., Rao, B., Rao, P.P., Thermomechanical Treatment of Spinodal
Cu-32Ni-2Cr Alloy, Z. Metallkd., 85(4), 237-240 (1994) (Experimental, Phase
Relations, 25)
[1994Wan] Wang, G.X., Effect of Microstructural Modification on Tensile and Fatigue Properties of
Cu-35Ni-3.5Cr (mass%) Alloy, Acta Metall. Mater., 42(7), 2547-2554 (1994)
[1995Xia] Xiao, P., Derby, B., The Wetting of Silicon Nitride by Chromium-Containing Alloys,
J. Mater. Sci., 30, 5915-5922 (1995) (Experimental, Phase Relations, Thermodyn., #, *, 16)
New Series IV/11C2
CrCuNi 215
Met. Ceram., 40(7-8), 432-440 (2001) (Experimental, Phase Relations, Phys. Prop., 12)
[2001Lop] Lopez-Hirata, V.M., Hernandez-Santiago, F., Dorantes-Rosales, H.J., Saucedo-Munoz,
M.L., Hallen-Lopez, J.M., Phase Decomposition During Aging for Cu-Ni-Cr Alloys,
Mater. Trans., JIM, 42(7), 1417-1422 (2001) (Experimental, Phase Relations, #, *, 12)
[2002Fin] Findik, M., Modulated Structures in Cu-32Ni-3Cr and Cu-46Ni-17Cr Alloys, Can.
Metall. Quart., 41(3), 337-347 (2002) (Experimental, Phase Relations, 25)
[2002Ans] Ansara, I., Ivanchenko, V., Cr-Cu (Chromium-Copper), MSIT Binary Evaluation
Program, in MSIT Workplace, Effenberg, G. (Ed.), Materials Science International Services,
GmbH, Stuttgart; Document ID: 20.19588.1.20, (2003) (Crys. Structure, Phase Diagram,
Assessment, 29)
[2002Leb] Lebrun, N., Cu-Ni (Copper-Nickel), MSIT Binary Evaluation Program, in MSIT
Assessment, 51)
[2003Cao1] Cao, Z.Q., Niu, Y., Wu, W.T., Effect of Microstructure on the Oxidation Behavior of
Cu-40Ni-20Cr Alloy (in Chinese), Acta Chim. Sin., 61(2), 166-170 (2003)
(Experimental, 15)
[2003Cao2] Cao, Z.Q., Niu, Y., Wu, W.T., Effect of Chromium Content on High-Temperature
Oxidation Behavior of Cu-Ni-30Cr Alloy, Rare Met. Mater. Eng., 32(4), 250-254 (2003)
(Experimental, 22)
Table 1: Investigations of the Cr-Cu-Ni Phase Relations, Structures and Thermodynamics

[1909Jae] Thermal analysis Cr-40.5Cu-19Ni (mass%)
[1923Sie] Thermal analysis and optical 1093-1498C; Cu: 1.5-80 mass%, Ni: 5-80 mass%,
metallography Cr: balance
[1939Ale] Hardness and optical metallography 400-1100C; Cr: up to 0.5 mass%, Ni: up to 29.97
mass%, Cu: balance
[1948Hib] Electrical resistivity, hardness and 400-1075C; Cr: 0.19-1.2 mass%, Ni: 10-30.3
optical metallography mass%, Cu: balance
[1955Mei1] Thermodynamic analysis 927C; entire composition range
[1955Mei2] Metallography and XRD 750-1120C; entire composition range
[1957Mei] Thermodynamic modeling 930C; entire composition range
[1958Man] XRD 550-800C; Cr-46Cu-44Ni (mass%)
[1960Bad] TEM, XRD and hardness <980C; Cu-(20.3-45.1)Ni-(0.75-3.6)Cr (mass%)
[1967Zak] XRD 700-1070C; Cr: 0.1-1.3 mass%, Ni: 0.35-1.45
mass%, Cu: balance
[1972Eag] Resistivity and magnetometry 271.65 to 173.15C; 5.5-23 at.% Ni and
1.38#103 - 1.21#102 at.% Cr, Cu: balance
[1973Ans] Thermodynamic modeling 930C; entire composition range
[1973Kni] TEM, hardness and electrical 500-750C; Cu-29.45 mass% Ni and 1.2
resistivity mass% Cr
[1973Kre] TEM, XRD and hardness 600-700C; Cu-30.09Ni-2.94Cr (mass%)
Landolt-Brnstein
New Series IV/11C2
MSIT
216 CrCuNi

[1977Wu] TEM 600-700C; Cu-28.9Ni-2.84Cr (mass%)
[1978Cho] TEM 650C; Cu-31.6Ni-1.7Cr (mass%)
[1978Sau] TEM 300-900C; Cu-(33.7-55.8)Ni-(3.8-15.5)Cr
(mass%)
[1978Wu] TEM 600-700C; Cu-28.9Ni-2.84Cr (mass%)
[1980Bow] TEM and hardness 550-850C, Cu-(9-56)Ni-(2.5-16)Cr (mass%)
[1983Rao] XRD Cu-30Ni-5Cr (mass%)
[1986Jia] TEM 580C; Cu-36Ni-4Cr (mass%)
[1986Rao] TEM, XRD and hardness 500-800C; Cu-26.7Ni-1.9Cr (mass%)
[1987Rao] TEM, SEM and XRD 500-650C; Cu-44.8Ni-9.6Cr (mass%),
Cu-51.9Ni-14.8Cr (mass%)
[1991Abe] Atom-probe field ion microscopy 550-650C; Cu-33.3Ni-1.7Cr (at.%)
[1991Rao] TEM, XRD and hardness 500-800C; Cu-26.73Ni-1.84Cr (mass%),
Cu-44.78Ni-9.61Cr (mass%),
Cu-51.91Ni-14.81Cr (mass%)
[1992Fin] TEM, SEM, XRD and hardness 300-800C; Cu-30Ni-2.5Cr (mass%),
Cu-45Ni-10Cr (mass%)
[1993Fin1] TEM, XRD and hardness 300-800C; Cu-(28.5-45.1)Ni-(2.7-15.2)Cr
[1993Fin2] (mass%)
[1993Fin3]
[1993Fin4]
[1994Bha1] DSC, XRD and hardness 550-600C; Cu-44.28Ni-5.4Cr (mass%)
[1994Bha2]
[1994Bha3]
[1994Rag] XRD and hardness 500C; Cu-31.8Ni-1.7Cr (mass%)
[1995Xia] Thermodynamic calculations 1200C; entire composition range
[2001Lop] Atom-probe field ion microscopy, 600-800C; Cu-34Ni-4Cr (mass%), Cu-45Ni-10Cr
analytical TEM, SEM, XRD and (mass%)
hardness
[2002Fin] TEM and XRD 300-800C; Cu-32.4Ni-3.4Cr (mass%),
Cu-45.6Ni-17.4Cr (mass%)
New Series IV/11C2
CrCuNi 217

[C] Prototype
, (Ni,Cu) cF4
Fm3m
(Ni) Cu a = 352.32 pure Ni at 25C [V-C2]
< 1455
(Cu) a = 361.46 pure Cu at 25C [V-C2]
< 1084.62
, (Cr) cI2 a = 288.4 pure Cr at 27C [V-C2]
< 1863 Im3m
W
CrNi2 oP6 a = 252.4 60 to 76.5 at.% Ni [V-C2]
Immm b = 757.1 [P]
MoPt2 c = 356.8
Table 3: Composition of phases defining the miscibility gap boundary at 800C

Alloy Composition (mass%) 1 Composition (mass%) 2 Composition (mass%)
Cr Cu Ni Cr Cu Ni Cr Cu Ni
4 62 34 1.8 69.5 28.7 15.1 25.9 59.0
10 45 45 1.9 69.9 28.2 18.4 18.0 63.6
Table 4: Investigations of the Cr-Cu-Ni Materials Properties

[1960Bad] Mechanical tests Hardness, yield stress, tensile stress and
elongation
[1969Pet] Welding Weldability
[1973And] Wear/erosion Sea water erosion
[1973Kre] Mechanical tests Tensile property
[1977Wu] Mechanical tests Yield stress
[1978Cho] Mechanical tests Yield stress
[1986Rao] Mechanical test Yield stress
[1987Rao] Tensile test Tensile properties
[1988Qin] Electrochemical Corrosion
[1990Elb] Electrochemical Corrosion
[1990Sof] Electrochemical Corrosion
[1991Rao] Mechanical test Hardness
[1992Fin] Mechanical test Hardness
[1992Wan] Mechanical test Fatigue
Landolt-Brnstein
New Series IV/11C2
MSIT
218 CrCuNi

[1993Wan1] Mechanical test Fatigue
[1993Wan2]
[1993Wan3]
[1994Bha1] Mechanical test Hardness
[1994Bha2]
[1994Bha3]
[1994Bom] Mechanical test Fatigue
[1994Wan] Mechanical test Low cycle fatigue, high cycle fatigue
[1995Xia] Wettability Joining
[2001Les] Wettability Joining
[2001Lop] Mechanical test Hardness
[2003Cao1] Oxidation Oxidation
[2003Cao2]

Fig. 1: Cr-Cu-Ni. Axes: at.%
Solubility isotherms
for Cr and Ni in (Cu)
840C
910
980
1030
1070
Cr 2.80 Cr 0.00
Ni 0.00 Ni 2.80
Cu 97.20 Cu 97.20
New Series IV/11C2
CrCuNi 219

Fig. 2: Cr-Cu-Ni. e2 Axes: at.%
Liquidus surface 1076.6C
20 1150 80
1200
40
60
1250
1350
60 1300
40
1400
1350
80
20

1400C
20 40 e1 60 80
Cr 1345C
Ni

section at 1200C
L
20
80
L+ 1
40
60
60
L+ 1+ 2
40
L+
80
L+ +
20
L+ 2
+
20 40 60 80
Cr Ni
Landolt-Brnstein
New Series IV/11C2
MSIT
220 CrCuNi

930C
20
80
40
60
+ 1
60
40
+ 1+ 2
1+ 2
80
20

+ 2
20 40 60 80
Cr Ni
1100
Fig. 5: Cr-Cu-Ni.
Polythermal section at
a constant mass ratio 1000
of Cu:Ni = 70:30,
plotted in at.%
900

Temperature, C
800
+
700
600
500
400
300
Cr 0.60 0.4 0.2 Cr 0.00
Ni 31.55 Ni 31.70
Cu 67.85 Cr, at.% Cu 68.30
New Series IV/11C2
CrCuNi 221
1100
Fig. 6: Cr-Cu-Ni.
Polythermal section at
a constant mass ratio 1000
of Cu:Ni = 80:20,
plotted in at.%
900
Temperature, C
800

700
+
600
500
400
300
Cr 0.72 0.6 0.4 0.2 Cr 0.00
Ni 21.15 Ni 21.30
Cu 78.13 Cr, at.% Cu 78.70
1200
Fig. 7: Cr-Cu-Ni. L
Isopleth at a constant
L+
Ni content of 1.4
mass%, plotted in 1100
at.%
L+ +
1000
Temperature, C
900
800
700
600
Cr 1.70 1.5 1.0 0.5 Cr 0.00
Ni 1.51 Ni 1.51
Cu 96.79 Cr, at.% Cu 98.49
Landolt-Brnstein
New Series IV/11C2
MSIT
222 CrCuSi
Chromium Copper Silicon

Riccardo Ferro, Svitlana Ilyenko
Introduction
A partial, tentative isothermal section at 800C (in the concentration range Cr-Cr5Si3-Cu) has been
constructed in the experimental investigation by [1979Sav]. A few more papers, however concerning the
Cr-Cu-Si system have been published: mainly experimental as [1972Jan, 1987Roi] or giving computed data
as [1992Rei, 1995Xia].
In the experimental investigations the alloys were generally prepared in vacuum melting furnaces from pure
metal mixtures [1995Xia] or by arc melting in purified He on water-cooled copper hearth [1979Sav] and
subjecting the alloys to several remelting. According to [1979Sav] the compositions of the resulting alloys
were established by chemical analysis. After melting the alloys were heat treated at 800C for 200 h in
evacuated quartz capsules. Rapid quenching experiments were also carried out.
A special technique was used by [1972Jan] in a study of the solubility of several disilicides (of Cr but also
of Ti, V, Nb, Ta, Mo, W) in metal melts (Cu or Ag or Au). Special crucibles were prepared by pressing (and
then sintering) the disilicide powder in an appropriate finger die. The disilicide crucibles were then used for
melting the other metals, which were subsequently analyzed for the Si content.
Binary Systems
Phase diagrams of the binary boundary systems are accepted as evaluated in the MSIT Binary Evaluation
Program: Cr-Cu from [2002Ans], Cu-Si from [2002Leb] and Cr-Si from [2006Leb].
Solid Phases
Data concerning the crystal structures of the solid phases are listed in Table 1. Notice that these are unary
or binary phases. No ternary phases have been found [1979Sav]. According to [1972Jan] Cr (as the other
metals of Group VI) forms no ternary silicide with Cu.
Isothermal Sections
A partial schematic isothermal section at 800C in the composition range Cu-Cr-Cr5Si3 was presented by
[1979Sav]. It is shown in Fig. 1 after correcting the homogeneity ranges of all phases at the binary boundary
sides according to the accepted binary systems. Isothermal section at 800C was also reported by [1995Vil]
referencing the same work of [1979Sav], however in fact the diagram in [1995Vil] differs from that in
[1979Sav]. Obviously it was modified by [1995Vil] without mentioning this or it was taken from another
unknown source. This diagram is not considered in the present evaluation.
Isothermal sections in the Cu rich corner at 700 and 1000C have been reported by [1987Roi]. However, an
agreement with the accepted binary systems is poor regarding the solubility data for the (Cu) solid solution.
These sections are not accepted in the present evaluaion.
Complete isothermal sections of the system have been computed. Tie lines have been calculated by
[1992Rei] at 700C, see Fig. 2. Stable tie lines were mapped on the premise of comparing the net Gibbs free
energies of a competing pair of tie lines at their respective point of intersection. The data of the Gibbs
energies relevant to the elements and binary compounds and used in the computation were taken from
different compilations. In an investigation [1995Xia] on wetting of Si3N4 by liquid Cr alloys, properties of
Cr-Cu-Si alloys were considered and an isothermal section at 1160C of the ternary phase diagram was
calculated using MTDATA. It is presented in Fig. 3. It should be noted that we introduced in Fig. 3 a
three-phase filed (Cr)+L+Cr3Si which was missed in the calculation by [1995Xia]. Both calculated sections,
at 700C (Fig. 2) and at 1160C (Fig. 3) can be considered as tentative as they do not consider solubility
ranges of binary phases and their extensions into the ternary.
New Series IV/11C2
CrCuSi 223

Because of the limited solubility in Cu, relatively economical cost and microstructure stability at high
temperature, Cr is a promising reinforcing metal for Cu based in situ composites [2001Sun]. Cu-15Cr
(mass%) in situ composite is superior to any monolithic Cu and conventional Cu alloys in terms of the
combination of tensile strength and electrical conductivity. For the further performance improvement, Si
has been selected by [2001Sun] as an alloying element for Cu-15Cr (mass%) in situ composites because the
addition of Si increases the softening temperature and high temperature strength of Cu-dilute Cr alloy.
[2001Sun] showed that the addition of 0.5 mass% Si produces solution hardening of Cr phase (solubility of
Si in Cr is about 1.8 mass% after solution treatment at 1000C) and formation of 4 vol% Cr3Si, it has been
found that both Cr3Si and Si rich layer attach to (Cr) phase. The higher hardness of Cr phase in
Cu-15Cr-0.5Si alloy makes the Cr phase more difficult to deform, i.e. the drawn structure of Cu-15Cr-0.5Si
in situ composite is coarser [2001Sun]. The tensile strength of as drawn Cu-15Cr-0.5Si in situ composites
is lower than that of Cu-15Cr in situ composites at higher drawing strain. However the strength of
Cu-15Cr-0.5Si in situ composites is higher than that of Cu-15Cr in situ composites at the same interphase
spacing due to the higher hardness of Cr phase [2001Sun].
Adhesive characteristics (wettability and formation of a transitional zone at the phase boundary) of the
Cr-Cu alloys with addition of 7mass% Si in the temperature range 1100 to 1300C have been studied in
[2001Les].
[1995Xia] outlined that Cr-Cu-Si alloys did not have very good wetting on Si3N4, however, additions of Ni
improve this property.
Superconducting properties of Cr-Cu-Si alloys have been studied by [1979Sav]. Mechanical properties
have been studied in [1930Cor].
References
[1930Cor] Corson, M.G., Copper Alloy Systems with Phase and Variable Limites and their
Employment for the Hardening of Copper (in French), Rev. Metall., 27, 194-213 (1930)
[1972Jan] Jangg, G., Kieffer, R., Blaha, A., Sultan, T., The Solubility of Disilicides in Auxiliary
Metal Melts (in German), Z. Metallkd., 61, 671-676 (1972) (Experimental, 24)
[1979Sav] Savitskii, E.M., Efimov, Yu.V., Frolova, T.M., Influence of Cooper on the Structure and
Superconducting Properties of Transition Metals, Inorg. Mater. (Engl. Trans.), 15(4),
[1987Roi] Roi, I.A, Fedyakina, N.N., Revina, I.N., Nikolaiev, A.K., Phase Diagram of the Cr-Cu-Si
System (in Russian), in Konstruktsionnye Pretsizionnye Splavy Tsvet. Met.,
Metallurgiya, Moscow, 28-33 (1987) (Experimental, Phase Diagram, Phase Relations, 4)
[1992Rei] Reid, J.S., Kolawa, E., Nicolet, M-A., Thermodynamics of (Cr, Mo, Nb, Ta, V or
W)-Si-Cu Ternary Systems, J. Mater. Res., 7, 2424-2428 (1992) (Phase Diagram, Phase
Relations, Thermodyn., Calculation, 26)
Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E., (Eds.), ASM International, Materials
[1995Vil] Villars, P., Prince, A., Okamoto, H., Handbook of Ternary Alloy Phase Diagrams, ASM
International, Metals Park, OH (1995) (Phase Diagram, 1)
[1995Xia] Xiao, P., Derby, B., The Wetting of Silicon Nitride by Chromium-Containing Alloys,
J. Mater. Sci., 30, 5915-5922 (1995) (Phase Relations, Experimental, Calculation, 16)
Met. Ceram., 40(7-8), 432-440 (2001) (Experimental, Phase Relations, Phys. Prop., 12)
[2001Sun] Sun, S., Sakai, S., Suzuki, H.G., Effect of Si on the Microctructure and Mechanical
Properties of as Drawn Cu-15Cr in Situ Composites, Mater. Sci. Eng. A, 303, 187-196
(2001) (Morphology, Experimental, Mechan. Prop., 18)
Landolt-Brnstein
New Series IV/11C2
MSIT
224 CrCuSi
[2002Ans] Ansara, I., Ivanchenko, V., Cr - Cu (Chromium - Copper), MSIT Binary Evaluation
[2002Leb] Lebrun, N., Dobatkina, T., Kuznetsov, V., Li, Ch., Cu-Si (Copper - Silicon), MSIT Binary
Structure, Phase Diagram, Assessment, 23)
[2006Leb] Lebrun, N., Cr-Si (Chromium-Silicon), MSIT Binary Evaluation Program, in MSIT

[C] Prototype
(Cu) cF4 a = 361.46 at 25C [Mas2]
Cu
(Cr) tI2 a = 288.2 at 25C, HP [Mas2]
I4/mmm c = 288.7
Cr
(Cr) cI2 a = 288.48 at 25C [Mas2]
< 1863 Im3m
W
( Si) hP4 a = 380 at 25C, 16 GPa -> 1 atm [Mas2]
P63/mmc c = 628
La
(Si) cI16 a = 663.6 at 25C, 16 GPa [Mas2]
Im3m
Si
(Si) tI4 a = 468.6 at 25C, 9.5 GPa [Mas2]
I41/amd c = 258.5
Sn
(Si) cF8 a = 543.06 at 25C [Mas2]
< 1414 Fd3m
C (diamond)
, Cu7Si hP2 a = 256.05 at 12.75 at.% Si [2002Leb]
842 - 552 P63/mmc c = 418.46
Mg 11.05 to 14.5 at.% Si
, ~ Cu6Si cI2 a = 285.4 at 14.9 at.% Si [2002Leb]
853 - 787 Im3m
W 14.2 to 16.2 at.% Si
, Cu5Si(h) t** a = 881.5 sample annealed at 700C
824 - 711 c = 790.3 17.6 to 19.6 at.% Si [2002Leb]
New Series IV/11C2
CrCuSi 225

[C] Prototype
< 729 P4132
Mn
< 800 I43d
Cu15Si4
, Cu3Si(h2) hR* 23.4 to 24.9 at.% Si [2002Leb]
859 - 558 R3m
or
t** a = 726.7 [2002Leb]
c = 789.2
, Cu3Si(h1) hR* 23.2 to 25.2 at.% Si
620 - 467 R3 [2002Leb]
, Cu3Si(r) o** a = 7676 23.3 to 24.9 at.% Si
< 570 b = 700 [2002Leb]
c = 2194
~ Cu5Si t** a = 647 at 17 at.% Si
c = 873 metastable [2002Leb]
Cr3Si cP8 a = 455.6 [V-C2]
< 1780 Pm3n
Cr3Si 20.8 to 25.3 at.% Si [2006Leb]
Cr5Si3 ? ? 37.5 - 37.7 at.% Si [2006Leb]
1666 - 1488
Cr5Si3 tI32 a = 917.0 [V-C2]
< 1488 I4/mcm c = 463.6 37.5 at.% Si [2006Leb]
W5Si3
CrSi cP8 a = 462.2 [V-C2]
< 1424 P213 50 at.% Si [2006Leb]
FeSi
CrSi2 hP9 a = 442.83 [V-C2]
< 1438 P6222 c = 636.80 66.3 - 68 at.% Si [2006Leb]
CrSi2
Landolt-Brnstein
New Series IV/11C2
MSIT
226 CrCuSi

Fig. 1: Cr-Cu-Si. Axes: at.%
Tentative partial
isothermal section at
800C in the Si poor
region 20
80
40
60
60
40
Cr5Si3
Cr3Si
80
20
(Cr) (Cu)
20 40 60 80
Cr Cu

section at 700C.
Alternative possible
trends of the tie-lines 20
80
are shown (dotted
lines)
CrSi2
40
60
CrSi Cr5Si3+CrSi2+
60
Cr5Si3 40
Cr3Si Cr3Si+Cr5Si3+(Cu) , Cu3Si

80 Cr , Cu15Si4
5 Si 20
3 + + , Cu5Si
(Cu
) , Cu7Si
(Cr)+Cr3Si+(Cu)
(Cr) (Cu)
20 40 60 80
Cr Cu
New Series IV/11C2
CrCuSi 227

Computed isothermal
section at 1160C. A
few tie-lines are
shown in the 20
80
two-phase fields
CrSi2 L+CrSi2+(Si)
40
60
CrSi
L+CrSi2+CrSi
L
60
40
Cr5Si3 L+CrSi+Cr5Si3
Cr3Si
L+Cr5Si3+Cr3Si
80
20
L+(Cr)+Cr3Si
(Cr)
20 40 60 80
Cr Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
228 CrCuZr
Chromium Copper Zirconium

Nataliya Bochvar
Introduction
[1956Gla, 1956Zak, 1957Gla, 1957Zak, 1960Gla] investigated the Cu rich corner of the Cr-Cu-Zr diagram
up to 3.5 mass% (Cr+Zr) by thermal and metallographic analyses and microhardness measurements.
Several isothermal sections within the temperature range from 600 to 1040C and five vertical sections were
constructed. The existence of two invariant eutectic equilibria at 980 and 935C and a quasibinary Cu-ZrCr2
section were assumed. The boundaries of the (Cu) solid solution determined in Cr-Cu-Zr system proved
much wider than those in the binary Cr-Cu and Cu-Zr systems. Using X-ray diffraction, [1967Kaw,
1972Fed] and [1979Kuz] have established that the ZrCr2 compound does not occur in the composition field
investigated (up to 20 at.% Zr and 5 at.% Cr); therefore the Cu-ZrCr2 section cannot be quasibinary.
[1967Kaw] determined the solubility of Cr and Zr in (Cu) alloys which had been cold worked, solution
treated at 900 and 950C and then quenched, to be 0.26 mass% Cr and 0.11 mass% Zr at 950C. [1972Fed]
obtained higher values for the solubility (0.4 mass% Cr and 0.3 mass% Zr) which appear to be
overestimated because these values exceed the solubility of Cr and Zr in (Cu) in the boundary systems. The
results of [1967Kaw] are preferential.
Using metallographic analysis, X-ray diffraction, DTA and the electron microprobe technique, [1979Kuz]
investigated alloys with a constant Cr content (0.5, 1.5 and 5 at.%) and alloys on the Cu:Zr = 5:1 section.
No ternary compounds were found; the presence of eutectic and peritectic invariant equilibria has been
established at 963 and 997C, respectively. Vertical sections and liquidus isotherms have been constructed
based on the experimental data and thermodynamic calculations.
The Zr rich corner of the phase diagram (Zr-ZrCr2-Zr2Cu) has been investigated by [1977Tre, 1979Mal].
Using metallographic, thermal and dilatometric analyses, [1977Tre] constructed two isothermal sections at
900 and 750C and a projection of a portion of the phase diagram (0 to 10 mass% (Cu+Zr)) on the
concentration triangle plane. The materials used were Zr (99.9%), Cr (99.8%) and Cu (99.996%). No
ternary phase was found in the system; the existence of a quasibinary section ZrCr2-Zr2Cu was assumed.
Eutectic and eutectoid equilibria occur in the system at 945 15 and 814 8C, respectively. Using X-ray
analysis, [1979Mal] constructed three isothermal sections at 875, 800 and 700C, confirming the data of
[1977Tre].
[1995Zen1] investigated the structure of alloys in the Cu corner after annealing at 940C for 4 h using
microstructural and EDS analyses. The results showed that only three phases, (Cr), ZrCu5 and (Cu), exist
after the heat treatment procedure. This result is in good agreement with [1967Kaw, 1972Fed, 1979Kuz].
Using the CALPHAD method and reliable experimental data, [1995Zen1, 1995Zen2] calculated a number
of isothermal and vertical sections together with the liquidus surface. The results of [1995Zen1, 1995Zen2]
show that the quasibinary Cu-ZrCr2 system does not exist.
Binary Systems
The Cr-Zr, Cr-Cu and Cu-Zr phase diagrams are accepted from the MSIT Evaluation Program [2002Per],
[2002Ans] and [2006Sem], respectively.
Solid Phases
There is no ternary compound in the Cr-Cu-Zr system. The binary phases appearing in the ternary system
as discussed are listed in Table 1. The solubility of Cr in the binary phases ZrCu5, Zr14Cu51, [1979Kuz] and
Zr2Cu [1977Tre], and of Cu in ZrCr2 [1977Tre] is virtually negligible.
New Series IV/11C2
CrCuZr 229
Quasibinary Systems
The existence of the quasibinary section ZrCr2-Zr2Cu has been assumed by [1977Tre, 1979Mal] where a
binary eutectic between these compounds occur. The temperature and composition of this eutectic have not
been established experimentally. According to the calculation of [1995Zen2], the eutectic reaction takes
place at 978C and 66.1 at.% Zr, 3.2 at.% Cr, 30.7 at.% Cu.
In the Cu rich corner of the diagram, two invariant equilibria have been found: a transition reaction U3 at
997C and a eutectic reaction E1 at 963C [1979Kuz]. Inside the Zr-ZrCr2-Zr2Cu field, two invariant
equilibria have been found. These are a eutectic E2 at 945 15C and a eutectoid E6 at 814 8C [1977Tre].
The temperatures of the invariant reactions calculated by [1995Zen2] for U3 (1001C) and E1 (963C) were
close to the experimental data in the Cu corner. In the Zr corner, the calculated values are 966C for E2 and
807C for E6. [1995Zen2] calculated other invariant equilibria including the three-phase equilibria of the
saddle points e5(max), e9(max) and e10(max). However, [1995Zen1], [1995Zen2] did not consider the
Zr13Cu24 compound of the binary Cu-Zr system which was accepted after [2006Sem]. Therefore, we
introduce three speculative invariant reactions (U4, U5, U6) in the middle part of Cr-Cu-Zr phase diagram.
The reaction scheme is shown in Figs. 1a, 1b. The compositions of the phases of the invariant reactions are
presented in Table 2. The compositions of liquid phase are given after [1995Zen2] except for that of point
E1. The calculated eutectic liquid composition (E1) is 7.717 at.% Zr and 0.706 at.% Cr that is close to 7.8
at.% Zr and 0.5 at.% Cr determined experimentally by [1979Kuz]. The reaction temperatures of points E1,
E2 and E6 are presented according to [1979Kuz, 1977Tre], the rest after [1995Zen2].
Liquidus and Solvus Surfaces

The calculated liquidus surface is presented in Fig. 2. It is based on data of [1995Zen1, 1995Zen2], however,
the part of the liquidus surface between points U6 and U4 was constructed here speculatively.
Figures 3 and 4 show the projection of the solvus surfaces of the (Zr) and (Cu) phases, respectively. The
solvus surfaces of the (Zr) phase are also displayed, which appear below 822C (e16) (Fig. 3). The
compositions of the (Zr) phase and the (Cu) phase at points E2, E1 and E6 were calculated by [1995Zen2].
Isothermal Sections
The isothermal section at room temperature is given in Fig. 5 as an overview, based on all the reported solid
state equilibria. The homogeneity range of ZrCr2 (~66 to ~68 at.% Cr at 300C, [2002Per]) is disregarded.
The mutual solubilities of the other phases are small. The equilibria are estimated based on the presented
reaction scheme (Fig. 1). In the Cu rich corner, two isothermal sections have been constructed by
[1967Kaw] at 950 and 900C (Fig. 6 and Fig. 7). The solubilities in (Cu) are (0.2 mass% Cr + 0.1 mass%
Zr) at 950C and (~0.14 mass% Cr+~0.08 mass% Zr) at 900C.

Two vertical sections at 0.5 and 1.5 at.% Cr are presented in Fig. 8 and Fig. 9 [1979Kuz]. The section with
constant Cr content of 0.5 at.% passes through the ternary eutectic point E1.

The Cr-Cu-Zr alloys have long been known as a series of copper alloys that possesses high strength and high
conductivity. In particular, the high electrical and thermal conductivity of these alloys have been used for
many applications such as trolley wire, electrode material for resistance welding and materials for
thermonuclear reactors. The properties of Cr-Cu-Zr alloys depend on the methods of preparation and the
heat treatment conditions. These questions have been the subject of much discussion in the literature.
Landolt-Brnstein
New Series IV/11C2
MSIT
230 CrCuZr
[2002Dur, 2002Iva, 2002Mer] investigated the physico-mechanical properties (electrical conductivity,

hardness, strength and ductility) of Cr-Cu-Zr alloys as a function of cooling rate after solution annealing,
[2002Iva], the temperatures of heat treatment, [2002Mer], cold deformation before aging [2002Dur].
[1999Mor] gave a review of spray deposition of high conductivity Cr-Cu-Zr alloys. Two features of interest
in spray formed and processed Cr-Cu-Zr alloys have been reported: the possibility for ductile Cr globules
to elongate as fine strengthening fibres during hot and cold mechanical working and the possibility of
improving specific properties by the presence of dispersed oxide particles.
[1995Sou] considered the possibility of using a composition of Zr(Cr1xCux)2 at x = 0.1; 0.2 synthesized
with the C14 or C15 type structures as electrodes in hydride batteries.
[1972Suz] investigated the precipitation processes of Cr-Cu-Zr alloys after quenching at 950C with
subsequent aging. The precipitation diagram (the time-temperature transformation, TTT, diagram) was
constructed, which was used to account for the property changes during isothermal aging. [1987Har]
reviewed copper-based materials (in particular, Cr-Cu-Zr alloys) for use in fusion reactors. [1997Fab]
investigated the effects of neutron irradiation on the mechanical properties of Cr-Cu-Zr alloys for use in
thermonuclear reactors.
A series of works were devoted to the study of Cr-Cu-Zr alloys with an ultra fine grain structure [1972Sar,
1993Bat, 1993Spa, 1994Cor, 1997Cor, 1997Anz1, 1997Anz2, 1997Lop, 2000Hol, 2001Tu, 2002Vin,
2003Qi, 2004Vin]. The structure, thermal stability and properties of Cr-Cu-Zr alloys with ultra fine grains
produced by equal-channel angular pressing have been investigated as a function of alloying element
concentration by [2002Vin, 2004Vin]. A non-linear relationship between the parameters of the rapidly
solidified aging processes and mechanical and electrical properties of Cr-Cu-Zr alloys was established by
use of an artificial neural network [2003Su, 2004Su]. [2001Tu, 2003Qi] investigated the friction and wear
behavior of peak aged Cr-Cu-Zr alloys by dry sliding against a brass counterface on a pin-on-disk tester.
The formation of fine and coherent precipitates in the Cu-matrix improve the hardness and wear resistance
of the Cr-Cu-Zr alloys. [2000Hol] estimated that a fine dispersion of precipitates with a mean size of 2.3 nm
produced after hot isostatic pressing of Cu-base alloys with 0.75 mass% Cr and 0.105 mass% Zr are
responsible for the mechanical strength of the aged alloy. [1997Anz1, 1997Anz2] investigated the
possibility of attaining a homogeneous fine cellular structure during continuous casting of a Cu base alloy
having 1.11 mass% Cr and 0.12 mass% Zr, for the achievement of the required mechanical properties.
[1994Cor, 1997Cor] produced the Cr-Cu-Zr alloy powders by water atomization and consolidation by warm
extrusion. The strengthening observed was interpreted in terms of theories of precipitation and dispersion
strengthening. [1993Spa] showed the strong influence of cooling and solidification rates on the structure of
a cast Cr-Cu-Zr alloy. [1997Lop] showed that rapidly solidified and aged Cr-Cu-Zr alloys have a good
combination of electrical properties, conductivity and microhardness.
For the development of materials with high conductivity and high strength, [1998Mih] investigated the
solidification structure, cold worked structure and aging characteristics of a Cu base alloy with 15 mass%
Cr and 0.15 mass% Zr. [1991Pia] carried out tensile tests at different temperatures on a heat treatable Cu
base alloy having 0.6 mass% Cr and 0.08 mass% Zr, of interest for nuclear fusion reactor applications as a
primary heat sink material. [1996Tsu] tested a Cu-base alloy having 1 mass% Cr and 1 mass% Zr as heat
sink material for the surface heat flux in the first wall in high power density devices.
Miscellaneous
[1974Nov] investigated the morphology and structure of the precipitated phases in a Cu-0.33 mass%
Cr-0.07 mass% Zr alloy during aging, using the method of diffraction electron microscopy.
A structural analysis of the hardening phases precipitated in the Cu matrix of Cr-Cu-Zr alloys after different
heat treatments was undertaken by [2000Zha, 2001Bat, 2003Bat, 2003Hua]. Using a scanning electronic
microscope and energy dispersive X-ray spectroscopy and a transmission electron microscope, [2003Hua]
has shown some types of phases in specimens of a Cu-base alloy having 0.31 mass% Cr and 0.21 mass%
Zr after quenching and aging; Cu matrix, (Cr), the coarse precipitation of ZrCu5 and the fine precipitation
of Zr14Cu51. [2001Bat, 2003Bat] has shown that precipitation in a Cu base alloy with 1 mass% Cr and
1 mass% Zr, takes place through the formation of a metastable ordered phase. [2000Zha] has shown that it
New Series IV/11C2
CrCuZr 231
enhances the precipitation hardening effect. The major mechanism of this enhancement may be through an
increase in the Cr rich precipitate nucleation rate and precipitate/matrix interfacial energy.
The recrystallization kinetics of Cr-Cu-Zr alloys was investigated by [1973Nag, 1979Fed, 1994Mor].
References
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Solubility in Ternary Systems by the Method of Microhardness (in Russian), Izv. Akad.
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Diagram (in Russian), Metall. Term. Obra. Metallov, (3), 23-27 (1956) (Experimental,
Phase Diagram, 12)
[1957Gla] Glazov, V.M., Zakharov, M.V., Stepanova, M.V., The Effect of Phase Composition on the
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[1957Zak] Zakharov, M.V., Stepanova, M.V., Glazov, V.M., The Cu Corner of the Cu-Cr-Zr
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[1967Kaw] Kawakatsu, I., Suzuki, H., Kitano, H., Properties of High Zr, Cu-Zr-Cr Alloys and the
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[1972Fed] Fedorov, V.N., Zakharov, M.V., Osintsev, O.E., Kucherov, V.I., On the Structure of the
Ternary Phase Diagram of the Cu-Cr-Zr System in the Cu-Rich Region (in Russian), Zh.
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[1972Sar] Sarin, V.K., Grant, N.J., Cu-Zr and Cu-Zr-Cr Alloys Produced from Rapidly Quenched
Powders, Met. Trans., 3(4), 875 (1972) (Experimental, Mechan. Prop., 9)
[1972Suz] Suzuki, H., Kanno, M., Precipitation Processes of Copper-Zirconium-Chromium Alloys
(in Japanese), Nippon Kinzoku Gakkai shi, 36(4), 363-368 (1972) (Electr. Prop.,
Experimental, 16)
[1973Nag] Nagai, T., Henmi, Z., Sakamoto, T., Koda, S., Effect of Precipitates on Recrystallization
Temperature in Cu-Cr, Cu-Zr and Cu-Zr-Cr Alloys, Trans. Jpn Inst. Met., 14(6), 462-469
(1973) (Experimental) cited from abstract
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of Aging Copper-Cromium Alloy (in Russian), Fiz. Met. Metalloved., 37(1), 201-203
(1974) (Experimental, Morphology, 6)
[1977Tre] Tregubov, I.A., Evseeva, L.N., Ivanov, O.S., The Zirconium Corner of the Zr-Cr-Cu Phase
Diagram (in Russian), Russ. Metall., (5), 183-186 (1977), translated from Izv. Akad. Nauk
SSSR, Met., (5), 228-231 (1977) (Experimental, Phase Diagram, #, 2)
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Alloys (in Russian), Metalloved. Term. Obrab. Met., (9), 53-54 (1979) (Experimental, 2)
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of the Phase Diagram Cu-Cr-Zr (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall.,
(1), 95-98 (1979) (Experimental, Phase Diagram, #, *, 2)
[1979Mal] Malakhova, T.O., Study of Phase Diagrams of the Zirconium Part of the Zirconium - Iron,
Zirconium - Chromium - Iron and Zirconium - Chromium - Copper Systems (in Russian)
in Splavy Atom. Energ., Ivanov, O.S., Alekseeva, Z.M. (Eds.), Nauka, Moscow, 123-130
(1979) (Experimental, Phase Diagram, #, 19)
Landolt-Brnstein
New Series IV/11C2
MSIT
232 CrCuZr
[1987Har] Harling, O.K., Grant, M.J., Kohse, G., Ames, M., Lee, T-S., Hobbs, L.W., Neutron
Irradiation Scoping Study of Twenty-Five Copper-Base Materials, J. Mater. Res., 2(5),
568-579 (1987) (Review, 28)
[1991Pia] Piatti, G., Boerman, D., Hot Tensile Characteristics and Microstructure of a
Cu-0.65Cr-0.08Zr Alloy for Fusion-Reactor Application, J. Nucl. Mater., 185(1), 29-38
(1991) (Experimental, Mechan. Prop.) cited from abstract
[1993Bat] Batawi, E., Biselli, C., Gunther, S, Morris, M.A., Morris, D.G., Thermomechanical
Processing of Spray-Formed Cu-Cr-Zr Alloy, Scr. Metall. Mater., 29(6), 765-769 (1993)
(Experimental, Mechan. Prop.) cited from abstract
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Structure, Metall, 47(4), 347-350 (1993) (Experimental, Morphology) cited from abstract
[1994Cor] Correia, J.B., Davies, H.A., Sellars, C.M., Deformation Structure of Water Atomized and
Extruded Cu-Cr-Zr Alloys, Plasticity Met. Alloys-ISPMA 6, 97-98, 43-48 (1994)
(Experimental, Morphology) cited from abstract
[1994Mor] Morris, M.A., Leboeuf, M., Morris, D.G., Recristallization Mechanisms in a Cu-Cr-Zr
Alloy with a Bimodal Distribution of Particles, Mater. Sci. Eng. A, 188(1-2), 255-265
(1994) (Experimental, Morphology) cited from abstract
[1995Sou] Soubeyroux, J.L., Bououdina, M., Fruchart, D., Pontonnier, L., Phase Stability and
Neutron Diffraction Studies of Laves Phases Yr(Cr1xMx)2 with M=Mn, Fe, Co, Ni, Cu and
0<x<0.2 and their Hydrides, J. Alloys Compd., 219, 48-54 (1995) (Crys. Structure,
Experimental, 20)
[1995Zen1] Zeng, K.J., Haemaelaeinen, M., Lilius, K., Phase Relationships in Cu-rich Corner of the
Cu-Cr-Zr Phase Diagram, Scr. Metall. Mater., 32(12), 2009-2014 (1995) (Experimental,
Phase Relations, 8)
[1995Zen2] Zeng, K.J., Haemaelaeinen, M., A Theoretical Study of the Phase Equilibria in the
Cu-Cr-Zr System, J. Alloys Compd., 220, 53-61 (1995) (Calculation, Phase Diagram,
Thermodyn., 29)
[1996Tsu] Tsuchiya, K., Kawamura, H., Mechanical Properties of Cu-Cr-Zr Alloy and SS316 Joints
Fabricated by Friction Welding Method, J. Nucl. Mater., 233, 913-917, Part B OCT (1996)
(Experimental) cited from abstract
[1997Anz1] Anzel, I., Kneissl, A.C., Krizman A., Cellular Solidification During Continuous Casting of
a Cu-Cr-Zr Alloys, Part I: Conditions for Cellular Morphology, Metall, 51(4), 181-185
(1997) (Experimental, Morphology) cited from abstract
[1997Anz2] Anzel, I., Kneissl, A.C., Krizman A., Cellular Solidification During Continuous Casting of
a Cu-Cr-Zr Alloys, Part II: Microstructure and Properties of Continuous Cast Rods, Metall,
51(11), 620-624 (1997) (Experimental, Morphology) cited from abstract
[1997Cor] Correia, J.B., Davies, H.A., Sellars, C.M., Strengthening in Rapidly Solidified Age
Hardened Cu-Cr and Cu-Cr-Zr Alloys, Acta Mater., 45(1), 177-190 (1997) (Experimental,
Mechan. Prop.) cited from abstract
[1997Fab] Fabritsiev, S.A., Pokrovsky, A.S., The Effect of Neutron Irradiation on the Mechan.
Properties of Precipitation Hardened Copper Alloys, J. Nucl. Mater., 249(2-3), 250-258
(1997) (Experimental) cited from abstract
[1997Lop] Lopez, F., Reyes, J., Campillo, B., AgularSahagun, G., JuarezIslas, J.A., Rapid
Solidification of Copper Alloys with High Strength and High Conductivity, J. Mater. Eng.
Perform., 6(5), 611-614 (1997) (Experimental, Mechan. Prop., Electr. Prop.) cited from
abstract
[1998Mih] Mihara, K., Takeuchi, T., Suzuki, H.G., Effect of Zr on Aging Characteristics and Strength
of Cu-Cr in situ Composite, J. Jpn Inst. Met., 62(3), 238-245 (1998) (Experimental, Mor-
phology) cited from abstract
[1999Mor] Morris, D.G., Recent Research on Advanced Copper Alloys: Possibilities for Osprey Spray
Deposition?, Powder Met., 42(1), 20-26 (1999) (Electr. Prop., Experimental, Mechan.
Prop., Phase Relations, Review, 35)
New Series IV/11C2
CrCuZr 233
[2000Hol] Holzwarth, U., Stamm, H., The Precipitation Behaviour of ITER-Grade Cu-Cr-Zr Alloy
after Simulating the Thermal Cycle of Hot Isostatic Pressing, J. Nucl. Mater., 279(1),
31-45 (2000) (Experimental, Morphology) cited from abstract
[2000Zha] Zhang, D.L., Mihara, K., Tsubokawa, S., Suzuki, H.G., Precipitation Chacacteristics of
Cu-15Cr-0.15Zr in situ Composite, Mat. Sci. Technol., 16(4), 357-363 (2000)
(Experimental, Mechan. Prop.) cited from abstract
[2001Bat] Batra, I.S., Dey, G.K., Kulkarni, U.D., Banerjee, S., Microstructure and Properties of a
Cu-Cr-Zr Alloy, J. Nucl. Mater., 299(2), 91-100 (2001) (Experimental, Mechan. Prop.)
cited from abstract
[2001Tu] Tu, J.P., Qi, W.X., Yang, Y.Z., Liu, F., Zhang, J.T., Gan, G.Y., Wang, N.Y., Zhang, X.B.,
Liu, M.S., Effect of Aging Treatmant on the Electrical Sliding Wear Behaviour of
Cu-Cr-Zr Alloy, Wear, 249(10-11), 1021-1027 (2001) (Experimental, Morphology) cited
from abstract
[2002Ans] Ansara, I., Ivanchenko, V., Cr-Cu (Chromium-Cupper), MSIT Binary Evaluation
Services GmbH, Stuttgart; Document ID: 20.19588.1.20, (2002) (Phase Diagram, Crys.
Structure, Thermodyn., Assessment, 29)
[2002Dur] Durashevich, G., Cvetkovski, V., Jovanovich, V., Effect of Thermomechanical Treatment
on Mechanical Properties and Electrical Conductivity of a CuCrZr Alloy, Bull. Mater. Sci.,
25(1), 59-62 (2002) (Experimental, Mechan. Prop., Electr. Prop.) cited from abstract
[2002Iva] Ivanov, A.D., Nikolaev, A.K., Kalinin, G.M., Rodin, M.E., Effect of Heat Treatments on
the Properties of Cu-Cr-Zr Alloys, J. Nucl. Mater., 307-311(1), 673-676 (2002) (Electrical
Prop., Experimental, Mechan. Prop., Morphology, 2)
[2002Mer] Merola, M., Orsini, A., Visca, E., Libera, S., Moreschi, L.F., Storai, S., Panella,
B.,Campagnoli, E., Ruscica, G., Bosco, C., Influence of the Manufacturing Heat Cycles on
the Cu-Cr-Zr Properties, J. Nucl. Mater., 307-311(1), 677-680 (2002) (Experimental,
Mechan. Prop., Morphology, Transport Phenomena, 3)
[2002Per] Perrot, P., Cr-Zr (Chrompum-Zirconium), MSIT Binary Evaluation Program, in MSIT
Stuttgart; Document ID: 20.15393.1.20, (2002) (Phase Diagram, Crys. Structure,
Thermodyn., Assessment, 14)
[2002Vin] Vinogradov, A., Patlan, V., Suzuki, Y., Kitagawa, K., Kopylov, V.I., Structure and
Properties of Ultra-Fine Grain Cu-Cr-Zr Alloy Produced by Equal-Channel Angular
Pressing, Acta Mater., 50(7), 1639-1651 (2002) (Experimental, Morphology, Mechan.
Prop.) cited from abstract
[2003Bat] Batra, I.S., Dey, G.K., Kulkarni, U.D., Banerjee, S., Precipitation in a Cu-Cr-Zr Alloy,
Mater. Sci. Eng. A, 356(1-2), 32-36 (2003) (Experimental) cited from abstract
[2003Hua] Huang, F.X., Ma, J.S., Ning, H.L., Geng, Z.T., Lu, C., Guo, S.M., Yu, X.T., Wang, T., Li,
H., Lou, H.F., Analysis of Phases in a Cu-Cr-Zr Alloy, Scr. Mater., 48(1), 97-102 (2003)
(Crys. Structure, Experimental, Phase Relations, 36)
[2003Qi] Qi, W.X., Tu, J.P., Liu, F., Yang, Y.Z., Wang, N.Y., Lu, H.M., Zhang, X.B., Guo, S.Y., Liu,
M.S., Microstructure and Tribological Behaviour of Peak Aged Cu-Cr-Zr Alloy, Mater.
Sci. Eng. A, 343(1-2), 89-96 (2003) (Experimental) cited from abstract
[2003Su] Su, J.H., Dong, Q.M., Liu, P., Li, H.J., Kang, B.X., Prediction of Properties in
Thermomechanically Treated Cu-Cr-Zr alloy by an Artificial Neural Network, J. Mater.
Sci. Technol., 19(6), 529-532 (2003) (Theory) cited from abstract
[2004Su] Su, J.H., Dong, Q.M., Liu, P., Li, H.J., Kang, B.X., Tian, B.H., Establishing the
Knowledge Repository of Rapidly Solidified Aging Cu-Cr-Zr Alloy on the Artificial Neural
Network, Rare Met., 23(2), 171-175 (2004) (Theory) cited from abstract
Landolt-Brnstein
New Series IV/11C2
MSIT
234 CrCuZr
[2004Vin] Vinogradov, A., Suzuki, Y., Ishida, T., Kitagawa, K., Kopylov, V.I., Effect of Chemical
Composition on Structure and Properties of Ultrafine Grained Cu-Cr-Zr Alloys Produced
by Equal-Channel Angular Pressing, Mater. Trans., 45(7), 2187-2191 (2004)
(Experimental, Mechan. Prop., Electrical Prop.) cited from abstract
[2006Sem] Semenova E., Cu-Zr (Cupper-Zirconium), MSIT Binary Evaluation Program, in MSIT
Stuttgart; to be published (2006) (Phase Diagram, Crys. Structure, Thermodyn.,
Assessment, 31)

Phase Pearson Symbol/ Lattice Parameters Comments/References
[C] Prototype
(Cu) cF4 dissolves 0.12 at.% Zr at 1000C
< 1084.62 Fm3m [2006Sem] and 0.82 at.% Cr at 1075C
Cu [2002Ans]
a = 361.46 pure Cu at 25C [Mas2]
(Cr) cI2 Dissolves 0.6 at.% Zr at 1592C]
< 1863 Im3m [2002Per] and 0.28 at.% Cu at 1800C
W [2002Ans]
a = 288.48 pure Cr at 25C [Mas2]
(Zr) cI2 dissolves up to 5.7 at.% Cu at 995C
1855 - 863 Im3m [2006Sem] and 8.4 at.% Cr at 1332C
W [2002Per]
a = 360.90 [2006Sem]
(Zr) hP2 Dissolves ~ 0.2 at.% Cu at 822C
< 863 P63/mmc [2006Sem] and 0.5 at.% Cr at 831C
Mg [2002Per]
a = 323.16 at 25C [Mas2]
c = 514.75
ZrCu5 cF24 a = 687.0 [2006Sem]
< 1032 F43m
AuBe5
Zr14Cu51 hP68 a = 1124.44 [2006Sem]
< 1112 P6/m c = 828.15
Gd14Ag51
Zr3Cu8 oP44 a = 786.93 [2006Sem]
< 1028 Pnma b = 815.47
Hf3Cu8 c = 998.48
Zr13Cu24 o*37 a = 1119.0 [2006Sem]
960 - 915 b = 791.2
c = 646.0
Zr7Cu10 oC68 a = 1267.29 [2006Sem]
< 935 C2ca b = 931.63
Zr7Ni10 c = 934.66
New Series IV/11C2
CrCuZr 235

[C] Prototype
ZrCu cP2 a = 325.87 [2006Sem]
960 - 725 Pm3m
CsCl
Zr2Cu(h) tI6 a = 322.04 [2006Sem]
1025 - 950 I4/mmm c = 1118.32
MoSi2
Zr2Cu(r) tP150 a = 1592.4 [2006Sem]
< 950 c = 1132.8
ZrCr2 hP12 a = 507.2 [2002Per]
1677 - 1624 P63/mmc c = 828.9
MgZn2
ZrCr2 hP24 a = 510.0 [2002Per]
1624 - 1546 P63/mmc c = 1661
MgNi2
ZrCr2 cF24 a = 720.4 [2002Per]
< 1560 Fd3m
MgCu2

Zr Cr Cu
L + ZrCr2 (Cr) + ZrCr2 1547 U1 L 18.3 75.6 6.1
ZrCr2 ~33.3 ~66.7 ~0
(Cr) ~0 ~100 ~0
ZrCr2 33.3 66.7 0
L + ZrCr2 Zr14Cu51 1100 e5 (max) L 20.5 1.4 78.1
ZrCr2 ~33.3 ~66.7 ~0
Zr14Cu51 21.54 ~0 78.46
L + ZrCr2 (Cr) + Zr14Cu51 1092 U2 L 18.0 1.4 80.6
ZrCr2 ~33.3 ~66.7 ~0
(Cr) ~0 ~100 ~0
Zr14Cu51 21.54 0 78.46
L + Zr14Cu51 ZrCu5 + (Cr) 997 * U3 L 10.2 0.8 89.0
Zr14Cu51 21.54 0 78.46
ZrCu5 16.7 0 83.3
(Cr) ~0 ~100 ~0
L ZrCr2 + Zr2Cu 978 e9 (max) L 66.1 3.2 30.7
ZrCr2 ~33.3 ~66.7 ~0
Zr2Cu 66.7 0 33.3
Landolt-Brnstein
New Series IV/11C2
MSIT
236 CrCuZr

Zr Cr Cu
L ZrCr2 + Zr2Cu + (Zr) 945 15 * E2 L 70.3 4.0 25.7
ZrCr2 ~33.3 ~66.7 ~0
Zr2Cu 66.7 0 33.3
(Zr) 94.9 1.4 3.7
L ZrCu5 + (Cu) + (Cr) 963 * E1 L 7.8 * 0.5 * 91.7 *
ZrCu5 16.7 0 83.3
(Cu) 0.11 0.36 99.53
(Cr) ~0 ~100 ~0
L ZrCr2 + ZrCu 927 e10 (max) L 48.7 0.6 50.7
ZrCr2 ~33.3 ~66.7 ~0
ZrCu 50 0 50
L ZrCr2 +ZrCu + Zr2Cu 915 E4 L 53.7 0.8 45.5
ZrCr2 ~33.3 ~66.7 ~0
ZrCu 50 0 50
Zr2Cu 66.7 0 33.3
L ZrCr2 +Zr7Cu10 + ZrCu 887.6 E5 L 42.7 0.3 57
ZrCr2 ~33.3 ~66.7 ~0
Zr7Cu10 41.18 0 58.82
ZrCu 50 0 50
(Zr) ZrCr2 + (Zr) + 814 8 * E6 (Zr) 97.2 0.99 1.81
Zr2Cu ZrCr2 ~33.3 ~66.7 ~0
(Zr) ~99.6 ~0.2 ~0.2
Zr2Cu 66.7 0 50
* - experimental data, the rest calculated data
New Series IV/11C2
New Series IV/11C2
Landolt-Brnstein
Cu-Cr Cr-Cu-Zr A-B-C Cr-Zr Cr-Cu
1625 d1
?
ZrCr2 ZrCr2, L
1625 d2
?
ZrCr2 ZrCr2, L
1592 e1
L ZrCr2 + (Cr)
1560 e2
1547 L+ZrCr2(Cr)+ZrCr2 U1 ZrCr2 L+ ZrCr2
1546 e3
(Cr)+ZrCr2+ZrCr2
ZrCr2(Cr)+ZrCr2
L+(Cr)+ZrCr2
1100 e5(max) 1332 e4
l Zr11Cu51+ZrCr2 L (Zr) + ZrCr2
1032 p1 1075 e6
1092 L+ZrCr2(Cr)+Zr14Cr51 U2
L +Zr14Cu51 ZrCu5 L (Cu) + (Cr)
ZrCr2+Zr14Cr51+(Cr)
CrCuZr
1028 p2
L+Zr14Cu51 Zr3Cu8 L+(Cr)+Zr14Cr51
1000 e7 997 L+Zr14Cu51ZrCu5+(Cr) U3
L (Cu) + ZrCu5
ZrCr5+Zr14Cr51+(Cr)
995 e8
L Zr2Cu + (Zr) ? L+Zr14Cu51Zr3Cu8+ZrCr2 U4
L+ZrCu5+(Cr)
978 e9(max)
965 p3 ZrCr2+Zr14Cr51+Zr3Cu8 l ZrCr2 + Zr2Cu
L+Zr3Cu8 Zr13Cu24
963 LZrCu51+ZrCu5+(Cr) E1
L+Zr3Cu8+ZrCr2
ZrCu5+(Cu)+(Cr)
94515 LZrCr2 +Zr2Cu+(Zr) E2
? L+Zr3Cu8Zr13Cu24+ZrCr2 U5
ZrCr2 +Zr2Cu+(Zr)
L+Zr13Cu24+ZrCr2 Zr13Cu24+Zr3Cu8+ZrCr2
MSIT
U6 E3 E6 E4
237
Fig. 1a: Cr-Cu-Zr. Reaction scheme, part 1
MSIT
238
Cu-Zr Cr-Cu-Zr A-B-C Cr-Zr Cr-Cu
U5 U5 E2 e9
927 e10(max)
925 e11 l ZrCr2 + ZrCu
L Zr7Cu10 + Zr13Cu24
? L+Zr13Cu24Zr7Cu10+ZrCr2 U6
920 e12 Zr13Cu24+Zr7Cu10+ZrCr2

Zr13Cu24Zr3Cu8+Zr7Cu10
? Zr13Cu24Zr3Cu8+Zr7Cu10+ZrCr2 E3
L+Zr7Cu10+ZrCr2 Zr3Cu8+Zr7Cu10+ZrCr2
915 e13
L ZrCu + Zr2Cu
<915 LZrCr2+ZrCu+Zr2Cu E4
CrCuZr
900 e14
L Zr7Cu10 + ZrCu
887.6 LZr7Cu10+ZrCu+ZrCr2 E5
831 e15
(Zr)(Zr)+ZrCr2
822 e16
(Zr) Zr2Cu + (Zr)
8148 (Zr)Zr2Cu+(Zr)+ZrCr2 E6 ZrCr2+ZrCu+Zr2Cu
Zr2Cu+(Zr)+ZrCr2 Zr7Cu10+ZrCu+ZrCr2
725 e17
ZrCu Zr7Cu10 + Zr2Cu
? ZrCuZr7Cu10+Zr2Cu+ZrCr2 E7
New Series IV/11C2
Landolt-Brnstein
Zr7Cu10+Zr2Cu+ZrCr2
Fig. 1b: Cr-Cu-Zr. Reaction scheme, part 2

CrCuZr 239

Fig. 2: Cr-Cu-Zr. (Cu) e6 Axes: at.%
Liquidus surface ZrCu5 e
7
p1 E 1
U3
20 U2
80
Zr14Cu51
e5max
Zr3Cu5
p2
e11 p3 U4
Zr27Cu1040 U5
60
U6 Zr13Cu24
e14
ZrCu E5 (Cr)
e13 e10max
E4
60
40
Zr2Cu
e9max
e8
E2
ZrCr2
80
20
ZrCr2
U1
( Zr)
20 e3 40 e2 d2 60 d1 80 e1
Zr ZrCr2 Cr
Zr 90.00
Cr 0.00
Cu 10.00 Data / Grid: at.%
Fig. 3: Cr-Cu-Zr. Axes: at.%
The lines of double
saturation of the
solvus surfaces of
(Zr) and (Zr) in the
Zr rich corner
( Zr), e 8
( Zr), E2
( Zr), e 16
( Zr),E6
(Zr), e16 ( Zr), E6

(Zr)
to RT ( Zr), e4
Zr (Zr), e15 ( Zr), e15 Zr 90.00
Cr 10.00
Cu 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
240 CrCuZr

The lines of double
saturation of solvus (Cu), e7
surface of (Cu) in the
Cu rich corner
(Cu), E1
(Cu), e6
Zr 1.00 Zr 0.00
Cr 0.00 Cr 1.00
Cu 99.00 Cu 99.00

Fig. 5: Cr-Cu-Zr. (Cu) Axes: at.%
room temperature,
disregarding the ZrCu5
ZrCr2 homogeneity 20
Zr14Cu51 80
range
Zr3Cu8
40
Zr7Cu10 60
60
40
Zr2Cu
80
20
(Zr) (Cr)
20 40 60 80
Zr ZrCr2 Cr
New Series IV/11C2
CrCuZr 241

950C
(Cu)
(Cu)+ZrCu5+(Cr)
Zr 10.00 Zr 0.00
Cr 0.00 Cr 10.00
Cu 90.00 Cu 90.00

900C
(Cu)
(Cu)+ZrCu5+(Cr)
Zr 10.00 Zr 0.00
Cr 0.00 Cr 10.00
Cu 90.00 Cu 90.00
Landolt-Brnstein
New Series IV/11C2
MSIT
242 CrCuZr
1100
Fig. 8: Cr-Cu-Zr.
Vertical section at 0.5
at.% Cr L+Zr14Cu51 L
L+ZrCu5
L+(Cu)
L+Zr14Cu51+(Cr)
1000
997
Temperature, C
L+ZrCu5+(Cr) L+(Cu)+ZrCu5
963
900
(Cu)+(Cr)+ZrCu5
(Cr)+ZrCu5+Zr14Cu51
800
Zr 19.50 85 90 95 Zr 0.00
Cr 0.50 Cr 0.50
Cu 80.00 Cu, at.% Cu 99.50
1100
Fig. 9: Cr-Cu-Zr. L
L+(Cu)
Vertical section at 1.5
at.% Cr
L+(Cr)+Zr14Cu51 L+(Cr)
L+(Cu)+ZrCu5
1000
997
Temperature, C
L+(Cr)+ZrCu5
963
900
(Cr)+ZrCu5+Zr14Cu51
(Cu)+(Cr)+ZrCu5
800
Zr 18.50 85 90 95 Zr 0.00
Cr 1.50 Cr 1.50
Cu 80.00 Cu, at.% Cu 98.50
New Series IV/11C2
CuFePt 243
Copper Iron Platinum

Vasyl Tomashik, Andy Watson
Introduction
A diagram of primary crystallization in the ternary system Cu-Fe-Pt was proposed for the first time by
[1909Jae], but the earliest experimental studies were by [1941Nem] and [1943Nem2]. They used thermal
analysis, optical microscopy hardness measurement, electrical resistivity and temperature coefficient
determination. The thermoelectric power with respect to Pt, the extension and the tensile strength of the
alloys were also determined.
Four isopleths were produced which suggested that all Cu-Fe-Pt alloys form solid solutions at high
temperatures except for Pt poor alloys with less than 20 at.% Pt. The compound FePt was found to separate
out of the solid solution and penetrates deep into the ternary system with a suggestion of the formation of a
ternary compound FePt2Cu at about 1200C. This ternary compound was seen on investigation of the
section Pt-(50 at.% Cu + 50 at.% Fe), forming an unbroken series of solid solutions with FePt and limited
solutions with PtCu [1941Nem, 1943Nem2]. These data were included in the reviews [1951Sol], [1969Gue]
and [1979Cha], but as stated in [1979Cha], by that time, the existence of the ternary compound hadnt been
confirmed.
Interest in this system and the proposed compound continued [1973Cab]. Tulameenite is a naturally
occurring deposit of the composition FePt2Cu adding weight to the hypothesis that this ternary compound
exists [1973Cab, 1991Cab, 2002Tol, 2002Coo, 2002Gar, 2004Dis]. [1973Cab] conducted an extensive
XRD, EPMA and optical microscopical study of tulameenite, but it was not until the work of [1986Sha] that
the true nature of the material came to light. Through XRD, EPMA, TEM and DTA studies, they determined
the relationship between FePt2Cu and the rest of the ternary system. Arc-melted samples were homogenized
at 1200C for 3 months before quenching into water, followed by a further heat treatment at 1200C for 1
week, followed by slow cooling (10C#d1) to 1000C where they were held for a further 3 months. Some
samples were cooled to 600C and held for 6 months before quenching. They postulated that the single
phase region of FePt2Cu extends all the way to FePt at 1000C and the FePt2Cu composition lies in a two
phase field at 600C. This would suggest that the ternary compound is in fact an extension of the binary
compound. Later work [1986Sha] confirmed that this is the case with the binary and ternary compounds
being isomorphous.
Little thermodynamic study has taken place on this system. [1989Par] measured the activity of Cu along
composition lines of constant Fe/Pt ratios by Knudsen cell effusion. [2004Wil] used electronic structure
calculations to calculate the Gibbs energy of mixing along the Fe1xCuxPt section, suggesting phase
separation with a critical temperature of 450C.
Experimental investigations of phase equilibria and thermodynamics are listed in Table 1.
Binary Systems
Binary systems Cu-Fe, Cu-Pt and Fe-Pt are accepted from [2006Tur], [2006Kuz] and [Mas2], respectively.
Solid Phases
The L10-FePt ordered phase extends into the ternary system by just over 30 at.% Cu at 1000C and includes
the composition FePt2Cu. Thus, there is no ternary compound in this system. The ordering temperature of
the L10 phase falls with increasing Cu content [2002Mae]. At the FePt2Cu composition, the ordering
temperature falls to 1150C [1986Sha]. It proved to be impossible to retain the high-temperature disordered
fcc structure by quenching [1986Sha].
In rapidly cooled polycrystalline material the grains are subdivided into twin-related domains with {101}
habit to compensate for the stress set up by the tetragonal distortion. Colonies of small twins are found
within larger twins on three levels of scale, and it is suggested that these smaller twins are formed by
Landolt-Brnstein
New Series IV/11C2
MSIT
244 CuFePt
successive re-ordering of a previously ordered matrix during cooling [1986Sha]. Cu substitutes for Fe in the
FePt lattice [1986Sha, 2004Wil]. Early crystallographic work indicates 4 atoms per unit cell in the structure
of the L10 compound, but later work by [1990Bay] did not reveal any additional reflections to indicate Fe
and Cu ordering. No information is available on the solubility of Cu in either Fe3Pt or FePt3.
PtCu dissolves about 4.3 mass% Fe [1979Cha], PtCu3 also dissolves a small quantity of iron [1943Nem1].
Crystallographic data for solid phases in the system are given in Table 2.
Isothermal Sections
Isothermal sections of the Cu-Fe-Pt ternary system at 1000 and 600C, based on the work of [1985Sha] are
shown in Figs. 1 and 2. At 1000C there is a single phase region based on FePt extending far into the ternary
system. Modification to the section presented in [1986Sha] is necessary, however, in order to take into
account equilibria involving FePt3. At 600C, equilibria involving the PtCu and PtCu3 binary phases are
also included, although dissolution of the third element in these compounds is fairly small [1979Cha,
1941Nem].

Two vertical sections CuPt - FePt and Pt - 50Cu50Fe (at.%) were constructed by [1941Nem, 1943Nem2]
and included in the review [1969Gue]. However, there are inconsistencies between these sections and the
binary systems, particularly Cu-Pt. In fact, their measurements of the CuPt-FePt section disagree with their
own determination of the liquidus and solidus of the Cu-Pt binary. For these reasons, the sections have not
been included here. Electronic structure calculations were used by [2004Wil] to calculate the Gibbs free
energy of mixing of disordered Fe1xPtCux alloys. This enabled the calculation of a
temperature-composition section revealing phase separation with a critical temperature of approximately
177C. The section is given in Fig. 3. It should be noted that this behavior has yet to be seen experimentally.
Thermodynamics
The partial pressures of Cu in the system Cu-Fe-Pt in the temperature range 1240 to 1360C have been
measured by the Knudsen effusion technique and the thermodynamic properties of this system at 1300C
have been derived [1989Par]. The activities of Fe in solid solutions at 1300C were calculated by
Gibbs-Duhem integration of the Cu activities. The experimental alloys were prepared from Cu (99.999
mass%), Fe (99.999 mass%) and Pt (99.99 mass%) by induction melting in an alumina crucible under an
Ar atmosphere. The alloy buttons were then homogenized in a H2 atmosphere for 5 to 30 days at 900 to
1300C.
The iso-aCu lines and the iso-aFe lines in the Cu-Fe-Pt system are shown in Figs. 4 and 5, respectively (the
dashed lines in these figures are the estimated solidus and liquidus lines at 1300C).

The alloys of the Cu-Fe-Pt enriched by Pt have practical interest as materials for electrical contacts
[1943Nem1]. Ordered alloys of this system are good candidate materials for ultrahigh recording density in
terms of both high magnetic anisotropy energy and preparation without high-temperature treatment
[2004Kai]. According to the data of [2004Wil], the magnetocrystalline anisotropy falls smoothly with
increasing Cu content, both for small and large additions of Cu. The calculations point to Cu as a promising
material with which it is possible to reduce the prohibitively high ordering temperature of L10 FePt while
not adversely affecting the magnetic properties. Furthermore, experimental data on the lower bound for the
ordering temperature of the L10 phase in FePt alloyed with Cu may aid in the future commercial viability
of this material.
The catalytic activity of Cu-Fe-Pt ternary alloy was investigated using an electrochemical method in a
polymer electrolyte fuel cell by [2000Shi]. It was established that the electrode prepared using a Cu-Fe-Pt
alloy catalyst showed higher cell performance than unalloyed Pt.
Brief detals of some studies of materials properties in Cu-Fe-Pt alloys are given in Table 3.
New Series IV/11C2
CuFePt 245
Miscellaneous
The compound FePt2Cu with minor substitution of Pd, Rh, Ir and Ni is a naturally occurring minor
constituent of platinum ores and placers (mineral tulameenite) [1973Cab, 1976Ura, 1985Sha, 1990Bay,
1991Cab, 2000Joh, 2002Coo, 2002Tol, 2004Dis]. An alloy with the composition FePt2Cu commonly
occurs as prismatic and needle-shaped crystals at the outer margin of altaite (PbTe) [2002Coo]. This mineral
is ferromagnetic [1973Cab]. According to [1973Cab], tulameenite has a range of composition with minor
amounts of Ir replacing Pt and with Ni replacing Cu and Fe. Minor amounts of Sb was also detected in some
grains. Studies along the FePt2Cu-FePt join by [1985Sha] indicate that the maximum substitution of Fe for
Cu in tulameenite is up to between Fe1.68 Pt2Cu0.32 and Fe1.28 Pt2Cu0.72. Comparison of the experimental
results with data for the tulameenite mineral suggests that some observed compositions may be metastably
preserved [1985Sha].
Tulameenite is white in reflected light in oil and air [1973Cab]. No bireflectance could be observed and the
mineral is very weakly anisotropic.
The Cu-Fe-Pt films show a high coercivity (HC) of around 5 kOe at 300C, whereas the HC of Fe-Pt films
is still several hundred oersted at this temperature and starts increase to around 4.5 kOe at 400C [2002Mae,
2005Che]. Cu-Fe-Pt films show a large HC value at around 15 at.% Cu.
The Mssbauer spectra of alloys of 0.1 and 1 at.% 57Fe in Cu with 5 at.% Pt have been obtained by
[1971Win]. Analysis shows electric field gradients and changes in the isomer shift with Pt neighbors that
can be explained by the increased density of states due to the virtual bound state on the Pt impurity.
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MSIT
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(2004) (Calculation, Crys. Structure, Electronic Structure, Magn. Prop., 16)
[2004Wil] Willoughby, S.D., Electronic and Magnetic Properties of Fe1xCuxPt, J. Appl. Phys.,
95(11), 6586-6588 (2004) (Calculation, Crys. Structure, Electronic Structure, Magn.
Prop., 14)
[2005Che] Chen, S.K.; Yuan, F.T.; Shiao, S.N., Magnetic Property Modification of L10 FePt Thin
Films by Interfacial Diffusion of Cu and Au Overlayers, IEEE Trans. Magn., 41(2),
921-923 (2005) (Crys. Structure, Experimental, Magn. Prop., Transport Phenomena, 13)
[2006Kuz] Kuznetsov, V., Cu-Pt (Copper - Platinum), MSIT Binary Evaluation Program, in MSIT
[2006Tur] Turchanin, M., Agraval, P., Cu-Fe (Copper - Iron), MSIT Binary Evaluation Program, in
MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services,
GmbH, Stuttgart; to be published, (2006) (Crys. Structure, Phase Diagram, Assessment, 36)
New Series IV/11C2
CuFePt 247
Table 1: Investigations of the Cu-Fe-Pt Phase Relations, Structures and Thermodynamics

[1941Nem, Thermal analysis, hardness Isopleths Fe0.5Pt0.5-Pt0.5Cu0.5, Pt-Fe0.5Cu0.5
1943Nem2] measurements, electrical resistance
[1973Cab] XRD, EPMA Pt2FeCu composition and alloys of the PtFe-
Pt2FeCu section
[1985Sha] XRD, TEM, EPMA, DTA Equilibria involving Pt2FeCu
[1986Sha] XRD, TEM, EPMA, DTA Crystal structure and morphology of Pt2FeCu
[1989Par] Weight loss Knudsen cell Activity of Cu in ternary alloys from 1239 - 1360C
[2002Mae] XRD Structure of PtFe with added Cu
[2004Wil] Total energy calculations - Phase separation in the Fe1xCuxPt section
Korringa-Kohn-Rostoker method

[C] Prototype
(JFe) hP2 a = 246.8 at 25C, 13 GPa [Mas2]
P63/mmc c = 396.0
Mg
( Fe) cI2 a = 293.15 [Mas2]
1538 - 1394 Im3m
W
(FexPt(1xy)Cuy) cF4 a = 361.46 to 392.36 x = 0, [2006Kuz]
Fm3m a = 364.67 to 392.36 y = 0,
Cu
(Fe) a = 364.67 at 915C [V-C2, Mas2]
1394 - 912
(Pt) a = 392.36 at 25C [Mas2]

< 1769.0
(Cu) a = 361.46 at 25C [Mas2];

< 1084.62 melting point [1994Sub]
(Fe) cI2 a = 286.65 at 25C [Mas2]
< 912 Im3m
W
PtCu hR32 a = 1071.3 [Mas2, V-C2]
< 816 R3m c = 1319.2
CuPt
PtCu3 cP4 a = 368.8 at 25 at.% Pt, 250C [2006Kuz]
735 Pm3m
AuCu3
1-D LPS tP28 ? [2006Kuz]; most probably - not unique
650 P4mm phase but a set of closely related phases
Cu3Pd
Landolt-Brnstein
New Series IV/11C2
MSIT
248 CuFePt

[C] Prototype
Fe3Pt cP4 a = 373.0 [Mas2], [V-C2]
820 Fm3m
AuCu3
FePt tP2 [Mas2]
1300 P4/mmm a = 384.1 [V-C2]
AuCu
FePt2Cu tP4 a = 389.1 0.2 [1973Cab, V-C2]; mineral tulameenite

< 1200 P4/mmm c = 357.7 0.2 [1973Cab]; synthetic compound
AuCu a = 388.5 0.1 [1986Sha, V-C2]; annealed at 1200C
c = 358.8 0.1 for 3 months
a = 389.5 [1985Sha]
c = 359.5
a = 380.5 0.1 [1991Cab]

c = 359.5 0.1
a = 390.18 0.07 [1990Bay]
c = 358.45 0.13
tP2 a = 274.77 0.04 [1985Sha]
P4/mmm c = 358.70 0.03
?
c** a = 379.2 [2000Shi]

? a = 385.0
?
FePt3 cP4 a = 387.2 [V-C2]
1350 Pm3m
AuCu3
Table 3: Investigations of the Cu-Fe-Pt Materials Properties

[1941Nem, Hardness measurements, tensile and Mechanical and electrical properties with
1943Nem2] ductility measurement, electrical respect to composition and temperature.
resistance, thermopower.
[1971Win] Mssbauer studies Spectra and hyperfine field distributions of 1.4,
1 and 0.2 at.% Fe in Cu-5Pt
[1973Cab] Ore microscopy, hardness measurement. Reflectance, microhardness
[2002Mae] Vibrating sample magnetometry Magnetic properties of PtFe with respect to Cu
addition
[2004Wil] Total energy calculations Magneto-crystalline anisotropy as a function of
Cu in Fe1xCuxPt
[2005Che] Vibrating sample magnetometer Coercivity change diffusion of Cu into PtFe
thin film.
New Series IV/11C2
CuFePt 249

Fig. 1: Cu-Fe-Pt. Axes: at.%
1000C
20
80
40
60
( Fe,Pt,Cu)
( Fe)+(Cu)
60
40
80
20
FePt
FePt3
20 40 60 80
Fe Pt

Fig. 2: Cu-Fe-Pt. (Cu) Axes: at.%
600C
PtCu3
20
80
1-D LPS
40
60
t)
u,P
PtCu
e,C
(F
60
40
80
20
FePt (Pt)
FePt3
(Fe) 20 Fe3Pt 40 60 80
Fe Pt
Landolt-Brnstein
New Series IV/11C2
MSIT
250 CuFePt
200
Fig. 3: Cu-Fe-Pt.
Calculated vertical
(Fe,Pt,Cu)
section for
FePt - PtCu
Temperature, C
100
(Fe,Pt,Cu)' +(Fe,Pt,Cu)''
Fe 50.00 40 30 20 10 Fe 0.00
Pt 50.00 Pt 50.00
Cu 0.00 Fe, at.% Cu 50.00

Isoactivity lines of Cu 0.9
at 1300C
0.8
0.7
20
80
0.6
0.5
0.4
40
60
0.3
0.2
60
40
0.1
80
20
0.05
20 40 60 80
Fe Pt
New Series IV/11C2
CuFePt 251

Isoactivity lines of Fe
at 1300C
20
80
40 0.2 0.04 60
0.06
0.1
0.4
0.05
60 0.6 0.5 40
0.7
0.8 0.01
80
20
0.9
0.002
20 40 0.3 600.03 0.02 0.008 80 0.006 0.004
Fe Pt
Landolt-Brnstein
New Series IV/11C2
MSIT
252 CuGaMn
Copper Gallium Manganese

Nataliya Bochvar, Lazar Rokhlin
Introduction
There is a few literature data on the Cu-Ga-Mn phase diagram. [1961Gla, 1963Tes] revealed two ternary
compounds in the Cu-Ca-Mn using X-ray investigations of crystal structure. These compounds were
established to be the Laves phases with compositions (in at.%), 1) 33.33Mn-16.7Ga-50Cu (MnCu1.5Ga0.5),
and 2) 33.3Mn-25Ga-41.7Cu (MnCu1.25Ga0.75). The first compound was of the MgCu2 type and the second
one was of the MgZn2 type. [1986Mar] studied phase equilibria at 500C in the region extended from the
binary system Cu-Mn to the line connecting points of the binary alloys Cu-40 at.% Ga and Mn-62 at.% Ga.
Using X-rays diffraction [1986Mar] confirmed existence of the two above mentioned compounds and
discovered two new ternary compounds, Mn1.05-1.42Cu0.95-0.58Ga with the crystal structure of the Ni2In
type and Mn5.4Cu0.6Ga5 of the Ti6Sn5 type. Moreover, [1986Mar] found the compound MnCu1.25Ga0.75 to
be characterized by a large homogeneity area so that its formula could be presented as MnCu1.4-1.2Ga0.6-0.8.
Besides, [1986Mar] established a large solubility of Cu (up to 38 at.%) at 500C in the binary Ga-Mn
compound with the crystal structure of the Cr5Al8 type. According to the assumed binary Ga-Mn system
[Mas2], this crystal structure belongs to the phase existing between 830 and 520C only and, therefore,
can not exist at 500C of the isothermal section studied by [1986Mar].
[1988Bar, 1989Bar] studied two isothermal sections and three vertical sections in the Cu corner of the
Cu-Ga-Mn phase diagram. The isothermal sections were at 700 and 550C and the vertical sections were
for constant contents of 65 mass% Cu, 75 mass% Cu and 6 mass% Mn. [1988Bar, 1989Bar] showed that
ternary compounds MnCu1.5Ga0.5 and MnCu1.4-1.2Ga0.6-0.8 were in equilibrium with Cu-base solid solution
at temperatures below 700C.
Details of the experiments of the above mentioned works are described in Table 1.
[1986Gan] presented review on the work [1986Mar]. [1969Tes] presented review on the intermetallic
compounds with structure of the Laves phases including two ternary compounds of the Cu-Ga-Mn system.
Binary Systems
The binary Cu-Ga, Cu-Mn and Ga-Mn systems are accepted from [2006Wat], [2005Tur] and [Mas2],
respectively. Temperatures of the Mn polymorphous transformation are accepted after [2005Tur].
Solid Phases
Four ternary compounds were found in the studied part of the system. They are designated in the Table 2 as
-1, -2, -3, -4. The compounds -1 and -4 are of constant composition. The compound -2 extends from ~20
to ~27 at.% Ga at 33.3 at.% Mn. The compound -3 extends from ~35 to ~47 at.% Mn at 33.3 at.% Ga.
Crystal structures and lattice parameters of the ternary, binary and unary phases are shown in Table 2.
Three invariant four-phase equilibria were established in Cu rich alloys of the Cu-Ga-Mn system in the solid
state [1989Bar]. Two of them are of the transition type and one of them is of the eutectoid type. They are
+ -1 (MnxCu1x) + -2 at 601 5C, + (MnxCu1x) + -2 at 540 5C, + + -2 at
520 5C. Compositions of the phases taking part in the equilibria were not determined.
Isothermal Sections
Isothermal section at 700C converted into at.% is shown in Fig. 1 after [1988Bar]. It is reasonable to notice
that the phase is stable only at high temperatures and can not be retained after quenching to room
temperature. During quenching the phase undergoes massive transformation. Depending on the
New Series IV/11C2
CuGaMn 253
composition phase is transformed into (MnxCu1x) massive phase or into massive phase. Samples
of the alloys where massive transformation proceeded had structure with a specific plate-like
morphology. Existence of this (MnxCu1x) massive phase confirmed by X-ray and microscopy methods
can be considered as proof of the phase existence at high temperatures.
Isothermal section at 550C converted into at.% is shown in Fig. 2 [1988Bar] after corrections made for
consistency with the Cu-Ga and Cu-Mn binary systems.
Isothermal section at 500C is shown in Fig. 3 after [1986Mar] with some correction. Since the binary
Ga-Mn system [Mas2] accepted in the present assessment differs from that accepted by [1986Mar] at the
concentrations above 30 at.% Mn, the phase equilibria in the section at 500C in the part adjoining to the
Ga-Mn side are constructed speculatively and, therefore, shown at these concentrations by dashed lines. It
is necessary to notice that the solid solution based on the compound with the structure of the Cr5Al8 type
does not lie on the Ga-Mn side at 500C.

Two vertical sections of the phase diagram for the Cu constant contents of 65 and 75 mass%, respectively,
converted to at.% are shown in Figs. 4 and 5 after [1989Bar]. Temperatures of the binary alloys are
corrected to meet the accepted binary phase diagrams. There are some insignificant discrepancies between
the positions of the phase boundaries in the vertical sections (Figs. 4, 5) and in the isothermal section at
500C (Fig. 3). They are caused by some differences in the conditions of the sample preparation. The phase
equilibria near the Cu-Mn side are not investigated and are not shown in Figs. 4 and 5.

[1979Bru] determined electrical resistivity of liquid Cu-Ga alloys with 2 at.% Mn by dc-method.
Experimental results were analyzed basing on the Fridel virtual bound state model. Authors concluded that
there are two well split impurity bands for the whole range between liquid Cu and Ga.
[1975Gar1, 1975Gar2, 1975Zol] measured magnetic properties of the liquid Cu-Ga alloys containing 2 to
5 at.% Mn. Basing on the results of the experiments estimation of polarization of spins near Mn atoms was
made. The Mn magnetic properties depended only on the conduction electron density.
The structure and magnetic properties of the Cu-Ga-Mn alloys were studied by [1949Ham, 2001Shi,
2004Oik]. According to [1949Ham], the alloy Mn1.00Cu1.97Ga1.05 demonstrated feeble magnetism after
quenching, influence of annealing on magnetism being very slight. The alloy had two-phase structure.
[2001Shi] found that the alloy Mn49.5Cu16.5Ga34 is a ferromagnetic with canted-spin arrangement for
208 T 335 K. The alloy exhibits an incommensurate magnetic state below 280 K. [2004Oik]
investigated martensitic transformation and magnetic properties of the Cu-Ga-Mn alloys in limits 21 to 25
at.% Ga, 10 to 20 at.% Mn. The alloy containing 21 at.% Ga and 12-15 at.% Mn demonstrated thermoplastic
martensitic transformation in ferromagnetic state associated with shape-memory effect. The effect was
observed after annealing at 750C for 12 h followed by quenching into ice water. Heating provided structure
of the alloy to be single phase.
Miscellaneous
[1953Gal] proposed formula for calculation of the magnetic moments of ferromagnetic materials.
Satisfactory agreement between calculated and experimental data were obtained, including for the alloy
MnCu2Ga.
[1983Pal] determined Curie temperatures of the homologous row of the Heusler alloys. The alloy
MnCu2Ga was included in the homologous row, although the alloy was not single-phase one according to
[1949Ham, 1986Mar].
Landolt-Brnstein
New Series IV/11C2
MSIT
254 CuGaMn
References
[1949Ham] Hames, F.A., Eppelsheimer, D.S., Ferromagnetic Alloys in the Systems Cu-Mn-In and
Cu-Mn-Ga, Trans. Am. Inst. Min. Metall. Eng., 185, 495-499 (1949) (Experimental, Crys.
Structure, Magn. Prop., 19)
[1953Gal] Galperin, F., Magnetic Moment and the Crystal Structure of Ferromagnetic Metals and
Alloys (in Russian), Dokl. Akad. Nauk SSSR, Phyzika, 88(4), 643-646 (1953) (Theory, 11)
[1961Gla] Gladyshevskii, E.I., Kripyakevich, P.I., Teslyuk, M.Yu., Zarechnyuk, O.S., Kuzma, Yu.,
V., Crystal Structure of Some Intermetallic Compounds, Sov. Phys. Crystallog., 6,
207-208 (1961), translated from Kristallografiya, 6, 267-268 (1961) (Crys. Structure,
Experimental, 11)
[1963Tes] Teslyuk, M.Yu., Markiv, V.Ya., Structure of Ternary Compounds in the Mn-Ga-Cu
System (in Ukrainian), Visn. Lviv. Derzh. Univ., Ser. Khim., (6), 37-41 (1963) (Crys.
[1969Tes] Teslyuk, M.Yu., Intermetallic Compounds with Structure of Laves Phases (in Russian),
in Intermetallic Compound with Structure of Laves Phases, Nauka, Moscow, 1-138 (1969)
(Crys. Structure, Review, 312)
[1975Gar1] Gardner, A., Zollner, R., Sotier, S., Magnetic Properties of Dilute Mn Impurities in Liquid
Cu-Ga Alloys, Phys. Rev. B, 12(11), 5245-5248 (1975) (Experimental, Magn. Prop., 11)
[1975Gar2] Gardner, A., Sotier, S., Zollner, R., Magnetic Properties of Mn Impurities in Cu-Ga Liquid
Alloys, Bull. Amer. Phys. Soc., 20(3), 320-320 (1975) (Abstract, 0)
[1975Zol] Zollner, R., Sotier, S., Holzhey, C., Luescher, E., Knight-Shift Liquid Cu-Ga Alloys with
Mn Impurities (in German), Z. Naturforsch., 30A, 1250-1255 (1975) (Experimental,
Magn. Prop., 23)
[1979Bru] Brunnhuber, J., Holzhey, C., Coufal, H.J., Sotier, S., Electrical Resistivity of Liquid CuGa
Alloys with Mn Impurities, Z. Phys. B, 33(2), 125-127 (1979) (Experimental, Electr.
Prop., 12)
[1983Pal] Palatnic, I.S., Falko, I.I., Curie Temperature in the Homologous Zones of Heusler Alloys
(in Russian), Dop. Akad. Nauk Ukr. SSR A, Fiz.-Mat. Tekh., 8, 51-53 (1983) (Theory, 12)
[1986Gan] Ganina, N.G., Zakharov, A.M., Olenicheva, B.G., Petrova, L.A., Cu-Ga-Mn (in Russian),
in Phase Diagram of Metallic Systems Published in 1986, VINITI, Moscow, 31, 477-478
(1987) (Review, 1)
[1986Mar] Markiv, V.Ya., Belyavina, N.N., Isothermal Section of the Mn-Cu-Ga Phase Diagram at
500C, Russ. Metall., (6), 204-207 (1986), translated from Izv. Akad. Nauk SSSR, Metally,
(6), 198-211 (1986) (Phase Diagram, Crys. Structure, Experimental, #, 11)
[1988Bar] Baranchikov, V.V., Grin, Yu.N., Bochvar, N.R., Lysova, E.V., Phase Constitution and
Structure of Copper-Rich Cu-Mn-Ga Alloys, Russ. Metall., (5), 206-211 (1988), translated
from Izv. Akad. Nauk SSSR, Metally, (5), 206-211 (1988) (Phase Diagram, Experimental,
Crys. Structure, #, *, 11)
[1989Bar] Baranchikov, V.V., Bochvar, N.R., Grin, Yu.N., Lysova, E.V., Phase Equilibria in the
Cu-Mn-Ga System, Inorg. Mater., 25(7), 953-956 (1989), translated from Izv. Akad. Nauk
SSSR, Neorg. Mater., 25(7), 1135-1139 (1989) (Phase Diagram, Experimental, Crys.
Structure, #, *, 5)
[2001Shi] Shiraishi, H., Iguchi, Y., Ohoyama, K., Yamaguchi, Y., Shimizu, K., Structural and
Magnetic Properties of Ni2In-Type (Mn1xCux)66Ga34 Compounds, Magn. Magn. Mater.,
226-230, 1081-1082 (2001) (Experimental, Crys. Structure, Magn. Prop., 3)
[2004Oik] Oikawa, K., Koeda, N., Sutou, Y., Omori, T., Kainuma, R., Ishida, K., Martensitic
Transformation and Magnetic Properties of Cu-Ga-Mn Beta Alloys, Mater. Trans., 45(8),
2780-2784 (2004) (Experimental, Crys. Structure, Magn. Prop., 25)
[2005Tur] Turchanin, M., Agraval, P., Groeber, J., Matusch, D., Turkevich, V., Cu-Mn
(Copper-Manganese), MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg,
New Series IV/11C2
CuGaMn 255
G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published,

(2005) (Crys. Structure, Phase Diagram, Assessment, 25)
[2006Wat] Watson, A., Wagner, S., Lysova, E., Rokhlin, L., Cu-Ga (Copper-Gallium), MSIT Binary
Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), Materials Science
International Services, GmbH, Stuttgart; to be published (2006) (Crys. Structure, Phase
Table 1: Investigations of the Cu-Ga-Mn Phase Relations, Structures and Thermodynamics

Studied
[1961Gla] X-ray powder method Crystal structure and lattice parameter of
MnCu1.5Ga0.5 and MnCu1.25Ga0.75
[1963Tes] Melting in electric furnace in soldered Four alloys with 33.3 at.% Mn and 12; 16.7;
vacuum ampoules. 25.0 and 33.3 at.% Ga.
Heat treatment at 600C for 120 h and Crystal structure and lattice parameter
quenching.
X-ray diffraction and powder method
[1986Mar] Arc melting in Ag atmosphere, 22 binary alloys and more than 120 ternary
homogenization at 750C for 600 h for alloys in the range of compositions up to 40
alloys with < 45 at.% Ga. at.% Ga and 60 at.% Mn.
X-ray diffraction and powder method Annealing at 500C for 800 h and quenching in
cold water.
Isothermal section at 550C.
Crystal structure and lattice parameters.
[1988Bar] Arc melting in He atmosphere. Cu-corner up to 40 Ga and 40 Mn (mass%), 60
Homogenization at 700C for 200 h and alloys.
quenching. Annealing at 550C for 200 h and quenching.
Microscopic observation, EMA, X-ray Isothermal sections at 700 and 500C.
diffraction and powder method, Crystal structure and lattice parameters for two
microhardness and electrical resistivity ternary compounds.
measurements.
[1989Bar] Arc melting in He atmosphere. Cu-corner up to 40 Ga and 40 Mn (mass%), 60
Homogenization at 550 to 700C for 200 h alloys.
and quenching. Three vertical sections at Cu = 75 and 85
Microscopic observation, EMA, X-ray (mass%) and Mn = 6 and Ga from 0 to 30
diffraction, DTA. (mass%), 50 alloys.
Landolt-Brnstein
New Series IV/11C2
MSIT
256 CuGaMn

[C] Prototype
(MnxCu1x) cF4 0 < x < 1 [2005Tur]
Fm3m
Cu maximum solubility 20.6 at.% Ga at
620C [2006Wat] and x = 0; dissolves
up to ~33 at.% Ga at 820C and x = 1
[Mas2]
(Mn) a = 386.0 pure Mn [Mas2]

1138 - 1087
(Cu) a = 361.46 pure Cu at 25C [Mas2]
< 1084.62
( Mn) cI2 dissolves up to 13 at.% Cu at 1097C
1246 - 1138 Im3m [2005Tur] and 42 at.% Ga at 715C
W [Mas2]
a = 308.0 pure Mn at >1138C [Mas2, 2005Tur]
(Mn) cP20 dissolves up to 2.03 at.% Cu at 706C
1087 - 727 P4132 [2005Tur] and 19.5 at.% Ga < 620C
Mn [Mas2]
a = 631.5 pure Mn [Mas2]
(Mn) cI58 dissolves up to 2 at.% Ga [Mas2]
< 727 I43m a = 891.26 pure Mn at 25 C [Mas2]
Mn
(Ga) oC8 a = 451.86 pure Ga [2006Wat]
< 29.7741 Cmca b = 765.70
Ga c = 452.58
(2Mn), Mn1xGax tI8 0 < x < 0.27,
1087 - ~700 I4/mmm - 0.34 < x < 0.38 at ~810-700C [Mas2]
Al3Ti
(3Mn), Mn1xGax tP4
720 P4/mmm 0.37 < x < 0.45
~760 - 620 AuCuI 0.16 < x < 0.24
a = 388.4 at 40 at.% Ga [1986Mar]
c = 369.0
J (Ga-Mn) tP4 27 to 30 at.% Ga [Mas2]
< 820 P4/mmm a = 398.8 at 33.3 at.% Ga [1986Mar]
AuCuI c = 358.6
(Ga-Mn) hR78 - ~45 to 60.5 at.% Ga [Mas2]
830 - 520 R3m
Cr5Al8
(Ga-Mn) - - 50 to 60 at.% Ga [Mas2]
< 600
New Series IV/11C2
CuGaMn 257

[C] Prototype
3 (Ga-Mn) tP14 - ~70 at.% Ga [Mas2]
< 480 P4/mbm
-
Q (Ga-Mn) - - ~76 to 78 at.% Ga [Mas2]
< 500
7 (Ga-Mn) oC26 - ~82 at.% Ga [Mas2]
< 410 Cmcm
Al6Mn
, ~Cu4Ga(h2) cI2 19.3 to 27.45 at.% Ga
915-616 Im3m a = 296.71 at 22.8 at.% Ga and 672C [2006Wat]
W
, ~Cu4Ga(h1) hP2 20.5 to 22.5 at.% Ga
620 - 325 P63/mmc a = 259.74 at 22.8 at.% Ga and 25C [2006Wat]
Mg c = 424.41
, ~Cu4Ga(r) - 21 to 22.4 at.% Ga, stability range
< ~322 questionable, structure most likely of
distorted D019 type
a = 259.46 at 22 at.% Ga [2006Wat]
c = 424.48
, Cu9Ga4(h) cP52 29.5 to 34.7 at.% Ga
836 - 490 P43m a = 874.7 at 32.13 at.% Ga and 604C [2006Wat]
Cu9Al4 c = 886.44
1, Cu9Ga4(r) cP52 29.8 to 37.4 at.% Ga, ordered form of
< 645 P43m a = 873.87 at 32 at.% Ga
Cu9Al4 a = 872.95 at 36 at.% Ga [2006Wat]
2, ~Cu2Ga cP* 33.9 to 37.7 at.% Ga
< 485 P43m a = 873.73 at 34.06 at.% Ga
or
oI12 a = 433 annealing at 800C [2006Wat]
CeCu2 b = 687
c = 733
3, ~Cu3Ga2 cP* 38.1 to 42.6 at.% Ga
< 468 P43m a = 869.49 at 38.4 at.% Ga [2006Wat]
, CuGa2 tP3 ~64.6 to 66.7 at.% Ga
< 254 P4/mmm a = 283.0 at 67 at.% Ga [2006Wat]
FeSi2 c = 583.9
, (Cu-Mn) c** - [2005Tur]
< 700
MnCu3 c** - critical point at ~24.5 at.% Mn
< 450 [2005Tur]
MnCu5 c** - critical point at ~17 at.% Mn,
< 410 ~9 to 31 at.% Mn at 512C [2005Tur]
Landolt-Brnstein
New Series IV/11C2
MSIT
258 CuGaMn

[C] Prototype
* -1, MnCu1.5Ga0.5 cF24 a = 691.1 [1963Tes, 1969Tes]
Fd3m a = 689.5 [1986Mar]
MgCu2 a = 691.2 [1988Bar]
* -2, MnCu2xGax hP12 0.68 < x < 0.8
P63/mmc a = 494.1 for MnCu1.25Ga0.75 [1963Tes, 1968Tes]
MgZn2 c = 800.5
a = 490.9 to 494.2 for MnCu1.4Ga0.6 to MnCu1.2Ga0.8
c = 793.1 to 794.8 [1986Mar]
a = 491.8 for MnCu1.25Ga0.75 [1988Bar]
c = 795.2
* -3, Mn2xCuxGa hP6 0.58 < x < 0.95
P63/mmc a = 420.2 for Mn1.38Cu0.62Ga [1986Mar]
Ni2In c = 535.3
* -4, Mn5.4Cu0.6Ga5 hP22 a = 834.3 [1986Mar]
P63/mmm c = 518.5
Ti6Sn5
Mn 0.00
Cu 50.00
Ga 50.00 Data / Grid: at.%
Fig. 1: Cu-Ga-Mn. Axes: at.%
Partial isothermal
section at 700C
10
40

20
30

30
20
40
10
( MnxCu1-x)
Mn 50.00 60 70 80 90
Cu
Cu 50.00
Ga 0.00
New Series IV/11C2
CuGaMn 259
Mn 0.00
Cu 30.00
Ga 70.00 Data / Grid: at.%
Partial isothermal
section at 550C
10
60
20
50
30
40
1
40

+
30
+
+
2 +( M
2 n x Cu )
50 1-x 20
1 ++( MnxCu1-x)
60 1+ 2+( MnxCu1-x)
10
( MnxCu1-x)
Mn 70.00 40 50 60 70 80 90
Cu
Cu 30.00
Ga 0.00
Ga Data / Grid: at.%

Partial isothermal
section at 500C
20
80
40
60

4 +
1 +

60 40
( 3Mn)
3 3+ 1+ 1
+ 3+ 2 + 3+ 2
2+ 1+ 2+( MnxCu1-x)+
80 2
20
( Mn) 1
1+ 2+( MnxCu1-x)
1+( MnxCu1-x)+(Mn)
( MnxCu1-x)
( Mn)
20 40 60 80
Mn +( MnxCu1-x)+(Mn) Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
260 CuGaMn
900
Fig. 4: Cu-Ga-Mn.
Vertical section from L
L+(MnxCu1-x)
Cu-38.4Mn to
Cu-32.9Ga (at.%) L+
800
L+
(MnxCu1-x)
+1+ (MnxCu1-x)
Temperature, C

700
+ + (MnxCu1-x)

++
601
600
+2+ (MnxCu1-x)
( Mn)+
(MnxCu1-x) 540
520
500
( Mn)+ 1+2+ (MnxCu1-x)
+2+ (MnxCu1-x)
400
Mn 38.40 10 20 ++2 30 Mn 0.00
Cu 61.60 Cu 67.10
Ga 0.00 Ga, at.% Ga 32.90
1000
Fig. 5: Cu-Ga-Mn. L
Vertical section from
Cu-27.8Mn to
Cu-23.3Ga (at.%) 900
L+(MnxCu1-x)
L+
800

Temperature, C
700
+1+ (MnxCu1-x)
(MnxCu1-x)
+2+ (MnxCu1-x)
+ + (MnxCu1-x)
601
600
540
500
1+2+ (MnxCu1-x)
400
Mn 27.80 10 20 Mn 0.00
+2+ (MnxCu1-x)
Cu 72.20 Cu 76.70
Ga 0.00 Ga, at.% Ga 23.30
New Series IV/11C2
CuGdSn 261
Copper Gadolinium Tin

Viktor Kuznetsov
Introduction
The phases of the system were studied mainly in the investigations aiming to find phases with unusual
physical properties (mainly magnetic). As a result, almost all investigations were conducted not for the
entire system, but rather for occurrence and properties of phases with particular stoichiometry, structural
types, etc. in a series of analogous systems.
[1976Dwi] studied crystal structures of a series of compounds RE(Cu,Au)Sn (hereafter RE = rare earth
metal), including GdCuSn. This phase was studied also by [1977Oes], [1983Kom] (magnetic properties),
[1997Bar] and [1998For] (refinement of crystal structure and magnetic properties), [1997Bia] (Mssbauer
study of magnetic properties of two Gd bearing phases). A series of the RE3Cu4Sn4 phases including
Gd3Cu4Sn4 were studied by [1983Thi] and [1984Sko] (the latter authors wrote the formula as RE6Cu8Sn8)
for crystal structure and magnetic properties, as well as by [2000Sin] (magnetic ordering at low
temperatures) and [2003Szy] (crystal structure and magnetic properties), [2004Szy] (magnetic properties).
[1984Kom, 1990Sko] found 6 ternary phases numbered from 1 to 6. Neither noticeable homogeneity ranges
nor solubility of a third component in the binary phases were detected. The crystal structures were
determined only for two of them with formulas GdCuSn and Gd6Cu8Sn8. A large series of phases with
CeNiSi2 type including GdCuSn2 were investigated by [1990Fra] using X-ray powder diffraction and
electron microprobe analysis. Investigation [1990Fra] showed deviation of the compound compositions
from the stoichiometry and existence of the homogeneity ranges. Also the series of RE2Cu4Sn5 phases was
synthesized by [1992Kom]. In this work structure and magnetic properties, resistivity and thermo-emf were
determined. Crystal structure and some physical properties of the ternary compound GdCu2Sn2 were
studied by [1993Kac]. Crystal structure and magnetic properties of the ternary compound GdCu5Sn were
investigated by [2001Mud].
Phase relations were studied in the only work [1984Kom] by the X-ray powder examination of 154 samples
annealed at 400C (670 K) (alloys composition and annealing time not specified). These data are briefly
presented also in the reference book [1990Gla]. Most other works, even [1992Kom] with the participation
of the same author, do not touch anyhow the phase relations.
[2000Sin] used low-temperature (2 to 40 K) heat capacity for Gd6Cu8Sn8, in addition to resistivity and
magnetization measurement, as a tool for studying magnetic ordering transitions in this phase.
The studies of the crystal structures of phases, phase relations and thermodynamic properties are referred in
Table 1.
Binary Systems
For Cu-Gd edge the version [2006Rok], evaluated within the MSIT Binary Evaluation Program is accepted.
Cu-Sn binary is accepted from [Mas2], and the Gd-Sn diagram was taken from a note [1995Oka], who
modified somewhat the version of [1991Pal], essentially identical to [Mas2].
Solid Phases
Crystallographic information for the solid phases is summarized in Table 2. From binary phases only those
appearing in the studied section of the ternary are included. Ternary compounds -1 to -6 correspond to those
with numbers from 1 to 6 found in [1984Kom, 1990Sko]. Neither noticeable homogeneity ranges nor
solubility of a third component in the binary phases were detected.
The solubility of Cu in the GdSn2 phase was accepted after [1990Fra].
The structures of the -2, -3 and -6 phases remain unknown.
Landolt-Brnstein
New Series IV/11C2
MSIT
262 CuGdSn
Isothermal Sections
Figure 1 presents isothermal section of the Cu-Gd-Sn system at 400C. It is based on [1984Kom, 1990Sko],
but with some corrections and additions by the present author. To bring the data [1984Kom, 1990Sko] in
agreement with the accepted binaries, we had to replace the GdCu4 phase by Gd2Cu9, add missed Gd3Sn,
Gd8Sn7 and Gd3Sn4 phases of the Gd-Sn edge and removed the GdSn2.75 phase. Finally, we restored
missed solubility range of Sn in (Cu).
The -7 and -8 phases were also accepted and added. The tie-lines with participation of added phases were
very tentatively estimated so as the equilibria established by [1984Kom, 1990Sko] were not destroyed (in
all the cases it could be done uniquely). Also the distribution of the tie-lines on the fcc (Cu) phase is
performed rather arbitrarily. All the added elements are given as uncertain by dashed lines.
Thermodynamics
No thermodynamic studies seem to be conducted except heat capacity measurements of Gd3Cu4Sn4 at 2 to
40 K, performed by [2000Sin]. The results were used for determination of the temperatures of magnetic
ordering. The entropy of magnetic transition was found to be ~3/4 of the theoretical value of R ln (7/2+1)
per Gd atom.

In the ternary compounds Gd3Cu4Sn4, GdCu5Sn and GdCuSn anti-ferromagnetism was observed at low
temperatures [1977Oes, 1993Kac, 1997Bar, 2001Mud, 2000Sin, 2002Sin, 2003Szy].
References
[1976Dwi] Dwight, A.E., Rare Earth-Au(Cu)-X Compounds with the Fe2P-, CaIn2-, and
MgAgAs-Types, Proc. Rare-Earth Research Conference, Vail, Colorado, II. (1976),
Experimental, 7)
[1977Oes] sterreicher, H., Magnetic Properties of GdCuSn and GdAuSn, J. Less-Common Met.,
55, 131-133 (1977) (Experimental, Magn. Prop., 16)
[1983Kom] Komarovskaja, L.P., Skolosdra, R.V., Filatova, I.V., Crystal Structure and Magnetic
Susceptibility of RCuSn Compounds (in Ukrainian), Dopov. Akad. Nauk Ukr. RSR, Ser. A,
Fiz-Mat. Tekh. Nauki, 45(1), 81-83 (1983) (Experimental, Magn. Prop., 4)
[1983Thi] Thirion, F., Steinmets, J., Malaman, B., Crystal Structures of Sc3Cu4Ge4, T.R.3Cu4Sn4
(T.R. = Y, Gd, Tb, Dy, Ho, Er), Isostructural with Gd3Cu4Ge4, and the Relevant Phase
Tm3Cu4Sn4 (in French), Mater. Res. Bull., 18, 1537-1542 (1983) (Crys. Structure,
Experimental, 10)
[1984Kom] Komarovskaya, L.P., Phase Equilibria, Crystal Structures and Properties of the
Compounds in R-(Ni, Cu)-Sn Systems where R = Ce, Pr, Gd, Lu (in Russian), Abstract of
Ph.D. Thesis (1984) (Crys. Structure, Electr. Prop., Experimental, Magn. Prop., Phase
Diagram, *, #, 0)
[1984Sko] Skolozdra, R.V., Komarovskaja, L.P., Aksel'rud, L.G., Crystal Structure and Magnetic
Properties of R6Cu8Sn8 Compounds (R = Gd, Tb, Dy, Ho, Er, Tm) (in Russian), Ukrain.
Fiz. Zhur., 29, 1395-1398 (1984) (Crys. Structure, Experimental, Magn. Prop., 6)
Systems R-M-X (R=La-Lu, M=Metals of the Groups 7 to 11). I: Compositions and
Structure Parameters (in French), J. Less-Common Met., 160, 197-213 (1990) (Crys.
Structure, Experimental, *, 15)
[1990Gla] Gladyshevsky, E.I., Bodak, O.I., Pecharsky, V.K., Gd-Cu-Sn, Ternary Rare Earth
Systems with Metallic Elements in Handbook on the Physics and Chemistry of Rare
Earths, 13, 105-106 (1990) (Crys. Structure, Phase Diagram, Review, *)
New Series IV/11C2
CuGdSn 263
[1990Sko] Skolozdra, R.V., Komarovskaya, L.P., Koretskaya, O.E., Interactions in the Ternary
Gadolinium-M-Tin Systems (M = Cobalt, Nickel, Copper) (in Russian), in: Fazovye
Ravnovesiya, Strukt. Svoistva Splavov, IPM, Kiev, 52-62 (1990) (Experimental, Phase
Diagram, 24)
[1991Pal] Palenzona, A., Girafici, C., The Gd-Sn (Gadolinium-Tin) System, J. Phase Equilib., 12,
690-695 (1991) (Phase Relations, Crys. Structure, Thermodyn., Review, 17)
[1992Kom] Komarovskaya, L.P., Skolozdra, R.V., Crystal Structure and Properties of R2Cu4Sn5
Compounds (R = Praseodymium, Neodymium, Samarium, Gadolinium, Terbium) (in
Russian), Metally, (2), 231-232 (1992) (Crys. Structure, Experimental, Magn. Prop., *, 6)
[1993Kac] Kaczmarska, K., Pierre, J., Slebarski, A., Starczewska, A., Structural, Magnetic and ESR
Properties of (Gd-R)T2Sn2 Compounds, J. Magn. Magn. Mater., 127, 151-158 (1993)
(Crys. Structure, Experimental, Magn. Prop., *, 20)
[1995Oka] Okamoto, H., Comment on Gd-Sn (Gadolinium-Tin), J. Phase Equilib., 16, 100-101
(1995) (Phase Relations, Crys. Structure, Review, 3)
[1997Bar] Baran, S., Ivanov, V., Leciejewicz, J., Stuesser, N., Szytula, A., Zygmunt, A., Ding, Y.F.,
Magnetism of Ternary Stannides RCuSn (R=Gd-Er), J. Alloys Compd., 257, 5-13 (1997)
[1997Bia] Bialic, D., Kruk, R., Kmiec, R., Tomala, K., 155Gd and 119Sn Moessbauer Investigations
of GdCuSn and GdAuSn, J. Alloys Compd., 257, 49-56 (1997) (Crys. Structure,
Experimental, 15)
[1998For] Fornasini, M.L., Marazza, R., Mazzone, D., Riani, P., Zanicchi, G., New Phases RCu5Sn
(R = La, Ce, Pr, Nd, Sm, Gd) and Ce2Cu9Sn2.65, Z. Kristallogr., 213, 108-111 (1998)
(Crys. Structure, Experimental, *, 17)
[1998Pac] Pacheco, J.V., Yvon, K., Gratz, E., Crystal Structure of LnCuSn (Ln = Nd, Sm, Gd),
Z. Kristallogr., 213, 510-512 (1998) (Crys. Structure, Experimental, 5)
[2000Sin] Singh, S., Dhar, S.K., Manfrinetti, P., Palenzona, A. Magnetic Properties of R3Cu4Sn4
(R = Ce, Gd, Y), J. Alloys Compd., 298, 68-72 (2000) (Crys. Structure, Experimental,
Magn. Prop., 7)
[2001Mud] Mudryk, Ya., Isnard, O., Romaka, L., Fruchart, D., Crystal Structure and Magnetic
Properties of RCu5Sn Compounds (R - Y, Gd-Yb), Solid State Commun., 119, 423-427
(2001) (Crys. Structure, Experimental, Magn. Prop., 16)
[2003Szy] Szytula, A., Wawrzynska, E., Penc, B., Stuesser, N., Zygmunt, A., Magnetic Properties of
R3Cu4X4 (R=Gd-Er,X=Ge,Sn) Compounds, Physica B, 327, 167-170 (2003) (Crys.
[2004Szy] Szytula, A., Wawrzynska, E., Penc, B., Stuesser, N., Tomkowicz, Z., Zygmunt, A.
Magnetic Properties and Electronic Structure of R3T4X4 (R: La-Nd, Gd-Er, T: Mn, Cu, X:
Ge, Sn) Compounds, J. Alloys Compd., 367, 224-229 (2004) (Crys. Structure, Electronic
Structure, Experimental, Magn. Prop., Phase Relations, 17)
[2006Rok] Rokhlin L., Bochvar N. Cu-Gd (Copper-Gadolinium), MSIT Binary Evaluation Program,
in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services,
GmbH, Stuttgart; to be published, (2006) (Crys. Structure, Phase Diagram, Thermodyn.,
Assessment, 31)
Landolt-Brnstein
New Series IV/11C2
MSIT
264 CuGdSn
Table 1: Investigations of the Cu-Gd-Sn Phase Relations, Structures and Thermodynamics

[1976Dwi] Powder XRD 800C, GdCuSn composition
[1983Kom] Powder XRD 500C, GdCuSn composition
[1983Thi] XRD Gd3Cu4Sn4 composition
[1984Kom] XRD (powder and single-crystal) 400C (annealing time not given), 154 samples in
the whole concentration range
[1984Sko] XRD Gd6Cu8Sn8, annealed at 500C, 700 h
[1990Fra] XRD, EPMA GdCuSn2, annealed at 800C (time not given)
[1992Kom] XRD 400C (annealed for 720 h), Gd2Cu4Sn5
[1993Kac] XRD GdCu2Sn2
[1998For] Powder XRD GdCu5Sn
[1998Pac] Single-crystal XRD GdCuSn
[2000Sin] Low-temperature heat capacity Gd3Cu4Sn4, 2 to 40 K
[2001Mud] Powder XRD 600C (annealed for 1000 h), GdCu5Sn

[C] Prototype
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m
Cu
(Gd) cI2 a = 406 [Mas2]
1313 - 1235 Im3m
W
(Gd) hP2 a = 363.36 at 25C [Mas2]
< 1235 P63/mmc c = 578.10
Mg
(Sn) tI4 a = 583.18 at 25C [Mas2]
231.9681 - 13 I41/amd c = 318.18
Sn
(Sn) cF8 a = 648.92 [Mas2]
< 13 Fd3m
C (diamond)
GdCu6 oP28 a = 802.6 0.5 [2006Rok]
< 865 Pnma b = 501.9 0.2
CeCu6 c = 1006.2 0.7
GdCu5 hP6 a = 503.6 ~16 to ~17.3 at.% Gd [2006Rok]
925 - 870 P6/mmm c = 410.2
CaCu5
a = 501 at 39 K
c = 412
New Series IV/11C2
CuGdSn 265

[C] Prototype
GdCu5 cF24 ~16 to ~17.3 at.% Gd
< 870 F43m a = 706 [2006Rok]
AuBe5
Gd2Cu9 h** a = 500 [2006Rok]
< 930 c = 1390
Gd2Cu7 - - [2006Rok]
870 - 825
Gd2Cu oI12 a = 432.9 0.4 [2006Rok]
< 860 Imma b = 690.9 0.5
CeCu2 c = 734.6 0.8
GdCu cP2 a = 305.2 [2006Rok]
< 870 Pm3m
CsCl
Gd3Sn - - [1995Oka]
< 1173
Gd5Sn3 hP16 a = 903.2 [1995Oka], [1991Pal]
< 1243 P63mcm c = 659.5
Mn5Si3
Gd5Sn4 oP36 a = 804.6 [1995Oka], [1991Pal]
< 1179 Pmna b = 1553
Sm5Ge4 c = 819.2
Gd8Sn7 - - [1995Oka]
< 1114
Gd11Sn10 tI84 a = 1167 [1995Oka], [1991Pal]
< 1095 I4/mmm c = 1715
Ho11Ge10
Gd3Sn4 - - [1995Oka]
< 995
GdSn2 oC12 a = 442.8 [1995Oka], [1991Pal]
< 1140 Cmcm b = 1641.0
ZrSi2 c = 432.2
a = 442.4 for GdCu0.17Sn2 composition [1990Fra]

b = 1670.0
c = 435.3
Gd3Sn7 oC20 a = 445.97 [1995Oka], [1991Pal]
< 945 Cmmm b = 2651.63
Gd3Sn7 c = 438.23
GdSn3 cP4 a = 467.6 [1995Oka], [1991Pal]
920 - 390 Pm3m
AuCu3
Landolt-Brnstein
New Series IV/11C2
MSIT
266 CuGdSn

[C] Prototype
GdSn3 oC16 a = 435.52 identified by [1995Oka] with
< 390 Amm2 b = 440.39 GdSn2.75 of [1991Pal] and [Mas2]
GdSn2.75 c = 2204.4
, ~Cu41Sn11 cF416 a = 1798.0 [Mas2]
590 - 350 F43m
Cu41Sn11
J, ~Cu3Sn oC80 a = 552.9 [Mas2]
< 675 Cmcm b = 4775
Cu3Sn c = 432.3
, ~Cu44Sn56 hP4 a = 419.0 [Mas2]
< 415 P63/mmc c = 508.6
NiAs
* -1, GdCu5Sn oP28 a = 825.0 [1998For]
Pnma b = 502.7
CeCu5Au c = 1049.7
* -2, ~Gd3Cu13Sn4 - - [1984Kom], [1990Gla]
* -3, ~GdCu7Sn2 - - [1984Kom], [1990Gla]
* -4, GdCuSn hP6 a = 453.41 [1998Pac]
P63mc c = 736.3
NdPtSb
* -5, Gd6Cu8Sn8 oI22 a = 1473.7 [1984Sko]
Immm b = 694.6
Gd6Cu8Ge8 c = 447.4
* -6, ~Gd3Cu6Sn11 - - [1984Kom], [1990Gla]
* -7, GdCu2Sn2 tP20 a = 430.8 [1993Kac]
P4/mmm c = 1032.4 sample with admixtures of several other
CaBe2Ge2 phases
* -8, Gd2Cu4Sn5 tP44 a = 439.2 [1992Kom]
I4mm c = 2489
Sm2Cu4Sn5
New Series IV/11C2
CuGdSn 267

Fig. 1: Cu-Gd-Sn. Axes: at.%
Isothermal section (Sn)
at 400C
20
80
GdSn3
Gd3Sn7
GdSn2
Gd3Sn4 40 60
Gd11Sn10 6
Gd8Sn7
8
Gd5Sn4

60
40
Gd5Sn3 5
7
Gd3Sn
4
2
3
80
20

1
(Cu)
20 40 GdCu 60 GdCu 80 GdCu6

Gd 2 Gd2Cu9 GdCu5 Cu
i 1 h l i 400C
Landolt-Brnstein
New Series IV/11C2
MSIT
268 CuGeMn
Copper Germanium Manganese

Nataliya Bochvar, Lazar Rokhlin
Introduction
Compositions in the Cu-Ge-Mn system are important Cu-base alloys for electronics applications having a
low electrical resistivity temperature coefficient.
Phase equilibria in the ternary Cu-Ge-Mn system have been investigated by [1961Coc, 1974Gav1,
1974Gav2, 1985Dri1, 1987Zav]. The crystal structures of the ternary compounds have been studied by
[1961Gla, 1963Oxl, 1963Tes, 1965Aoy, 1986Zav, 1987Zav].
[1979Dri] reviewed the Cu-Ge-Mn system based on the work of [1963Tes, 1974Gav1, 1974Gav2].
The experimental work has been summarized in Table 1.
Binary Systems
The Cu-Mn, Ge-Mn and Cu-Ge binary phase diagrams are accepted from [2005Tur], [Mas2, 1990Gok] and
[2002Fer], respectively. The temperatures of the Mn polymorphous transformations are accepted from
[2005Tur].
Solid Phases
Seven ternary compounds have been discovered in the Cu-Ge-Mn system. The ternary Laves phase -1
(Mn2Cu3Ge or MnCu1.5Ge0.5) was initially found by [1961Gla] and later confirmed by [1963Tes, 1986Zav,
1987Zav]. According to [1986Zav], this compound has a wide homogeneity range due to both mutual
substitution of Cu and Ge, and subtraction of Mn atoms. At 600C the limits of the homogeneity region have
been determined by [1987Zav] as 10 to 20 at.% Ge at 33 at.% Mn and 30 to 37 at.% Mn at 15 at.% Ge.
According to [1986Zav], at this temperature, the composition 31 at.% Mn, 51.7 at.% Cu, 17.3 at.% Ge is
located within the homogeneity range. [1974Gav1, 1974Gav2] report on the M-phase being in equilibrium
with (Al) at 500 and 220C, having the composition ~29 at.% Mn, 52 at.% Cu, 19 at.% Ge. Despite the
crystal structure not being determined by [1974Gav1, 1974Gav2], the above composition allows it to be
identified as -1.
[1963Oxl] reported the ferromagnetic Heusler phase MnCu2Ge (-2) with slight tetragonal deformation
(c/a = 0.96). [1987Zav] confirmed the existence of the compound but failed to determine its crystal
structure.
[1965Aoy] discovered a phase with the Ni3Sn2 type crystal structure existing close to the composition
Mn2CuGe2 (-6). Some discrepancies exist in the results of [1965Aoy]. Thus, the phase is reported as
ferromagnetic below 339 K. On the other hand, it is given as a high-temperature phase, stable at 600C, and
decomposing below this temperature into non-ferromagnetic phases. According to [1965Aoy], the
composition Mn2CuGe2 is not an exact composition of the ternary compound, as traces of Ge and hexagonal
phases were present in the sample of this composition. [1987Zav] determined the composition of the phase
as (Mn0.8Cu0.2)3Ge2, thus locating the composition Mn2CuGe2 in the three-phase region (Ge) + -6 + J.
Ternary compounds -3, -4, -5 and -7 were found by [1987Zav] at 600C. The crystal structure was not
determined for the first two. Additional examination is required. The compound -7 extends into the ternary
system along the line with constant Ge content of 28.5 at.% Ge, from ~2 to 30 at.% Mn.
At 400C, -3, -6 and -7 were not observed by [1987Zav] suggesting their decomposition between 400 and
600C. This should be studied in addition.
The T-phase, having the composition 30 at.% Mn, 5 at.% Cu, 65 at.% Ge, was observed by [1974Gav1,
1974Gav2] at 500 and 220C in equilibrium with (Mn,Cu) and -1. It was confirmed to exist in equilibrium
with and -1 at 650C by [1985Dri1]. The phase was not observed by [1987Zav] at 600C, who assumed
the T-phase to be the ternary compound MnCu2Ge (-2). This also needs examination.
New Series IV/11C2
CuGeMn 269
The ternary phases -1 and -7 have a wide homogeneity region; other ternary compounds have a fixed
composition.
The binary phase (Cu5Ge3) has a large region of homogeneity which extends at 610C from 0 to ~9 at.%
Mn at 14 at.% Ge, and from ~12 to ~18 at.% Ge at 5 at.% Mn [1961Coc]. The binary J1 (Cu3Ge) compound
dissolves up to 10 at.% Mn at 600C [1987Zav]. The binary (Mn5Ge3) phase extends into the ternary
system dissolving up to 15 at.% Cu [1987Zav]. All of the solid phases are presented in Table 2.
Three four-phase invariant equilibria were established in the Cu corner of the Cu-Ge-Mn system at 700, 675
and 655C, respectively, by [1985Dri1]. They are all of eutectic type. In addition, there are two saddle
eutectic points in the system, located at 695 and 720C along the - -1 and - -2 sections, respectively. A
partial reaction scheme for the Cu corner is shown in Fig. 1. The only liquid phase composition of all of the
invariant reactions was determined by [1985Dri1]; for the reaction at 655C as 18Mn-65.5Cu-16.5Ge
(mass%), or 20.7Mn-55Cu-14.3Ge (at.%). The compositions of the solid phases in the equilibrium were
determined as 10.3Mn-82.3Cu-7.4Ge (at.%) for (Mn,Cu); 2.8Mn-83.1Cu-14.1Ge (at.%) for ;
32.3Mn-52.2Cu-15.5Ge (at.%) for M or -1. In addition, the solubility of Mn in the phase (about 3 at.%)
seems to be too low, as does not correspond to that determined by [1961Coc, 1987Zav, 1974Gav1,
1974Gav2] at 610, 600 and 500C, respectively, where it is about 9 at.%. Thus, at 655C it also should be
about 9 at.%.
Liquidus Surface
Only a Cu rich fragment of the liquidus surface was studied by [1985Dri1]. A tentative liquidus surface is
shown in Fig. 2. The positions of the monovariant curves L + (Cu) , L + J and of the eutectic point
E3 were located using experimental data [1985Dri1]. Other lines and critical points were drawn, supposedly
taking into account the vertical sections [1985Dri1].
Isothermal Sections
Cu rich fragments of isothermal sections for 220, 500, 850C and at 610C were constructed by [1974Gav1,
1974Gav2] and by [1961Coc], respectively. Only [1987Zav] reported the isothermal section at 600C for
the whole concentration range. It is given in Fig. 3 with some corrections to maintain consistency with the
accepted binary phase diagrams [Mas2, 1990Gok]. Therefore, in Fig. 3 the Mn7Ge3 -phase, is presented
instead of the Mn5Ge2 phase. The Mn5Ge2 phase is absent at 600C according to the accepted Ge-Mn
binary. The section in Fig. 3 omits details of the Mn corner of the phase diagram because they were shown
speculatively in the original article.

The vertical sections at 75 and 85 mass% Cu and at 2 mass% Mn were published by [1985Dri1]. The section
at 2 mass% Mn considers the low solubility of Cu in the phase, as discussed above, and is not accepted.
Figures 4 and 5 show the vertical sections of the phase diagram for constant Cu contents of 75 and 85
mass%, respectively, given in at.%. These sections are made between points on the binary systems at
Cu-22.58 at.% Ge and Cu-27.82 at.% Mn (Fig. 4) and Cu-13.38 at.% Ge and Cu-16.95 at.% Mn (Fig. 5).
Minor corrections have been made to maintain consistency with the accepted binaries and the published
isothermal sections. There is some disagreement between the vertical (Fig. 4) and isothermal (Fig. 3)
sections in relation to the extension of phase boundaries at 600C. The disagreement can be attributed to the
possible deviation from equilibrium of the presented vertical section at temperatures below that of the
invariant reaction. This part of the section shown in Fig. 4 was constructed taking into account only results
of thermal analysis, studies of transformations involving the liquid phase and observations of the alloy
structures obtained after thermal analysis experiments.
Landolt-Brnstein
New Series IV/11C2
MSIT
270 CuGeMn

Details of experimental studies are summarized in Table 3.
[1963Oxl, 1965Aoy] measured the magnetic properties of the MnCu2Ge alloy quenched from 800C
[1063Oxl] and the Mn2CuGe2 alloy cooled from 600C [1965Aoy]. The Curie temperature was determined
to be 300 K for MnCu2Ge and 339 K for Mn2CuGe2. [1965Aoy] established the temperature dependence
of the inverse susceptibility of Mn2CuGe2.
The electrical properties and structure of Cu-Ge-Mn alloys (bulk samples) and films deposited via
evaporation under vacuum for the use in microelectronics were investigated by [1975Boc, 1984Boc,
1985Dri2, 1990Boc]. A pronounced concentration gradient was observed across the thickness of the film
as a consequence of the considerable difference between the saturation vapor pressures of copper and the
alloying elements (Ge and Mn) during evaporation. The concentration gradient brought about a difference
in the electric properties of the films and bulk samples. The films produced in this way consisted of three
layers, each of them having a special function. The upper and lower layers were enriched in alloying
elements whereas the middle layer was almost pure Cu. Therefore, the films showed high electrical
conductivity, excellent adhesion with the substrate and good corrosion resistance.
Miscellaneous
Using X-ray phase analysis, [1977Pop] studied the structure of Cu-Ge-Mn alloys with 2 to 36 mass% Mn
and 0.5 to 7 mass% Ge and the films deposited by the evaporation of these alloys in vacuum. The difference
in phase compositions of the films and bulk samples were due to the presence of manganese oxides in the
films. Another difference was a reduced effect of the alloying elements (Mn and Ge) on the lattice parameter
of Cu in the films as compared with bulk samples.
[1978Nes] examined the effect of 0.5 to 4 mass% Mn additions on the saturated vapor pressure and
evaporation rate of a Cu-Ge alloy with 9 mass% Ge, in the temperature range 830 to 1090C. The
experimental data indicated that the addition of more than 0.5 mass% Mn to the Cu-Ge alloy increased the
total vapor pressure and evaporation rate of the alloy components in all cases.
Using neutron and X-ray diffraction, [1981Vin] investigated the influence of Ge (up to 8 at.%) on the
structural layering of Cu-Mn alloys with 65 and 70 at.% Mn, and the low-temperature metastable f.c.c.
f.c.t. transformation. The dispersion factor had a decisive influence on this transformation.
References
[1961Coc] Cockayane, B., Raynor, G.V., The Apparent Metallic Valencies of Transition Metals in
Solid Solution, Proc. Roy. Soc. London A, 261A, 175-188 (1961) (Crys. Structure,
Experimental, Phase Diagram, 5)
[1961Gla] Gladyshevskii, E.I., Kripyakevich, P.I., Teslyuk, M.Yu., Zarechnyuk, O.S., Kuzma, Yu.B.,
Crystal Structure of Some Intermetallic Compounds, Sov. Phys.- Crystallogr., 6, 207-208
(1961), translated from Kristallografiya, 6, 267-268 (1961) (Crys. Structure, 11)
[1963Oxl] Oxley, D.P., Tebble, R.S., Williams, K.C., Heusler Alloys, J. Appl. Phys., 34, 1362-1364
(1963) (Crys. Structure, Magn. Prop, Experimental, 13)
[1963Tes] Teslyuk, M.Yu., Gladyshevskii, E.I., Crystal Structure of the Ternary Compound
MnCu1.5Ge0.5 (in Ukrainian), Vestn. Lvov. Univ., Ser. Khim., (6), 42-45 (1963) (Crys.
[1965Aoy] Aoyagi, K., Uchida, N., A New Magnetic Phase in the Manganese-Germanium-Copper
System, J. Phys. Soc. Jpn., 20, 617 (1965) (Crys. Structure, Magn. Prop., Experimental, 1)
[1974Gav1] Gavrilova, I.V., Zolotorevskaya, A.Yu., Novikov, I.I., Shpichinetskii, E.S., The
Investigation of Copper-Manganese-Germanium Phase Diagram in the Copper-Rich
Region (in Russian), Strukt. Faz, Fazov. Prevrasch., Diagram. Sostoyan. Metal. Syst.,
[1974Gav2] Gavrilova, I.V., Zolotorevskaya, A.Yu., Novikov, I.I., Shpichinetskii, E.S.,
Copper-Manganese-Germanium Phase Diagram in the Copper-Rich Region (in Russian),
New Series IV/11C2
CuGeMn 271
Nauchn. Tr., Gos. Nauchno-Issled. Proekt. Inst. Obrab. Tsvetn. Met., (41), 81-84 (1974)
(Phase Diagram, Experimental, 2)
[1975Boc] Bochvar, N.R., Lysova, E.V., Moiseeva, L.B., Popov, V.I., Rokhlin, L.L., Trofimenko, B.I.,
Electro-Physical Properties of the Film of Copper Alloys with Manganese and
Germanium (in Russian), Electron. Techn., Ser. Mater., (6), 37-41 (1975) (Experimental,
Electr. Prop., 8)
[1977Pop] Popov, V.I., Structural Characteristics of Vacuum Condensates of Copper-Base Alloys,
Met. Sci. Heat Treat., 19(3-4), 214-217 (1974), translated from Metalloved. Term. Obrab.
Met., (3), 47-51 (1977) (Experimental, Crys. Strucrure, 13)
[1978Nes] Nesmeyanov, A.N., The Effect of Additions of Manganese and Silver on the Evaporation
of Copper Germanium, Welding Prod., 25(2), 29-33 (1978) (Experimental, 12)
Turkina, N.I., Copper-Germanium-Manganese (in Russian), Binary and
Multicomponent Copper-Base Systems, Nauka, Moscow, 103 (1979) (Phase Diagram,
Review, 3)
[1981Vin] Vintaykin, Ye.Z., Sahno, V.M., Udovenko,V.A., Fine Crystal Structure of MnCuGe
Alloys, Phys. Met. Metall., 51(4), 93-97 (1981), translated from Fiz. Met. Metalloved.,
51(4), 783-787 (1981) (Experimental, Crys. Structure, 5)
[1984Boc] Bochvar, N.R., Vigdorovich, V.N., Leonova, N.P., Lysova, E.V., Resistivity of Alloys of
Cu-Mn-Ge, Cu-Mn-Sn and Cu-Ge-Sn Systems (in Russian), Metalloved. Term. Obrab.
Met., (2), 61-64 (1984) (Experimental, Electr. Prop., 9)
[1985Dri1] Drits, M.E., Leonova, N.P., Bochvar, N.R., Baranchikov, V.V., Kulbachevskaya, E.V.,
Phase Equilibria in Copper-Rich Alloys of the Cu-Mn-Ge System, Russ. Metall., (4),
200-203 (1985), translated from Izv. Akad. Nauk SSSR, Met. (4), 205-209 (1985) (Phase
Diagram, Experimental, #, *, 8)
[1985Dri2] Drits, M.E., Leonova, N.P., Bochvar, N.R., Lysova, E.V., A Study of the Nature of
Component Interaction in Copper-Base Alloys Containing Manganese, Tin and
Germanium (in Russian), Stable and Metastable Phase Equilibria in Metallic Systems,
55-59 (1985) (Phase Diagram, Experimental, Electr. Prop., 5)
[1986Zav] Zavalii, I.Yu., Crystal Structures of the Cu65Ni15Ge20, Cu60Ni16Ge24, Cu3Mn1.8Ge
Compounds (in Russian), Vestn. Lviv. Univ., Ser. Khim., 29, 23-24 (1986) (Crys.
[1987Zav] Zavalii, I.Yu., Pecharskii, V.K., Bodak, O.I., Phase Equilibria and Crystal Structure of
Some Compounds in the System Cu-Mn-Ge, Inorg. Mater., 23(11), 1635-1640 (1987),
translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 23(11), 1858-1862 (1987) (Phase
Diagram, Crys. Structure, Experimental, #, *, 18)
[1990Boc] Bochvar, N.R., Lysova, E.V., Correlation Between Phase Diagrams and Electrical
Properties of Cu-Alloys and Films Deposited via Evaporation in Vacuum, in User Aspects
of Phase Diagrams, Proc. Conf., Petten, Nethelands, June 1990, Hayes, F.H., (Ed.),
UMIST, Manchester, UK, 180-184 (1990) (Experimental, Electr. Prop., Phase Diagram, 5)
[1990Gok] Gokhale, A.B., Abbaschian, R., The Ge-Mn (Germanium-Manganese) System, Bull.
Alloy Phase Diagrams, 11(5), 460-468 (1990) (Phase Diagram, Review, Crys. Structure,
Thermodyn., 47)
[2002Fer] Ferro, R., Bochvar, N., Sheftel, E., Ding, J.-J., Cu-Ge (Copper-Germanium), MSIT
Science International Services GmbH, Stuttgart; Document ID: 20.22339.1.20 (2002)
(Phase Diagram, Crys. Structure, Thermodyn., Assessment, 6)
[2005Tur] Turchanin, M., Agraval, P., Groeber, J., Matusch, D., Turkevich, V., Cu-Mn
(Copper-Manganese), MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg,
G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; to be published
(2005) (Phase Diagram, Crys. Structure, Thermodyn., Assessment, 25)
Landolt-Brnstein
New Series IV/11C2
MSIT
272 CuGeMn
Table 1: Investigations of the Cu-Ge-Mn Phase Relations, Structures and Thermodynamics

Reference Method/Experimental Technique Temperature/Composition/ Phase Range
Studied
[1961Coc] Induction melting at 1300C in graphite Cu corner, Ge and Mn up to 20 at.%.
crucibles under Ar; casting in a mild steel Isothermal section at 610C, lattice
mold; homogenization at 690C for 10 to parameters of phase versus Ge
14 d; annealing at 650 and 610C, water concentration at 2.5, 5.0 and 7.5 at.% Mn,
quenched. lines of constant axial ratio in phase
Metallography, X-ray powder diffraction.
[1961Gla] X-ray powder diffraction MnCu1.5Ge0.5, crystal structure.
[1963Tes]
[1963Oxl] Melting under argon at a few millimeters MnCu2Ge, crystal structure.
pressure, homogenization at 800C,
quenching down to room temperature,
annealing at 200C for 10 d.
X-ray powder diffraction, magnetization.
[1965Aoy] Induction melting in Ar atmosphere; Alloy 40 at.% Mn, 20 at.% Cu, 40 at.% Ge
crushing, remelting in Tamman tubes; (Mn2CuGe2), crystal structure, magnetic
annealing at 600C for 3 h under Ar, rapid or behavior.
slow cooling.
X-ray powder diffraction, magnetic
susceptibility.
[1974Gav1] Induction melting; homogenization at 800C Cu corner, Ge up to 18 at.%, Mn up to 32
[1974Gav2] for 24 h; rolling to 50 % deformation; at.%.
annealing at 750C for 2 h; annealing at 850, Isothermal sections at 850, 500 and 220C
500 and 220C for 4, 48 and 500 h,
respectively, water quenching.
Metallography, X-ray diffraction, EMA,
microhardness.
[1985Dri1] Arc-melting under purified He atmosphere, Cu corner, Ge and Mn up to 30 mass%.
homogenization at 650C for 100 h, water Vertical sections at 75 and 85 mass% Cu,
quenching. and at 2 mass% Mn, partial liquidus
Metallography, DTA, microprobe, projection.
microhardness.
[1985Dri2] Preparation as in [1985Dri1]. Partial vertical section at 2 mass% Mn, Ge
DTA, metallography, electrical resistivity. up to 15 mass%. Electrical resistivity of
bulk and film specimens along the section.
[1986Zav] Arc-melting in Ar atmosphere, Mn2Cu3Ge, crystal structure.
homogenization at 600C for 300 h.
X-ray diffraction, crystal structure
refinement.
[1987Zav] Arc-melting in an Ar atmosphere; Isothermal section at 600C, whole
homogenization at 600C for 250 h and at concentration interval (200 alloys).
400C.
X-ray powder diffraction.
New Series IV/11C2
CuGeMn 273

[C] Prototype
(Mn,Cu) cF4
Fm3m
Cu
< 1084.62
(Mn) a = 386.0 pure Mn at 25C [Mas2]
1138 - 1087
( Mn) cI2 a = 308.0 pure Mn at >1138C [Mas2, 2005Tur]
1246 - 1138 Im3m
W
(Mn) cP20 a = 631.5 pure Mn [Mas2]
1087 - 707 P4132
Mn
(Mn) cI58 a = 891.26 pure Mn at 25C [Mas2]
< 707 I43m
Mn
(Ge) cF8 a = 565.74 pure Ge [Mas2, 1990Gok, 2002Fer]
< 938.3 Fd3m
C(diamond)
3 c** - [2005Tur]
700
2, MnCu3 c** - [2005Tur]
450
1, MnCu5 c** - [2005Tur]
410
J, Mn3.4Ge hP8 ~22 to 23.5 at.% Ge,
930 - 680 P63/mmc a =536 3 at 22.7 at.% Ge,
Ni3Sn c = 432 4
a = 538 7 at 23.5 at.% Ge [1990Gok]

c = 431 8
J1, Mn3.4Ge tI8 ~22 to 23.5 at.% Ge,
< 680 I4/mmm a = 381 6 at 22.7 at.% Ge [1990Gok]
Al3Ti c = 363 1
, Mn5Ge2 hP128 ~28.0 to ~30 at.% Ge,
953 - 620 P3c1 a = 718.5 at 28.6 at.% Ge [1990Gok]
c = 3917
, Mn7Ge3 o** a = 612.8 ~30 at.% Ge [1990Gok]
< 690 b = 873.8
c = 2229.2
Landolt-Brnstein
New Series IV/11C2
MSIT
274 CuGeMn

[C] Prototype
3, Mn2Ge hP6 32 to 34.4 at.% Ge,
965 - 790 P63/mmc a = 417.1 0.1 at 33.4 at.% Ge [1990Gok]
Ni2In c = 527.8 0.2
, Mn5Ge3 hP16 a = 719.7 ~37.5 at.% Ge [1990Gok]
< 966 P63/mcm c = 504.2
Mn5Si3
Mn3Ge2, o** a = 1320.1 0.1 at 40 at.% Ge [1990Gok]
796 b = 1587.8 0.4
c = 508.7 0.1
, ~Cu5Ge3 hP2 12.8 to 18.3 at.% Ge [2002Fer]
< 824 P63/mmc a = 259.93 at 17.2 at.% Ge [2002Fer]
Mg c = 422.47
J, ~ Cu3Ge hP8 23.1 to 23.5 at.% Ge,
747 - 549.5 P63/mmc a = 416.9 at 24 at.% Ge, 700C [2002Fer]
AsNa3 c = 749.9
J1, ~Cu3Ge hP8 23.1 to 25.1 at.% Ge
< 636 Pmmn a = 528 [2002Fer]
Cu3Ti b = 422
c = 454
J2, Cu3Ge cF16 a = 590.6 at 28.6 at.% Ge [2002Fer]
698 - 614 Fm3m
BiF3
-1, Mn2Cu3Ge hP12 a = 492.9 0.1 for MnCu15Ge0.5
P63/mmc c = 786.4 0.2 (33.3 at.% Mn, 50 at.% Cu, 16.7 at.%
Mg2Cu3Si Ge) [1961Gla],
a = 491.6 0.1 for Mn1.8Cu3Ge

c = 785.2 0.2 (31.0 at.% Mn, 51.7 at.% Cu, 17.3 at.%
Ge) [1986Zav]
-2, MnCu2Ge t** - c/a = 0.96 [1963Oxl]
-3, Mn33Cu42Ge25 - - [1987Zav]
-4, Mn66Cu4Ge30 - - [1987Zav]
-5 , tI32 a = 955.9 0.1 Mn62.5Cu5Ge32.5
Mn5(Cu0.133Ge0.866)3 I4/mcm c = 491.8 0.2 (62.5 at.% Ge, 5 at.% Cu, 32.5 at.% Ge)
W5Si3 [1987Zav]
New Series IV/11C2
CuGeMn 275

[C] Prototype
-6, (Mn0.8Cu0.2)3Ge2 hP6 a = 815 4 in the alloy with 40 at.% Mn, 20 at.%
P63/mmc c = 516 1 Cu, 40 at.% Ge [1965Aoy],
Ni2In
a = 816.9 0.1 for Mn48Cu12Ge40, single-phase
c = 515.6 0.1 (48 at.% Mn, 12 at.% Cu, 40 at.% Ge)
[1987Zav]
-7, (MnCu)5Ge2 hP42 a = 718.5 to 715.5 at 5 to 30 at.% Cu [1987Zav]
P63cm c = 1306.5 to 1314 Lattice parameters are taken from figure
Ni5As2 3 in [1987Zav]
Table 3: Investigations of the Cu-Ge-Mn Materials Properties

[1975Boc] Bulk and film samples of Cu-(20 to 35) Electrical conductivity at 25, 125 and 196C
mass% Mn-(0.5 to 7.0) mass% Ge alloys.
Measurements of electrical conductivity
[1977Pop] Bulk and film samples of Cu-(2.0 to 36) The phase analysis of films
mass% Mn-(0.5 to 7.0) mass% Ge alloys.
X-ray analysis
[1978Nes] The films of Cu-9 % Ge-(0.5 to 4 % Mn The dependence of the rate evaporation and
(mass) alloys. the partial vapor pressure from the alloy
Effusion method, using open crucibles as constitutions.
effusion chambers.
[1981Vin] The layer of Cu-(0 to8) at.% Ge-(65 to 70) The structural investigations
at.% Mn.
Neutron and X-ray diffraction
[1984Boc] Bulk and film samples of Cu-(2.0 to 15) Electrical resistivity at 25 and 125C.
mass% Mn-(0.5 to 2.0) mass% Ge alloys
[1985Dri2] Bulk and film samples of Cu-2.0 mass% Electrical resistivity at 25 and 125C. The
Mn-(0 to 15.0) mass% Ge alloys. structural investigations of film surfaces.
Measurements of electrical resistivity of
standard four-probe method. Auger
spectroscopy.
[1990Boc] Bulk and film samples of Cu-(0 to 15) mass% Electrical resistivity at 25 and 125C. The
Mn-(0 to 15) mass% Ge alloys. structural investigations of film surfaces.
X-ray analysis, Auger spectroscopy,
measurement of electrical resistivity
Landolt-Brnstein
New Series IV/11C2
MSIT
276 CuGeMn
Cu-Ge Cu-Ge-Mn
824 p1
L + (Cu)
743 e1
L + (Cu) + L++2 720 e2(max)
l + 2
700 L + + 2 E1
++2 L+1+2
695 e3(max)
l + 1
675 L + 1 + 2 E2
L+1+(Cu)
+1+2
655 L (Cu) + + 1 E3
(Cu)++1
Fig. 1: Cu-Ge-Mn. Reaction scheme in the Cu corner
Mn 0.00
Cu 50.00
Fig. 2: Cu-Ge-Mn. Axes: at.%
Tentative liquidus
surface projection
10
40
20
30

e2(max) e1
30 2
20
E2 E1 p1
1
e3(max)
E3
40
10
( Mn,Cu)
Mn 50.00 60 70 80 90
Cu
Cu 50.00
Ge 0.00
New Series IV/11C2
CuGeMn 277

Fig. 3: Cu-Ge-Mn. Axes: at.%
600C
20
80
40
60
Mn3Ge2 6+(Ge)+
60 6 40

4 5
7 2++
1' 2 1
1+ 7+ 1' 5+ 7+
80
3
20
1+ 2+
( Mn) 1 + 1
1 '+
( M
( Mn) n,Cu 1++( Mn,Cu)
) ( Mn,Cu)
( Mn)
Mn
20 40 60 80 3 Cu
900
Fig. 4: Cu-Ge-Mn.
Vertical section L
between binary L+(Mn,Cu)
compositions
Cu-27.82Mn and
800
Cu-22.58Ge (at.%)
L+
Temperature, C
(Mn,Cu) L+
720
695
700
700
675
655
+ +2
600
1+ +(Mn,Cu) ++1
1+2+
3 +1
530
1+ 2+2
500
Mn 27.82 10 20 Mn 0.00
Cu 72.18 Cu 77.42
Ge 0.00 Ge, at.% Ge 22.58
Landolt-Brnstein
New Series IV/11C2
MSIT
278 CuGeMn
1000
Fig. 5: Cu-Ge-Mn. L
Vertical section
bewen binary L+(Mn,Cu)
compositions
900
Cu-16.95Mn and
Cu-13.38Ge (at.%)
L+(Mn,Cu)+
Temperature, C
L+
800
(Mn,Cu)
700
600
(Mn,Cu)+
3
500
Mn 16.95 4 6 10 Mn 0.00
Cu 83.05 Cu 86.62
Ge 0.00 Ge, at.% Ge 13.38
New Series IV/11C2
CuGeNi 279
Copper Germanium Nickel

Lesley Cornish, Andy Watson
Introduction
Copper is used extensively for electrical and electronic applications because of its high electrical
conductivity. By adding alloying elements producing solid solutions, the resistivity of the alloys can be
lowered giving rise to their application as resistance materials. Little work has been carried out on the study
of the phase equilibria in the Cu-Ge-Ni system. The earliest and most extensive work was by [1959Bur]
who used X-ray analysis and optical microscopy to determine a partial isothermal section at 500C for Ge
contents less than 60 at.%. Later, [1985Boc] used DTA, optical microscopy, X-ray analysis and
microhardness measurements to produce a partial isothermal section, also at 500C (for Cu and Ni contents
less than 30 mass%) and isopleths at 75 and 85 mass% Cu. The isothermal sections produced by [1959Bur]
and [1985Boc] are in broad agreement with each other but the vertical sections violate the phase rule in that
several two-phase regions are missing. Three ternary compounds have been found in the system [1959Bur,
1985Boc, 1986Zav]. The effect of adding Ni to the binary phase in the Cu-Ge system and the apparent
valency of the transition metal has been studied by [1961Coc]. Experimental details of the phase diagram
studies are summarized in Table 1.
Binary Systems
The Cu-Ni system is isomorphous with complete mutual solubility of both components in the liquid and the
fcc solid solution phases, but with a miscibility gap in the latter below 354C. The Cu-Ni binary system is
accepted from [2002Leb]. Both the Cu-Ge and Ge-Ni systems comprise a number of intermetallic
compounds. These binary systems are accepted from [Mas2].
Solid Phases
Details of the solid phases are given in Table 2. Three ternary phases were reported by [1959Bur, 1985Boc]
to be stable at 500C, with compositions of Ni3Cu2Ge2 (-1), Ni15Cu55Ge20 (-2) and Ni15Cu58Ge22 (-3). In
addition, [1986Zav] reports a ternary compound with the composition Ni16Cu60Ge24. This phase has the
same -brass structure as -3 as given by [1959Bur] and is therefore considered to be the same compound.
No ternary phases were found by [1961Coc] at 690C.
[1961Coc] measured the lattice spacings of the binary , Cu5Ge phase on the addition of Ni.
Spectroscopically pure materials were inducton melted under Ar, cast and homogenised at 690C for
10-14 d before quenching into water. Optical microscopy and XRD of strain relieved fillings of the material
using CuK radiation revealed that Ni addition reduced both the a and c parameters of the crystal lattice.
The relationship between the lattice parameters and Ni content for this phase are shown in Fig. 1. The
variation of composition for constant c/a ratio is shown in Fig. 2. The binary compound was found to
dissolve ~5 at.% Ni at 690C. It was found that the electron to atom ratio (e/a) for the compound remained
constant for constant c/a ratio, and hence it was possible to determine the contribtion of Ni to the valency
electron concentration. At low e/a ratio, the effective Ni valency approaches 1, whereas as e/a increases, the
effective valency of Ni decreases (Fig. 3). This decrease begins at lower e/a ratios as the Ni content
increases. The explanation given for this observation was that Ni supplies 1 electron/atom to the conduction
band at low e/a, but with increasing e/a, the contribution per Ni atom decreases owing to a decrease in the
density of states as filling of the first Brillouin zone for the alloy approaches completion. Therefore, it is
energetically more favorable for added electrons to be accommodated in a virtual bound 3d state
assoociated with the individual Ni atoms.
Landolt-Brnstein
New Series IV/11C2
MSIT
280 CuGeNi
Five invariant equilibria were given by [1985Boc], one peritectic reaction, three transition reactions and a
solid state eutectoid reaction. These are listed in Table 3, but unfortunately, no compositions associated with
these reactions were reported in the original work.
Isothermal Sections
Partial isothermal sections for 500C were presented by [1959Bur] and [1985Boc]. Both are in broad
agreement with each other. The more extensive is that by [1959Bur] but the Ge-Ni binary edge of the section
does not agree with the accepted binary. In the original work, the B8 phase is mistakenly labelled as Ni2Ge.
However, in the accepted binary system, the Ni2Ge phase has the Strukturbericht designation C23. The B8
phases are actually the JNi5Ge3 and Ni3Ge2 phases which are separated by the Ni19Ge12 phase. It is most
likely, therefore, that the B8 phase in [1959Bur], which is capable of dissolving up to about 20 at.% Cu at
500C according to the experimental studies, refers to the JNi5Ge3 phase; the Ni3Ge2 phase being unstable
at this temperature. In a further complication, the real Ni2Ge phase, which appears at a composition of 33.5
at.% Ge in the accepted binary system, is missing in this isothermal section. According to [Mas2], this
compound decomposes peritectoidally at 506C. The possibility then, is that the experimental study was
made at a slightly higher temperature than 500C. The isothermal section is given in Fig. 4 with
amendments to equilibria at the Ge-Ni side of the diagram to bring it into agreement with the accepted
binary; but for a temperature slightly higher than 500C (above the peritectoid decomposition temperature
of the Ni2Ge phase). Minor alterations have also been made to the Cu-Ge side to maintain consistency with
the accepted Cu-Ge phase diagram. [1961Coc] presented a partial isothermal section for 690C. This is
shown in Fig. 5 with appropriate modifications to ensure agreement with the edge binary phase diagrams.

Microhardness measurements were used by [1985Boc] to distinguish the visually similar ternary phases. A
pyramidal diamond indenter was used and gave values of 4230 MPa for Ni15Cu65Ge10, 5310 MPa for
Ni15Cu58Ge2and 7210 MPa for Ni3Cu2Ge2. Details of experimental studies of materials properties are
given in Table 4.
Miscellaneous
[2000Gie] studied the diffusion of Cu and Ni into (Ge) between 700 and 900C, using rapid isothermal lamp
annealing and spreading-resistance profiling. Typical double-hump diffusion profiles were found for both
Cu and Ni.
[2000Wan] studied the effect of Cu clusters on nucleation on an undercooled Ge73.7Ni26.3 alloy. In the
binary alloy, solidification begins at a maximum undercooling of 205 K resulting in a eutectic mixture of
Ge and NiGe, as opposed to a mixture of primary Ge crystals and eutectic that would result from normal
cooling directly from the melt. However, by sputtering Cu on the undercooled melt, solidification begins at
an undercooling of 136 K, suggesting that the Cu clusters interfere with the nucleation process.
References
[1959Bur] Burkhardt, W., Schubert, K., Phase Construction of the Nickel-Copper-Germanium
System (in German), Z. Metallkd., 50(4), 196-198 (1959) (Crys. Structure, Experimental,
Phase Diagram, 13)
[1961Coc] Cockayne, B., Raynor, G.V., The Apparent Metallic Valencies of Transition Metals in
Solid Solution, Proc. Roy. Soc. (London) A, 261A, 175-188 (1961) (Crys. Structure,
Electronic Structure, Experimental, Phase Diagram, 5)
N.I., Cu-Ge-Ni (in Russian) in Binary and Multicomponent Copper-Base Systems,
New Series IV/11C2
CuGeNi 281
[1985Boc] Bochvar, N.R, Kinzhibalo, V.V., Lysova, E.V., Baranchikov, V.V., Phase Equilibria in the
System Cu-Ge-Ni, Russ. Metall., 1, 204-207 (1985), translated from Izv. Akad. Nauk SSSR,
Met., 1, 200-203,(1985) (Crys. Structure, Experimental, Phase Diagram, 4)
[1986Zav] Zavalij, I.Yu., Crystal Structures of the Cu65Ni15Ge20, Cu60Ni16Ge24, Cu3Mn1.8Ge
Compounds (in Russian), Vestn. Lvov. Univ, Ser. Khim., 29, 23-24 (1986) (Crys.
[2000Gie] Giese, A., Stolwijk, N.A., Bracht, H., Double-Hump Diffusion Profiles of Copper and
Nickel in Germanium Wafers Yielding Vacancy-Related Information, Appl. Phys. Lett.,
77(5), 642-644 (2000)
[2000Wan] Wang, W.K., Liu, R.P., Zhou, Z.H., Cao, L.M., Sun, L.L., Nucleation in Undercooled
Ge73.7Ni26.3 Alloy Melt Induced by Ni, Cu and Si Clusters, Mater. Sci. Forum, 329-330,
[2002Leb] Lebrun, N., Cu-Ni (Copper Nickel), MSIT Binary Evaluation Program, in MSIT
Assessment, 28)
Table 1: Investigations of the Cu-Ge-Ni Phase Relations, Structures and Thermodynamics

[1959Bur] Metallography, X-ray diffraction Isothermal section at 500C; < 30 at.% Ge
[1961Coc] X-ray diffraction Isothermal section at 690C; 25 at.% Ni and < 40
at.% Ge. Change in lattice parameters with Ni
dissolved in ,Cu5Ge
[1985Boc] Metallography, X-ray diffraction, DTA, Isothermal section at 500C; > 70 at.% Cu.
hardness measurements Isopleth at 75 and 85 mass% Cu
[1986Zav] X-ray diffraction Crystal structure of Ni15Cu65Ge20 and
Ni16Cu60Ge24. Compounds prepared at 597C

[C] Prototype
, (Ni1xCux) cF4
Fm3m
Cu
(Ni) a = 352.4 pure Ni at 25C [2002Leb].
< 1455 Dissolves 12 at.% Ge at 1124C [Mas2]
a = 361.46 at 25C [Mas2]

(Cu) Dissolves 12 at.% Ge at 824C [Mas2]
< 1084.62
( Ge) cI16 a = 692 LT, 12 GPa [Mas2]
Im3m
Si
Landolt-Brnstein
New Series IV/11C2
MSIT
282 CuGeNi

[C] Prototype
(Ge) tP12 a = 593 at 25C, 12 GPa1 atm [Mas2]
P41212 c = 698
Ge
(Ge) tI4 a = 488.4 at 25C, 12 GPa [Mas2]
I41/amd c = 269.2
Sn
(Ge) cF8 a = 565.74 at 25C [Mas2]
< 938.3 Fd3m
C (diamond)
, Cu5Ge hP2 a = 260.5 [Mas2], [V-C2]
< 824 P63/mmc c = 422.6
Mg
J2, Cu3Ge cF16 a = 590.6 73.5-73.95 at.% Cu [Mas2], [V-C2]
636 - 698 Fm3m
BiF3
J1, Cu3Ge oP8 a = 418.8 74.9-76.9 at.% Cu [Mas2], [V-C2]
< 638 Pmnm b = 452.7
Cu3Ti c = 262.4
J, Cu3Ge hP8 a = 416.9 76.2-76.9 at.% Cu [Mas2], [V-C2]
549.5 - 747 P63/mmc c = 749.9
IrAl3
NiGe oP8 a = 538.1 [Mas2], [V-C2]
< 850 Pnma b = 342.8
FeAs c = 581.1
Ni3Ge2 hP6 a = 386.3 41-43 at.% Ge [Mas2], [V-C2]
515 - 990 P63/mmc c = 499.8
Ni2In
Ni19Ge12 mC62 a = 1163.1 38-41 at.% Ge [Mas2], [V-C2]
382 - 1050 C121 b = 671.5
Ni19Ge12 c = 1004.8
JNi5Ge3 hP6 a = 393.4 35-44 at.% Ge [Mas2], [V-C2]
290 - 1195 P63/mmc c = 505.6
Ni2In
JNi5Ge3 mC32 a = 1168.2 0.6 ~37 at.% Ge [Mas2], [V-C2]
< 394 C121 b = 673.7 0.3
Ni5Ge3 c = 636.4 0.3
= 52.11 0.01
Ni2Ge oP12 a = 511.3 0.3 33.5 at.% Ge [Mas2], [V-C2]
< 506 Pnma b = 383.0 0.2
Co2Si c = 726.4 0.4
New Series IV/11C2
CuGeNi 283

[C] Prototype
Ni5Ge2 hP42 28 at.% Ge [Mas2].
1045 - 1110 P63cm a = 682.7 0.3 [V-C2]
Pd5Sb2 c = 1239.5 0.5
Max temp. given incorrectly in [Mas2]
as 1082
Ni3Ge cF16 a = 574.36 25.6 at.% Ge, [Mas2], [V-C2]
1082 - 1118 Fd3m
NaTl
Ni3Ge cP4 a = 357.0 22.5-25 at.% Ge [Mas2], [V-C2]
< 1132 Pm3m
AuCu3
* -1, Ni3Cu2Ge2 hP42 a = 689.2 Quenched from 500C. ~10-~46 at.% Cu
P63cm c = 1255.0 [1959Bur], [V-C2] (as Ni47Cu25Ge28)
Ni5As2
* -2, Ni15Cu65Ge20 cP20 a = 627.3 Quenched from 500C [1959Bur],
P4132 [V-C2] (as Ni3Cu13Ge4)
Mn
or
Au4Al a = 627.1 [1986Zav] quenched from 597C
* -3, Ni15Cu58Ge25 c** a = 826.7 [1959Bur], [V-C2] (as Ni15Cu58Ge22).
-
Cu9Al4 a = 866.1 [1986Zav] (as Ni16Cu60Ge24)

Reaction T [C] Type Phase Composition (at.%)*
Cu Ge Ni
L + (Cu) + -1 -2 830 P - - - -
L + (Cu) + -2 785 U - - - -
L + -2 + -3 745 U - - - -
L + J1 + -3 712 U - - - -
J1 J+ + -3 515 E - - - -
* phase compositions unknown
Table 4: Investigations of the Cu-Ge-Ni Materials Properties

[1985Boc] Microhardness measurements Microhardness
[2000Gie] Rapid isothermal lamp annealing and Diffusion of Cu and Ni into Ge between 700
spreading-resistance profiling and 900C
Landolt-Brnstein
New Series IV/11C2
MSIT
284 CuGeNi
260.5 422.5
(a) (b)
Fig. 1: Cu-Ge-Ni.
Variation of (a) a
lattice parameter, (b)
c-spacing, pm
c lattice parameter 260.0 422.0
and (c) c/a ratio
of , Cu5Ge with Ge
content for 0 (filled
circles), 1 (open 421.5
259.5
a-spacing, pm
squares), 2 (open
circles), 3 (filled 1.635
(c)
squares) and 4 (open
triangles) at.% Ni.
259.0
1.630
axial ratio c/a

258.5
1.625
258.0 1.620
12.0 14.0 16.0 12.0 14.0 16.0 18.0
Ge, at.%
Ni 0.00
Cu 78.00
Fig. 2: Cu-Ge-Ni. Axes: at.%
Lines of constant c/a
ratio for , Cu5Ge
with added Ni
1.6345
1.6340
1.6320
1.6297
1.6266
1.6229
Ni 12.00 Ni 0.00
Cu 78.00 Cu 90.00
Ge 10.00 Ge 10.00
New Series IV/11C2
CuGeNi 285
Fig. 3: Cu-Ge-Ni.
1.0
Variation with
electron
concentration and
composition of the
apparent valency of
Ni dissolved in
, Cu5Ge
apparent valency
0.6
0.2
1.36 1.39 1.42 1.45 1.48 1.51
electron concentration

Partial isothermal
section at around
500C
20
80
40
60
NiGe
Ni19Ge12 60 40
Ni5Ge3
3
1
Ni3Ge 1,Cu3Ge
80
20
2
,Cu5Ge
20 40 60 80
Ni Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
286 CuGeNi
Ni 0.00
Cu 50.00
Partial isothermal
section at 690C
10
40
L
20
30
2

30
20
40
10
Ni 50.00 60 70 80 90
Cu
Cu 50.00
Ge 0.00
New Series IV/11C2
CuHNi 287
Copper Hydrogen Nickel

Vasyl Tomashik, Pierre Perrot
Introduction
The dissolution of hydrogen in the Cu-Ni alloys has been investigated since [1910Sie]: the first experiments
indicated an increasing hydrogen solubility at 1225C and p(H2) = 0.1 MPa in the Cu-Ni melts with
increasing Ni content up to 21 at.% [1910Sie, 1929Sie, 1950Him]. Some of these results were included in
the review [1938Kub]. All Cu-Ni alloys had a greater solubility for hydrogen than that of Cu [1933All].
Later investigations of the Cu-H-Ni ternary system are indicated in Table 1.
The hydrogen solubility in the solid and liquid Cu-Ni alloys was investigated mainly using Sieverts method
[1936Fuk, 1966Bag, 1966Sch1, 1966Sch2, 1970Deg, 1971Jon, 1974Lin, 1976Ger, 1976Str, 1979Tel,
1980Bar, 1982Sak1, 1982Sak2, 1983Str] and cathodic saturation [1968Bar, 1968Bau1, 1969Lip, 1970Lip,
1975Bar1]. Solubility isobars at a pressure of 0.1 MPa have been measured by [1993Ko] for hydrogen in
the Cu-Ni solid solutions in the entire range of compositions. The solubility data gave the values for the
partial molar enthalpy and excess entropy of the dissolved H atoms.
It was established that under hydrogen pressures lower than 0.01 MPa, the Cu-Ni alloys are only able to
adsorb hydrogen [1969Lip, 1970Lip]. The behavior of hydrogen in Cu-Ni alloys is affected by nickel in a
complicated manner: 1) a quick decreasing of solubility up to ~10 at.% Cu is observed; 2) the sorption
properties change very slowly at 10-30 at.% Cu; 3) a new quick decreasing of solubility is again observed
within the interval from 35 to (60-63) at.% Cu. The hydrogen dissolution in the Cu-Ni melts, containing up
to 8.5 at.% Ni, obeys the Sieverts law [1974Lin].
Calculation of the hydrogen solubility in the Cu-Ni alloys at 830 and 1050C, using the method of cluster
components without the correlation in the solution [1977Kar], well coincides with the experimental data of
[1936Fuk, 1971Jon].
Absorption of hydrogen by the Cu-Ni alloys at p(H2) = 80-120 kPa decreases when the Cu content increases
[1934Bau]. [1939Ger] noted that the hydrogen dissolution in the Cu-Ni alloys leads to a decrease of lattice
parameter which can be explained by the hydrogen diffusion in the alloys.
Thermodynamic properties of the Cu-H-Ni alloys were investigated by [1966Bag, 1966Sch2, 1970Deg,
1971Jon, 1974Lin, 1974Sig, 1979Tel, 1985Tka, 1993Ko].
Binary Systems
Cu-Ni is taken from MSIT Binary Evaluation Program [2002Leb]. The solubility of H in solid and liquid
metals are given by the following expression taken from [1984Fro], which may be used up to 50 MPa of
hydrogen pressure:
log10 (cH / at.%) = 0.5 log10 (pH2 / Pa) 2.77 2426 / T (Cu solid, 770 < T / K < 1356)
log10 (cH / at.%) = 0.5 log10 (pH2 / Pa) 2.35 2250 / T (Cu liquid, 1356 < T / K < 1823)
log10 (cH / at.%) = 0.5 log10 (pH2 / Pa) 3.00 870 / T (Ni solid, 620 < T / K < 1670)
log10 (cH / at.%) = 0.5 log10 (pH2 / Pa) 2.48 1176 / T (Ni liquid, 1670 < T / K < 1970 K)
The hydrogen solubility in solid and liquid copper given above is in a good agreement with the Cu-H
diagram given by [Mas2] under 50 MPa of hydrogen pressure. The solubility of H in solid nickel given by
[1984Fro] is affected by a typing error which has been corrected in the expression given above (2.00 has
been replaced by 3.00). It must be pointed out that the H-Ni diagram given by [Mas2] under 50 MPa of
hydrogen pressure cannot be accepted, because it gives a eutectic composition of 0.036 at.% H at 1406C
whereas the actual composition would be 2.14 at.% H at the same temperature. The solubility of hydrogen
in liquid Ni has also been reviewed by [1987Sch]. The best H-Ni phase diagram available to date is that
given in [2002Shi] experimentally determined up to 800C and 5 GPa of hydrogen pressure. The solid
solution H-Ni presents a miscibility gap, with a critical point evaluated by [2004Fuk] around 360C,
1.4 GPa and 50 at.% H.
Landolt-Brnstein
New Series IV/11C2
MSIT
288 CuHNi
Solid Phases
No ternary compound exists in the Cu-H-Ni system. All unary and binary phases are listed in Table 2.
The first results on the hydrogen solubility in the Cu-Ni alloys were obtained by [1910Sie, 1929Sie,
1933All, 1936Fuk, 1950Him]. Solubility has been investigated both in liquid and solid states at 350, 700
and 1050C by [1936Fuk, 1957Lie], 1500 and 1600C by [1966Sch2], 1600C by [1966Bag, 1966Sch1],
430, 730 and 1030C by [1968Bla1], 830, 920, 1000, 1070, 1160 and 1220C by [1971Jon] and 25, 35, 45
and 55C by [1982Sak1]. The calculation of hydrogen solubility at 1500 and 1600C using a model of
microheterogeneity of metal melts [1971Pet] are in a good agreement with the experimental data of
[1966Sch2]. Some isotherms of the hydrogen solubility in the Cu-Ni alloys, obtained by [1966Bag,
1966Sch2, 1971Jon, 1983Str] are shown in the Fig. 1. The experimental results of [1910Sie, 1929Sie,
1950Him] practically coincide with those given in Fig. 1 and the data of [1968Bla1] are consistently lower
than that presented across the entire range of alloy compositions. According to the data of [1968Bla1] the
solubility of hydrogen increases approximately by a factor of 2.8 when the pressure increases from 0.1 to
0.89 MPa. The hydrogen solubility in Cu-Ni alloys at the temperature 25-55C is given in Fig. 2 according
to the experimental data of [1982Sak1]. At low temperatures, the behavior of hydrogen seems very peculiar:
its solubility increases with the copper content of the alloy up to a maximum around 75 at.% Cu, then
decreases sharply down to the solubility of H in pure Cu, which is several orders of magnitude lower than
its solubility in pure Ni. At high temperature, the atomic ratio H/Ni decreases approximately linearly with
the composition when the Ni content in the alloy decreases from 85.0 to 33.4 at.% Ni [1968Bar]. At
100 at.% Ni the lattice parameter of Ni hydride is about 6% larger than the lattice parameter of pure Ni.
A continuous decrease of the difference between the hydrogen charged and uncharged specimens is
observed when the Cu concentration increases. The fcc lattice of such Cu-H-Ni alloys remains unchanged.
No difference between the lattice parameters of charged and uncharged alloys could be detected for alloys
containing ~36.8 at.% Ni. Since the lattice parameter of charged specimens differs in a discontinuous way
from values characteristic for uncharged alloys, a new hydride phase could form in the Cu-H-Ni system
[1968Bar].
The interstitial dissolution of hydrogen gives rise to a reversible lattice expansion by few percent without
change of structure [1968Bau1]. During the hydrogen desorption, two different values of lattice parameters
appear simultaneously on Cu-Ni alloys containing 10 to 35 at.% Cu. This is due to the transition between
two CuNi-H phases of different hydrogen concentrations ( and phases). With increasing Cu content a
decreasing lattice expansion of hydrogen-rich non-ferromagnetic phase is observed: up to 35 at.% Cu, this
expansion is proportional to the mean magnetic moment per atom of the corresponding hydrogen-free alloy
[1968Bau1]. The comparison with the quantity of absorbed hydrogen suggests further proportionality
between lattice expansion of the phase (as a function of the Cu content) and the corresponding H/Me
atomic ratio.
According to the measurements of magnetization, an increase of the Ni content in the (Ni,Cu) solid
solutions leads to a decrease of the critical segregation temperature of Cu-H-Ni solutions: for Cu20Ni80-H
and Cu40Ni60-H such temperatures are equal respectively 200 and 100C, but no segregation was observed
using XRD for the composition Cu40Ni60-H [1982Ant].
Investigation by thermoemf of Cu-Ni alloys up to 100 MPa of hydrogen pressure shows that alloying of Ni
with Cu displaces weakly the pressure of the transition in the H-Ni system at room temperature and
decreases its hysteresis, which achieves ~30 MPa for Ni, 5 MPa for Cu38Ni62 and is absent in the case of
the Cu55Ni45 alloy [1982Ant].
[1983Str] noted that the solubility of hydrogen in the Cu-Ni alloys, containing 3.7, 7.3, 11.0 and
14.6 at.% Ni could be expressed under 0.1 MPa of hydrogen pressure respectively by the following
equations:
log10 (s / at.%) = (0.56 0.16) (2767 290)/T (1150 - 1310C, 3.7 at.% Ni)
log10 (s / at.%) = (0.40 0.17) (2444 230)/T (1150 - 1310C, 7.3 at.% Ni)
log10 (s / at.%) = (0.07 0.13) (1738 180)/T (1200 - 1310C, 11.0 at.% Ni)
log10 (s / at.%) = (0.32 0.13) (2074 180)/T (1200 - 1310C, 14.6 at.% Ni)
where T is the temperature in K.
New Series IV/11C2
CuHNi 289
Isothermal Sections
It is known that in the H-Ni system two fcc phases and with different hydrogen contents can be in
equilibrium at room temperature under suitable conditions of electrolytic charging or under high hydrogen
pressure [1982Sak2]. In the Cu-H-Ni system, although the width of the two-phase region decreases
gradually with the Cu content down to 50 at.%, there is no critical composition for the disappearance of the
miscibility gap: two-phase region appears to continue up to pure Cu as shown in Fig. 3. The hydride phase
is stable only under very high hydrogen pressure at compositions above ~60 at.% Cu.
The absorption-desorption isotherms at 25 and 67C for the Cu-Ni alloys containing up to 50 at.% Cu have
been investigated by [1975Bar1, 1980Bar]. The isotherm at 25C for the Cu10Ni90 alloy within the pressure
range 0.15-0.9 GPa is shown in Fig. 4 [1975Bar1]. The plateau of absorption occurs at higher pressure than
the desorption one due to hysteresis. The width of the hysteresis loop in Fig. 4 is about 0.25 GPa and the
minimum pressure necessary to form phase is about 0.34 GPa [1975Bar1]. The alloy Cu50Ni50 exhibits
no hysteresis and no two-phase region [1980Bar]. It can be concluded that between the alloys Cu38Ni62 and
Cu50Ni50 the miscibility gap ( + ) at 25C is closed (at 67C this happens at a lower Cu content).
The formation pressures of hydrides in the Cu-H-Ni system increase from 0.500 GPa to 0.612 GPa at 25C
and from 0.520 GPa to 0.635 GPa at 67C at the decreasing Cu content from 38 to 5 at.% [1980Bar]. The
decomposition pressures of these hydrides lie between 0.342 and 0.495 GPa.
Thermodynamics
The enthalpy changes in Cu20Ni80-H2 system under high hydrogen pressure were measured by [1985Tka].
It was established that fH = 7950 209 J#(mol H2)1 (p = 0.560 0.005 GPa) and decH = 5146 209
J#(mol H2)1 (p = 0.380 0.005 GPa). These values were used for the calculation of the reaction enthalpies
under normal pressure (fH = 13703 418 J#(mol H2)1 and decH = 8535 293 J#(mol H2)1). The
considerable difference between the decomposition and formation enthalpy of the hydrides is connected
with the hysteresis, observed in this system, but so far no unique and generally accepted interpretation can
be offered.
The heat of hydrogen dissolution in the Cu-Ni solid alloys is equal 19.2, 13.4 and 6.7 kJ#(0.5 mol H2)1 at
10, 20 and 50 at.% Ni, respectively and 35.6, 27.6, 25.1, 25.9 and 19.2 kJ#(0.5 mol H2)1 for the liquid alloys
containing respectively 5, 13, 15, 26 and 52 at.% Ni [1976Fro]. It was shown that the partial molar entropy
of dissolved hydrogen does not depend on the Cu-Ni alloys composition [1979Tel].
The enthalpy of solution of hydrogen is plotted as a function of concentration for the Cu-Ni system in Fig. 5
[1971Jon]. This system exhibits a quasi-regular behavior with constant entropy of solution of hydrogen.
At low temperature (25-55C), the enthalpy of solution of hydrogen presents the behavior shown in Fig. 6.
The hydrogen solutions in the Cu-Ni alloys obey the Sieverts law in the (low hydrogen content) domain
[1970Deg]. The interaction parameters defined by
JH(Ni) = 0 log10 fH / 0 (mass% Ni) or JH(Ni) = 0 ln H / 0 (xNi),
with fH = (mass% H in alloy) / (mass% H in pure Cu) and H = (xH in the alloy) / (xH in pure Cu)
measure the influence of Ni on the solubility of H in copper. A positive interaction parameter means that Ni
increases the hydrogen activity coefficient in Cu, thus decreases its solubility. There is a large discrepancy
between the interaction parameters measured by various authors, JH(Ni) being negative between 1150 and
1240C for [1970Deg, 1974Lin, 1974Sig], negative at 1500-1600C for [1966Sch2] and positive at 1600C
for [1966Bag].
According to the data of [1976Ger, 1976Str] the temperature dependence of the interaction parameter
JH(Ni) = (123 34)/T + (0.0640 0.0011), where T is the temperature in K (up to 15 at.% Ni and within
the interval of temperature from 1150 to 1300C). The interaction parameter of Cu has been measured by
[1966Sch2] which proposes JH(Cu) = 0 ln H / 0 (xCu) = +0.33 at 1500-1550C, which means that Cu
decreases the solubility of H in liquid Ni.
Landolt-Brnstein
New Series IV/11C2
MSIT
290 CuHNi

Hydrogen dissolution has detrimental effect on the exploitation and mechanical properties of the Cu-Ni
alloys [1974Lin]. All the alloys of the Cu-Ni system dissolve hydrogen, and, if chill-cast when saturated
with the gas, produce unsound ingots [1933All]. In every case the hydrogen can be removed by degassing
with nitrogen.
The shrinkage of surface with increase of reduction temperature is smaller for Cu-Ni catalyst than for pure
Cu catalyst [1957Tak]. The rates of H2 adsorption on Cu and Cu-Ni catalysts are much smaller than that of
Ni, and the adsorption amount per unit area is the greatest for Cu-Ni catalyst, while that of Ni catalyst is the
smallest among the three.
Ferromagnetic Cu-Ni alloys can be charged with cathodic hydrogen in high concentrations whereby they
loose their ferromagnetic behavior [1968Bau1, 1968Bau2]. Measurements of magnetization of these alloys
show a quicker absorption of H2 compared to Ni. By measuring the temperature dependence on saturation
magnetization in different states of hydrogen desorption [1968Bau2] established that two ferromagnetic
phases exist in the hydrogenated Cu-Ni alloy with 30 at.% Cu. The influence of magnetization on the
magnetic properties of Cu-Ni disordered alloys containing 20 and 40 at.% Cu was also investigated by
[1982Ant].
The domain of temperatures over which serrated yielding occurs for the hydrogenated Cu-Ni alloys at the
strain rate 1.37#104 sec1 is shown in Fig. 7 for three H2 concentrations [1968Bla2]. In addition, the effect
of increasing the strain rate is shown in Fig. 7, where the results of a series of static strain-aging experiments
are also plotted. It can be seen from Figs. 7 and 8 that the region of serrated yielding is strongly dependent
on hydrogen level, but under no circumstances were yield points noted in alloys containing >58 at.% Cu,
even in the more critical static tests. The increase in the lower critical temperature with increasing Cu
content implies that the diffusion coefficient of hydrogen in Ni is lowered by the addition of Cu [1968Bla2].
At the same time, the upper critical temperature is falling.
Increase of hydrogen content in the phase leads to monotonous decrease of TC [1982Ant]. The phase of
the Cu20Ni80-H ingot and both and phases of the Cu40Ni60-H solution are paramagnetic at the
temperature above 27C. Alloy containing 40 at.% Cu is characterized by TC 162 K. Magnetization of the
Cu20Ni80-H ingots in the + two-phase region decreases approximately linearly when the hydrogen
content increases. These solutions have no spontaneous magnetization at the temperatures above 4.2 K in
the phase domain [1982Ant].
Miscellaneous
The activation energy of the hydrogen diffusion in the Cu-Ni solid solutions is equal to 146.4 kJ#mol1
[1939Ger].
The differential heat of hydrogen adsorption at near zero coverage of the Cu-Ni catalyst, containing
1 at.% Ni, was calculated as 44.4 kJ#mol1 [1957Tak].
The temperature dependence of hydrogen diffusion coefficient in the Cu-Ni alloys has been investigated by
the electrochemical permeation method [1982Sak1]. The concentration dependence of activation energy for
hydrogen diffusion in Cu-Ni alloys is shown in Fig. 9. Figure 10 plots the diffusion coefficient of hydrogen
at different temperatures.
Solid solutions Cu-H-Ni are kinetically unstable under atmospheric pressure and T > 250 K and decompose
forming metals and hydrogen [1982Ant]. After interruption of the cathodic saturation an intensive
desorption of hydrogen from the Cu-H-Ni alloys is observed at room temperature [1968Bar].
References
[1910Sie] Sieverts, A., About Dissolution of Gases in Metals (in German), Z. Elektrochem., 17,
707-713 (1910) (Experimental, Phase Relations, Transport Phenomena, 13)
[1929Sie] Sieverts, A., Absorption of Gases by the Metalls (in German), Z. Metallkd., 21, 37-46
(1929) (Review, Phase Relations, 26)
New Series IV/11C2
CuHNi 291
[1933All] Allen, N.P., Street, A.C., An Investigation of the Effects of Hydrogen and Oxygen on the
Unsoundness of Copper-Nickel Alloys, J. Inst. Met., 51, 233-256 (1933) (Experimental,
Phase Relations, Interface Phenomena, Phys. Prop., 12)
[1934Bau] Baukloh, W., Kayser, H., Hydrogen Absorption of Nickel, Copper and their Alloys (in
German), Z. Metallkd., 26(7), 156-158 (1934) (Experimental, Interface Phenomena, 2)
[1936Fuk] Fukusima, M., Mitui, S., Solubilities of Hydrogen in Binary Alloys in Relation to their
Equilibrium Diagrams, Sci. Rep. Imp. Univ. Prof. Honda Anniv. Vol., 940-948 (1936)
[1938Kub] Kubaschewki, O., Absorption of Gases into the Metals (in German), Z. Elektrochem.,
44(2), 152-167 (1938) (Review, Phase Relations, Interface Phenomena, 187)
[1939Ger] Gerzriken, S.D., Golubenko, Z.P., About Hydrogen Diffusion in the Copper-Nickel
Alloys (in Ukrainian), Fiz. Zapysky, 8(1), 67-71 (1939) (Experimental, Phase Relations, 4)
[1950Him] Himmler, W., Solubility of the Hydrogen in Copper-Zinc and Copper-Nickel Alloys (in
German), Z. Phys. Chem., 195(4), 244-252 (1950) (Experimental, Phase Relations, 12)
[1957Lie] Lieser, K.H., Witte, H., Solubility of Hydrogen in Alloys. IV. Discussion (in German), Z.
Elektrochem., 61(3), 367-376 (1957) (Review, Phase Relations, 29)
[1957Tak] Takeuchi, T., Sakaguchi, M., The Surface of Copper-Nickel Catalyst. II. Adsorption of
Hydrogen on Copper, Nickel, and Copper-Nickel Catalysts, Bull. Chem. Soc. Jap., 30(2),
182-186 (1957) (Experimental, Transport Phenomena, 8)
[1966Bag] Bagshaw, T., Mitchell, A., Solubility of Hydrogen in Some Liquid Alloys of Nickel,
J. Iron Steel Inst., 204, 87-90 (1966) (Experimental, Phase Relations, 18)
[1966Sch1] Schenck, H., Lange, K.W., Application of the Hydrogen Solubility to the Physical and
Thermodynamic Description of the Solvents (in German), Z. Metallkd., 57(5), 378-384
(1966) (Experimental, Thermodyn., 34)
[1966Sch2] Schenck, H., Lange, K.W., Research on the Solubility of Hydrogen in Iron, Nickel, Cobalt,
Copper and in their Binary Nickel Alloys (in German), Arch. Eisenhuettenwes., 37(9),
739-748 (1966) (Experimental, Phase Relations, Interface Phenomena, Thermodyn., 54)
[1968Bar] Baranowski, B., Majchrzak, S., Formation and Disintegration of Hydride Phases in Cu-Ni
Alloys, Rocz. Chem., 42(6), 1137-1143 (1968) (Experimental, Phase Relations, Crys.
Structure, 22)
[1968Bau1] Bauer, H.J., Berninger, G., Zimmerman, G., Proof of Interstitial Hydrogen Absorption in
NiCu-Alloys in Magnetic and X-Ray Ways (in German), Z. Naturforsch., 23A, 2023-2029
(1968) (Experimental, Crys. Structure, Magn. Prop., 36)
[1968Bau2] Bauer, H.J., Temperature Dependence of Spontaneous Magnetization of Ni-Cu30 with
Interstitial Occluded Hydrogen (in German), Z. Angew. Phys., 26(1), 87-90 (1968)
(Experimental, Crys. Structure, Magn. Prop., 16)
[1968Bla1] Blakemore, J.S., Oates, W.A., Hall, E.O., The Solubility of Hydrogen in Solid Ni-Cu
Alloys, Trans. AIME, 242, 332-333 (1968) (Experimental, Phase Relations, 18)
[1968Bla2] Blakemore, J.S., Hall, E.O., The Portevin-Le Chatelier Effect in Nickel-Copper Alloys,
Trans. AIME, 242, 333-335 (1968) (Experimental, Interface Phenomena, 11)
[1969Lip] Lipets, T.V., Vert, Zh.L., Tvardovsky, I.P., Solubility of Hydrogen in the Alloys of Nickel
with Copper, Gold and Zinc, Russ. J. Phys. Chem., 43(7), 1029-1032 (1969), translated
from Zh. Fiz. Khim., 43(7), 1841-1844 (1969) (Experimental, Phase Relations, 15)
[1970Deg] Degtyarev, Yu.V., Linchevsky, B.V., Chursin, V.M., Solubility and Activity of Hydrogen
in Liquid Copper and its Alloys with Manganese, Iron and Nickel, Russ. Metall., (4), 30-33
(1970) translated from. Izv. Akad. Nauk SSSR. Met., (4), 42-45 (1970) (Experimental, Phase
Relations, Thermodyn., 6)
[1970Lip] Lipets, T.V., Vert, Zh.L., Solubility of Hydrogen in Binary Alloys of Nickel and Palladium
with Copper (in Russian), Trudy Gosudarst. Inst. Priklad. Khim., (64), 94-100 (1970)
[1971Jon] Jones, F.G., Pehlke, R.D., Solubility of Hydrogen in Solid Ni-Co and Ni-Cu Alloys,
Metall. Trans., 2, 2655-2663 (1971) (Experimental, Phase Relations, Thermodyn., 32)
Landolt-Brnstein
New Series IV/11C2
MSIT
292 CuHNi
[1971Pet] Petrushevski, M.S., Geld, P.V., Calculation of Hydrogen Solubility in the Liquid Alloys
of Nickel with Iron, Gold, Cobalt and Copper (in Russian), Izv. Vyssh. Uchebn. Zaved.,
Chern. Metall., (2), 9-13 (1971) (Calculation, Phase Relations, 9)
[1974Lin] Linchevsky, B.V. Degtyarev, Yu., V., Chursin, V.M., Solubility of Hydrogen in Binary
Copper Based Alloys (in Russian) in Kinet. Termodin. Vzaimodeistviya Gazov Zhidk.
Met., Nauka, Moscow, 15-20 (1974) (Experimental, Phase Relations, Thermodyn., 5)
[1974Sig] Sigworth, G.K., Elliott, J.F., The Thermodynamics of Dilute Liquid Copper Alloys, Can.
Metall. Quart., 13(3), 455-461 (1974) (Review, Thermodyn., 50)
[1975Bar1] Baranovski, B., Tkacz, M., Bujnowski, W., Determination of Absorption-Desorption
Isotherms in Metal-Hydrogen Systems in the High Pressure Region, Roczn. Chem., 49(2),
437-439 (1975) (Experimental, Thermodyn., 10)
[1975Bar2] Baranovski, B., Tkacz, M., Thermopower of Nickel-Copper Alloys in High Pressure of
Gaseous Hydrogen, Europhys. Conf. Abstracts, 1A, 108-110 (1975) as quoted in
[1982Ant]
[1976Fro] Fromm, E., Gebhardt, E., Ternary Systems (Copper) in Gase und Kohlenstoff in
Metallen (in German), Springer-Verlag Berlin, Heidelberg, New York, 26, 662-677 (1976)
(Review, Phase Diagram, 132)
[1976Ger] Gershkovich, V.K., Streltsov, F.N., Kunin, L.L., Solubility of Hydrogen in Copper Based
Alloys, Russ. Metall., (2), 55-57 (1976), translated from Izv. Akad. Nauk SSSR, Met., (2),
[1976Str] Streltsov, F.N., Gershkovich, V.K., Kunin, L.L., About Solubility of Hydrogen in the
Copper Cast Alloys (in Russian), Liteynoye Proizvod., (2), 24-25 (1976) (Experimental,
Phase Relations, 7)
[1977Kar] Karamysheva, G.A., Men, A.N., Calculation of the Concentration-Dependence of
Hydrogen Solubility in Binary Alloys Using the Cluster Component Method, Russ.
Metall., (2), 82-83 (1977), translated from Izv. Akad. Nauk SSSR, Met., (2), 95-96 (1977)
(Calculation, Phase Relations, 5)
[1979Tel] Telkov, V.I., Andreev, L.A., The Solubility of Hydrogen in Nickel-Copper Alloys, Russ.
J. Phys. Chem., 53(1), 127-129 (1979), translated from Zh. Fiz. Khim., 53(1), 231-233
[1980Bar] Baranovski, B., Tkacz, M., Ab- and Desorption Isotherms of Hydrogen in Ni-Cu Alloys in
the high Pressure Range, Polish J. Chem., 54(4), 819-825 (1980) (Experimental, Phase
[1982Ant] Antonov, V.E., Belash, I.T., Degtyareva, V.F., Ponyatovskiy, E.G., Thiessen, V.G.,
Magnetic Properties of Solid Solutions of Nickel-Copper Alloys, Phys. Met. Metallogr.
(Engl. Transl.), 53(4), 47-56 (1982), translated from Fiz. Met. Metalloved., 53(4), 677-686
(1982) (Experimental, Phase Relations, Magn. Prop., 31)
[1982Sak1] Sakamoto, Y., Hirayama, K., The Electrochemical Determination of Diffusivity and
Solubility of Hydrogen in Ni-Cu Alloys, Hydrogene Mater., Congr. Int., 1, 377-382 (1982)
(Experimental, Phase Relations, Thermodyn., 27)
[1982Sak2] Sakamoto, Y., Yuwasa, K., Hirayama, K., X-Ray Investigation of the Absorption of
Hydrogen by Several Palladium and Nickel Solid Solution Alloys, J. Less-Common Met.,
88, 115-124 (1982) (Experimental, Crys. Structure, Phase Diagram, Phys. Prop., 22)
[1983Str] Streltsov, F.N., Solubility of Hydrogen in Copper Melts, Russ. Metall., (6), 46-49 (1983),
translated from Izv. Akad. Nauk SSSR, Metally, (6), 55-58 (1983) (Experimental, Phase
[1984Fro] Fromm, E., Jehn, H., Hydrogen in Elements, Bull. Alloys Phase Diagrams, 5(3), 323-326
(1984) (Phase Relatios, Review, 3)
[1985Tka] Tkacz, M., Baranowski, B., Heats of Formation and Decomposition of Nickel and
Ni0.8Cu0.2 Hydrides Measured in High Pressures of Gaseous Hydrogen, J. Less-Common
Met., 113(1), 83-87 (1985) (Experimental, Thermodyn., 11)
New Series IV/11C2
CuHNi 293
[1987Sch] Schuermann, E., Sittard, M., Voelker, R., Equivalent Influence of Alloying Elements on
the Nitrogen and Hydrogen Solubility in Liquid Ternary and Multicomponent Nickel-Base
Alloys (in German), Z. Metallkd., 78(6), 457-466 (1987) (Review, Phase Diagram,
Thermodyn., 53)
[1993Ko] Ko, C., McLellan, R.B., The Thermodynamics of Ni-Cu-H Solid Solutions, Acta Metall.
Mat., 41(8), 2473-2476 (1993) (Experimental, Thermodyn., 16)
[2002Shi] Shizuku, Y., Yamamoto, S., Fukai, Y., Phase Diagram of the Ni-H System at high
Hydrogen Pressures, J. Alloys Compd., 336, 159-162 (2002) (Phase Diagram,
Experimental, *, #, 19)
[2002Leb] Lebrun, N., Cu-Ni (Copper - Nickel), MSIT Binary Evaluation Program, in MSIT
Stuttgart; Document ID: 20.14832.1.20, (2002) (Assessment, Crys. Structure, Phase
Diagram, 51)
[2004Fuk] Fukai, Y., Yamamoto, S., Harada, S., Kanazawa, M., The Phase Diagram of the Ni-H
System Revisited, J. Alloys Compd., 372, L4-L5 (2004) (Phase Diagram, Experimental,
#, 14)
Table 1: Investigations of the Cu-H-Ni Phase Relations, Structures and Thermodynamics

Studied
[1910Sie, Sieverts method 1225C / (Cu-Ni) + H2 up to 21 at.% Ni
1929Sie]
[1933All] MSA, density measurements (Cu-Ni) + H2
[1934Bau] Sieverts method (Cu-Ni) + H2
[1936Fuk] Sieverts method (Cu-Ni) + H2
[1939Ger] XRD (Cu-Ni) + H2 at 15, 25 and 75 at.% Ni
[1950Him] Sieverts method 642-944C / (Cu-Ni) + H2 at 5, 10 and 20
at.% Ni
[1957Tak] Pressure measurements 100-130C / (Cu-Ni) + H2 at 1 at.% Ni
[1966Bag] Sieverts method (Cu-Ni) + H2
[1966Sch1] Sieverts method 1600C / Cu-H-Ni
[1966Sch2] Sieverts method 1500 and 1600C / Cu-H-Ni
[1968Bar] XRD, electrolytic saturation 25C / Cu-H-Ni
[1968Bau1] XRD (Cu-Ni) + H2 at 10-35 at.% Cu
[1968Bla1] Pressure measurements 430, 730 and 1030C / (Cu-Ni) + H2
[1969Lip] Cathodic saturation 20C / Cu-H-Ni
[1970Deg] Sieverts method 1240C / (Cu-Ni) + H2 up to 9.7 at.% Ni
[1970Lip] Cathodic saturation 20C / Cu-H-Ni
[1971Jon] Sieverts method 830-1220C / (Cu-Ni) + H2 at 21-88.8 at.%
Ni
[1974Lin] Sieverts method 1250C / (Cu-Ni) + H2 up to 8.6 at.% Ni
Landolt-Brnstein
New Series IV/11C2
MSIT
294 CuHNi

Studied
[1975Bar1] High pressure apparatus 25C / Cu10Ni90 + H2
[1975Bar2] Measuring of thermoemf (Cu-Ni) + H2 at 38 and 55 at.% Cu
[1976Ger, Sieverts method 1150-1300C / (Cu-Ni) + H2 up to 15 at.%
1976Str] Ni
[1979Tel] Sieverts method 400-700C / (Cu-Ni) + H2
[1980Bar] Sieverts method 25 and 67C / (Cu-Ni) + H2 at 5-50 at.%
Cu
[1982Ant] XRD, measurements of magnetization 250C / Cu-Ni-H
[1982Sak1] Cathodic saturation 24-56C / (Cu-Ni) + H2
[1982Sak2] Cathodic saturation 25C / Cu-H-Ni
[1983Str] Modified Sieverts method 1150-1310C / (Cu-Ni) + H2 at 3.7, 7.3,
11.0 and 14.6 at.% Ni
[1985Tka] Twin calorimeter method 25C / Cu20Ni80-H
[1993Ko] Equilibrate-quench-analyze technique 441-1157C / Cu-H-Ni

[C] Prototype
, (Ni,Cu,H) cF4 phase: low hydrogen content
Fm3m
, (Ni,Cu,H) Cu phase: high hydrogen content
(Ni) a = 352.40 at 25C [Mas2]

< 1455
(Cu) a = 361.46 at 25C [Mas2]
< 1084.62 melting point [1994Sub]
(H) hP2 a = 377.6 [Mas2]
< 259.34 P63/mmc c = 616.2 triple point
Mg
(H) cF4 a = 533.8 [Mas2]
< 271.9 Fm3m
Cu
NiH cF8 a = 374.0 [V-C2]
Fm3m
NaCl
NiH2 hP3 a = 266 [V-C2]
P3m1 c = 433
NiH2
New Series IV/11C2
CuHNi 295
0.25
Fig. 1: Cu-H-Ni.
Solubility of
hydrogen under 0.1 1600C
MPa H2 pressure in
0.20
the Cu-Ni solid
alloys at 350, 700,
1500C
920, 1050, 1220C,
and in the Cu-Ni
liquid alloys at 0.15
H, at.%
1500 and 1600C
0.10
1200C
1050C
0.05
920C
700C
350C
0
Ni 20 40 60 80 Cu
Cu, at.%
Fig. 2: Cu-H-Ni.
Solubility of
hydrogen in the
Cu-Ni alloys at
25-55C 104
H2, mol.m3
103
25C
35C
45C
55C
102
101
1.0
Ni 20 40 60 80 Cu
Cu, at.%
Landolt-Brnstein
New Series IV/11C2
MSIT
296 CuHNi
H Data / Grid: at.%

Fig. 3: Cu-H-Ni. Axes: at.%
room temperature
20
80
40
60
60
40
80
20
+

20 40 60 80
Ni Cu
0.9
Fig. 4: Cu-H-Ni.
Pressure-compositi
0.8
on isotherms for
hydrogen in
Cu10Ni90 at 25C 0.7
(the upper and
lower curves
0.6
correspond to
Pressure, GPa
formation and
decomposition 0.5
conditions
respectively) 0.4
0.3

0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
H/Me
New Series IV/11C2
CuHNi 297
40
Fig. 5: Cu-H-Ni.
Standard enthalpy
of hydrogen
solutions in the
Cu-Ni alloys
30
H0, kJ.g-at1
20
10
Ni 20 40 60 80 Cu
Cu, mass%
46
Fig. 6: Cu-H-Ni.
Heat of hydrogen
solution in the Cu-Ni
alloys at 25-55C 10.0
5.0
HC, kJ.mol1
-5.0
-10.0
-15.0
Ni 20 40 60 80 Cu
Cu, at.%
Landolt-Brnstein
New Series IV/11C2
MSIT
298 CuHNi
-20
Fig. 7: Cu-H-Ni.
The upper (UCT)
and lower (LCT) -40
critical temperatures
UCT
for Ni-Cu alloys at
three hydrogen
-60
concentrations (the
stress/strain curve is
Temperature, C
serrated between
-80
these temperatures)
1 2 3
-100
-120
H2, mass%
LCT
1 - 0.67
2 - 1.34
-140
3 - 2.23
-160
Ni 20 40 60 80
Cu, mass%
-20
Fig. 8: Cu-H-Ni.
The upper (UCT)
and lower (LCT) -40
critical , sec1
1 - 1.37.103
temperatures at 2 - 1.37.104
strain rates 3 - ~0
-60
1.37#103 (1) and UCT
1.37#104 (2) sec1
Temperature, C
and at 25 cm3 H2
-80
per 100 g of alloy
1 2 3
-100
LCT
t
c tes
-120 t in stati
ld poin
r yie
uppe
-140
-160
Ni 20 40 60 80
Cu, mass%
New Series IV/11C2
CuHNi 299
46
Fig. 9: Cu-H-Ni.
Activation energy for
hydrogen diffusion in
Cu-Ni alloys 44
42
HD, kJ.mol1
40
38
36
Ni 20 40 60 80 Cu
Cu, at.%
10-12
Fig. 10: Cu-H-Ni.
Diffusion coefficient
of hydrogen in Cu-Ni
alloys at 25-55C
10-13
D, m2.s1
10-14
25C
35C
45C
55C
10-15
Ni 20 40 60 80 Cu
Cu, at.%
Landolt-Brnstein
New Series IV/11C2
MSIT
300 CuInYb
Copper Indium Ytterbium

Oksana BodakA, Volodymyr Ivanchenko
Introduction
The Cu-In-Yb ternary system was investigated over the whole concentration range at 400C. The isothermal
section is presented in [1998Kal, 2005Kal]. The crystal structure characteristics of the compounds of the
Cu-In-Yb system were determined by [1987Fel1, 1987Adr, 1987Fel2, 1989Sys, 1989Koj, 1990Koj,
1998Kal, 1999Sar, 2001Tsu, 2001Gio, 2003Luk, 2003Mor, 2005Kal]. The temperature dependence of the
lattice constants for the YbCu4In compound was obtained by [1990Koj]. Thermodynamic, magnetic and
electrical properties of these compounds (temperature and pressure dependencies of magnetic susceptibility
and electrical resistivity) as well as electronic structure were studied by many authors using different
methods and techniques (see Table 1). Particular attention was paid to the YbCu4In based compound. While
being a Curie - Weiss paramagnet, YbCu4In undergoes a first-order valency isostructural phase transition
at a temperature (Tv) of approximately 40 to 80 K at atmospheric pressure. Ytterbium ions in YbCu4In
change their valency from +3 at 300 K to an average value of about +2.9 between 40 and 70 K. Below Tv,
the ytterbium in this compound is in a mixed-valence state and the compound as a whole is sometimes called
a light heavy-fermion system. Above Tv, the compound is known as a Curie - Weiss paramagnet of localized
magnetic moments and, below Tv, a Pauli paramagnet in a nonmagnetic Fermi-liquid state. The exact
temperature of the phase transition has been an issue for many years, and experiments using different
samples of YbCu4In have given different results. [1999Loe1, 1999Loe2] shows, that the temperature of
the phase transition depends on the composition of the sample. Between the stoichiometric composition and
the congruent melting composition, the valence transition temperature changes from 40 to 70 K. Electrical
resistivity strongly increases at Tv. Specific heat measurements reveal a characteristic increase in Cp around
Tv. The valence phase transition temperature of YbCu4In decreases with increasing pressure [1992Mat,
2002Uch, 2003Wad]. So, the Yb0.4Cu2In0.6 compound exhibits characteristic properties associated with a
heavy-fermion system [1987Fel1, 1987Fel2]. In [1987Fel2, 1989Koj, 1998Fis, 2000Yos], the dependence
of Tv on composition and substitutions of Yb or In by other elements was studied in more detail. [2002Koy]
proposed a schematic phase diagram for YbCu4In which corresponds to Doniachs phase diagram. The
magnetic susceptibility of YbCu4In as a function of pressure was measured by [1999Sve2, 1999Sve3] at 78,
150 and 300 K. On the basis of an extrapolation of the experimental dependence, a p-T phase diagram was
proposed for YbCu4In. Also, the temperature-pressure phase diagram for YbCu4In was presented by
[2003Mit]. The magnetic phase diagram for this compound was published by [2003Mus1, 2003Mus2].
There is good agreement between these results. Depending on the synthesis pressure the YbCu2In
compound crystallizes in two different structural types, but in both cases it is almost non-magnetic and Yb
ions are very close to the divalent state [2001Gio, 2001Tsu]. Table 1 lists a summary of the works performed
on the study of phase equilibria, crystal structure and thermodynamics in this ternary system.
Some problems concerning electronic structure, theory of phase transformation in the YbCu4In compound
have been resolved in [1999Sar, 1999Sve1, 2000Dze, 2000Yos, 2002Dze1, 2002Dze2, 2003Fre].
Binary Systems
The In-Yb binary system is accepted from [Mas2], Cu-In is from [2000Goe], based mainly on [1972Jai].
The Cu-Yb system is taken from the MSIT Evaluation Program [2002Rog].
Solid Phases
Crystallographic characteristics of the solid phases are presented in Table 2. In this system, five ternary
compounds are stable at 400C [2005Kal]. The crystal structures of two compounds, Yb3CuIn2 and
Yb4CuIn, are unknown. The compound -2, YbCu4.8-4.0In0.2-1.0 has a region of homogeneity between 3.3
and 16.7 at.% In. The -3, Yb2Cu2In (I) ternary compound with the tetragonal Mo2B2Fe structure has been
New Series IV/11C2
CuInYb 301
prepared by [2001Tsu] using a high pressure technique. This compound synthesized under a pressure of
3.5 GPa has the same stoichiometry as the -3 phase obtained at ambient pressure with the W2CoB2
structural type [2001Gio].
Quasibinary Systems
From the composition Yb1.0Cu4.2In0.8 on the solidus surface, a ridge with constant ytterbium content
extends to Yb2Cu9 (YbCu2 in the original publication), reaching the compound at 930C [1999Loe1,
1999Loe2]. But a quasibinary section was not presented.
[1999Loe1, 1999Loe2] showed that the congruent melting point of Yb1.0Cu4+xIn1x is 1005C at a
composition of Yb1.0Cu4.2In0.8 (70Cu-13.3In-16.7Yb (at.%)). No other invariant equilibria in the ternary
system have been established.
Liquidus Surface
Some liquidus isotherms in the vicinity of the Yb2Cu9 - YbCu4In section are presented in Fig. 1 in
accordance with [1999Loe1, 1999Loe2].
Isothermal Sections
The isothermal section of the Cu-In-Yb system at 400C is accepted from the review [2005Kal], which is
an updated version of the section presented in [1998Kal] taking into account the later discovery of the -3
ternary compound [2001Gio]. The 400C isothermal section is shown in Fig. 2 after modifications made to
ensure agreement with the accepted binary diagrams and also to remove artificial homogeneity ranges of
the binary and ternary phases, not reported in the literature. The Yb2Cu9 stoichiometry is accepted here
according to the accepted Cu-Yb binary system, rather than the YbCu5 stoichiometry given in [2005Kal].
Thermodynamics
Specific heat measurements through the valency transition in YbCu4In were made by [1987Fel1, 1996Hau,
1998Sar, 1999Sar]. [1998Sar] showed, that just above 40 K, Cp/T for YbCu4In rises from 1 J#mol1#K2 to
8 J#mol1#K2 in less than 1 K and than drops equally rapidly. The Sommerfeld coefficient of YbCu4In in
the low-temperature valency structure is approximately 50 mJ#mol1#K2. The entropy change, S, at the
valency transition was measured as 10 J#mol1#K1. [1996Hau] reported an essentially linear increase in
entropy from ~3 J#mol1#K1 at 40 K to ~11 J#mol1#K1 at 70 K. [1987Fel1] observed a two-peak structure
(at ~40 K and ~60 K) in the specific heat leading to an integrated entropy of 13.3 J#mol1#K1 at 70 K. These
three measurements yield similar entropy changes through the transition range.

Temperature dependent electrical measurements for YbCu4In at high pressure (3.3 GPa) indicate that Tv
decreases linearly with increasing pressure to 1 GPa [2002Uch]. Similar results were obtained in [1992Mat,
1998Sar, 2003Mit]. The substitution by ions larger than the Yb ion increases the valency transition
temperature and vice versa, substitution by smaller ions than the Yb ion decreases Tv [1987Fel1, 1987Fel2].
The temperature of the phase transition depends also on the composition of the samples [1999Loe1,
1999Loe2, 1999Sar, 2000Yos, 2003Mor]. The temperature-pressure phase diagram for YbCu4In is shown
in Fig. 3 [2003Mit] and it suggests a first-order-like transition between the two magnetic phases at the
critical pressure of ~2.45 GPa. According to the calculated phase diagram for YbCu4In [2003Mus1] the
largest critical field is observed for the {110} axis and the smallest field is observed for the {100} axis (Fig.
4). The change in the valency transition temperature in relation to the crystal composition of YbCu4In
compound is presented in Fig. 5.
Details of property studies of Cu-In-Yb alloys are listed in Table 3.
Landolt-Brnstein
New Series IV/11C2
MSIT
302 CuInYb
References
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Review, 50)
New Series IV/11C2
CuInYb 303
[1995Alt] Altshuler, T.S., Bresler, M.S., Schlott, M., Elschner, B., Gratz, E., Electron Spin
Resonance Studies at the Phase Transition in YbInCu4, Eur. Phys. J. B, 99(1), 57-60 (1995)
(Phase Relations, Experimental, 14)
[1995Koj] Kojima, K., Hiraoka, K., Takahashi, H., Mori, N., Hihara, T., Pressure Effect on Valence
Phase-Transition of YbInCu4, J. Magn. Magn. Mater., 140(2), 1241-1242 (1995) (Phase
Relations, Electr. Prop., Experimental, 12)
[1996Hau] Hauser, R., Naber, L., Schaudy, G., Bauer, E., Hilscher, G., Kindler, B., Assmus, W.,
Pressure and Field Dependent Studies of Single-Crystalline YbCu4In, Czechoslov.
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[1996Law] Lawrence, J.M., Kwei, G.H., Sarrao, J.L., Fisk, Z., Mandrus, D., Thompson, J.D., Structure
and Disorder in YbInCu4, Phys. Rev. B, 54(9), 6011-6014 (1996) (Crys. Structure,
Electronic Structure, Experimental, 7)
[1996Oku] Okusawa, M., Weschke, E., Meier, R., Kaindl, G., Ishii, T., Sato, N., Komatsubara, T.,
Temperature Dependence of the Valence-Band Photoemission Spectra in YbInCu4,
J. Electron Spectrosc. Relat. Phenom., 78, 139-142 (1996) (Crys. Structure,
Experimental, 12)
[1996Ter] De Teresa, J.M., Arnold, Z., del Moral, A., Ibarra, M.R., Kamarad, J., Adroja, D.T.,
Rainford, B., Pressure and Magnetic Field Effects on the Volume Anomaly Associated
with First-Order Valence Change in YbInCu4, Solid State Commun., 99(12), 911-915
[1997Avi] Aviani, I., Miljak, M., Zlatic, V., Finsterbusch, D., Assmus, W., Luthi, B., Magnetic
Properties of YbInCu4, Physica B, 230, 275-278 (1997) (Magn. Prop., Experimental, 8)
[1997He] He, J.H., Tsujii, N., Yoshimura, K., Kosuge, K., Goto, T., Crossover from First-Order
Valence Transition to Kondo Behavior in C15b-Type YbCu5-xInx System, J. Phys.
Soc. Jpn., 66(8), 2481-2486 (1997) (Crys. Structure, Electr. Prop., Magn. Prop.,
Experimental, 23)
[1997Imm] Immer, C.D., Sarrao, J.L., Fisk, Z., Lacerda, A., Mielke, C., Thompson, J.D.,
Magnetic-Field, Pressure, and Temperature Scaling of the First-Order Valence Transition
in Pure and Doped YbInCu4, Phys. Rev. B, 56(1), 71-74 (1997) (Magn. Prop.,
Experimental, 28)
[1997Law] Lawrence, J.M., Shapiro, S.M., Sarrao, J.L., Fisk, Z., Inelastic Neutron Scattering in
Single-Crystal YbInCu4, Phys. Rev. B, 55(21), 14467-14472 (1997) (Electronic Structure,
Experimental, 14)
[1997Ret] Rettori, C., Oseroff, S.B., Rao, D., Pagliuso, P.G., Barberis, G.E., Sarrao, J., Fisk, Z.,
Hundley, M., ESR of Gd3+ in the Intermediate-Valence YbInCu4 and its Reference
Compound YInCu4, Phys. Rev. B, 55(2), 1016-1020 (1997) (Electronic Structure,
Experimental, 33)
[1998Fis] Fischbach, E., Loeffert, A., Ritter, F., Assmus, W., Thermoanalytical Investigations to
Understand the Dependence Between the Growth Method and Crystal Properties of Valence
Changing YbInCu4, Cryst. Res. Technol., 33(2), 267-273 (1998) (Phase Relations,
Experimental, 7)
[1998Kal] Kalychak, Ya.M., Isothermal Cross Sections of Phase Diagrams and Crystal Structure of
the Compounds for REM-Cu-In Systems, Russ. Metall., 4, 138-148 (1998) (Crys.
Structure, Phase Relations, Review, 32)
[1998Nak] Nakamura, H., Nishiuma, S., Shiga, M., Kindler, B., Ritter, F., Assmus, W., Copper and
Indium Knight Shifts Above and Below First-Order Valence Transition in YbInCu4,
J. Phys.: Condens. Matter., 10(40), 9123-9127 (1998) (Electronic Structure,
Experimental, 7)
[1998Rei] Reinert, F., Claessen, R., Nicolay, G., Ehm, D., Hufner, S., Ellis, W.P., Gweon, G.H., Allen,
J.W., Kindler, B., Assmus, W., Photoemission Experiments on YbInCu4: Surface Effects
and Temperature Dependence, Phys. Rev B, 58(19), 12808-12816 (1998) (Electronic
Structure, Phys. Prop., Experimental, 44)
Landolt-Brnstein
New Series IV/11C2
MSIT
304 CuInYb
[1998Sar] Sarrao, J.L., Ramirez, A.P., Darling, T.W., Freibert, F., Migloiri, A., Immer, C.D., Fisk, Z.,
Uwatoko, Y., Thermodynamics of the First-Order Valence Transition in YbInCu4, Phys.
Rev. B: Condens. Matter, 58(1), 409-413 (1998) (Thermodyn., Experimental, 27)
[1999Joy] Joyce, J.J., Arko, A.J., Sarrao, J.L., Graham, K.S., Fisk, Z., Riseborough, P.S.,
Photoemission from YbInCu4: Testing the Single Impurity Model, Philos. Mag. B, 79(1),
1-8 (1999) (Electronic Structure, Phase Relations, Experimental, 21)
[1999Law] Lawrence, J.M., Osborn, R., Sarrao, J.L., Fisk, Z., Time-of-Flight Neutron-Scattering
Study of YbInCu4 and YbIn0.3Ag0.7Cu4, Phys. Rev B, 59(2), 1134-1140 (1999) (Electronic
Structure, Magn. Prop., Thermodyn., Experimental, 19)
[1999Loe1] Loeffert, A., Aigner, M.L., Ritter, F., Assmus, W., Elements of the Phase Diagram of
YbInCu4, Cryst. Res. Technol., 34(2), 267-271 (1999) (Phase Relations, Experimental,
#, 8)
[1999Loe2] Loeffert, A., Hautsch, S., Ritter, F., Assmus, W., The Phase Diagram of YbInCu4,
Physica B (Amsterdam), 259-261, 134-135 (1999) (Phase Relations, Experimental, #, 6)
[1999Sar] Sarrao, J.L., Physics of YbInCu4 and Related Compounds, Physica B, 261, 128-133
(1999) (Crys. Structure, Phys. Prop., Thermodyn., Experimental, 38)
[1999Smi] Smirnov, I.A., Parfen'eva, L.S., Jezowski, A., Misiorek, H., Krempel-Hesse, S., Ritter, F.,
Assmus, W., Thermal Conductivity of YbInCu4, Phys. Solid State, 41(9), 1418-1421
(1999) (Phase Relations, Electr. Prop., Experimental, 24)
[1999Sok] Sokolov, A.Y., Nakamura, H., Shiga, M., Magnetostriction of Ytterbium-Based Kondo
Compounds YbXCu4 (X = In, Ag and Au), J. Phys.: Condens. Matter, 11(33), 6463-6473
[1999Sve1] Svechkarev, I.V., Dolya, S.N., The Role of Chemical Disorder in the Magnetism of
YbInCu4 Compound, Low Temp. Phys., 25, 889-894 (1999) (Magn. Prop.,
Experimental, 29)
[1999Sve2] Svechkarev, I.V., Panfilov, A.S., Dolja, S.N., Nakamura, H., Shiga, M., Effect of Pressure
on Magnetic Susceptibility in YbInCu4 Compound, J. Magn. Magn. Mater., 197, 893-894
(1999) (Magn. Prop., Phase Relations, Experimental, 10)
[1999Sve3] Svechkarev, I.V., Panfilov, A.S., Dolja, S.N., Nakamura, H., Shiga, M., The Effect of
Pressure on the Magnetic Susceptibility of RInCu4 (R = Gd, Er and Yb), J. Phys.: Condens.
Matter, 11(22), 4381-4390 (1999) (Magn. Prop., Phase Relations, Experimental, 44)
[2000Dze] Dzero, M.O., Gor'kov, L.P., Zvezdin, A.K., First-Order Valence Transition in YbInCu4 in
the (B, T)-Plane, J. Phys.: Condens. Matter, 12(47), L711-L717 (2000) (Calculation,
Phase Relations, Experimental, 23)
[2000Gar] Garner, S.R., Hancock, J.N., Rodriguez, Y.W., Schlesinger, Z., Bucher, B., Fisk, Z., Sarrao,
J.L., Optical Study of the Electronic Phase Transition of Strongly Correlated YbInCu4,
Phys. Rev. B, 62(8), R4778-R4781 (2000) (Phase Relations, Experimental, 32)
[2000Goe] Goedecke, T., Haalboom, T., Ernst, F., Phase Equilibria of Cu-In-Se. II. The
In-I2Se3-Cu2Se-Cu Subsystem, Z. Metallkd., 91(8), 635-650 (2000) (Experimental, Phase
Relations, 13)
[2000Hir] Hiraoka, K., Murakami, K., Tomiyoshi, S., Hihara, T., Shinohara, T., Kojima, K., 63Cu
NQR and 113Cd NMR Studies of YbMCu4 (M = In, Cd), Physica B (Amsterdam), 281-282,
173-174 (2000) (Phys. Prop., Experimental, 5)
[2000Moo] Moore, D.P., Joyce, J.J., Arko, A.J., Sarrao, J.L., Morales, L., Hochst, H., Chuang, Y.D.,
Bulk Electronic Structure of YbInCu4 from Photoemission: A Unique Test of the Single
Impurity Model, Phys. Rev. B, 62(24), 16492-16499 (2000) (Phase Relations,
Experimental, 26)
[2000Yos] Yoshimura, K., Tsujii, N., Sorada, K., Kawabata, T., Mitamura, H., Goto, T., Kosuge, K.,
Systematics of Mixed Valence and Heavy Fermion Behaviors in YbCu5 and Related
Systems, Physica B (Amsterdam), 281-282, 141-143 (2000) (Crys. Structure, Phys. Prop.,
Experimental, 13)
New Series IV/11C2
CuInYb 305
[2001Gio] Giovannini, M., Bauer, E., Michor, H., Hilscher, G., Galatanu, A., Saccone, A., Rogl, P.,
Characterization and Physical Properties of the Indides Yb2T2In (T = Cu, Pd, Au),
Intermetallics, 9, 481-485 (2001) (Crys. Structure, Magn. Prop., Experimental, 12)
[2001Koy] Koyama, T., Matsumoto, M., Wada, S., Sarrao, J.L., Yb-171 and Cu-63 Magnetic
Resonance Studies on the Fluctuating Valence Compound YbInCu4, Phys. Rev. B, 63(17),
Art. No. 172410 (2001) (Electronic Structure, Magn. Prop., Experimental, 25)
[2001Rei] Reinert, F., Claessen, R., Nicolay, G., Ehm, D., Hufner, S., Ellis, W.P., Gweon, G.H., Allen,
J.W., Kindler, B., Assmus, W., Reply to Comment on Photoemission Experiments on
YbInCu4: Surface Effects and Temperature Dependence, Phys. Rev. B, 63(19), Art. No.
197102 (2001) (Electronic Structure, Experimental, 16)
[2001Sus] Susaki, T., Fujimori, A., Okusawa, M., Sarrao, J.L., Fisk, Z., High-Resolution
Photoemission Study of the Valence Transition in YbInCu4, Solid State Commun., 118(8),
413-417 (2001) (Electronic Structure, Phase Relations, Experimental, 18)
[2001Tsu] Tsujii, N., Kito, H., Kitazawa, H., Kido, G., High-Pressure Synthesis of Yb2Cu2In and its
Physical Properties, J. Alloys Compd., 322, 74-76 (2001) (Crys. Structure, Magn. Prop.,
Experimental, 6)
[2002Dze1] Dzero, M.O., Gor'kov, L.P., Zvezdin, A.K., Entropy First Order Transition in YbInCu4,
Physica B. Condens. Matter., 312, 321-323 (2002) (Phase Relations, Theory, Magn. Prop.)
cited from abstract
[2002Dze2] Dzero, M., Crystall Field Effects in the First Order Valence Transition in YbInCu4 Induced
by External Magnetic Field, Int. J. Mod. Phys. B, 16(20-22), 3306-3306 (2002) (Phase
Relations, Theory, Magn. Prop.) cited from abstract
[2002Jai] Jaime, M., Movshovich, R., Harrison, N., Sarrao, J.L., Two Energy Scales in YbInCu4
from Specific Heat in High Magnetic Fields, Physica B: Condens. Matter., 312-313,
344-345 (2002) (Magn. Prop., Thermodyn., Experimental, 7)
[2002Koy] Koyama, T., Matsumoto, M., Tanaka, T., Ishida, H., Mito, T., Wada, S., Sarrao, J.L.,
Physical Properties of the Dense Kondo Compounds YbXCu4 (X = Au, Ag, In, Cd, Tl, and
Mg) Probed by 63Cu NMR, Phys. Rev. B: Condens. Matter, 66(1), 014420-1-014420-9
[2002Mur] Murani, A.P., Richard, D., Bewley, R., Transformations in the Ground and Excited
Spin-Orbit Multiplets at the -> Phase Transition in YbInCu4, Phys. B: Condens.
Matter, 312, 346-348 (2002) (Electronic Structure, Phase Relations, Experimental, 9)
[2002Par] Parfen'eva, L.S., Smirnov, I.A., Misiorek, H., Mucha, J., Jezowski, A., Ritter, F., Assmus,
W., Unusual Behavior of the Lattice Thermal Conductivity and of the Lorenz Number in
the YbIn1xCu4+x System, Phys. Solid State, 44(7), 1212-1217 (2002) (Electronic
Structure, Electr. Prop., Experimental, 14)
[2002Rog] Rogl, P., Van Rompaey, T., Cu-Yb (Copper-Ytterbium), MSIT Binary Evaluation
Program, in MSIT Workplace, Effenberg, G., (Ed.), MSI, Materials Science International
Services, GMBH, Stuttgart; Document ID: 20.13889.1.20 (2002) (Crys. Structure, Phase
[2002Sat] Sato, H., Nishikawa, Y., Nagasaki, F., Fujino, H., Takeda, Y., Arita, M., Shimada, K.,
Namatame, H., Kimura, A., Taniguchi, M., Hiraoka, K., Kojima, K.,
Temperature-Dependent High-Resolution Photoemission Spectroscopy of YbXCu4
(X = In, Cd, Mg), Surf. Rev. Letters, 9(2), 1079-1083 (2002) (Electronic Structure,
Experimental) cited from abstract
[2002Uch] Uchida, A.H., Kosaka, M., Mori, N., Malsumoto, T., Uwatoko, Y., Sarray, J.L., Thompson,
J.D., Effect of Pressure on the Electrical Resistivity of a Single Crystal of YbInCu4,
Phys. B: Condens. Matter, 312-313, 339-340 (2002) (Electr. Prop., Experimental, 6)
[2002Zha1] Zhang, W., Sato, N., Yoshimura, K., Mitsuda, A., Goto, T., Kosuge, K., Effect of Pressure
and Substitution for Yb on the First-Order Valence Transition in YbInCu4, Phys. Rev. B,
66(2), Art. No. 024112 (2002) (Crys. Structure, Magn. Prop., Experimental) cited from
abstract
Landolt-Brnstein
New Series IV/11C2
MSIT
306 CuInYb
[2002Zha2] Zhang, W., Sato, N., Yoshimura, K., Mitsuda, A., Sorada, K., Mitamura, H., Goto, T.,
Kosuge, K., Effect of Partial Substitution of Yb on Valence Transition of YbInCu4,
J. Phys. Chem. Solids, 63(6-8), 1215-1218 (2002) (Magn. Prop., Experimental) cited from
abstract
[2003Fre] Freericks, J.K., Zlatic, V., Application of the Multicomponent Falicov-Kimball Model to
Intermediate-Valence Materials: YbInCu4 and EuNi2(Si1-xGex)(2), Phys. Status Solidi B,
236(2), 265-271 (2003) (Electronic Structure, Experimental) cited from abstract
[2003Hed] Hedo, M., Uwatoko, Y., Matsumoto, T., Sarrao, J.L., Thompson, J.D., The Restraint of
Valence Transition in YbInCu4 by High Pressure, Acta Phys. Pol. B, 34(2), 1193-1196
(2003) (Electr. Prop., Experimental) cited from abstract
[2003Luk] Lukachuk, M., Poettgen, R., Intermetallic Compounds with Ordered U3Si2 or Zr3Al2 Type
Structure - Crystal Chemistry, Chemical Bonding and Physical Properties, Z. Kristallogr.,
218, 767-787 (2003) (Crys. Structure, Electr. Prop., Magn. Prop., Review,
Thermodyn., 197)
[2003Mis] Misiorek, H., Mucha, J., Golubkov, A.V., Parfenieva, L.S., Smirnov, I.A., Assmus, W.,
Ritter, F., Transport Properties of Heavy Fermion Compounds: YbIn1xCu4+x and
YbIn1yAgyCu4, Int. J. Thermophys., 24(5), 1415-1426 SI (2003) (Electronic Structure,
Electr. Prop., Magn. Prop., Experimental) cited from abstract
[2003Mit] Mito, T., Koyama, T., Shimoide, M., Wada, S., Muramatsu, T., Kobayashi, T.C., Sarrao,
J.L., Magnetic Ordering in the Pressure-Stabilized High-Temperature Phase of YbInCu4,
Phys. Rev. B: Condens. Matter, 67(22), 224409-1-224409-5 (2003) (Electr. Prop., Magn.
Prop., Phase Relations, Experimental, 20)
[2003Mor] Moriyoshi, C., Shimomura, S., Itoh, K., Kojima, K., Hiraoka, K., Crystal Structure and
Valence Transition Temperature of YbInCu4 Single Crystals, J. Magn. Magn. Mater., 260,
206-210 (2003) (Calculation, Crys. Structure, Electr. Prop., Electronic Structure,
Experimental, 10)
[2003Mus1] Mushnikov, N.V., Goto, T., Rozenfeld, E.V., Yoshimura, K., Zhang, W., Yamada, M.,
Kageyama, H., Magnetic Anisotropy of Pure and Doped YbInCu4 Compounds at Ambient
and High Pressures, J. Phys.: Condens. Matter, 15(17), 2811-2823 (2003) (Calculation,
Electronic Structure, Magn. Prop., Phase Relations, Experimental, 32)
[2003Mus2] Mushnikov, N.V., Goto, T., Yoshimura, K., Zhang, W., B-T Phase Diagram of Pure and
Doped YbInCu4, Phys. B, Condens. Matter, 334(1-2), 54-59 (2003) (Electronic Structure,
Magn. Prop., Experimental) cited from abstract
[2003Wad] Wada, S., Mito, T., Koyama, T., Kobayashi, T.C., Muramatsu, T., Sarrao, J.L., Transport,
Ac-Susceptibility and PQR Measurements of Strongly Electron Correlated Compound
YbInCu4 at High Pressures, Int. J. Modern Phys. B, 17(18-20), 3661-3663 Part 2 (2003)
(Electronic Structure, Electr. Prop., Magn. Prop., Phys. Prop., Experimental) cited from
abstract
[2004Got] Goto, T., Mushnikov, N.V., Rozenfeld, E.V., Yoshinmura, K., Zhang, W., Anisotropic
Magnetization Processes of Pure YbInCu4 Compounds at Ambient and High and Doped
Pressures, Phys. B: Condens. Matter, 346, 150-154 (2004) (Calculation, Electronic
Structure, Magn. Prop., Phase Relations, Experimental) cited from abstract
[2004Mus1] Mushnikov, N.V., Magnetoelastic Effects and Magnetic Anisotropy in a Compound
YbInCu4 with Variable Valence, Phys. Met. Metallogr., 98, S70-S77 Suppl. 1 (2004)
(Electronic Structure, Magn. Prop., Experimental) cited from abstract
[2004Mus2] Mushnikov, N.V., Goto, T., High-Field Magnetostriction of the Valence-Fluctuating
Compound YbInCu4, Phys. Rev. B, 70(5), Art. No. 054411 (2004) (Electronic Structure,
[2004Sat1] Sato, H., Shimada, K., Arita, M., Hiraoka, K., Kojima, K., Takeda, Y., Yoshikawa, K.,
Sawada, M., Nakatake, M., Namatame, H., Taniguchi, M., Takata, Y., Ikenaga, E., Shin, S.,
Kobayashi, K., Tamasaku, K., Nishino, Y., Miwa, D., Yabashi, M., Ishikawa, T., Valence
Transition of YbInCu4 Observed in Hard X-Ray Photoemission Spectra, Phys. Rev.
New Series IV/11C2
CuInYb 307
Letters, 93(24), Art. No. 246404 (2004) (Electronic Structure, Experimental) cited from
abstract
[2004Sat2] Sato, H., Shimada, K., Arita, M., Takeda, Y., Sawada, M., Nakatake, M., Yoshikawa, K.,
Namatame, H., Takata, Y., Kobayashi, K., Ikenega, E., Shin, S., Yabashi, M., Miwa, D.,
Nishino, Y., Tamasaku, K., Ishikawa, T., Hiraoka, K., Kojima, K., Taniguchi, M., Hard
X-Ray Photoemission Spectroscopy of YbInCu4, Phys. B, Condens. Matter, 351(3-4),
298-300 (2004) (Electronic Structure, Experimental) cited from abstract
[2004Sat3] Sato, H., Yoshikawa, K., Hiraoka, K., Arita, M., Fujimoto, K., Kojima, K., Muro, T., Saitoh,
Y., Sekiyama, A., Suga, S., Taniguchi, M., Soft-x-Ray High-Resolution Photoemission
Study on the Valence Transitions in YbInCu4, Phys. Rev. B, 69(16), Art. No. 165101
(2004) (Electronic Structure, Experimental) cited from abstract
[2004Yos] Yoshikawa, K., Sato, H., Tsuji, K., Arita, M., Takeda, Y., Namatame, H., Taniguchi, M.,
Hiraoka, K., Kojima, K., Electronic States Near the Fermi Edge of YbInCu4, Phys. B,
Condens. Matter, 351(3-4), 301-303 (2004) (Electronic Structure, Experimental) cited from
abstract
[2005Kal] Kalychak, Ya.M., Zaremba, V.I., Pttgen, R., Lukachuk, M., Hoffmann, R., Rare
Earth-Transition Metal-Indides in Handbook on the Physics and Chemistry of Rare
Earths, 34, 1-133 (2005) (Crys. Structure, Phys. Prop., Phase Relations, Phase Diagram,
Review, #, 402)
[2005Koy] Koyama, T., Nakamura, M., Mito, T., Wada, S., Sarrao, J.L., Valence and Magnetic
Transitions in YbInCu4 Probed Using Cu-63 Nuclear Quadrupole Resonance under High
Pressure, J. Phys.: Condens. Matter, 17(11), S901-S904 SI (2005) (Electronic Structure,
Table 1: Investigations of the Cu-In-Yb Phase Relations, Structures and Thermodynamics

Range Studied
[1987Adr] X-ray powder diffraction YbCu4In
Neutron diffraction
[1987Fel1] X-ray diffraction study 4.2 - 300 K / Yb0.4In0.6Cu2
Neutron diffraction/IRR-2 nuclear reactor 10 and 300 K / Yb0.4In0.6Cu2
X-ray absorption/EXAFS-II 6 - 300 K / Yb0.4In0.6Cu2
Specific-heat measurements 4.2 - 80 K / Yb0.4In0.6Cu2
[1987Fel2] X-ray powder diffraction YbxIn1xCu2, x = 0.3, 0.4, 0.45,
0.5, 0.55
[1989Sys] X-ray single crystal and powder diffraction/DRON-3.0 YbCu5.1In6.9
Laue method
Weissenberg method
[1989Koj] X-ray analysis YbxIn1xCu2, x = 0.4 and 0.5
Electron probe X-ray microanalysis
[1990Koj] X-ray powder diffraction/ Rigaku RAD-IIC 4.2 - 300 K / YbCu4In
diffractometer
TOF neutron powder diffraction/HRP diffractometer
[1992Gra] Pressure dependence of the Cu-63 NQR YbCu4In
[1992Mat] X-ray powder diffraction YbCu4In
Landolt-Brnstein
New Series IV/11C2
MSIT
308 CuInYb

Range Studied
[1993Nak] Magnetic susceptibility, electrical resistivity and low 1.5 - 300 K, YbCu4In
temperature specific heat
[1994Bau] Transport and magnetic properties YbCu4In
[1994Kin] Magnetic susceptibility, electrical resistivity and X-ray YbCu4In
study of single crystal
[1994Oom] X-ray diffraction at high pressure Room temperature, YbCu4In
3+
[1995Alt] Gd - ESR and the static susceptibility 1.5 - 300 K, YbCu4In
[1995Koj] Electrical resistance as a function of temperature under 4.2 - 300 K, YbCu4In
various pressures
[1996Hau] Pressure and field dependent study of magnetic 20 - 295 K, YbCu4In
susceptibility, electrical resistivity and low
temperature specific heat
[1996Law] Rietveld refinement of structure based on the neutron 20 - 295 K, YbCu4In
diffraction results
[1996Oku] Valence-band photoemission spectra measurement 4.2 - 300 K, YbCu4In
[1996Ter] Volume thermal expansion measurements, effect of 4.2 - 300 K, YbCu4In
pressure and magnetic field on magnetic properties
[1997He] Electrical resistivity, magnetic susceptibility and high YbInxCu5x, 0.1 x 1.0
field magnetization measurements
[1997Imm] High-field magnetoresistance under high pressure 4.2 - 300 K, YbCu4In
[1997Law] Inelastic neutron scattering YbCu4In
[1997Avi] Magnetic anisotropy and the susceptibility of single YbCu4In
crystals, using the torque and Faraday method
[1997Ret] Electron-spin resonance measurements YbCu4In
[1998Fis] X-ray powder diffraction/ Siemens D500 10 - 350 K / YbCu4In
Thermoanalytical measurements/Netzsch STA 409
thermoanalyser
DTA, SEM and EDX analyses/Zeiss DSM 940A
scanning electron microscope, EDAX 9800
[1998Kal] X-ray powder/ DRON-2.0, DRON-3.0, HZG-4a 670 K / Cu-In-Yb in the whole
diffractometers and single crystal/SyntexP2 concentration range
diffractometer phase analysis, Laues method,
Weissenberg method, Debye-Scherrer method,
Microstructural analysis, Microhardness
measurements
[1998Nak] Cu-63 and In-115 Knight shifts YbCu4In
[1998Rei] Temperature-dependent photoemission measurements Single-crystalline YbCu4In
[1998Sar] Specific heat investigations/Standard semiadiabatic YbCu4In
heat pulse technique. Pressure-dependent magnetic
susceptibility
[1999Joy] High resolution photoelectron spectroscopy YbCu4In
New Series IV/11C2
CuInYb 309

Range Studied
[1999Law] Neutron-scattering in the time-of-flight mode, 30 K and 60 K, YbCu4In
magnetic susceptibility
[1999Loe1] Wavelength dispersive X-ray analysis, DTA YbCu4In
[1999Loe2] Wavelength dispersive X-ray analysis, DTA YbCu4In
[1999Sar] X-ray powder diffraction 1.5 - 20 K, YbCu4In
Specific heat measurements/thermal relaxation
technique
X-ray absorption study (Stanford Synchrotron
Radiation Laboratory)
[1999Sok] Magnitostriction measurements, using the 5 - 100 K, YbCu4In
three-terminal capacitance method up to magnetic field
of 8 T
[1999Smi] Electrical and thermal conductivity 4.2 - 300 K, YbCu4In
[1999Sve2] Magnetic susceptibility under helium pressure up to 2 78, 50 and 300 K, YbCu4In
[1999Sve3] kbar
[2000Gar] Infrared, visible and near-UV reflectivity YbCu4In
measurements
[2000Hir] X-ray single crystals and powder diffraction/flux YbCu4In
method
[2000Moo] Photoelectron spectroscopy YbCu4In
[2001Gio] X-ray diffraction Yb2Cu2In
Metallographic examination
SEM and EPMA analyses
Specific heat measurements
[2001Koy] Nuclear magnetic resonance 1.9 - 4.2 K, YbCu4In
[2001Rei] Temperature-dependent photoemission spectroscopy YbCu4In
at photon energies of h = 1486 eV (XPS)
[2001Sus] High-resolution photoemission spectroscopy 4.2 - 100 K, YbCu4In
[2001Tsu] X-ray powder diffraction Yb2Cu2In
[2002Jai] Measuring of specific heat in the high magnetic field YbCu4In
by means of the adiabatic calorimeter
[2003Hed] Electrical resistivity under high pressures Up to 33 mK, YbCu4In
[2002Koy] 63Cu NMR study, superconducting-quantum 10 - 300 K, YbCu4In
interference magnetometer
[2002Mur] Inelastic neutron scattering YbCu4In
[2002Par] Low-temperature X-ray diffractometry, total thermal 4 - 300 K, YbIn0.905Cu4.095 -
conductivity, electrical resistivity YbCu4In
[2002Sat] Photoemission spectroscopy 10 - 300 K. YbCu4In
Landolt-Brnstein
New Series IV/11C2
MSIT
310 CuInYb

Range Studied
[2002Uch] Temperature-dependent electrical resistivity 1.5 - 300 K, YbCu4In
measurements under hydrostatic pressure to p = 3.3
GPa
[2002Zha1] Temperature dependence of magnetic susceptibility in 2 - 320 K, YbCu4In
[2002Zha2] the magnetic field of 0.2 T and high-field
magnetization up to 41 T under various fixed pressures
[2003Luk] X-ray single crystal diffraction Yb2Cu2In
Czochralski technique
[2003Mis] Thermal conductivity 4.2 - 300 K, YbCu4+xIn1x,
x = 0, 0.015, 0.095, 0.17
[2003Mit] Electrical resistivity and ac-susceptibility at high 1.5 - 100 K, YbCu4In
pressures
[2003Mor] X-ray single crystal diffraction YbCu4In
Bridgman method
Wavelength dispersive X-ray analysis/JCMA-733 II
[2003Mus1] X-ray single crystal diffraction/Laue diffractometer, 1.5 - 100 K, YbCu4In
[2003Mus2] magnetic susceptibility and high field magnetization of
single crystalline samples have been measured for
different field orientations at ambient and high
pressures
[2003Wad] Electrical resistivity, static susceptibility, Cu-63 1.5 - 100 K, YbCu4In
pure-quadrupole-resonance at high pressures
[2004Got] High-field magnetization Single crystalline YbCu4In
[2004Mus1] Pressure effect on magnetic susceptibility Single crystalline YbCu4In
[2004Mus2] Magnetization and magnetostriction in pulsed 4.2 - 120 K, YbCu4In
magnetic fields up to 40 T
[2004Sat1] High-resolution photoemission spectroscopy 1.5 - 220 K, YbCu4In
[2004Sat2]
[2004Sat3]
[2004Yos] High resolution low-energy excited photoemission YbCu4In
spectroscopy
[2005Koy] Cu-63 NQR measurements under pressure up to 2.5 1.5 - 250 K, YbCu4In
GPa
New Series IV/11C2
CuInYb 311

[C] Prototype
(Yb) cI2 a = 444 [Mas2]
819 - 795 Im3m no appreciable solid solubility of Cu in
W (Yb),
dissolves up to ~2 at.% In at 750C
(Yb) cF4 a = 548.5 [Mas2]
795 - (3) Fm3m dissolves up to ~3 at.% In at 750C
Cu
(Yb) hP2 a = 301.5 [Mas2]
< 3 P63/mm c = 482.3
Mg
(Cu) cF4 a = 361.46 pure Cu at 25C [Mas2]
Cu dissolves up to 0.03 at.% Yb at 859C
dissolves 10.9 at.% at 574C
(In) tI2 a = 325.3 pure In at 25C [Mas2]
I4/mmm c = 494.7 no appreciable solid solubility of Cu and
In Yb in (In)
, Cu4In cI2 a = 301.40 20.50 at.% In at 625C [1994Sub]
710 - 574 Im3m a = 304.61 18.64 at.% In at 672C [1941And]
W
, Cu7In3 aP40 a = 107.1 30.0 at.% In [1980Vro]
< 631 P1 b = 913.1
Cu7In3 c = 672.6
= 90.2
= 90.4
= 106.82
a = 1000 29.6 at.% In [1994Sub]
b = 910
c = 672
= 89.9
= 82.6
= 106.9
, Cu9In4 cP52 a = 925.03 29.6 at.% In at 650C [1951Rey]
684 - 631 P43m
InMn3 or Al4Cu9
1, Cu2In hP6 a = 412.0 [V-C2]
667 - 440 P63/mmc c = 526.3
Ni2In
480 - 350 ? b = 740.5 type
c = 521.8
Landolt-Brnstein
New Series IV/11C2
MSIT
312 CuInYb

[C] Prototype
450 - 298 ? b = 739.5 type
c = 526.2
4, Cu7In4(r) - - [1972Jai]
< 389
5, Cu15In8 - - [1972Jai]
< 350
YbCu oP8 a = 756.53 [2002Rog]
< 628 Pnma b = 425.53
FeB c = 576.67
YbCu2 oI12 a = 428.6.6 to [2002Rog]
< 757 Imma 429.1
CeCu2 b = 689.4 to 689.9
c = 738.2 to 738.6
YbCu2(HP) hP12 a = 526.0 0.5 [2002Rog]
P63/mm c = 856.7 0.8
MgZn2
Yb2Cu7 - - [2002Rog]
Yb2Cu9 mC7448 a = 4896.1 Monoclinic superstructure derived from
< 937 C2* b = 4899.4 cubic AuBe5 type via the introduction of
Yb2Cu9 c = 4564.3 anti-phase boundaries and
= 91.24 copper-deficient shear planes [2002Rog]
YbCu6.5 hP6 a = 499.2 to 500 [2002Rog], the composition Yb2Cu13
< 879 P6/mmm c = 412.6 to 413 was attributed to a structure described
CaCu5 with same lattice parameter with a
random substitution of 18% of Yb-sites
by Cu-pairs
YbCu5 cF24 a = 696.9 prepared at 1.5 GPa, 1000C, but also
P6/mmm found in as-cast alloys prepared under
AuBe5 ambient pressure [2002Rog]
Yb6Cu23(HP) cF116 a = 1203 1 [2002Rog]
Fm3m
Th6Mn23
Yb5In2 hR132 a = 954.5 0.1 [Mas2]
< 810 R3c c = 5427.2 0.7 [V-C2] gives stoichiometry Yb8In3
Yb5In2
Yb2In oP12 a = 707.2 0.2 [V-C2], [Mas2]
< 820 Pnma b = 534.0 0.1
Co2Si c = 986.6 0.5
YbIn cP2 a = 380.76 0.04 [V-C2], [Mas2]
< 1067 Pm3m
CsCl
New Series IV/11C2
CuInYb 313

[C] Prototype
YbIn2 hP6 a = 489.08 0.03 [V-C2], [Mas2]
< 890 P63/mm c = 764.06 0.09
CaIn2
YbIn3 cP4 a = 461.5 0.1 [V-C2], [Mas2]
< 630 Pm3m
AuCu3
* -1, YbCu5.1In6.9 tI26 a = 921.9 [1998Kal, 2005Kal]
I4/mmm c = 538.9
ThMn12
* cF24 a = 703.5 to 714.5 [1998Kal, 2005Kal]
-2,YbCu4.84.0In0.21.0 F43m
MgCu4Sn
* -3, Yb2Cu2In oI10 a = 438.8 0.5 [2001Gio]
Immm b = 574.30 0.06
W2CoB2 c = 873.37 0.09
* -3, Yb2Cu2In (I) tP10 a = 747.3 [2001Tsu],
P4/mbm c = 389.2 prepared under a pressure of 3.5 GPa at
Mo2B2Fe 600C
* -4, Yb3CuIn2 - - [1998Kal, 2005Kal]
* -5, Yb4CuIn - - [1998Kal, 2005Kal]
Table 3: Investigations of the Cu-In-Yb Materials Properties

[1987Fel1] Magnetic and electrical investigations Magnetic susceptibility and electrical
Mssbauer spectroscopy resistivity
For 170Yb isotope
[1987Fel2] Magnetic study/RAR vibrating sample Susceptibility
magnetometer
[1989Koj] Magnetic measurements Magnetic susceptibility
[1992Mat] Magnetic and electrical investigations Magnetic susceptibility, electrical resistivity
as a function of pressure and temperature
63
[1992Gra] Cu NQR YbCu4In
[1997Avi] Torque and Faraday methods Magnetic anisotropy and susceptibility
[1998Sar] Calorimetry, pressure-dependent magnetic Specific heat, complete elastic moduli,
measurements magnetic susceptibility, Gruneisen parameter
[1999Law] Neutron scattering experiments Magnetic susceptibility
[1999Sar] Magnetic study/ superconducting - quantum Magnetic susceptibility,
- interference - device magnetometer Magnetization measurements
Electrical measurements Resistivity
[1999Smi] Measurement of transport properties Electrical and thermal conductivity
Landolt-Brnstein
New Series IV/11C2
MSIT
314 CuInYb

[1999Sok] Three-terminal capacitance method Magnetostriction
63
[2000Hir] Cu NQR YbCu4In
NMR measurements /conventional phase Magnetic susceptibility
coherent pulsed spectrometer
[2000Yos] Magnetic study Magnetic susceptibility
[2001Tsu] Magnetic measurements / superconducting - Magnetic susceptibility
quantum - interference - device
magnetometer
[2001Gio] Magnetic and electrical investigations Magnetic susceptibility, electrical resistivity
[2002Par] Measurements of transport properties Total thermal conductivity and electrical
resistivity
[2002Uch] Electrical measurements Electrical resistivity
63
[2002Koy] Cu NMR Magnetic susceptibility
Magnetic study
[2003Luk] Magnetic and resistivity measurements Magnetic susceptibility and electrical
resistivity
[2003Mit] Magnetic and resistivity measurements Electrical resistivity, ac susceptibility at high
pressures
[2003Mis] Measurements of transport properties Thermal conductivity and electrical
resistivity
[2003Mor] Electrical investigations Electrical resistivity
[2003Mus1] Magnetic measurements, Susceptibility and high-field magnetization
[2003Mus2] superconducting-quantum-interference-devi at ambient and high pressures
ce magnetometer
[2003Wad] Measurements of magnetic properties in the Magnetization and magnetostriction at high
pulsed magnetic field pressures
New Series IV/11C2
CuInYb 315
Yb 0.00
Cu 60.00
In 40.00 Data / Grid: at.%
Fig. 1: Cu-In-Yb. Axes: at.%
Liquidus isotherms in
the vicinity of the
Yb2Cu9-YbCu4In
section
10
30
20
20
30
10
Yb 40.00 70 80 90
Cu
Cu 60.00
In 0.00
In Data / Grid: at.%

400C
20
80
YbIn2
Yb8In3
40
60
YbIn
1
60
40
Yb2In 2
3
4
YbIn3

80 3 20
5
Yb
20 40
YbCu
60 YbCu2 80
Cu
YbCu5Yb2Cu13
Landolt-Brnstein
New Series IV/11C2
MSIT
316 CuInYb
10
Fig. 3: Cu-In-Yb.
The temperature
-pressure phase
diagram for
8.0
YbCu4In.
TV - temperature of
valence transition,
TM - temperature of
Temperature, K
magnetic transition 6.0

TV
4.0
TM
2.0
0
2.1 2.2 2.3 2.4 2.5 2.6 2.7
Pressure, GPa
Fig. 4: Cu-In-Yb.
The calculated
magnetic phase 40
[100]
diagram for YbCu4In
[111]
[110]
30
Temperature, K
20
10
0
0 10 20 30
Magnetic field, T
New Series IV/11C2
CuInYb 317
Yb 12.00
Cu 64.00
In 24.00 Data / Grid: at.%
Dependence of the
valence transition
temperature on the
crystal composition of
YbCu4In
40 K
50 K
65 K
stoichiometric YbCu4In 70-75 K
Yb 24.00 Yb 12.00
Cu 64.00 Cu 76.00
In 12.00 In 12.00
Landolt-Brnstein
New Series IV/11C2
MSIT
318 CuLaNi
Copper Lanthanum Nickel

Gautam Ghosh
Introduction
A summary of experimental studies of phase equilibria is given in Table 1. A large number of studies in this
system are related to hydrogen absorption/desorption behavior of stoichiometric LaNi5xCux with
0 x 5 and non-stoichiometric LaNi6xCux with 0 x 6 phases [1974Mal, 1978Shi, 1980Bel,
1982Lia, 1983Sem, 1984End, 1985Kon, 1985Per, 1996Luo, 1997Lat, 2000Nak, 2002Jou], as they are
promising candidates for hydrogen storage materials with applications in the field of rechargeable
nickel/metal hydride batteries. In addition, the absorption and desorption behavior of deuterium in
stoichiometric LaNi4Cu and non-stoichiometric LaNi5Cu have also been studied [1997Lat]. These studies
are driven primarily by the fact that long-term electrochemical cycling stability of LaNi5 in alkaline media
can be substantially improved by partial replacement of La and/or Ni by another transition metal. In
particular, LaNi6xCux compounds are very attractive due to their good long-term stability with an excellent
charge/discharge capability [1992Coe].
Only recently, an isothermal section at 400C has been determined [2005Liu]. They prepared 152 alloys
using 99.9% Cu, 99.8% La and 99.99% Ni. The ternary alloys were prepared either by arc melting or by
induction melting in an argon atmosphere. Subsequently, the alloys were sealed in evacuated quartz tubes
and homogenized in the temperature range of 420 to 600C for up to 400 h followed by cooling to 400C
at 9C#h1, and kept at this temperature for 400 h followed by quenching into liquid nitrogen. The phase
equilibria were established by means of X-ray diffraction, electron probe microanalysis and differential
thermal analysis.
Binary Systems
The Cu-La binary phase diagram is accepted from [1993Cha1, 2006Gry]. The Cu-Ni binary system is
accepted from [1993Cha2, 2002Leb]. The La-Ni binary system is accepted from [1991Oka].
Solid Phases
Both LaCu5 and LaNi5 are isotypic, and they form a continuous solid solution La(Ni,Cu)5. The crystal
chemistry of hydride forming multicomponent compounds La(Ni,Cu)5 and La(Ni,Cu)6 has received
significant attention due to their applications in nickel metal hydride (NiMH) batteries. Random substitution
of only Ni-sites by Cu gives rise to stoichiometric compound LaNi5xCux with 0 x 5, while random
substitution of La by dumbbell pairs of (Ni/Cu) atoms gives rise to non-stoichiometric compound
LaNi6xCux with 0 x 6 [1992Coe, 1999Lat]. The lattice parameters of stoichiometric LaNi5xCux have
been measured several times [1978Dwi, 1982Lia, 1982Pas1, 1982Pas2, 1984End, 1984Pas, 1992Mal,
1996Luo, 1999Lat], and in general they show a good agreement. Along the stoichiometric composition of
LaNi5xCux, both a- and c-parameters increase linearly as Ni is substituted by Cu giving a constant value
of c/a ratio [1992Mal]. However, earlier experimental data of [1978Dwi, 1982Lia] show a negative
deviation of both a- and c-parameters from ideal behavior. The lattice parameters of non-stoichiometric
LaNi6xCux have also been measured [1992Coe, 1996Luo, 1997Sri, 1999Lat]. In LaNi6xCux, 0 x 3,
the a-parameter shows a negative deviation while the c-parameter shows a positive deviation from ideal
behavior [1992Coe], and these have been attributed to the orientation of dumbbell pairs of (Ni/Cu) atoms
along the c-axis.
At 400C, LaCu and LaCu2 dissolve about 4 and 15 at.% Ni, respectively [2005Liu]. The solubility of Cu
in La2Ni7 and LaNi3 is about 2 at.%, in La7Ni16 and La2Ni3 is about 3 at.%, and in LaNi is about 5 at.%
[2005Liu]. Recently, a ternary phase Cu85La10Ni5 with cubic symmetry has been reported [2005Liu].
The crystallographic details of all solid phases are listed in Table 2.
New Series IV/11C2
CuLaNi 319
Isothermal Sections
The isothermal section at 400C is shown in Fig. 1 [2005Liu]. However, they failed to detect phase
boundaries involving La3Ni, hence, they are shown dashed.

The vertical section LaCu5-LaNi5 was determined by [1982Lia], it is shown in Fig. 2. It is almost a
quasibinary section except for the incongruent melting of LaCu5. Dash solidus and liquidus lines at
70-83.33 at.% Cu was drawn by us because [1982Lia] did not take into account that in this part must be
present a three-phase region La5(Ni,Cu)+LaCu6+L and a two-phase region LaCu6+L since LaCu5 forms by
a peritectic reaction L+LaCu6LaCu5.
Thermodynamics
The heat of mixing of liquid alloys over a wide composition range was measured at 850C in a solution
calorimeter using the isoperibolic procedure [1999Zho]. In addition, [1999Zho] also measured the specific
heat of liquid Cu25Ni50La25 alloy in the temperature range of 817 to 937C. They used elements of 99.99%
purity to prepare the alloys. [1999Zho] used a generalized associate solution model [2000Kru] to analyze
the experimental data. They assumed the presence of a ternary associate, Cu1La1Ni1, in addition to the
binary associates Cu2La1 and Ni2La1 to calculate the composition and temperature dependence of heat of
mixing and specific heat of liquid alloys. Their results are shown in Figs. 3 and 4. The specific heat data
suggest a temperature dependent heat of mixing of liquid alloys.
The standard heat of formation of LaNi5xCux intermetallic with CaCu5 structure was determined by an
isoperibolic calorimetric method [1982Pas1, 1982Pas2, 1984Pas], and their results are listed in Table 3.
These results were also reviewed by [1985Per]. [1996Gon] extended Miedemas model to calculate the
enthalpy of formation of LaNi4Cu, and obtained a value of 126 kJ#mol1 which agrees reasonably well
with the experimental value of 143.16 kJ#mol1 [1982Pas1, 1982Pas2].
The Gibbs energy of formation of La(Ni1xCux)5 hydrides was reported by [1978Shi]. With the knowledge
of heat of formation of LaNi5xCux, [1982Pas1, 1982Pas2, 1984Pas] calculated their enthalpies of
hydrogenation. Also, the enthalpies of hydrogen absorption of LaNix1Cu intermetallics with CaCu5
structure were measured using calorimetry [1996Luo]. In addition, they derived the entropy changes
associated with hydrogen absorption at 25C. [1999Shu] extended Miedemas model to calculate the
enthalpy of hydrogenation of LaNi3Cu2 and LaNi4Cu, and obtained a reasonably good agreement with the
experimental data.

The Cu-La-Ni alloys have been known as promising candidates for hydrogen storage materials with
applications in the field of rechargeable nickel/metal hydride batteries. A series of studies in this system are
related to hydrogen absorption/desorption behavior of stoichiometric LaNi5xCux with 0 x 5 and
non-stoichiometric LaNi6xCux with 0 x 6 phases [1974Mal, 1978Shi, 1980Bel, 1982Lia, 1983Sem,
1984End, 1985Kon, 1985Per, 1996Luo, 1997Lat, 2000Nak, 2002Jou]. A summary of experimental
investigation of properties is given in Table 4. At 40C, the hydrogen absorption capacity of La(Ni5xCux)5
is less than that of LaNi5 [1974Mal, 1978Shi].
The effect of hydrogen cycling on the lattice distortion [2000Nak] and defect generation [2002Jou] has been
discussed in detail.
[1985Kon] reported specific magnetic susceptibility of LaNi5xCux intermetallics with CaCu5 structure.
Miscellaneous
[1984Zhe] has discussed the direct synthesis method of LaNi5xCux intermetallic with CaCu5 structure,
starting with the powders of Cu, Ni and La2O3 by a reduction-diffusion process at 825C.
Landolt-Brnstein
New Series IV/11C2
MSIT
320 CuLaNi
References
[1974Mal] Mal, H.H. van, Buschow, K.H.J., Miedema, A.R., Hydrogen Absorption in LaNi5 and
Related Compounds: Experimental Observations and their Explanation, J. Less-Common
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[1978Dwi] Dwight, A.E., Phase Relations in The Lanthanum-Nickel-Copper LaNi5xCux,
Lanthanum- Nickel-Aluminum LaNi5xAlx and Related Systems in The Rare Earths in
Modern Scince and Technology, Rare Earth Res. Conf. 1977, Mccarthy, Gregory J., Rhyne
J.J. (Eds.), Plenum, New York, N.Y., 325-330 (1978) (Crys. Structure, Experimental, 7)
[1978Shi] Shinar, J., Shaltiel, D., Davidov, D., Grayevsky, A., Hydrogen Sorption Properties of the
La1xCaxNi5 and La(Ni1xCux)5 Systems, J. Less-Common Met., 60(2), 209-219 (1978)
(Crys. Structure, Experimental, Thermodyn., 19)
[1980Bel] Belkbir, L., Joly, E., Gerard, N., Achard, J.C., Percheron-Guegan, A., Evolution of the
Kinetic Properties in a Family of Substituted LaNi5 Hydrides During Activating
Formation-Decomposition Cycling, J. Less-Common Met., 73(1), 69-77 (1980)
(Electrochemistry, Experimental, Kinetics, 18)
[1982Lia] Liang, J., Wang, C., Phase Equilibrium and Hydrogen Absorption of LaNi5-LaCu5
System (in Chinese), Acta Metall. Sin. (China), 18(5), 592-598 (1982) (Crys. Structure,
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[1982Pas2] Pasturel, A., Chatillon, C., Percheron-Guegan, A., Achard, J.C., Thermodynamic
Properties of LaNi4M Compounds and Their Hydrides, in The Rare Earth in Modern
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Hydride Phases Based on the Compounds LaNi5xTx, where T is Al, Cr, Fe, or Cu, Russ.
J. Inorg. Chem., 28(1), 107-111 (1983), translated from Zh. Neorg. Khim, 28, 195 (1983)
(Experimental, 15)
[1984Pas] Pasturel, A., Liautand, F., Collinet, F., Allibert, C., Perchero, A., Thermodynamic Study
of the LaNi5xCux System, J. Less-Common Met., 96, 93-97 (1984) (Experimental,
Thermodyn., 12)
[1984Zhe] Zheng, C., Dong, C., Qian, J., Ye, Y., On the Synthesis by Reduction-Diffusion and the
Properties of LaNi5xCux Alloys, Jinshu Xuebao, 20(6), B352-B358 (1984) (Crys.
[1984End] Endrzheevskaya, S.N., Lukyanchikov, V.S., Shablina, A.G., Skorokhod, V.V.,
Denbnovetskaya, E., Reactions of Intermetallic Compounds of the La-Ni-Cu System with
Hydrogen and Hydrogen-Containing Gas Mixtures, Sov. Powder Metall. Met. Ceram.,
23(9), 710-713 (1984) (Experimental, Kinetics, Phase Diagram, Phase Relations, 6)
[1985Kon] Konenko, I.P., Starodubtseva, E.V., Stepanov, Yu.P., Fedorovskaya, E.A., Slinkin, A.A.,
Klabunovskii, E.I., Savitskii, E.M., Mordovin, V.P., Savostyanova, T.P., Intermetallic
Compounds LaNi5xCux and their Hydrides in the Sorption of Hydrogen and the
Hydrogenation of Olefins, Kinet. Katal., 26(2), 291-295 (1985), translated from Kinet.
Katal., 26(2), 340-344 (1985) (Catalysis, Experimental, Magn. Prop., Phase Relations, 12)
[1985Per] Percheron-Guegan, A., Lartigue, C., Achard, J.C., Correlations Between the Structural
Properties, the Stability and the Hydrogen Content of Substituted LaNi5 Compounds,
J. Less-Common Met., 109, 287-309 (1985) (Crys. Structure, Electrochemistry, Review,
Thermodyn., 78)
[1991Oka] Okamoto, H., La-Ni (Lanthanum-Nickel), J. Phase Equilib., 12(5), 615-616 (1991)
(Phase Diagram, Review, #, *, 3)
New Series IV/11C2
CuLaNi 321
[1992Coe] Coene, W., Notten, P.H.L., Hakkens, F., Einerhand, R.E.F., Daams, J.L.C., Transmission
Electron Microscopy Study of Order-Disorder Phenomena in Non-Stoichiometric LaNi5+x
and LaNi6xCux Electrode Materials, Philos. Mag. A, 65(6), 1485-1502 (1992) (Crys.
Structure, Electronic Structure, Experimental, 21)
[1992Mal] Malani, G.K., Mohanty, R.C., Raman, A., Ternary and Quaternary Solid Solutions in Rare
Earth Alloy Phases with the CaCu5-Type Structure, Z. Metallkd., 83(5), 342-348 (1992)
[1993Cha1] Chakraborty, D.J., Laughlin, D.E., Cu-La (Copper-Lanthanum), in Phase Diagrams of
Binary Copper Alloys, Subramanian, P.R, Chakrabarty, D.J., Laughlin, D.E. (Eds.), ASM
International, Materials Park, OH, 235-238 (1993) (Crys. Structure, Phase Diagram,
Review, #, *, 23)
[1993Cha2] Chakraborty, D.J., Laughlin, D.E., Chen, S.W., Chang, Y.A., Cu-Ni (Copper-Nickel), in
Phase Diagrams of Binary Copper Alloys, Subramanian, P.R, Chakrabarty, D.J.,
Laughlin, D.E. (Eds.), ASM International, Materials Park, OH, 266-270 (1993) (Crys.
Structure, Phase Diagram, Review, #, *, 85)
[1996Gon] Goncalves, A.P., Almeida, M, Extended Miedema Model: Predicting the Formation
Enthalpies of Intermetallic Phases with more than Two Elements, Physica B (Amsterdam),
228, 289-294 (1996) (Calculation, Review, Thermodyn., 19)
[1996Luo] Luo S., Flanagan T.B., Notten P.H.L., Thermodynamic Properties of Non-Stoichiometric
LaNix-1Cu-H Systems, J. Alloys Compd., 239, 214-225 (1996) (Crys. Structure,
Experimental, Thermodyn., 42)
[1997Lat] Latroche, M., Notten, P.H.L., Percheron-Guedan, A., In Situ Neutron Diffraction Study of
Solid Gas Desorption of Non-Stoichiomtric AB5 Type Hydrides, J. Alloys Compd.,
253-254, 295-297 (1997) (Crys. Structure, Experimental, 8)
[1997Sri] Srinivasan, S., Raman, A., Ferrel, R.E.Jr., Grenier, C.G., Lanthanum-containing Ternary
Solid Solutions with NaZn13-, ThMn12- and Th2Zn17-Type Crystal Structures,
Z. Metallkd., 88(6), 474-479 (1997) (Crys. Structure, Experimental, Magn. Prop., Phase
Relations, Review, 22)
[1999Lat] Latroche, M., Joubert, J.-M., Percheron-Guegan, A., Notten, P.H.L., Crystal Structure of
Nonstoichiometric Copper-Substituted La(Ni1zCuz)x Compounds Studied by Neutron and
Synchrotron Anomalous Powder Diffraction, J. Solid State Chem., 146, 313-321 (1999)
[1999Shu] Shuang, Z., Qin, L., Ning, C., Li, M., Wen, Y., Calculation and Prediction for the
Hydriding Properties of LaNi5xMx Alloys, J. Alloys Compd., 287, 57-61 (1999)
(Calculation, Thermodyn., 18)
[1999Zho] Zhou, S.H., Sommer, F., The Enthalpy of Formation and the Heat Capacity of Liquid
Cu-La-Ni Alloys, J. Alloys Compd., 289, 145-151 (1999) (Experimental, Thermodyn., 13)
[2000Kru] Krull, H.-G., Singh, R.N., Sommer, F., Generalized Association Model, Z. Metallkd.,
91(5), 356-365 (2000) (Review, Thermodyn., 46)
[2000Nak] Nakamura, Y., Oguro, K., Uehara, I., Akiba, E., X-ray Diffraction Peak Broadening and
Lattice Strain in LaNi5-based Alloys, J. Alloys Compd., 298, 138-145 (2000) (Crys.
[2002Jou] Joubert, J.-M., Latroche, M., Cerny, R., Percheron-Guegan, A., Yvon, K., Hydrogen
Cycling Induced Degradation in LaNi5type Materials, J. Alloys Compd., 330-332,
208-214 (2002) (Crys. Structure, Experimental, Phase Relations, 13)
[2002Leb] Lebrun, N., Cu-Ni (Copper - Nickel), MSIT Binary Evaluation Program, in MSIT
Stuttgart, Document ID: 20.14832.1.20, (2002) (Crys. Structure, Phase Diagram, Phase
Relations, Assessment, #, *, 51)
[2005Liu] Liu, J.Q., Ma, F.Q., Zhuang, Y.H., Jiao, F.W., Yan, J.L., The Isothermal Section of the
Phase Diagram of the La-Ni-Cu Ternary System at 673 K, J. Alloys Compd., 386, 174-176
(Experimental, Phase Relations, Phase Diagram, #, *, 8)
Landolt-Brnstein
New Series IV/11C2
MSIT
322 CuLaNi
[2006Gry] Grytsiv, A., Cu-La (Copper - Lanthanum), Diagrams as Published, in MSIT Workplace,
Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart, to be
published (2006) (Phase Diagram, Phase Relations, #, *, 16)
Table 1: Investigations of the Cu-La-Ni Phase Relations, Structures and Thermodynamics

[1978Dwi] X-ray diffraction 700C; LaNi5xCux, 0x5
[1978Shi] Thermal analysis, optical metallography <1050C; 2-22.5 mass% Ni and 5-40 mass% Cu
[1982Lia] Thermal analysis, XRD 800-1350C; LaNi5xCux, 0x5
[1982Pas1, Calorimetry, XRD 800C, LaNi4Cu
[1982Pas2]
[1984End] XRD LaNi5xCux, 0x5
[1984Pas] Calorimetry, XRD 800C; LaNi5-LaCu5
[1984Zhe] XRD 825C; LaNi5xCux, 0x5
[1992Mal] XRD 750-950C, LaNi5-LaCu5
[1992Coe] TEM, XRD LaNi6xCux, 0x3
[1996Luo] XRD 1050-1200C; LaNi4Cu and Non-stoichiometric
La(Ni,Co)z, 5 z 6
[1997Lat] XRD LaNi4Cu and LaNi5Cu
[1997Sri] XRD Non-stoichiometric La(Ni,Cu)z, 5 z 6
[1999Lat] XRD and Neutron diffraction LaNi4Cu and non-stoichiometric La(Ni,Cu)z,
5z6
[1999Zho] Calorimetry 850C; 23.2-74.2 at.% La, 4.9-61.1 at.% Ni; liquid
phase
[2000Nak] XRD 1100C, LaNi4.5Cu0.5
[2002Jou] XRD LaNi4Cu
[2005Liu] DTA, EPMA, XRD 400C

[C] Prototype
, (Ni,Cu) cF4
Fm3m
(Ni) Cu a = 352.32 pure Ni at 25C [Mas2]
< 1455
< 1084.62
(La) cI2 a = 426 pure La [Mas2]
918 - 865 Im3m
W
New Series IV/11C2
CuLaNi 323

[C] Prototype
(La) cF4 a = 530.3 pure La [Mas2]
865-310 Fm3m
Cu
(La) hP4 a = 377 pure La at 25C [Mas2]
< 310 P63/mmc c = 1217.1
La
Cu6La oP28 a = 816.5 [1993Cha1]
905-218 Pnma b = 514.8
CeCu6 c = 1023
Cu6La mP28 a = 514.67 at 27C [2006Gry]
< 218 P21/C b = 1021.03
Cu6La c = 814.55
= 91.51
Cu2La hP3 a = 434.5 [1993Cha1]
< 830 P6/mmm c = 381.9
AlB2
CuLa oP8 a = 754.3 [1993Cha1]
< 525 Pnma b = 461.6
FeB c = 572.4
La3Ni oP16 a = 722 [V-C2]
< 532 Pnma b = 1024
Fe3C c = 660
La7Ni3 hP20 a = 1014 [V-C2]
< 530 P63/mc c = 638.3
Fe3Th7
LaNi oC8 a = 390.7 [V-C2]
< 715 Cmcm b = 1081
CrB c = 439.6
La2Ni3 oC20 a = 511.38 [V-C2]
< 688 Cmca b = 973.15
La2Ni3 c = 790.75
La7Ni16 tI46 a = 735.5 [V-C2]
< 714 I42m c = 1451.1
La7Ni16
La2Ni7 hR54 a = 505.6 [V-C2]
1014 - 977 R3m c = 3698.1
Er2Co7
La2Ni7 hP36 a = 505.8 [V-C2]
< 977 P63/mmc c = 2471
Ce2Ni7
Landolt-Brnstein
New Series IV/11C2
MSIT
324 CuLaNi

[C] Prototype
La(Ni,Cu)5 hP6 a = 513.0 LaNiCu4, at 25C [1992Mal]
P6/mmm c = 408.7
CaCu6
a = 509.6 LaNi2Cu3, at 25C [1992Mal]
c = 405.0
a = 506.6 LaNi3Cu2, at 25C [1992Mal]

c = 402.5
a = 503.3 LaNi3.98Cu0.96, at 25C [1982Pas1]

c = 400.7
a = 503.94 LaNi4Cu, at 25C [1996Luo]

c = 400.52
a = 503.79 LaNi4.02Cu0.99, at 25C [1999Lat]

c = 400.64
a = 502.8 LaNi4.75Cu0.25, at 25C [1984End]

c = 399.5
a = 502.72 LaNi4.5Cu0.5, at 25C [2000Nak]

c = 399.46
a = 502.52 LaNi4.2Cu, at 25C [1996Luo]

c = 401.27
a = 501.12 LaNi4.36Cu0.99, at 25C [1999Lat]

c = 402.04
a = 501.02 LaNi4.4Cu, at 25C [1996Luo]

c = 402.04
a = 498.64 LaNi4.5Cu1.49, at 25C [1999Lat]

c = 404.81
a = 499.84 LaNi4.6Cu, at 25C [1996Luo]

c = 402.84
a = 498.68 LaNi4.8Cu, at 25C [1996Luo]

c = 403.47
a = 498.61 LaNi4.84Cu0.95, at 25C [1999Lat]

c = 403.24
a = 498.75 LaNi5Cu, at 25C [1996Luo]

c = 403.88
Cu5La a = 518.7 [1993Cha1]

< 805 c = 410.9
LaNi5 a = 501.8 [V-C2]

< 1350 c = 397.8
New Series IV/11C2
CuLaNi 325

[C] Prototype
* -1, Cu85La10Ni5 cF* a = 1158.0 [2005Liu]
Fm3c
Table 3: Standard Heat of Formation of La(Ni,Cu)5 with CaCu5 Structure

Phase Temperature [C] Heat of formation [kJ#mol1]
LaCu5 298.15 75.77
LaNiCu4 298.15 93.35
LaNi2Cu3 298.15 107.58
LaNi3Cu2 298.15 128.51
LaNi4Cu 298.15 143.16
LaNi5 298.15 161.16
Table 4: Investigations of the Cu-La-Ni Materials Properties

[1974Mal] Absorption/desorption Hydrogen absorption in LaNi4Cu
[1978Shi] Absorption/desorption Hydrogen absorption in LaNi5xCux
[1980Bel] Absorption/desorption Hydrogen absorption in LaNi4.9Cu0.1
[1982Lia] Absorption/desorption Hydrogen absorption in LaNi5xCux
[1983Sem] Absorption/desorption Hydrogen absorption in LaNi5xCux
[1984End] Absorption/desorption Hydrogen absorption in LaNi5xCux
[1985Kon] Absorption/desorption Catalytic and magnetic properties, and hydrogen
absorption of LaNi5xCux
[1996Luo] Absorption/desorption Hydrogen absorption in LaNi5xCux
[1997Lat] Absorption/desorption Deuterium absorption in LaNi4Cu, and LaNi5Cu
[2000Nak] Absorption/desorption Hydrogen absorption in LaNi4.5Cu0.5
[2002Jou] Absorption/desorption Hydrogen absorption in LaNi4Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
326 CuLaNi

Fig. 1: Cu-La-Ni. Axes: at.%
400C LaCu6
LaCu 5
1
20
80
LaCu 2
40
60
LaCu
60
40
80
20
20 40 60 80 LaNi5
La La3Ni La7Ni3 LaNi La2Ni3 La7Ni16 LaNi3
La2Ni7
Ni
1400
Fig. 2: Cu-La-Ni.
Vertical section
LaNi5 - LaCu5
1300
L
1200
Temperature, C
1100
La(Ni,Cu)5
1000
900
800
La 16.67 10 20 30 40 50 60 70 80 La 16.67
Ni 83.33 Ni 0.00
Cu 0.00 Cu, at.% Cu 83.33
New Series IV/11C2
CuLaNi 327
Fig. 3: Cu-La-Ni.
Specific heat of liquid 46.0
Cu25La50Ni25 alloy.
Points are
experimental data, 44.0
dashed line represents
mechanical mixture
of liquid and 42.0
Cp, Jmol1K1
undercooled liquid
components; solid
line is calculated 40.0
using an associated
solution model.
38.0
36.0
34.0
1080 1100 1120 1140 1160 1180 1200 1220
Temperature, K

Fig. 4: Cu-La-Ni. Axes: at.%
Isocontours of
enthalpy of mixing (in
kJ#mol1) of liquid
alloys at 850C 20
80
calculated using an
associate solution -15
model
40
60
60
-20
40
-25
80
20
-30
20 40 60 80
La Ni
Landolt-Brnstein
New Series IV/11C2
MSIT
328 CuMgZr
Copper Magnesium Zirconium

Lazar Rokhlin, Evgeniya Lysova, Christian Btzner, updated by Svitlana Ilyenko
Introduction
[1959Ich] studied the solubility of zirconium in molten magnesium at 700C with copper additions up to
about 0.4 at.%. According to [1959Ich] copper diminishes the zirconium solubility in molten magnesium.
Moreover [1959Ich] determined the phases formed in the Mg rich alloys with copper and zirconium after
solidification by X-ray analysis and metallography. [1968Bab] studied the solubility of zirconium in molten
magnesium between 780 and 800C with copper additions up to 0.6 at.%. According to [1968Bab] copper
does not change the zirconium solubility in molten magnesium in contradiction to [1959Ich]. [1982Kuz]
constructed the vertical section of the phase diagram using differential thermal analysis, X-ray phase
analysis, and metallography.
[1991Soa] studied liquid-solid equilibria in the Cu rich part of the Cu-Mg-Zr system by diffusion couple
experiments and electron microprobe analysis (SEM). Pure copper crucibles where used containing Mg and
Zr. An annealing treatment at 787C followed by rapid quenching in water has been applied before
analyzing the revealed phase structure and composition.
Binary Systems
The three binary systems Cu-Mg [2002Iva], Cu-Zr [2006Sem], and Mg-Zr [Mas2] are used as boundary
systems.
Solid Phases
No ternary compounds have been found. All the binary solid phases are listed in Table 1, together with the
small mutual solubilities of each metal. They may be used to estimate the expected small homogeneity areas
of each metal in the ternary system.
Isothermal Sections
Figure 1 shows the influence of copper on the solubility of zirconium in molten magnesium at 700C after
[1959Ich] slightly adjusted to the Mg-Zr binary [Mas2]. It may be considered as a part of the isothermal
section of the phase diagram at 700C. In view of the more detailed experimental description, the results of
[1959Ich] are preferred with respect to those of [1968Bab]. In the solid state, according to X-ray
investigations [1959Ich], (Zr), Zr2Cu, and CuMg2 are in equilibrium with the (Mg) phase. The results of
[1991Soa] in the Cu rich corner revealed at 787C a three-phase-equilibrium between Cu, liquid and
probably Zr2Cu9 (named ZrCu4 by [1991Soa]). The composition of the liquid phase was determined to be
87.0 at.% Cu, 13.0 at.% Mg (Zr was not detectable), the composition of the needle shaped Zr2Cu9 as 82.3
at.% Cu, 17.7 at.% Zr (Mg was not detectable) and the composition of the Cu based solid solution as 95.9
at.% Cu, 4.1 at.% Mg.

Figure 2 displays the vertical section of the ternary phase diagram at constant Mg concentration of 1 at.%
constructed by [1982Kuz]. The stoichiometry of the phase Zr2Cu7 proposed by [1982Kuz] has been
changed to Zr14Cu51 given by [1990Ari, 2006Sem] in the accepted Cu-Zr binary phase diagram.
New Series IV/11C2
CuMgZr 329
References
[1959Ich] Ichikawa, R., On Favorable Alloying Elements for Mg-Zr System Alloys (in Japanese),
Nippon Kinzoku Gakkaishi, 23, 612-616 (1959) (Experimental, Phase Diagram, 10)
[1968Bab] Babkin, V.M., Solubility of Zirconium in Molten Magnesium and Magnesium Alloy ML5
(in Russian), Metall. Term. Obra. Metallov, (3), 61-64 (1968) (Experimental, Phase
Diagram, 4)
[1982Kuz] Kuznetsov, G.M., Fedorov, V.N., Tokarchuk, I.N., Zhizhchenko, O.P., Kozlov, V.V.,
Phase Equilibria in the Cu-Cr-Zr-Mg System (in Russian), Izv. Vyss. Uchebn. Zaved.
Tsvetn. Metall., (6), 90-93 (1982) (Experimental, Phase Diagram, 3)
[1990Ari] Arias, D., Abrita, J.P., The Cu-Zr (Copper-Zirconium) System, Bull. Alloy Phase
Diagrams, 11, 452-459 (1990) (Review, Phase Diagram, 50)
[1991Soa] Soares, D., Malheiros, L.F., Castro, F., Phase Equilibria and Thermodynamic Properties of
the System Cu-Cr-Mg-Zr, COST 507 Leuven Proceedings, Part A, KU Leuven, December
1991 (Experimental, Phase Diagram, 13)
[2000Kov] Koval, Yu.N., High Temperature Shape Memory Effect in Some Alloys and Compounds,
Mater. Sci. Forum, 327-328, 271-278 (2000) (Experimental, Mechan. Prop., 19)
[2002Iva] Ivanchenko, V., Ansara I., Cu-Mg (Copper - Magnesium), MSIT Binary Evaluation
[2006Sem] Semenova, E., Sidorko, V., Cu-Zr (Copper-Zirconium), MSIT Binary Evaluation
Services, GmbH, Stuttgart; to be published, (2006) (Crys. Structure, Phase Diagram,
Assessment, 31)

[C] Prototype
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m
Cu
(Mg) hP2 a = 320.94 at 25C [Mas2]
< 650 P63/mmc c = 521.07
Mg
(Zr) cI2 dissolves up to 5.7 at.% Cu [2006Sem]
1855 - 863 Im3m a = 356.8 pure Zr [V-C2]
W
(Zr) hP2 dissolves up to ~0.2 at.% Cu [2006Sem]
< 863 P63/mmc a = 323.2 pure Zr at 25C [V-C2]
Mg c = 514.7
Landolt-Brnstein
New Series IV/11C2
MSIT
330 CuMgZr

[C] Prototype
CuMg2 oF48 a = 907 [2002Iva]
< 568 Fddd b = 528.4
CuMg2 c = 1825
a = 905
b = 528.3
c = 1824.7
a = 904.4 0.1
b = 527.5 0.1
c = 1832.8 0.2
Cu2Mg cF24 a = 702.1 64.7 to 69 at.% Cu [2002Iva]
< 797 Fd3m
Cu2Mg
ZrCu5 cF24 a = 687.0 [2006Sem]
< 1032 F43m
AuBe5
or
t** long period superstructure derived from
Zr2Cu9 AuBe5 type
Zr14Cu51 hP68 a = 1124.44 [2006Sem]
1112 P6/m c = 828.15
Gd14Ag51
Zr3Cu8 oP44 a = 786.93 [2006Sem]
1028 Pnma b = 851.47
Hf3Cu8 c = 646.0
Zr24Cu13 o*37 a = 1119.0 [2006Sem]
960 - 915 b = 791.2
c = 998.48
Zr7Cu10 oC68 a = 1267.29 [2006Sem]
< 935 C2ca b = 931.63
Zr7Ni10 c = 934.66
ZrCu(h) cP2 a = 326.6 at 49.9 at.% and 25C [2006Sem]
960 - 725 Pm3m
CsCl
ZrCu(l) mP4 a = 328.2 martensite, [2000Kov]
< 140 P21/m b = 414.8
TiNi c = 524.9
= 103.7
mC16 a = 633.7 martensite, [2000Kov]
Cm b = 856.3
c = 534.5
= 105.6
Zr2Cu(h) tI6 a = 322.04 [2006Sem]
1025 - 950 I4/mmm c = 1183.2
MoSi2
Zr2Cu(r) tP150 a = 1592.4 [2006Sem]
< 950 c = 1132.8
New Series IV/11C2
CuMgZr 331
Mg 99.50
Zr 0.00
Fig. 1: Cu-Mg-Zr. Axes: at.%
Influence of copper
on the zirconium
solubility in molten
magnesium at 700C
L+( Zr)
Mg Mg 99.50
Zr 0.50
Cu 0.00
1100
Fig. 2: Cu-Mg-Zr.
Vertical section at 1075C
constant 1 at.% Mg L
L+Zr14Cu51+Zr2Cu9 1031C
L+Zr14Cu51 L+(Cu)
1000
Temperature, C
L+Zr2Cu9
L+(Cu)+Zr2Cu9
(Cu)
900
(Cu)+Zr2Cu9
800
Mg 1.00 90 96 Mg 1.00
Zr 15.00 Zr 0.00
Cu 84.00 Cu, at.% Cu 99.00
Landolt-Brnstein
New Series IV/11C2
MSIT
332 CuMnSi
Copper Manganese Silicon

Nathalie Lebrun
Introduction
The Cu rich part of the ternary system Cu-Mn-Si has been extensively studied. All the experimental data on
this system have been reported in Table 1.
Two ternary phases -1 and -2 have been observed and agreement is noticed concerning their compositions.
Several isothermal sections have been determined experimentally in the Cu rich part of the ternary system.
[1930Smi, 1942Smi, 1945Smi] investigated alloys containing up to 10 mass% Mn and 10 mass% Si and
presented some partial isothermal sections ranging from 450 to 800C. More recently, [1974Muk] studied
Mn rich alloys containing up to 25 mass% Si and 70 mass% Cu and reported a partial isothermal section at
700C. General agreements have been observed. However, the data of [1930Smi] considerably deviate from
those of the other studies at 800 and 700C, if the manganese content is higher than 2 mass%. This has been
noticed by [2003Mie] who carried out a complete thermodynamic description in the Cu rich part of the
ternary system using ThermoCalc software. The calculations are in quite good agreement with the
experimental data reported previously. Nevertheless, some calculated phase equilibria involving two
ternary compounds -1 and -2 are not in agreement with those measured experimentally by [1974Muk].
In the review made by [1979Cha], a liquidus surface has been reported which is inferred from the studies
of the Cu rich region by [1930Smi, 1942Smi, 1958Tur] as well the sections Cu-Mn5Si3 [1953Dre,
1962Smi], Cu-MnSi [1962Smi] and Cu-MnSi2 [1962Smi]. The calculated liquidus surface presented by
[2003Mie] in the Cu rich part (up to 30 mass% Mn and 10 mass% Si) correlates well with the experimental
data mentioned previously.
The quasibinary system Cu-Mn5Si3, reported as a eutectic type, has been well established and experimental
data of [1953Dre] and [1962Smi] are in agreement. The Cu-MnSi section was also considered as
quasibinary by [1962Smi]. Others isopleths have also been reported at Mn:Si = 1.96 [1962Smi], at 2 and
4 mass% Si [1930Smi, 1958Tur], and at 2 and 4 mass% Mn [1930Smi, 1958Tur]. The calculated isopleths
[2003Mie] are in quite good agreement with those reported experimentally.
As [1979Cha], [1969Gue, 1961Die] undertook a review of the system Cu-Mn-Si.
Binary Systems
The binary systems Cu-Mn and Cu-Si are taken from [2005Tur] and [2002Leb], respectively. The phase
diagram Mn-Si is accepted from [1991Oka].
Solid Phases
All the crystallographic data for the unary, binary and ternary phases are reported in Table 2.
Two ternary compounds have been reported in the literature [1973Muk, 1974Muk]. -1 crystallizes in the
MgZn2 type structure and exhibits a very small phase region around the mean composition
Mn50.2Cu32.5Si17.3. Its crystallographic parameters have been reported in Table 2. -2 has an approximate
composition of Mn60.5Cu28.3Si11.2. These compounds exist at 700C [1974Muk] but no information can be
found concerning their temperature domain of existence.
Quasibinary Systems
The quasibinary system Cu-Mn5Si3 is of eutectic type and the eutectic point is located at 800C and at about
24 mass% Mn5Si3 [1953Dre, 1962Smi] as shown in Fig. 1. The Cu-MnSi system is also quasibinary with
the eutectic point located at 21 mass% MnSi and 775C [1962Smi]. The diagram shown in Fig. 2 and is a
compilation of [1962Smi] and [2003Mie].
New Series IV/11C2
CuMnSi 333
A tentative reaction scheme is reported in Fig. 3. The invariant equilibria are reported in Table 3. The
location of the ternary four-phase reactions have been taken from [1979Cha]. Two three-phase reactions
have been also reported and were deduced from the quasibinary sections Cu-MnSi and Cu-Mn 5Si3.

The liquidus surface reported in Fig. 4 is a compilation of the experimental works done by [1930Smi,
1942Smi, 1958Tur]. The liquidus surface is drawn to be consistent with the binary systems and with the
experimental polythermal sections available in the literature [1953Dre, 1930Smi, 1962Smi] as well as with
the calculated liquidus curves suggested by [2003Mie]. The extrapolated curves are indicated as dotted lines
in the drawing. Lack of data is observed near the Mn rich part. Consequently, the phase equilibria could not
be determined and were symbolized as a question mark on the drawing.
Isothermal Sections
At 700C [1974Muk] investigated the phase equilibria and found some solubility ranges for the binary
phases inside the ternary system. The solubility of Cu in the (Mn), (Mn) and R phases is small. The region
limits of the , Mn3Si and Mn5Si3 inside the ternary were not determined accurately. Figure 6 shows the
partial isothermal section at 700C which is a compilation of the experimental work of [1974Muk] and the
thermodynamic calculations by [2003Mie]. The phase equilibria involving the two ternary phases have been
taken from the experimental work [1974Muk]. These equilibria were not reproduced by the thermodynamic
calculations [2003Mie]. Other isothermal sections were measured and calculated from 450 to 800C. Some
of them are reported in Figs. 5, 7 and 8. General good agreement was observed between the experimental
data [1930Smi, 1942Smi, 1945Smi, 1953Dre, 1958Tur, 1962Smi] and the calculated curves [2003Mie].
However, the solubility range of the (Mn,Cu) measured by [1930Smi] has not been in agreement with
those of the other studies at 800 and 700C if the Mn content is higher than 2 mass%. The data of the latter
studies have been retained in this assessment.

Partial polythermal sections have been reported in the literature: from 1 to 4 mass% Si [1958Tur], from 1
to 12 mass% Mn [1930Smi, 1958Tur]. [2003Mie] calculated isopleths which are in quite good agreement
with measured data deduced from experimental isothermal sections and isopleths. Nevertheless, the
calculated isopleth at Mn:Si = 1.96 in the Cu rich part presents large discrepancies with the isothermal
section measured at 700C by [1974Muk]. The three-phase equilibrium (Mn,Cu) +-1 + -2 suggested by
[2003Mie] was not observed by [1974Muk]. This latter study measured a very narrow (Mn,Cu) - Mn3Si
region splitting the (Mn,Cu) +-1 + -2 region into two separate triangles, (Mn,Cu) + -1 + Mn3Si and
(Mn,Cu) + -2 + Mn3Si. Since these last three-phase equilibria have not been mentioned in the work
[2003Mie], the isopleth Cu-Mn1.96Si was not retained in this assessment. Some isopleths are shown in
Figs. 9, 10 and 11.

Experimental data on materials properties are reported in Table 4.
[1930Voc] studied the mechanical and physical properties of Cu-Mn-Si alloys in the cast, drawn and rolled
conditions with a view to developing and extending their uses. It was concluded that Cu alloys containing
between 2 and 5 mass% Si and 0 - 5 mass% Mn have been the most useful alloys combining good strength
and hardness with reasonable malleability. The mechanical properties of Cu rich alloys containing 1-2
mass% Mn and up to 2.5 mass% Si were investigated also by [1952Dre]. These alloys are found to be
amenable to age hardening. In quenched alloys with 1.2 mass% Mn, a rise in silicon concentration from 2.5
to 4.4 mass% first increases and then reduces the effect of stress rise under relaxation test conditions at 200
and 300C [1968Gay]. The hardness is found to be non-monotonic function by [1973Fri] with tow peaks,
Landolt-Brnstein
New Series IV/11C2
MSIT
334 CuMnSi
low temperature at 250-300C and high temperature at 500-550C. An increase of the maximum of the
hardening is observed in alloys Cu-Mn5Si3 as the Mn5Si3 content increases [1953Dre] leading to a value of
about 177 kg#mm2 at 12.5 mass% of Mn5Si3. [1967Mil] observed that the alloys Cu-3 at.% Si-1 at.% Mn
with high reduction (80%) after annealing (30 min at 450C) have a hardness (59 kg#mm2) higher than
those which were only annealed (40.7 kg#mm2).
Miscellaneous
[1988Pra] investigated the microstructure in the cold-worked state of Cu-Mn-Si alloys in the fcc phase of
Cu and studied the effects of Mn and Si. It was concluded that the presence, even in small amounts of Mn
and Si, has a pronounced effect on the stacking fault probability of deformed Cu-Mn-Si alloys. [1948Ray]
examined the effect of the compound Mn2Si on the solid solubility isotherms of Cu-Mn-Si alloys and
showed that the (Mn,Cu) / (Mn,Cu) + Mn2Si obey to the relation dlogK / d = Q / (R2) with
Q = 7.6#103 cal., where is the absolute temperature, Q is analogous to the heat of formation, K is a constant
deduced from the solid solubility isothermls.
[1965Bra] developed a technique to prevent cracking in the welding of highly restrained 95.8 at.% Cu - 3.1
at.% Si - 1.1 at.% Mn alloys by controlling segregation in the weld. It has been observed that centerline
cracking is associated with the dendritic type of structure and becomes arrested at the point where the
structure changed from dendritic to cellular. Beyond a certain reduction (about 35%), the deformation by
slip of Cu-3 at.% Si - 1 at.% Mn is accompanied by significant macroscopic shearing [1967Mil]. Annealing
does not produce any restoration but a recrystallization alone which is done in two enough distinct stages
for high reductions (> 50%). The use of high reductions makes it possible to obtain recrystallized states with
very fine grains.
[1969Vas1] studied copper alloys containing about 3.48 mass% Si and 1.14 mass% Mn at liquid nitrogen
temperature. The faulting parameters (an average of 111-200 and 200-220) and were determined at
various annealing times after filling (1 and 3 h, 1 and 4 d). It was observed that the value of the parameter
was about 35% more at liquid nitrogen temperature than at room temperature estimated as 0.022 by
[1969Vas2]. Using variance method on copper alloys containing 6.7 at.% Si and 1.3 at.% Mn, [1970Vas]
found an apparent particle size and strain of 98 ' and 0.0018, respectively which are closer to those given
by Fourier analysis than by integral breadth measurements.
References
[1930Smi] Smith, C.S., Alpha-Phase Boundary of the Ternary System Copper-Silicon-Manganese,
Trans. AIME, 89, 164-193 (1930) (Experimental, Phase Diagram, 22)
[1930Voc] Voce, E., Silicon-Copper Alloys and Silicon-Manganese-Copper Alloys, J. Inst. Met., 44,
331-359 (1930) (Electr. Prop., Experimental, Mechan. Prop., Morphology, 22)
[1942Smi] Smith, C.S., Hibbard, W.R., The Constitution of Copper-Rich Copper-Silicon-Manganese
Alloys, Trans. AIME, 174, 222-225 (1942) (Electr. Prop., Experimental, Phase
Diagram, 3)
[1945Smi] Smiryagin, A. P., Phase Diagrams of Cu-Si, Cu-Si-Zn and Cu-Si-Mn, in Spetsialnye
Bronzi i Latuni, Metallurgizdat, Moscow, 5, 5-20 (1945) (Experimental, Phase
Diagram, 30)
[1948Ray] Raynor, G.V., XXVIII. Equilibrium Relationships in Ternary Alloys, Philos. Mag.,
39(290), 218-229 (1948) (Phase Diagram, Review, Theory, 12)
[1952Dre] Dreyer, K.L., About Based Structure and Hardness of the Copper-Manganese-Silicon
Alloys (in German), Metall, 6(15/16), 440-444 (1952) (Experimental, Mechan. Prop.,
Phase Diagram, 12)
[1953Dre] Dreyer, K.L., About Based Structure and Hardness of Copper-Manganes-Silicon Alloys
(in German), Metall, 7(5/6), 186-189 (1953) (Experimental, Mechan. Prop., Phase
Diagram, 3)
New Series IV/11C2
CuMnSi 335
[1958Tur] Turkin, V.D., Kushnikova, L.I., Investigation of Alloys of the System Cu-Mn-Si.,
Sb. Nauchn. Tr., Moskovskii. Inst. Tsvet. Metallov i Zolota, 29, 18-25 (1958) as quoted by
Ageev, N.V., Phase Diagrams of Metallic Systems (in Russian), 1958 (Publ. 1961)
[1961Die] Dies, K., Manganese Bronses (in German), Metall, 15(12), 1161-1172 (1961)
[1962Smi] Smiryagin, A.P., Martinyuk, R.P., Investigation of the Cu-Si-Mn System, Issled. Splavov
Tsvet. Metallov, (3), 98-107 (1962) (Experimental, Phase Diagram, 17)
[1965Bra] Bray, R.S., Lozano, L.J., Controlling Weld Segregation to Avoid Cracking in a Cu-Mn-Si
Alloy, Welding J., 44(9), S424-S432 (1965) (Experimental, 5)
[1967Mil] Mills, D., Blanchard, P., Whitwham, D., Herenguel, J., Deformation and Controlled
Annealing of Sheet in U S3M (Cu 3 % Si 1 % Mn) Alloy (in French), Mem. Sci. Rev.
Metall., 64(4), 377-384 (1967) (Experimental, Mechan. Prop., 9)
[1968Gay] Gaydukov, M.G., Pavlov, V.A., Frizen, E.N., Smirnov, L.V., Anomalous Stress
Relaxation in the Ternary Alloy Cu-Mn-Si, Phys. Met. Metallogr. USSR, 25(2), 167-174
(1968) (Experimental, Mechan. Prop., 14)
[1969Gue] Guertler, W., Guertler, M., Anastasiadias, E., Copper-Manganese-Silicon, A Comp. of
Const. Ternary Diagr. Met. Systems, Isr. Pro. Sci. Tr., Jerusalem, 549-552 (1969) (Phase
Diagram, Phase Relations, Review, 8)
[1969Vas1] Vasudevan, R., Gerold, V., Stacking Faults in a Face-Centred-Cubic
Copper-Silicon-Manganese Alloy Deformed by Filling at Liquid Nitrogen Temperature,
Naturwissenschaften, 56(10), 512 (1969) (Experimental, 3)
[1969Vas2] Vasudevan, R., Analysis of X-ray Line Broadening in a Faced-Centred-Cubic
Copper-Silicon-Manganese Alloy Due to Cold-Work at Room Temperature, J. Mater. Sci.,
4(12), 1116-1117 (1969) (Experimental, 7)
[1970Vas] Vasudevan, R., Determination of Particle Size and Strain in a Filed Face-Centred-Cubic
Copper-Silicon-Manganese Alloy by the Method of Variance, J. Mater. Sci., 5(1), 85-86
[1973Fri] Frizen, E.N., Structural Changes in Copper-Silicon-Manganese Alloys During
Tempering, Fiz. Met. Metalloved., 35(5), 1027-1033 (1973) (Experimental, Mechan.
Prop., 16)
[1973Muk] Mukerjee, K.P., Gupta, K.P., A MgZn2 Type Laves Phase in the Mn-Cu-Si System, Met.
Trans., 4(2), 618-619 (1973) (Crys. Structure, Experimental, 6)
[1974Muk] Mukherjee, K.P., Gupta, K.P., Phase Equilibria in the Mn-Cu-Si System at the High Mn
End, Trans. Indian Inst. Met., 27(3), 169-172 (1974) (Experimental, Phase Diagram, Crys.
Structure, 6)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Cu-Mn-Si, INCRA Monograph
Series 6 Phase Diagrams and Thermodynamic Prop. of Ternary Copper-Metal Systems,
NSRD, Washington, 543-548 (1979) (Review, Crys. Structure, Phase Diagram, 11)
[1988Pra] Pradhan, S.K., De, M., An X-Ray Diffraction Line Profile Analysis on the Microstructure
of Cold-Worked Face-Centered-Cubic Cu-Mn-Si Alloys: Effects of Mn and Si as Solutes,
J. Appl. Phys., 64(5), 2324-2327 (1988) (Crys. Structure, Experimental, 16)
[1991Oka] Okamoto, H., Mn-Si (Manganese-Silicon), J. Phase Equilib., 12(4), 505-507 (1991)
(Review, Phase Diagram, 11)
[2002Leb] Lebrun, N., Cu-Si (Copper-Silicon), MSIT Binary Evaluation Program, in MSIT
Workplace, Effenberg G. (Ed.), MSI, Materials Science International Services GmbH,
Stuttgart; Document ID: 20.12505.1.20 (2002) (Crys. Structure, Phase Diagram,
Assessment, 23)
Landolt-Brnstein
New Series IV/11C2
MSIT
336 CuMnSi
[2003Mie] Miettinen, J., Thermodynamic Description of the Cu-Mn-Si System in the Copper-Rich
Corner, Calphad, 27(4), 395-401 (2003) (Assessment, Phase Diagram, Thermodyn., 23)
[2005Tur] Turchanin, M., Agraval, P., Grbner, J., Matusch, D., Turkevich, V., Cu-Mn (Copper -
Manganese), MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg G. (Ed.),
MSI, Materials Science International Services GmbH, Stuttgart; to be published (2005)
Table 1: Investigations of the Cu-Mn-Si Phase Relations, Structures and Thermodynamics

[1930Smi] Thermal analysis 450 - 1100C / Cu rich alloys up to 10 mass% Mn
and 8 mass% Si
[1942Smi] Thermal analysis 450-800C / Cu rich alloys up to 10 mass% Mn and 8
mass% Si
[1945Smi] Microstructural analysis 500 - 800C / Cu based alloys with up to 8 mass% Si
and Mn
[1953Dre] Thermal analysis and 400 - 100C / Cu based alloys with 0 to 50 mass%
microstructure Mn5Si3
[1958Tur] Thermal analysis 400 - 900C / Cu based alloys with 1-12 mass% Mn
and 1-4 mass% Si
[1962Smi] Thermal analysis and X-ray 500 - 1200C / Cu-MnSi, Cu-Mn5Si3, from Cu to 8
diffraction mass%MnSi2
[1973Muk] Metallography and X-ray 25C / Cu based alloys with 11.5 to 25 at.% Si and 33
diffraction to 62.5 at.% Mn
[1974Muk] X-ray diffraction 700C / Cu based alloys with 60 to 10 at.% Si and 30
to 100 at.% Mn

[C] Prototype
(Mn,Cu) cF4 a = 362.63 at x = 0.04 [V-C2]
Fm3m a = 375 at x = 0.80 [V-C2]
Cu
(Cu) a = 361.46 at x = 0 [Mas2]
< 1084.62 a = 360.82 at x = 0 [V-C2] melting point [2005Tur]
(Mn) a = 386 at x = 1 [Mas2]

1138 - 707
( Mn) cI2 a = 308.0 [Mas2]
1246 - 1138 Im3m
W
(Mn) cP20 a = 631.52 [Mas2]
1087 - 707 P4132
Mn
New Series IV/11C2
CuMnSi 337

[C] Prototype
(Mn) cI58 a = 891.26 at 25C [Mas2]
< 707 I43m
Mn
(Si) cF8 a = 543.06 0 to 0.003 at.% Cu [2002Leb]
< 1414 Fd3m
C-diamond
3 c** - [2005Tur]
700
MnCu3 (2) c** - [2005Tur]
450
MnCu5 (1) c** - [2005Tur]
410
R, Mn6Si hR159 12 to 15.75 at.% Si [1991Oka]
< 880 R3 a = 1087.1 0.5 [V-C2]
Co5Cr2Mo3 c = 1918.0 0.9
, Mn4Si oI186 16.2 to 18.75 at.% Si [1991Oka]
< 1060 Immm a = 1699.2 0.4 [V-C2]
Mn4Si b = 2863.4 0.7
c = 465.6 0.1
Mn3Si cF16 a = 572.2 24 to 25.6 at.% Si [1991Oka]
1075.3 - 677 Fm3m [V-C2]
BiF3
Mn3Si - - 25 to 25.6 at.% Si [1991Oka]
< 677
Mn5Si2 tP56 28.6 at.% Si [1991Oka]
< 850 P41212 a = 890.97 0.2 [V-C2]
Mn5Si2 c = 871.53 0.3
Mn5Si3 hP16 37.5 at.% Si [1991Oka]
< 1283.2 P63/mcm a = 691 [V-C2]
Mn5Si3 c = 468.4
MnSi cP8 40.5 to 50.2 at.% Si [1991Oka]
< 1269.6 P213 a = 455.8 [V-C2]
FeSi
Mn11Si19 tP120 a = 552 63.3 at.% Si [1991Oka]
< 1150.2 P4n2 c = 4820
Mn11Si19
, Cu7Si hP2 11.05 to 14.5 at.% Si
842 - 552 P63/mmc a = 256.06 at 12.75 at.% Si [2002Leb]
Mg c = 418.46
, ~Cu6Si cI2 14.2 to 16.2 at.% Si
853 - 787 Im3m a = 285.4 at 14.9 at.% Si [2002Leb]
W
Landolt-Brnstein
New Series IV/11C2
MSIT
338 CuMnSi

[C] Prototype
, Cu5Si(h) t** a = 881.5 17.6 to 19.6 at.% Si
[2002Leb]
< 729 P4132
Mn
< 800 I43d
Cu15Si4
859 - 558 R3m = 109.74
or
t** a = 726.7 [V-C2]

c = 789.2
620 - 647 R3 = 95.72
< 570 b = 700
c = 2194
* -1 , hP12 a = 483 [1974Muk]
Mn50.2Cu32.5Si17.3 P63/mmc c = 783.4
MgZn2
* -2 , - - [1974Muk]
Mn60.5Cu28.3Si11.2
New Series IV/11C2
CuMnSi 339

Cu Mn Si
L + Mn11Si19 (Si) + MnSi < 1144 U1 L 8.01 30.65 61.34
Mn11Si19 0 36.66 63.34
(Si) 0 0 100
MnSi 0 50 50
L+ + < 820 U2 - - - -
L + (Si) + MnSi < 802 U3 (Si) 0 0 100
MnSi 0 50 50
l (Mn,Cu) + Mn5Si3 800 e6 l 69.10 19.31 11.59
Mn5Si3 0 62.5 37.5
L + + MnSi < 800 U4 MnSi 0 50 50
l (Mn,Cu) + MnSi 775 e7 l 71.08 14.46 14.46
MnSi 0 50 50
L Mn5Si3 + MnSi + < 775 E1 L 70.85 16.82 12.33
(Mn,Cu) Mn5Si3 0 62.5 37.5
MnSi 0 50 50
L + MnSi + (Mn,Cu) 760 E2 L 74.43 9.34 16.23
MnSi 0 50 50
Table 4: Investigations of the Cu-Mn-Si Materials Properties

[1930Voc] Tensile tests Mechanical properties
[1942Smi] Electrical conductivity measurements Electrical conductivity
[1952Dre] Mechanical measurements Mechanical properties
[1953Dre] Hardening measurement Mechanical properties
[1961Die] Hardening measurement Mechanical properties
[1967Mil] Hardening measurement Mechanical properties
[1968Gay] Stress relaxation measurement Mechanical properties
[1973Fri] Hardness measurement Mechanical properties
Landolt-Brnstein
New Series IV/11C2
MSIT
340 CuMnSi
1300
Fig. 1: Cu-Mn-Si.
Quasibinary system
1200
Cu - Mn5Si3 L
1100
1000
L+(Mn,Cu)
Temperature, C
L+Mn5Si3
900
800C
800
(Mn,Cu)
700
(Mn,Cu)+Mn5Si3
600
500
400
60 Cu
Cu 10 20 30 40 50 0.00
Mn 62.50
Mn, at.% Si 37.50
1300
Fig. 2: Cu-Mn-Si.
Quasibinary system
Cu - MnSi 1200
L
1100
Temperature, C
1000
L+(Mn,Cu)
900
L+MnSi
800
(Mn,Cu) 775C
700
(Mn,Cu)+MnSi
600
500
Cu 10 20 30 40 Cu 0.00
Mn 50.00
Mn, at.% Si 50.00
New Series IV/11C2
New Series IV/11C2
Landolt-Brnstein
Cu-Mn Cu-Si Cu-Mn-Si Mn-Si

1234 e1
l Mn5Si3+MnSi
1205 p1
l + (Mn) (Mn)
?
1156 p2
l + (Mn) (Mn)
1155 p3
l + MnSi Mn11Si19
1150 e2
<1144 L + Mn11Si19 (Si) + MnSi U1 l Mn11Si19+ (Si)
1097 p4
? 1070 p5
l + (Mn) (Mn,Cu) Mn11Si19+(Si)+MnSi l+ Mn5Si3 Mn3Si
1060 p6
CuMnSi
l + (Mn)
?
853 p7 1040 e3
l + (Mn,Cu) l + Mn3Si
824 p8
l +
820 e4
l+
802 e5 <820 L + + U2
l + (Si) <802 L + (Si) + MnSi U3
++
(Si)+MnSi+ 800 e6
<800 L + + MnSi U4 775 e7 l(Mn,Cu)+Mn5Si3
+MnSi+ l(Mn,Cu)+MnSi
<775 L Mn5Si3+MnSi+(Mn,Cu) E1
760 L + MnSi + (Mn,Cu) E2
(Mn,Cu)+MnSi+Mn5Si3 ?
(Mn,Cu)+MnSi+
MSIT
341
Fig. 3: Cu-Mn-Si. Reaction scheme
342 CuMnSi

Fig. 4: Cu-Mn-Si. Axes: at.%
1400
Liquidus surface
(Si)
20
80
1300
e2
p3
40 1200 Mn11Si19
60
U1
MnSi
1100
1250 e1
60 1000 40
1250
e5
900
e4 Mn5Si3
U3 1200 p5
80 U2 e3
p8 20
p7 U4 e7 p6
( Mn3Si)
e6 ?
900 E2 ( Mn)
E1 1100 p2
?
( Mn) p1
1000 ( Mn,Cu)
20 40 60 80 (Mn)
Cu p4 Mn
Cu 70.00
Mn 0.00
Partial isothermal
section at 800C in
the Cu rich corner
80
20
+L
L

+

+( Mn,Cu)
( Mn,Cu)+L
90
10
n Si 3
( Mn,Cu)+ ,Cu)+M 5
n
(M
( Mn,Cu)+L
( Mn,Cu)
10 20
Cu Cu 70.00
Mn 30.00
Si 0.00
New Series IV/11C2
CuMnSi 343

Partial isothermal
section at 700C
20
80
40
60
MnSi
60
40
Mn5Si3
Mn2Si
?
Mn3Si
80
1
20

2 R
( Mn)
( Mn,Cu)
(Mn)
20 40 60 80
Cu Mn
Cu 75.00
Mn 0.00
Partial isothermal
section at 600C ?
80
20
+MnSi

( Mn,Cu)+

( Mn,Cu)+
90 ( Mn,Cu)+MnSi
10
( Mn,Cu)+Mn5Si3
( Mn,Cu) ?
( Mn,Cu)+ 1
10 20
Cu Cu 75.00
Mn 25.00
Si 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
344 CuMnSi
Cu 70.00
Mn 0.00
Partial isothermal
section at 450C
80
20
( Mn,Cu)+
90
10
( Mn,Cu)+MnSi
n Si 3
Cu)+M 5
( Mn,
( Mn,Cu)+ 1
( Mn,Cu)
10 20
Cu Cu 70.00
Mn 30.00
Si 0.00
1100
Fig. 9: Cu-Mn-Si.
Partial isothermal
L
section at 450C 1000
L+(Mn,Cu)
900
Temperature, C
L+(Mn,Cu)+Mn5Si3
800
(Mn,Cu)
700
(Mn,Cu)+Mn5Si3
(Mn,Cu)+MnSi
600
(Mn,Cu)+Mn5Si3+MnSi (Mn,Cu)+1
500
(Mn,Cu)+Mn5Si3+1
400
Cu 95.59 10 20 Cu 73.82
Mn 0.00 Mn 21.90
Si 4.41 Mn, at.% Si 4.28
New Series IV/11C2
CuMnSi 345
1100
Fig. 10: Cu-Mn-Si.
Isopleth at the L
constant Mn content 1000
of 2 mass%, plotted in
at.% (Mn,Cu)+L
(Mn,Cu)+L+
900
Temperature, C
800
(Mn,Cu) (Mn,Cu)+
(Mn,Cu)+
700
+
600
(Mn,Cu)+MnSi+Mn5Si3
500
(Mn,Cu)+MnSi (Mn,Cu)+MnSi+
400
Cu 97.69 2 6 10 14 Cu 81.51
Mn 2.31 (Mn,Cu)+Mn5Si3 Mn 2.10
Si 0.00 Si, at.% Si 16.39
1100
Fig. 11: Cu-Mn-Si.
Isopleth at the L
constant Mn content 1000
of 4 mass%, plotted in
at.%
L+(Mn,Cu)
900
Temperature, C
L+(Mn,Cu)+MnSi
800
(Mn,Cu)
700
(Mn,Cu)+Mn5Si3 (Mn,Cu)+MnSi
600
500
(Mn,Cu)+1 (Mn,Cu)++MnSi
(Mn,Cu)+MnSi+Mn5Si3
400
Cu 95.40 2 6 10 14 Cu 79.47
Mn 4.60 (Mn,Cu)+Mn5Si3+1 Mn 4.18
Si 0.00 Si, at.% Si 16.35
Landolt-Brnstein
New Series IV/11C2
MSIT
346 CuMnZn
Copper Manganese Zinc

Dirk Matusch, Joachim Grbner, Vladimir Turkevich
Introduction
The results of phase diagram investigations, carried out in the early years of the last century, are not
considered for the construction of the phase diagram [1905Gui, 1906Gui, 1912Car, 1924Hei, 1926Heu,
1928Heu], because manganese used contained significant amounts of impurities and therefore results are
questionable. Copper rich sections of the ternary system were investigated by [1933Bau, 1934Bau,
1945Dea, 1949Gra]. [1933Bau, 1934Bau] used copper and zinc with 99.99% purity, respectively for mixing
with a copper 67.7 mass%-manganese 30.92 mass% alloy containing 1.38 mass% impurities, to produce
samples containing up to 7.5 mass% manganese. The temperature of the peritectic reaction + melt ,
was determined for increasing amount of manganese employing thermal analysis and optical microscopy.
The authors of [1945Dea, 1949Gra] prepared their samples from electrolytic metals with high purity and
determined the solubility of manganese and zinc in -brass for different temperatures employing X-ray and
microscopic methods. [1949Gra] reports in addition the stability ranges of the beta phase in isothermal
sections at 593C and 648C. The equilibrium between and phases was independently investigated by
[1952Haw] on 56 samples, annealed at 672C and investigated by optical microscopy. The results are
similar to [1949Gra]. [1975Gon] and [1977Wat5] determined order-disorder transition temperatures for
compositions of -brass, containing 0.6-5.9 at.% manganese, by means of electrical resistivity and specific
heat measurements. The transformation drops from 466C in binary Cu-Zn to 402C at the maximum
solubility of manganese in phase.
Reviews on the Cu-Mn-Zn system were presented by [1949Jae, 1979Cha, 1979Dri, 1980Bra].
Binary Systems
The binary Cu-Zn is accepted from [2006Leb], which is a compilation of [1994Mio], [1993Kow] and
[2001Her]. Although [2006Leb] suggested the value of 665C for the temperature of the p4 reaction
L + , in this assessment we accepted the value of 700C adopted from [1994Mio], which is now
consistent with the ternary invariant reaction U4.
The binary Cu-Mn was taken from [2005Tur], based on a critical assessment and thermodynamic
calculation.
The Mn-Zn binary, presented in [Mas2, 1990Oka], tried to incorporate all information from older sources
in respect to the various J phases (J, J1, J2). The J phase adopts a simple close packed hexagonal structure
and changes in lattice parameters are smoothly decreasing on the exchange of zinc with manganese. [Mas2]
postulated different J phases on the basis of speculations and investigations carried out before electrolytic
manganese was available. The peritectic temperatures, corresponding to the formation of J1, J2 show a
scattering range resulting obviously from impurities in the alloys. [1960Tez, 1964Nak] found a metastable
J phase with Ni3Sn structure as a transition phase from J phase to ' phase, but the changes of lattice
parameters in the J' phase measured by [1964Hen, 1970Far] show no anomalies. Therefore the existence of
a thermodynamic stable J1 phase and J2 phase is doubtful. Superseding older data, it was clearly shown by
[1971Rom], that there is only one field of a hcp J phase extending from 42 to 88.6 at.% of Zn and no
evidence for J1, J2. Throughout this assessment we therefore will adopt the J phase region of [1971Rom]
and assume the version of [Mas2] for the rest of the diagram. The low temperature region of the binary
( Mn) phase field (called 2 phase in this assessment) was in many reports addressed as an ordered CsCl
type structure; authors, however, gave little justification for a phase transition ( Mn) 2 at about 900C.
New Series IV/11C2
CuMnZn 347
Solid Phases
The Cu-Mn-Zn system includes a ternary Laves phase -1, designated as 3, , T or T1 phase in literature,
with the composition MnCuZn without any significant range of homogeneity at 400C [1946Dea, 1962Tes,
1963Tes, 1969Tes]. The crystal structure of the -1 phase, was reexamined in detail from X-ray powder
diffraction [1976Gon, 1977Wat4] revealing a random distribution of Cu,Zn atoms in the 16d-sites. The
transformation temperature of the -1 phase to the high temperature 2 phase, obtained by high temperature
X-ray diffraction, is given as 502C, in contradiction to [1946Dea] who gave a decomposition temperature
at about 593C without presenting any evidence.
On the basis of the X-ray results of [1977Wat5], showing 2,MnZn and ,CuZn in a two-phase equilibrium,
we assume that neither the phases ,CuZn, ( Mn) nor the phases ',CuZn, 2,MnZn form a continuous
ternary solid solution. In both phase regions ,CuZn as well as ( Mn) there is, however, a concentration and
temperature dependent tendency towards ordering from the W type high temperature modification (,CuZn,
( Mn)) to a CsCl type low temperature modification (',CuZn, 2,MnZn). There is no evidence for a
connection between phases 2 and 1. For details see Table 1.
Investigations of the crystal structure of the J phase, a Hume-Rothery phase, was carried out by [1939Moe1,
1939Moe2, 1943Moe]. A ternary solid solution connecting the J phase of the Cu-Zn and Cu-Mn systems at
400C was reported after investigation of 5 compositions. Without specification of the temperature a
continuous solid solution J,(Cu,Mn,Zn) was also reported by [1954Agl].
A ternary solid solution corresponding to the binary phase from the Mn-Zn system was observed by
[1991Kam]. The work includes only investigations by microscopy and microprobe analysis. [1991Kam]
observed also a phase of the composition MnCuZn10, it could be understood as a solid solution from the
binary 1 phase of the MnZn system or the phase of the CuZn system. The observed phase shows a
decreasing gradient of copper and an increasing gradient of manganese from the centre to the grain surface.
However, in the case of the 1 phase, the authors could not give evidence for an existing connection to the
binary 1 phase. Lattice parameters for the -brass solid solution are given in [1960Cha]. The author has
investigated 23 samples, prepared from ultra pure starting materials and found, that zinc and manganese
together expand the copper lattice on a greater extend than the sum of the expansions when each of the
solutes was considered separately.
The solid phases pertinent to the ternary diagram are listed in Table 1.
A part of the liquidus surface with copper- and zinc rich compositions was investigated by [1972Wat], who
prepared 76 samples from pure electrolytic metals. The author shows 7 invariant reactions by using inverse
rate differential thermal analysis, thermal dilatation, electrical resistance measurements, X-ray diffraction
and microscopic examination. [1977Wat5] added three invariant equilibria in the Zn rich area. A eutectoid
decomposition of the 2 phase to and -1 at about 498C, was observed [1977Wat3]. A transformation
from the disordered ,CuZn phase to the ordered ' phase as a function of Mn concentration is reported,
however, the shown temperature vs concentration section is in contradiction to phase rules and was not
considered among the presented phase diagrams. The invariant reactions are given in Table 2, temperature
and compositions of the phases are taken as reported by [1977Wat5]. A diagram for the partial reaction
scheme comprising the reactions in the Zn corner and for the Mn poor side of the diagram is shown in Fig. 1.
It is in agreement with the experimental phase distribution in the Zn corner at room temperature
[1977Wat5].
Landolt-Brnstein
New Series IV/11C2
MSIT
348 CuMnZn
Liquidus Surface
A liquidus surface and two isothermal sections for the ternary Cu-Mn-Zn have been constructed from
literature data, including all relevant data from 1926 to 1976 [1979Cha]. However the result is partially in
contradiction to the known binary of Mn-Zn. These data have not been considered here. The ternary liquidus
data as collected by [1977Wat5] are accepted and with some modifications to adapt to the known binary
systems are used to construct the liquidus surface as shown in Fig. 2 and for the Zn corner of the diagram
in Fig. 3.
Isothermal Sections
Figures 4 and 5 show the phase relations for the Mn poor region of the diagram for alloys annealed at 600C
and cooled to room temperature (Fig. 4) and for 600C (Fig. 5). Both sections are after [1977Wat5] with
some adaptation to ensure agreement with the accepted binary systems and to remove violation of the
Schreinmaker rule. The original Fig. 5 was labelled qualitative by [1977Wat5].
Thermodynamics
Thermodynamic functions for zinc- and copper rich solutions with manganese were derived from
measurements of vapor pressure of zinc by [1961Cha]. In addition, magnetic susceptibilities of these alloys
were determined in the range of 78C to 200C by using a Sucksmith ring balance. [1986Tak] carried out
interdiffusion experiments of the solid solution at 800C. The obtained interaction parameter was used
for the calculation of the bond strengths, received by dilute solution approximation. The effect of
manganese on the order-disorder transformation in the phase was investigated by [1977Wat1]. It is shown
that the transition temperature is decreasing linearly with increasing manganese content. The ordering
parameter and activation energy are obtained from heat capacity and resistivity measurements.

The interest in manganese addition for the production of brass alloys was the observation of an enhanced
hardness of brass, without becoming brittle [1912Car]. The hardness, tensile and yield strengths and
ductility of brass by adding manganese were discussed by [1926Sma, 1944Lon, 1946Dea, 1961Die,
1966Lah]. It was shown that with increasing amount of manganese the ductility increases and hardness and
tensile- and yield-strengths decrease and the alloys possess good cold working proportions; they are more
resistant to stress corrosion cracking than pure Cu-Zn alloys. The elongation of single phase alloys increases
with zinc content. These alloys could be prepared in conventional furnaces [1966Lah]. The age hardening
behavior of an Cu-25.2Zn-19.1Mn (mass%) alloy, aged at 200C, is due to the eutectoid decomposition of
2 phase [1977Wat2]. The dispersion-strengthening effect was investigated using scanning electron
microscopy (SEM) with electron dispersion spectroscopy (EDS) techniques by [2004Sar].
Miscellaneous
[1985Kan] investigated the diffusion in the phase at 775C. A not explicitly described metastable phase
was observed after decomposition of the 2 phase. The effect of cold working procedures on lattice
parameters and substructures of solid solutions has been investigated by [1984Gho] using X-ray
diffraction with calculation of peak shift, peak broadening and peak asymmetry analyses. It is reported, that
a changing manganese content has no significant effect in deformed substructures. The variation of zinc
indeed ends up in an enhanced faulting concentration.
New Series IV/11C2
CuMnZn 349
References
[1905Gui] Guillet, M.L., Investigations of the Effect of Different Elements in Copper Alloys (in
French), Rev. Metall., 2, 97-120 (1905) (Experimental, 0)
[1906Gui] Guillet, M.L., General Investigation of Brass Alloys (in French), Rev. Metall., 3, 159-204
[1912Car] Carpender, H.C.H., The Effect of Other Metals on the Structure of the -Constituent in
Copper-Zinc Alloys, J. Inst. Met., 8, 59-73 (1912) (Experimental, 2)
[1924Hei] Heike, W., Ledebur, K., The ( + )-Eutectoid of Brass (in German), Z. Metallkd., 16,
380-381 (1924) (Experimental, 2)
[1926Heu] Heusler, O., About the Ternary System Copper-Zinc-Manganese (in German), Z. Anorg.
Chem., 159, 37-54 (1926) (Experimental, 12)
[1926Sma] Smalley, O., Special Nickel Brasses, Trans. Amer. Inst. Min. Met. Eng., 73, 799-833
(1926) (Experimental, Phys. Prop., 0)
[1928Heu] Heusler, O., About the Ternary System Copper-Zinc-Manganese (in German),
Z. Metallkd., 25, 17-22 (1928) (Experimental, Phase Diagram, 7)
[1933Bau] Bauer, O., Hansen, M., The Influence on the Constitution of Copper-Zinc Alloys by a
Third Element V. The Influence of Manganese (in German), Z. Metallkd., 25, 17-22 (1933)
(Experimental, Phase Diagram, #, 13)
[1934Bau] Bauer, O., Hansen, M., The Influence on the Constitution of Copper-Zinc Alloys by a
Third Element V. The Influence of Manganese (in German), Mitt. Material., 23, 43-49
[1939Moe1] Moeller, K., On Mixed Crystals in the Ag-Mn-Zn and Cu-Mn-Zn Ternary System (in
German), Naturwissenschaften, 27, 167 (1939) (Abstract, Experimental, 0)
[1939Moe2] Moeller, K., Two Series of Mixcrystals Between Hume-Rothery Compounds in
Silver-Copper-Zinc Ternary System (in German), Naturwissenschaften, 27, 176 (1939)
(Abstract, Experimental, 0)
[1943Moe] Moeller, K., X-Ray and Optical Investigations in the Zinc-Manganese-Copper-Silver
System (in German), Z. Metallkd., 35, 27-28 (1943) (Crys. Structure, Experimental, 4)
[1944Lon] Long, J.R., Graham, T.R., Physical Properties of a 65-Cu, 10-Mn, 25-Zn Alloy, Trans.
AIME, 156, 222-239 (1944) (Experimental, Phase Diagram, 6)
[1945Dea] Dean, R.S., Long, J.R., Roberson, A.H., The Alpha Solid Solution Field of the
Copper-Manganese-Zinc System, Trans. Am. Inst. Min. Metall. Pet. Eng., 161, 232-243
[1946Dea] Dean, R.S., Long, J.R., Feustel, R.G., Physical Properties of Copper-Manganese-Zinc
Alloys Containing 60 Per Cent Copper and 5 to 25% Manganese, Trans. Am. Inst. Min.
Metall Pet. Eng., 166, 185-196 (1945) (Experimental, #, 8)
[1949Gra] Graham, T.R., Long, J.R., Armantrout, C.E., Roberson, A.H., The Ternary System,
Copper-Manganese-Zinc, Trans. Am. Inst. Min. Metall. Pet. Eng., 185, 675-682 (1949)
(Phase Diagram, Experimental, #, 15)
[1949Jae] Jnecke, E., Kurzgefasstes Handbuch aller Legierungen, (in German), Carl Winter
Universitts-Verlag, Heidelberg, 502-503 (1949) (Review, 3)
[1952Haw] Haworth J.B., Hume-Rothery W., The Effect of Four Transition Metals on the / Brass
Type of Equilibrium, Philos. Mag., 43, 613-629 (1952) (Experimental, Phase Diagram, 23)
[1954Agl] Agladze, R.I., Topchiashvili, L.I., The Zn-Corner of the Ternary System Zn-Mn-Cu (in
Russian), Splavy Margantsa s Medyu, Nikelem i Tsinkom, Tibilisi: Izd. Akad. Nauk. Gruz.,
[1960Cha] Chadwick, G.A., Argent, B.B., The Lattice Parameters of the Alpha Solid Solutions of
Copper-Zinc-Nickel and Copper-Zinc-Manganese, J. Inst. Met., 88, 318-319 (1960)
(Experimental, Crys. Structure, 8)
Landolt-Brnstein
New Series IV/11C2
MSIT
350 CuMnZn
[1961Cha] Chadwick, G.A. and Argent, B.B., Thermodynamic Properties of Solid Solutions Part 3.-
Copper-rich Solid Solutions of Copper+Zinc+Manganese, Trans. Far. Soc., 57, 619-624
(1961) (Thermodyn., 26)
[1960Tez] Tezuka, S., Sakai, S., Nakagawa, Y., Ferromagnetism of Mn-Zn Alloy, J. Phys. Soc. Jpn.,
15, 931 (1960) (Crys. Structure, Phys. Prop., 2)
[1961Die] Dies, K., Manganese Bronses (in German), Metall, 15(12), 1161-1172 (1961)
(Experimental, 8)
[1962Tes] Teslyuk, M.Yu., Markiv, V.Ya., New Ternary Laves Phases in Systems Containing Zn,
Ga, In and Ge (in Russian), Kristallografiya, 7, 128 (1962) (Crys. Structure, 4)
[1963Tes] Teslyuk, M.Yu., Markiv V.Ya., Crystal Structure of a Ternary Compound in the
Mn-Cu-Zn System (in Russian), Visn. Lviv. Derzh. Univ. Ser. Khim., 6, 50-53 (1963)
(Crys. Structure, Phase Diagram, 11)
[1964Hen] Henderson, B., Willcox, R.J.M., Lattice Spacing Relationships in Hexagonal
Close-Packed Solver-Zink-Manganese Alloys, Philos. Mag., 9, 829-846 (1964) (Crys.
Structure, Phase Diagram, 10)
[1964Nak] Nakagawa, Y., Hori, T., Neutron Diffraction Studies of Mn-Zn Alloys, J. Phys. Soc. Jpn.,
19, 2082-2087 (1964) (Crys. Structure, 9)
[1966Lah] Lahiri, A.K., Mukherjee, K.P., Banerjee, T., Studies on Properties of Some Ternary
Copper Alloys of the Cu-Mn-Zn and Cu-Mn-Ni System, Trans. Indian Inst. Met., 19,
141-146 (1966) (Phys. Prop., 10)
[1969Tes] Teslyuk, M.Yu., Intermetallic Compounds with Structure of Laves Phases, (in Russian),
Nauka, Moscow, 1-138 (1969) (Review)
[1970Far] Farrar, R.A., King, H.W., Axial Ratios and Solubility Limits of hcp and J Phases in the
Systems Cd-Mn and Zn-Mn, Metallography, 3, 61-70 (1970) (Crys. Structure, 19)
[1971Rom] Romer, O., Wachtel, E., On the Constitution of the System Zinc-Manganese and
Zinc-Manganese-Aluminium (in German), Z Metallkd, 62, 820-825 (1971) (Experimental,
Phase Diagram, 27)
[1972Wat] Watanabe, H., Kono, N., Gonda, M., A Study of the Phase Diagram of the Ternary
Cu-Zn.Mn System (in Japanese), J. Jpn. Inst. Met., 36, 297-305 (1972) (Phase Diagram,
#, 6)
[1975Gon] Gonda, M., Takahashi, T., Watanabe, H., The Effect of Mn on the Order-Disorder
Transformation in -Brass (in Japanese), J. Jpn. Inst. Met., 39, 939-943 (1975) (Phys.
Prop., 16)
[1976Gon] Gonda, M., Okayama, N., Kono, N., Watanabe, H., Takahashi, T., A Study of the Ternary
Compound T and Phases of the Cu-Zn-Mn System (in Japanese), Shindo Gijutsu
Kenkyukai-Shi, 15, 222-227 (1976) (Crys. Structure, 3)
[1977Wat1] Watanabe, H., Kono, N., Gonda, M., Okayama, K., Takahashi, T, Effect of Manganese in
the Order-Disorder Transformation in -Brass (in Japanese), Chiba Kogyo Daigaku
Kenkyu Hokoku, Rico Hen 22, 95-102 (1977) (Phys. Prop., 27)
[1977Wat2] Watanabe, H., Kono, N., Okayama, K., Study of the Ternary Copper-Zinc-Manganese
System Part 5. Age Hardening of -T Pseudo Binary Alloys of the Copper-Zinc-Manganese
System (in Japanese), Chiba Dai. Bun. Gak. Kiyo Shi. Kag., 22, 109-115 (1977) (Crys.
Structure, Phys. Prop., 2)
[1977Wat3] Watanabe, H., N. Kono, Gonda, M., Takahashi, T., On the Tempering Process in '-T
Pseudo-Binary Alloys of the Cu-Zn-Mn System (in Japanese), Chiba Kogyo, 22, 103-108
(1977) (Phase Diagram, Phys. Prop., 10)
[1977Wat4] Watanabe, H., Kondo, N., Gonda, M.,A Study on the Ternary Compound T and Phase
of the Cu-Zn-Mn System (in Japanese), Chiba Kogyo Daigaku Kenkyu Hokoku, Rico Hen
22, 81-94 (1977) (Phase Diagram, Crys. Structure, 4)
[1977Wat5] Watanabe, H., Kono, N., Gonda, M., A Study of the Phase Diagram of the Ternary
Cu-Zn.Mn System (in Japanese), Chiba Kogyo Daigaku Kenkyu Hokoku, Rico Hen 22,
67-79 (1977) (Crys. Structure, Phase Diagram, #, 6)
New Series IV/11C2
CuMnZn 351
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., INCRA Monograph Series 6 Phase
Diagrams and Thermodynamic Properties of Ternary Copper-Metall Systems, NSRD,
Washington, 558-565 (1979) (Review, Phase Diagram, 12)
[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhonova, Rokhlin, L.L.,
Turkina, N.I., Binary and Multicomponent Copper-Base Systems, (in Russian), Nauka
Moscow, 172-174 (1979) (Review, Phase Diagram, 12)
[1980Bra] Brandes, E.A., Flint, R.F., Manganese Phase Diagrams, Manganese Centre, Paris, 112
(1980) (Review, Phase Diagram, 1)
[1984Gho] Ghosh, S.K., Sen Gupta, S.P., An X-Ray Diffraction Study on the Microstructures of
Cold-Worked Face-Centered-Cubic Cu-Mn-Zn Alloys. III. Role of Additions of
Transitional Solute Mn, J. Appl. Phys., 56, 1213-1217 (1984) (Phys. Prop., 19)
[1985Kan] Kansky, K.E., Dayananda, M.A., Quaternary Diffusion in the
Copper-Nickel-Zinc-Mangan System at 775C, Metall. Trans. A, 16A(6), 1123-1132
[1986Tak] Takahashi, T., Katoh, M., Minamino, Y., Yamane, T., Interdiffusion and Thermodynamic
Study of a Solid Solution of Cu-Mn-Zn System at 1073 K (in Japanese), Nippon Kessho
Gakkaishi, 50, 243-249 (1986) (Thermodyn., 23)
[1990Oka] Okamoto, H., Tanner, L.E., The Mn-Zn (Manganese-Zink) System, Bull. Alloy Phase
Diagrams, 11(4), 377-384 (1990) (Review, Phase, Diagram, Crys. Structure, 38)
[1991Kam] Kamenova, T.S., Valkanov, S., Zadgorskii, S., Nenchev, N., Phase Structure of Wrought
Alloys of the System Zinc-Manganese-Copper (in Bulgarian), Tekhnicheska Misul, 28,
101-106 (1991) (Experimental, 0)
[1993Kow] Kowalski, M., Spencer, P.J., Thermodynamic Reevaluation of the Cu-Zn System, J.
Phase Equilib., 14(4), 432-438 (1993) (Phase Diagram, Review, Calculation, 36)
[1994Mio] Miodownik, A.P., Cu-Zn (Copper-Zinc), in Phase Diagrams of Binary Copper Alloys,
Park, OH, 487-496 (1994) (Review, Crys. Structure, Phase Diagram, Review,
Thermodyn., 98)
[2001Her] Hertz, J., What will be Done in the Future with O.J. Kleppas Enthalpy Data Set?,
J. Alloys Compd., 321(2), 201-222 (2001) (Phase Relations, Review, Thermodyn., 50)
[2004Sar] Sari, U., Agan, S., Aksoy, I., Gueven, K., Kahveci, N., Dispersion-Strengthening Effect of
Cu-Based Mn, Al, and Zn Rich Alloys, J. Mat. Proc. Tech., 150(3), 208-214 (2004)
(Experimental, Kinetics, Morphology, Phase Relations, 16)
[2005Tur] Turchanin, M., Agraval, P., Grbner, J., Matusch, D., Turkevich, V., Cu - Mn (Copper -
Manganese), MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.),
MSI, Materials Science International Services, GmbH, Stuttgart; to be published, (2005)
(Crys. Structure, Phase Diagram, Thermodyn., Assessment, 25)
[2006Leb] Lebrun, N., Perrot, P., Cu - Zn (Copper - Zinc), MSIT Binary Evaluation Program, in
MSIT Workplace, Effenberg, G. (Ed.), Materials Science International Services, GmbH,
Stuttgart; to be published (2006) (Crys. Structure, Phase Diagram, Assessment, 18)
Landolt-Brnstein
New Series IV/11C2
MSIT
352 CuMnZn

[C] Prototype
, Cu1xyMnxZny cF4 a = 371.31 x = 0.116, y = 0.256 [1960Cha]
(Cu) Fm3m a = 361.46 x = y = 0, at 25C [Mas2]
< 1084.62 Cu melting point [1994Sub]
complete solid solution with (Mn) and
dissolves 38.95 at.% Zn at 454C
[Mas2]
(Mn) a = 386.0 x = 1, [Mas2] dissolves 34 at.% Zn

1138 - 1100
( Mn) a = 308.0 [Mas2] dissolves 50 at.% Zn

1246 - 1138 dissolves 12.5 at.% Cu
2, (MnZn)Cu1) cP2 described as low temperature ordering
Pm3m variant of ( Mn) [Mas2], at 39.8 at.% Zn
MnZn CsCl [1990Oka]
ca. 900 - 620 a = 306.0 at 550C [1977Wat4]
a = 296.8
(Mn) cP20 a = 631.52 [Mas2]
1100 - 727 P4132 dissolves 48 at.% Zn
Mn a = 649 at 46 at.% Zn [1990Oka]
(Mn) cI58 a = 891.26 at 25C [Mas2]
< 727 I43m dissolves 1.7 at.% Zn
Mn
(Zn) hP2 a = 267.73 [V-C2]
< 425C P63/mmc c = 483.17
Mg dissolves 2.8 at.% Cu at 425C [Mas2]
dissolves 1 at.% Mn at 417.25C [Mas2]
, (CuZn)Mn cI2 dissolves 36.1 to 55.8 at.% Zn [Mas2]
CuZn(h)1) Im3m a = 295.39 at 52.3 at.% Cu [V-C2]
902 - 454 W a = 294.90 at 54.9 at.% Cu [V-C2]
dissolves about 10 at.% Mn at 600C
and 19 at.% Mn at 799C [1977Wat5]
', CuZn(r)1) cP2 dissolves 44.7 to 48.2 at.% Zn [Mas2]
< 468C Pm3m a = 294.9 at 44.7 at.% Cu [V-C2]
CsCl a = 295.9 at 50.5 at.% Cu [V-C2]
low temperature dissolves about 8 at.% Mn at 25C
variant of ,CuZn(h) [1977Wat5]
, Cu5Zn8 cI52 a = 885.9 to 888.7 [2006Leb]
< 834C I43m dissolves 57.0 to 70.0 at.% Zn
Cu5Zn8 dissolves about 15 at.% Mn at 600C
and about 12 at.% Mn at 25C
[1977Wat5]
New Series IV/11C2
CuMnZn 353

[C] Prototype
, CuZn3 hP3 a = 427.5 dissolves 72.45 to 76 at.% Zn [2006Leb]
700 - 560 P6 c = 259.0
CuZn3
1, MnZn cP2 dissolves from ? to 50 at.% Zn [Mas2]
< 180 Pm3m a = 306.5 at 43.5 at.% Zn [1990Oka]
CsCl
J, MnxCu1xyZny hP2 [1943Moe] described a complete solid
P63/mmc solution from the Cu-Zn to the Mn-Zn
Mg system at 400C
MnxZny2) [1971Rom] reported a continuous

815 - 220 solution from 42 to 88.6 at.% Zn
a = 273.1 at 45.7 at.% Zn [1990Oka]

c = 445.5
a = 276.60 at 85.4 at.% Zn [1990Oka]

c = 444.52
a = 275.0 33.8 at.% Cu and 66.2 at.% Zn

c = 442.4
a = 273.1 18.9 at.% Cu and 81,1 at.% Zn

c = 428.4
'(h), Mn7.5xZn2.5+x cP4 69 to 75 at.% Zn; 0 < x < 6 [Mas2]
< 325 Pm3m a = 386 [V-C2]
AuCu3
1'(r), Mn7.5xZn2.5+x tP2 70 to 75 at.% Zn; 0 < x < 5 [Mas2]
< 143 P4/mmm a = 390 [V-C]
AuCu c = 372
and 1, MnZn4 cI52 a = 916.0 [Mas2] solves 77 to 84.4 at.% Zn
< 420 I43m [1990Oka]
Cu5Zn8 eventually shows ordering at lower
temperatures (1)
2, MnZn~10 hP* - 86.5 - 90.6 at.% Zn [Mas2]
462 - 380 a solid solution to 1 is assumed by
[1991Kam]
1, MnZn10 hP* a = 1283 88.9 - 90.8 at.% Zn [Mas2] [1990Oka]
< 424 c = 577 a solid solution to is assumed by
[1991Kam]
Landolt-Brnstein
New Series IV/11C2
MSIT
354 CuMnZn

[C] Prototype
, MnZn13 mC28 a = 1348.3 [V-C]
< 428 C2/m b = 766.26 solves 92.6 to 92.9 at.% Zn [Mas2]
CoZn13 c = 513.4
= 127.78
* -1, MnCuZn cF24 a = 697.96 [1976Gon]
< 502 Fd3m a = 696.6 [1962Tes]
Cu2Mg a = 695.0 from multi-phase alloy Cu1.5MnZn0.5
[1963Tes]
Designations used in different
publications: T, T1, , 3
1) On the basis of the X-ray results of [1977Wat5], showing 2,MnZn and ,CuZn in a two-phase equilibrium, we
assume that neither the phases ,CuZn, ( Mn) nor the phases ',CuZn, 2,MnZn form a continuous ternary solid
solution. In both ternary phase regions starting from binary ,CuZn as well as ( Mn) there is, however, a
concentration and temperature dependent tendency towards ordering from the W type high temperature modification
(,CuZn, ( Mn)) to a CsCl type low temperature modification (',CuZn, 2,MnZn). There is no evidence for a
connection between phases 2 and 1.
2) According to [1971Rom] a continuous solution with hexagonally closed packed Mg type structure extends from 42
to 88.6 at.% Zn comprising the J phases, which in several reports are listed as J (Mg type), J1 (Ni3Sn type), J2
(hexagonal, hp*) of which J1, J2 likely are metastable.

Cu Mn Zn
L + + 2 799 U1 L 35.9 28.2 35.9
L + 2 + 786 U2 L 32.3 21.5 46.2
L + 2 J + 743 U3 L 26.6 18.6 54.9
L+J+ 682 U4 L 21.1 7.0 71.9
2 + + -1 490 D1 - - - -
2 + J + -1 477 D2 - - - -
2 + + -1 473 D3 - - - -
L + J 2 + (Zn) 422 U5 - - - -
L + 2 (Zn) + 419.5 U6 - - - -
2 (Zn) + + 1 341 D4 - - - -
New Series IV/11C2
CuMnZn 355
Mn-Zn Cu-Mn-Zn A-B-C Cu-Zn

903 p1
L++
L+
L+2+ 835 p2
815 p3 L+
L + 2 799 L + 2 + U1
L+2+ +2+
L+2+
786 L + 2 + U2
L+2+ +2+
743 L + 2 + U3
+2+
L++ ca.700 p4
L+
682 L++ U4
620 e1
2 + 574 p5
L++
L+
548 e2
++
462 p6 +
L + 2
428 p7
L + 2
424 p9 424 p8
2 + 1 L + (Zn)
422 L + 2 + (Zn) U5
L+2+(Zn)
+2+(Zn)
419 L + 2 (Zn) + U6
418 e3
L + (Zn)
380 e4
2 + 1
2++(Zn)
341<T<380 2+ 1+(Zn) U7
+1+(Zn) 2+ 1+ (Zn)
341 2 (Zn) + , 1 D4
(Zn) + + 1
Fig. 1: Cu-Mn-Zn. A partial reaction scheme
Landolt-Brnstein
New Series IV/11C2
MSIT
356 CuMnZn

Fig. 2: Cu-Mn-Zn. Axes: at.%
Liquidus surface of
the Cu-Zn rich region p5, 574
625
650 600 p , 665
4
20
80
725
750 675 775
U4
p3,815 70
0
40
60
p2

80
U3
0
2 U2

82
60
5
40
p1, 903
U1
950
975
80
20
1025
85
0
875
Mn
20 40 60 900 925 80 1000 Cu

Fig. 3: Cu-Mn-Zn. (Zn) Axes: at.%
Liquidus surface of p8
e3
the Zn corner p7 U6 425

U5
450
p6
475
500

525
10
90
550
575C
Mn 15.00 10 Mn 0.00
Cu 0.00 Cu 15.00
Zn 85.00 Zn 85.00
New Series IV/11C2
CuMnZn 357

Partial isothermal
section at room
temperature
20
80
+
40
60
'+
++ 1 + 1
'++1 '

60 '+ 1 40
+ '+ 1
'+
1
+ 1
80
20
+(Mn)
20 40 60 80
Mn Cu

Partial isothermal
section at 600C
(qualitative) L
20
80
L++

++
40
60

++2
60

40
+2+
2
80 ++2
20
20 40 60 80
Mn Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
358 CuNbSi
Copper Niobium Silicon

Volodymyr Ivanchenko
Introduction
Copper is a component of many composites, which contain superconductive A15 phases. This induced
significant interest in ternary systems of the NbSi-M type, including Cu-Nb-Si. Unfortunately, the existence
of the ternary Nb5Cu4Si4 phase, the crystal structure of which was determined by [1968Gan], makes this
system useless for bronze technology. Nevertheless, the solubility of NbSi2 in liquid copper was studied
by [1972Jan]. Some controversy exists on the existence of the Nb5Cu4Si4 phase. Although the existence of
Nb5Cu4Si4 was confirmed by [1979Sav1, 1979Cha], the authors of [1981Zan] reported that no ternary
phases could be observed in their phase equilibria studies. [1981Zan] explained the appearance of
Nb5Cu4Si4 by non-equilibrium crystallization conditions. Such an explanation, however, is in contradiction
with the findings of [1979Sav1] on annealed alloys. [1982Pan] studied the influence of alloying with copper
on the phase formation in the Nb-Si system and reported on the existence of a further ternary phase:
Nb4CuSi. At 1500C this phase was said to be in equilibrium with Nb based solid solution and Nb5Si3. The
ternary compound Nb5Cu4Si4 was also detected in several as-cast specimens with the crystal structure and
lattice parameters virtually the same as presented by [1968Gan] and [1979Sav1]. [1982Pan] reported that
Nb5Cu4Si4 melts at 1170 10C. [1992Mat] studied the silicide formation and phase separation from
Cu/Nb and Nb/Cu bilayers on silicon. The formation of the ternary phase Nb5Cu4Si4 was observed after
annealing Cu/Nb at 700C and Nb/Cu at 800C.
Phase equilibria and physical property investigations of Cu-Nb-Si alloys were further stimulated by
theoretical predictions of [1974Pal] that a hypothetical, stoichiometric Nb3Si with A15 structure may reach
a superconducting transition temperature TC of about 25 to 29 K. This prediction was confirmed by
[1975Pan], who obtained a metastable compound Nb3Si with A15 structure under a high-pressure shock
wave: the onset temperature of the transition in the superconducting state was measured at 18.5 K.
There were two suggestions about how to form Nb3Si with A15 structure: (i) using the possibility to
stabilize the Nb3Si compound with A15 structure by alloying Nb-Si with Cu (but [1978Sav] and [1982Pan]
have shown that in equilibrium alloys copper does not stabilize the A15 type structure); (ii) formation of a
metastable phase due to strong non-equilibrium crystallization during rapid cooling from the liquid state.
The latter idea was confirmed by [1978Sav, 1979Sav1, 1979Sav2, 1980Sav]: indeed high cooling rates from
the melt in the presence of Cu lead to the appearance of some quantity of superconductive phase. The
superconducting properties of various intermetallic phases in equilibrium and metastable states were shortly
reviewed by [1983Sav].
The methods and experimental techniques used in experimental studies of Cu-Nb-Si alloys are summarized
in Table 1.
There was only one attempt to calculate phase equilibria in the Cu-Nb-Si system. However, these
calculations by [1992Rei] for 25 and 700C did not take into account the presence of the ternary phases and
therefore are considered inaccurate.
Binary Systems
The Cu-Si phase diagram is taken from [2002Leb]. The Cu-Nb phase diagram is accepted from [2002Rom].
The Nb-Si phase diagram is from [Mas2], who excluded Nb5Si3 with Mn5Si3 type as a metastable phase
from the binary system. For a complete listing of metastable binary Nb-Si phases see [Mas2]. A critical
assessment and thermodynamic calculation of the Nb-Si system is due to [2002Fer].
Solid Phases
Solid phases observed in this system are given in Table 2. Existence of two ternary phases is accepted: -1,
Nb5Cu4Si4 and -2, Nb4CuSi.
New Series IV/11C2
CuNbSi 359
Liquidus Surface
The liquidus surface was presented by [1981Zan]. It is not accepted here because ternary phases were not
observed in this investigation and were not shown in the liquidus surface.
Isothermal Sections
The partial 800C isothermal section has been constructed by [1979Sav2]. It is presented in Fig. 1 after
minor modifications described below. The isothermal section at 1500C for the entire composition range is
presented in Fig. 2 basically from [1982Pan]. In both isothermal sections some modifications of the original
diagrams have been made to ensure agreement with the lower solubility of Cu in (Nb) and narrower regions
of Nb5Si3 and liquid in the accepted binary systems.

In cast and annealed Cu-Nb-Si alloys supeconductivity above 4.2 K is exhibited only by the Nb base solid
solution. Simultaneous alloying of Nb with Si and Cu, decreases the TC of Nb to 7.9 K at the total content
of alloying elements of 2-3 at.% and to 7.3 K at 40%. This is somewhat below the TC of the saturated Nb
base solid solution in the binary Nb-Si system (8.5 K) [1976Mue]. After rapid quenching and tempering
ternary Cu-Nb-Si alloys, the TC of the Nb based supersaturated solid solutions decreases to less then 4.2 K.
This is due to enhanced solubility of Cu and Si in Nb during quenching from liquid state, and due to the
appearance of thermal stresses. Rapidly quenched alloys of Nb with 20-27 at.% Si and 20-30 at.% Cu had
two transitions in the superconducting state: one at 7.7 K, corresponding to transition of Nb base solid
solution, the other at 13.85-14.1 K for a small amount (10-20 vol%) of metastable Nb3Si with A15 structure.
This superconductive phase was not observed in binary Nb-Si alloys quenched with the same rate. Whereas
rapid quenching of alloys of the Nb-Si system is insufficient to stabilize the superconducting metastable
phase, the effect of the high cooling rate in the presence of copper promotes the appearance of the
superconductive metastable phase with TC = 14.1 K. However, this value is less than the one for the
metastable Nb3Si produced under an extremely high pressure shock wave [1975Pan], for which the onset
of the superconducting state was measured at 18.5 K.
Miscellaneous
One way to produce superconductors with high TC was proposed by [1983Sav]. It consists in producing
superconducting alloys in amorphous state with further crystallization by heat treatment.
References
[1968Gan] Ganglberger, E., The Crystal Structure of Nb5Cu4Si4 (in German), Monatsh. Chem., 99,
549-556 (1968) (Crys. Structure, 7)
[1972Jan] Jangg, G., Kieffer, R., Blaha, A., Sultan, T., Solubility of Disilicides in Auxiliary Metal
Melts (in German), Z. Metallkd., 63, 670-676 (1972) (Experimental, 24)
[1974Pal] Palatnik, L.S., Falko, I.I., Crystallochemical Analysis of the AV3BIV-type
Superconductive Compounds (in Russian), Doklady Acad. Nauk SSSR, 217(3), 573-576
(1974) (Crys. Structure, Theory, Superconduct., 15)
[1975Pan] Pan, V.M., Alekseevskiy, V.P., Popov, A.G., Beletskiy, Yu.I., Yupko, L.M., Yarosh, V.V.,
New Hightemperature Superconductor Nb3Si, (in Russian), Pisma Zhur. Eksper. Teor.
Fiz., 21(8), 494-496 (1975) (Experimental, Crys. Structure, Superconduct., 2)
[1976Mue] Mller, P., Structure of Niobium-Silicon Alloys (in German), Kristall und Technik, 11(1),
K3-K6 (1976) (Experimental, Crys. Structure, Phase Relations, Superconduct., 12)
[1978Sav] Savitsky, E.M., Yefimov, Y.V., Muchin, G.G., Frolova, T.M., Structure and Properties of
Equilibrium and Rapidly Quenched Cu-Containing Alloys, Rapidly Quenched Metals III,
1, 167-170 (1978) (Crys. Structure, 20)
Landolt-Brnstein
New Series IV/11C2
MSIT
360 CuNbSi
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Cu-Nb-Si, in INCRA
Copper-Metall Systems, NSRD, Washington, 573-574 (1979) (Crys. Structure, Review, 3)
[1979Sav1] Savitskii, E.M., Efimov, Yu.V., Frolova, T.M., Influence of Copper on the Structure and
Superconducting Properties of Transition Metals, Inorg. Mater.(Engl. Trans.), 15(4),
512-515 (1979) (Phase Diagram, Superconduct., 14)
[1979Sav2] Savitskii, E.M., Efimov, Yu.V., Bodak, O.I., Frolova, T.M., Structure and
Superconducting Properties of Nb-Si-Cu Alloys (in Russian), Fiz.-Khim. Anal.
Sverkhprovodyashchikh Splavov Savitski, E.M. (Ed.), 38-43 (1979) (Crys. Structure,
Experimental, Phase Diagram, Superconduct., 13)
[1980Sav] Savitsky, E.M., Yefimov, Yu.V., Frolowa, T.M., Schamowa, N.A., Structure and
Characterization of V(Nb)-Al(Ga, Sr, Ge, Sn)-Cu Compounds (in German),
J. Less-Common Met., 76, 81-98 (1980) (Crys. Structure, Experimental, Phase Diagram, 41)
[1981Zan] Zankl, R., Malter, R., Phase Equilibria in the System Copper-Niobium-Silicon (in
German), Z. Metallkd., 72(10), 720-724 (1981) (Experimental, Phase Diagram, 12)
[1982Pan] Pan, V.M., Latysheva, V.I., Kulik, O.G., Popov, A.G., Influence of Alloying with
Germanium and Copper on the Conditions of Formation of the Superconducting Compound
Nb3Si, Russ. Metall., (3), 167-171 (1982), translated from Izv. Akad. Nauk SSSR, Met.,
[1983Sav] Savitskii, E.M., Efimov, Yu.V., Bychkova, M.I., Giller, I.D., Myasnikova, E.A.,
Sumarokov, V.N., Frolova, T.M., Metastable Superconducting Phases (in Russian), Dokl.
Akad. Nauk SSSR, 269(1), 114-116 (1983) (Review, Superconduct., 10)
[1992Mat] Mattoso Filho, N., Achete, C., Freire, F.L., Jr., Silicide Formation and Phase Separation
from Cu/Nb and Nb/Cu Bilayers on Silicon, Thin Solid Films, 220, 184-190 (1992)
(Experimental, 16)
[1992Rei] Reid, J.S., Kolawa, E., Nicolet, M.A., Thermodynamics of (Cr, Mo, Nb, Ta, V, or
W)-Si-Cu Ternary Systems, J. Mater. Res., 7(9), 2424-2428 (1992) (Phase Diagram,
Thermodyn., 26)
[2002Fer] Fernandes, P.B., Coelho, G.C., Ferreira, F., Nunes, C.A., Sundman, B., Thermodynamic
Modeling of the Nb-Si System, Intermetallics, 10, 993999 (2002) (Phase Diagram, Phase
[2002Leb] Lebrun, N., Dobatkina, T., Kuznetsov, V., Li, Ch.,Cu-Si (Copper-Silicon), MSIT Binary
[2002Rom] Van Romplay, T., Cu-Nb (Copper-Niobium), MSIT Binary Evaluation Program, in MSIT
Assessment, 16)
Table 1: Investigations of the Cu-Nb-Si Phase Relations, Structures and Thermodynamics

[1968Gan] Single crystal X-ray determination of Annealing at 1100C, 36Nb-32Cu-32Si (at.%)
crystal structure of Nb5Cu4Si4
[1972Jan] Dissolving of NbSi2 in liquid Cu 1200C, Cu-NbSi2, (Cu)
[1978Sav, Optical microscopy, SEM, EMPA, As-cast, annealed at 800C, and rapidly
1979Sav2, magnetic susceptibility quenched from liquid state alloys
1980Sav] (106-107 K#s1), < 40 at.% Si and < 80 at.% Cu
New Series IV/11C2
CuNbSi 361

[1979Sav1] Optical microscopy, X-ray analysis, As-cast, annealed at 800C, and rapidly
microhardness quenched from liquid state alloys
(106-107 K#s1), < 40 at.% Si and < 80 at.% Cu
[1981Zan] Optical microscopy, X-ray analysis, 800, 875C, entire ternary system
EMPA
[1982Pan] Optical microscopy, X-ray analysis 1500C, < 80 at.% Si and < 40 at.% Cu
[1992Mat] Auger electron spectroscopy, Rutherford 200 - 800C, Nb/Cu and Cu/Nb bilayers
backscattering spectrometry, X-ray electron-beam evaporated on silicon
diffraction, TEM

[C] Prototype
(Cu) cF4 a = 361.46 0 to 11.1 at.% Si [2002Leb]
< 1084.62 Fm3m
Cu
(Si) cF8 a = 543.06 0 to 0.003 at.% Cu [2002Leb]
< 1414 Fd3m
C-diamond
(Nb) CI2 a = 330.04 dissolves up to 1.2 at.% Cu at 1080C
< 2469 Im3m [2002Rom]
W
Cu7Si hP2 a = 256.05 11.05 to 14. 5 at.% Si;
842 - 552 P63/mmc c = 418.46 at 12.75 at.% Si [2002Leb]
Mg
Cu6Si cI2 14.2 to 16.2 at.% Si
853 - 787 Im3m a = 285.4 at 14.9 at.% Si [2002Leb]
W
Cu5Si(h) t** 17.6 to 19.6 at.% Si [2002Leb]
824 - 711 sample was annealed at 700C [V-C2]
a = 881.5
c = 790.3
Cu5Si(r) cP20 a = 619.8 17.15 to 17.6 at.% Si [2002Leb]
< 729 P4132
Mn
Cu15Si4 cI76 a = 961.5 21.2 at.% Si [2002Leb, V-C2]
< 800 I43d
Cu15Si4
Cu3Si(h2) hR* a = 247 23.4 to 24.9 at.% Si [2002Leb]
859 - 558 R3m = 109.74
or a = 726.7 [V-C2]
t** c = 789.2
Landolt-Brnstein
New Series IV/11C2
MSIT
362 CuNbSi

[C] Prototype
Cu3Si(h1) hR* a = 472 23.2 to 25.2 at.% Si [2002Leb]
620 - 467 R3m = 95.72
Cu3Si(r) o** a = 7676 23.3 to 24.9 at.% Si [2002Leb]
< 570 b = 700
c = 2194
Cu5Si t** a = 647 at 17 at.% Si
c = 873 metastable [2002Leb]
Nb3Si tP32 25 at.% Si [Mas2]
1980 - 1770 P42/n a = 1023.0 R.T. [V-C2]
Ti3P c = 518.0
Nb5Si3 tI32 37.5 to 40.5 at.% Si [Mas2]
2520 - 1650 I4/mcm a = 1002.6 R.T. [V-C2]
W5Si3 c = 507.17
Nb5Si3 tI32 a = 657.1 37.5 to38.5 at.% Si [Mas2]
< 1940 I4/mcm c = 1188.9 R.T. [V-C2]
Cr5B3
NbSi2 hP9 a = 481.9 66.7 at.% Si [Mas2]
< 1940 P6222 c = 659.2 R.T. [V-C2]
CrSi2
Nb3Si cP8 a = 515.5 Nb3.24Si0.76, high pressure
Pm3n [V-C2]
Cr3Si
Nb3Si cP4 a = 422.0 [V-C2], metastable ?
Pm3m
AuCu3
Nb5Si3 hP16 a = 753.6 Carbon stabilized phase
P63/mcm c = 524.9 [V-C2]
Mn5Si3
* -1, Nb5Cu4Si4 tI26 a = 1019.08 36Nb-32Cu-32Si (at.%),
< 1170 I4/m c = 360.04 [1968Gan, V-C2]
Nb5Cu4Si4 melting point [1982Pan]
* -2, Nb4CuSi tP12 a = 620.5 formed above 1500C
< at least 1500 P4/mmc c = 506.8 [1982Pan, V-C2]
Nb4CoSi
New Series IV/11C2
CuNbSi 363

Fig. 1: Cu-Nb-Si. Axes: at.%
Partial isothermal
section at 800C
20
80
40
60
60
40
Nb5Si3
(Nb)+ Nb5Si3+ 1 1
80
20
(Nb)+(Cu)+ 1
(Cu)
20 40 60 80
Nb Cu

Fig. 2: Cu-Nb-Si. Axes: at.%
1500C
20
80
L+NbSi2
NbSi2
40
60
Si 2
+ Nb L
i
b 5S
3
Nb5Si3+NbSi2 N
L+
60
Nb5Si3 40
L+Nb5Si3
(Nb)+ Nb5Si3
2

L+ Nb5Si3+ 2
3+
80
20
5 Si
2
Nb
L+ 2
+
b)
(N
L+(Nb)+ 2
L+(Nb)
20 40 60 80
Nb (Nb) Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
364 CuNbSn
Copper Niobium Tin

Pierre Perrot, Julius C. Schuster
Introduction
Practical interest in the Cu-Nb-Sn ternary system started with the discovery of the bronze process for the
production of Nb3Sn superconductors. Filaments of Nb are drawn down in a Cu-Sn bronze matrix and
reacted to produce a fully stabilized Nb3Sn wire which has very good superconducting properties
[1978Dew]. The success of this process for making Nb3Sn is partly due to the fact that there are no stable
ternary compounds in the Cu-Nb-Sn system [1987Nei] and no interference of a more stable phase between
Nb3Sn and (Cu). Isothermal sections have been investigated between 675 and 1100C mainly by diffusion
of tin-copper alloys with niobium.
Binary Systems
Cu-Nb, assessed by [1982Cha] and Cu-Sn, assessed by [1990Sau] are accepted as given by [Mas2]. As for
the Nb-Sn system, [Mas2] gives a diagram redrawn from [S], which is anterior to 1969. [1970Cha] reported
the most extensive investigation on the Nb-Sn phase diagram by diffusion experiment and detected the
formation of Nb3Sn, Nb6Sn5 and NbSn2 in a 6 weeks diffusion experiment at 650C. Figure 1 gives the
Nb-Sn system as proposed by [1970Cha] and later accepted by [1977Kru, 1984Ino, 1987Nei]. Below
800C, the absence of Nb3Sn and Nb6Sn5 is due to the low diffusion rate rather then to the instability of the
compounds.
Solid Phases
Solid phases are given in Table 1. The crystal parameter and the critical temperature of Nb3Sn, measured at
16.5 K are nearly independent of the stoichiometry [1996Sve]. There is no ternary compounds whose
existence has been clearly established. However, diffusion experiment made by [2001Nau] suggests the
formation of an intermetallic phase whose approximate composition is Cu2Nb3Sn8. The existence of this
compound has not been confirmed and its crystal structure is unknown.
Liquidus Surface
The liquidus surface has been qualitatively drawn by [1972Die] and more precisely investigated by
[1975Zwi, 1979Cha, 1979Dri]. The melting grooves separating 10 areas of primary crystallization are
shown in Fig. 2. The dominant feature is the large field of primary crystallization of Nb3Sn and (Nb). The
8 remaining fields stand close to the Cu-Sn border, containing less than 0.15 at.% Nb. The invariant
equilibria given in Table 2 are from [1979Cha, 1979Dri]. Although these authors present the invariant point
at 225C as a ternary peritectic, it is more surely a eutectic.
Isothermal Sections
The isothermal section at 675C given Fig. 3 has been mainly investigated by [1987Nei]. Compositional
analysis of intermetallic compounds formed in diffusion couples bronze-niobium after 528 h and 675 h
shows that Nb3Sn and Nb6Sn5 may dissolve 3 at.% Cu whereas the solubility of copper in NbSn2 does not
exceed 0.6 at.%. [1975Zwi] gives an isothermal section at 785C without formation of the ,Cu17Sn3 phase.
[1972Die] presents at 700C an isothermal section showing a three-phase field Nb-Nb3Sn-liquid Cu45Sn55
which is questionable. On the other hand, [1974Sha] prepares a Cu93Nb3Sn2 melt followed by an annealing
at 700C and shows the precipitation of Nb3Sn crystals in the copper matrix. [1975Sch] charges Cu-Nb
alloys with Sn by a vapor transport reaction and forms Nb3Sn by a diffusion reaction during 21 h at 725C.
[1980Pan] prepares 105 alloys by the method of electric arc welding followed by 100 h annealing at 800C
and proposes an isothermal section [1980Pan, 1981Pan] showing solubilities of Nb in liquid Cu-Sn higher
New Series IV/11C2
CuNbSn 365
than 10 at.%. Such high solubilities coming from the oversaturation of the melt are not confirmed by further
studies. However, [1977Kru] shows that the solubility of Nb in liquid Cu-Sn (0 to 20 at.% Cu) increases
with Cu content (see Fig. 1). Figure 4 gives an isothermal section at 800C, mainly from [1980Pan,
1983Bar] in essential agreement with the isothermal section given at 785C by [1979Cha].
Phase relations at 1000C (Fig. 5) and 1100C (Fig. 6) have been determined from diffusion experiments
by [1975Zwi, 1977Hop, 1980Sav]. The isothermal section proposed at 1000C by [1977Hop] is preferred
because [1975Zwi] gives a three-phase field (Nb)-Nb3Sn-liquid Cu95Sn5. Such a section prohibits the
existence of a tie line between (Cu) and Nb3Sn, which contradicts further experimental evidences given by
[1977Hop, 1978Dew, 1980Pan, 1983Bar, 1987Nei]. The solubility of Nb in liquid is small; less than 5 at.%
Nb are sufficient to crystallize the Nb3Sn phase from most liquid compositions.

The Cu-Nb-Sn system is important because the alloys are used in engineering as superconducting materials
for the production of high magnetic fields and in the transmission of alternative current electrical power
[1999Hel]. The Nb3Sn based composite superconductors are prepared by the so-called bronze technique
[1996Pop]: multifilamentary Nb is prepared in a Cu-Sn matrix and superconducting Nb3Sn layers are
obtained by diffusion. The plastic deformation behavior of such composites has been investigated by
[2000Pop] which showed that, with increasing the degree of deformation, the dislocation density decreases
in the bronze matrix and increases in the Nb filaments. The critical current increases with the Sn
concentration up to the single phase limit of Sn in Nb3Sn, then decreases with the excess of Sn once the
solubility limit reached [1974Sue]. The structure formed by long term diffusion of Cu-Sn alloys and Nb
metal has been shown to consist of fcc (Cu) and A15 (Pm3n) Nb3Sn phases. Small filaments of Nb3Sn
fabricated in a ductile copper base matrix may present a critical current density of 10 kA#cm2 at 4.2 K under
a magnetic field of 12 T [1977Fon]. Similar results are obtained when preparing Cu-Nb alloys by a chill
casting technique. After drawing a fine wire, Nb3Sn is formed by plating and diffusion of Sn [1978Ver].
Superconducting Nb3Sn presents a high critical temperature, from 17.6 K (Nb81Sn19) to 18.3 K (Nb75Sn25)
and carries large [1975Gol1, 1975Gol2] superconducting currents in very high magnetic fields. The
dissolution of copper does not change significantly the critical temperature [1979Efi, 1984Ino], but
increases by one order of magnitude the critical current density [1974Sha] and improves the capacity of
shielding high magnetic fields of Nb3Sn [1976Lef].
High cooling rates (106-107 K#s1) from the Nb-Sn melts in presence of Cu favors the appearance of some
quantities (10-20 vol%) of a metastable superconducting phase whose critical temperature lies between 13.8
and 14.1 K [1978Sav, 1980Sav]. If pure copper is not a superconductor, even at low temperatures, a small
amount of dispersed superconducting particles in a copper matrix induces superconductivity. The best
superconducting properties (critical temperature of 12.0 K and critical current density of 130 kA#cm2) were
observed in a Cu99.55Nb0.30Sn0.15 alloy quenched from the liquid state and aged at 550C for 384 h
[1978Nag]. Superconductivity may also be obtained from a Cu92.5Nb5Sn2.5 alloy rapidly quenched into a
powder by ultrasonic gas atomization [1991Ino]. The powder has been consolidated by hot extrusion at
650C then annealed for 100 h at the same temperature in order to synthesize Nb3Sn. The critical
temperature of the as quenched alloy is 8.0 K, but increases to 15.6 K after annealing. The critical current
density is 74 kA#cm2 at zero applied field and 4.2 K.
The solid state diffusion behavior in a layered Cu-Nb/Cu couple was investigated by using very thin Nb
filaments as a marker for studying the Kirkendall phenomena [1998Luo]. Results show that the Nb
filaments, during annealing at 400-450C, shift towards the Cu-Nb side, which is due to the volume
expansion resulting from the formation of the J,Cu3Sn phase prior to A15 (Nb3Sn) formation. A similar
observation has been performed by [2001Nau] which pointed out the impossibility of a complete mixing of
Cu and Sn before the formation of Nb3Sn, so that the Nb filaments have to react with different Cu-Sn
phases, however, without any consequences for the superconducting properties of the fully reacted samples.
Formation of an amorphous phase may be obtained by mechanical alloying of the Cu44Nb42Sn14 and
Cu45Nb35Sn20 alloys, which are in a domain where no amorphous phase may be obtained by rapid
quenching, but not with the Cu45Nb50Sn5 alloy, not rich enough in tin [1987Ino]. Indeed, amorphization
Landolt-Brnstein
New Series IV/11C2
MSIT
366 CuNbSn
requires a negative heat of mixing providing the necessary chemical driving force, which is not realized in
an alloy in which the two major constituents, Cu and Nb present repulsive interactions. The amorphous
alloy Cu44Nb42Sn14 present, in differential scanning calorimetry, a broad exothermic peak between 480 and
590C, which corresponds to the precipitation of copper [1988Mat].
Miscellaneous
Ingots of the ternary composites (Cu-13% Sn)-30% Nb and (Cu-8% Sn)-30%Nb has been prepared by direct
crystallization in a high temperature gradient (~40 K#mm1) and quenched at a cooling rate (~100 K#s1)
high enough to prevent the formation of the brittle compound Nb3Sn [1998Arz]. The internal friction
measurements showed the existence of a minimum around ~175C, which is correlated with the temperature
at which the plasticity dip occurs in tin bronzes. Wetting angles of liquid Sn or Cu-Sn alloys on Cu, Nb
or Cu-Nb substrates was measured by [1988Mor]. The fraction of Nb or Cu in the solid substrate was
considered as a controlling factor in wetting behavior.
References
[1970Cha] Charlesworth, J.P., Macphail, I., Madse, P.E., Experimental Work on the Niobium-Tin
Constitution Diagram and Related Studies, J. Mater. Sci., 5, 580-603 (1970) (Phase
Diagram, Experimental, 49)
[1972Die] Dietrich, I., Lefranc, G., Mueller, A., Shielding Behavior of Niobium-Tin Materials
Sintered by Adding a Third Element (in German), J. Less-Common Met., 29, 121-132
(1972) (Phase Diagram, Experimental, 33)
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of Phase Transformation Temperature (in Czech), Kovove Mater., 15(2), 125-128 (1977)
(Experimental, #, 7)
New Series IV/11C2
CuNbSn 367
[1978Dew] Dew-Hugues, D., Luhmann, T.S., The Thermodynamics of A15 Compound Formation by
Diffusion from Ternary Bronzes, J. Mater. Sci., 13, 1868-1876 (1978) (Experimental, 41)
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101-102 (1978) (Electr. Prop., Experimental, 7)
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System (in Russian), Nauka, Moscow, 186-187 (1979) (Phase Diagram, Review, #, 1)
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the Superconducting Compound Nb3Sn, Russ. Metall., (5), 168-172 (1979)
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Monograph Series 6, Phase Diagrams and Thermodynamics Properties of Ternary
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Characterization of V(Nb)-Al(Ga, Sr, Ge, Sn)-Cu Compounds (in German),
J. Less-Common Met., 76, 81-98 (1980) (Crys. Structure, Experimental, Phase
Relations, 41)
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and the Superconductive Properties of Niobium-Tin-Copper Alloys, Phys. Met.
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(1980) (Phase Diagram, Superconduct., 7)
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Superconducting Properties of Alloys with Niobium and Vanadium (in Russian), Fazovye
Ravnovesiya v Metallicheskich Splavach, 201-208 (1981) (Review, 23)
[1982Cha] Chakrabarti, D.J., Laughlin, D.E., The Cu-Nb System, Bull. Alloy Phase Diagrams, 2(4),
455-460 (1982) (Review, #, 11)
[1983Bar] Baron, V.V., Gladishavskii, E.I., Kadirbaev, A.R., Skolozdra, R.B. Superconducting
Properties of Nb-Sn-Cu Alloys (in Russian), Sverkhprovod. Mater., 53-55 (1983)
(Experimental, Superconduct., #, 14)
[1984Ino] Inoue, T., Komatsu, H., Shimizu, M., Toyota, N. Growth of Large Grained Nb3Sn
Polycrystals from Cu-Sn-Nb Solutions by Top Seeded Solution Growth, J. Cryst. Growth,
69, 260-268 (1984) (Experimental, 16)
[1987Ino] Inoue, A., Kimura, H.M., Matsuki, K., Masumoto, T., Preparation of New Amorphous
Cu-Nb-Sn Alloys by Mechanical Alloying of Elemental Copper, Niobium and Tin
Powders, J. Mater. Sci. Lett., 6, 979-981 (1987) (Experimental, Morphology, 14)
[1987Nei] Neijmeijer, W.L., Kolster, B.H., The Ternary System Nb-Sn-Cu at 675C, Z. Metallkd.,
78(10), 730-737 (1987) (Experimental, Phase Relations, Phase Diagram, #, *, 28)
[1988Mat] Matsuki, K., Inoue, A., Kimura, H.M., Masumoto, T., New Amorphous Cu-Nb-(Si, Ge or
Sn) Alloys Prepared by Mechanical Alloying of Elemental Powders, Mater. Sci. Eng., 97,
47-51 (1988) (Experimental, Morphology, 14)
Landolt-Brnstein
New Series IV/11C2
MSIT
368 CuNbSn
[1988Mor] Mori, N., Hongou, H., Ogi, K., Wettability and Interaction Between Cu-Nb Alloys and
Liquid Sn Alloys (in Japanese), J. Jpn. Inst. Met., 52(3), 355-362 (1988) (Phys. Prop.,
Experimental, 22)
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278-287 (1990) (Review, #, 57)
[1991Ino] Inoue, A., Masumoto, T., Arnberg, L., Baeckstroem, N., Production of Superconducting
Cu-Nb-Sn Alloy by Hot Extrusion of Rapidly Solidified Powder, J. Mater. Sci., 26,
3951-3954 (1991) (Experimental, Morphology, Electr. Prop., 8)
[1996Pop] Popova, E.N., Popov, V.V., Romanov, E.P., Rodionova, L.A., Sudareva, S.V., Vorobeva,
A.E., Shikov, A.K., Effect of Alloying on the Kinetics of the Formation of
Superconducting Layers and Fine Structure of the Nb/Cu-Sn Composites, Phys. Met.
Metallogr., 81(6), 653-659 (1996) (Morphology, Transport Phenomena, Experimental, 24)
[1996Sve] Sverdlov, V.Ya., Tikhinsky, G.F., Tikhonovsky, M.A., Lazareva, L.S., Chupikov, A.A.,
Martynyuk, L.I., Lapina, N.V., Structure and Properties of Nb3Sn in Ternary Cu-Nb-Sn
Alloys., IEEE Trans. Magn., 32(4), 2882-2885 (1996) (Crys. Structure, Electr. Prop.,
Experimental, 10)
[1998Arz] Arzhavitin, V.M., Sverdlov, V.Ya, Internal Friction in Directed Crystallization
(Cu-Sn)-Nb Alloys, Tech. Phys., 43(11), 1376-1378 (1998) (Mechan. Prop., Morphology,
Experimental, 11)
[1998Luo] Luo, L., Gong, Y.G., Gong, S.M., Hu, S.H., Aggregation of Nb Filaments in Cu-Nb/Sn
Composite During Low Temperature Intermetallic Growth, Mater. Lett., 35, 357-363
(1998) (Morphology, Phase Relations, Transport Phenomena, Experimental, 14)
[1999Hel] Heller, R., Schneider, T., Optimization of the Niobium-Tin Inserts for the 80 kA Current
Lead to be Used in the TOSKA Facility for the ITER Toroidal Field Mosel Coil Test, IEEE
Trans. Appl. Supercond., 9(2), 511-514 (1999) (Electr. Prop., Experimental, 6)
[2000Pop] Popova, E.N., Sudareva, S.V., Popov, V.V., Rodionova, L.A., Romanov, E.P., Vorobeva,
A.E., Dergunova, E.A., Malafeeva, O.V., Khlebova, N.E., Shikov, A.K., Plastic
Deformation of Composites Cu/Nb, Cu/Nb(Ti) and Cu-Sn/Nb(NbTi), Phys. Met.
Metallogr., 90(2), 199-208 (2000), translated from Fiz. Met. Metalloved., 90(2), 125-124
(2000) (Morphology, Mechan. Prop., Experimental, 33)
[2001Nau] Naus, M.T., Lee, P.J., Larbalestier, D.C., The Influence of the Starting Cu-Sn Phase on the
Superconducting Properties of Subsequently Reacted Internal Sn Nb3Sn Conductors, IEEE
Trans. Appl. Supercond., 11(1), 3569-3572 (2001) (Morphology, Phase Relations,
Transport Phenomena, Experimental, 12)
New Series IV/11C2
CuNbSn 369

[C] Prototype
(Cu) cF4 0 to 9.1 at.% Sn [Mas2]
< 1084.62 Fm3m 0 to 0.1 at.% Nb at 1080C
Cu a = 361.6 0 at.% Sn [V-C2]
a = 368.8 6.8 at.% Sn [V-C2]
(Nb) cI2 a = 330.04 0 to 1.2 at.% Cu at 1080C [Mas2]
< 2469 Im3m
W
(Sn) tI4 a = 583.18 ~ 0 at.% Cu [Mas2]
I41/amd c = 318.18 ~ 0 at.% Nb [Mas2]
Sn
(Sn) cF8 a = 648.92 ~ 0 at.% Cu [Mas2]
< 13 Fd3m ~ 0 at.% Nb [Mas2]
C diam.
, ~Cu17Sn3 cI2 a = 302.61 13.1 to 16.5 at.% Sn [Mas2]
798-586 Im3m at 710C and 15 at.% Sn [V-C2]
W
, ~Cu3Sn cF16 15.5 to 27.5 at.% Sn [Mas2]
755 - 520 Fm3m a = 611.66 at 710C [V-C2]
BiF3
, ~Cu41Sn11 cF416 a = 1798.0 20 to 21 at.% Sn [Mas2, V-C2]
585 - 350 F43m
Cu41Sn11
, ~Cu7Sn2 hP26 a = 733.0 20.3 to 22.5 at.% Sn [Mas2, V-C2]
640 - 582 P63 c = 786.4
Cu10Sn
J, ~Cu3Sn oC80 a = 552.9 24.5 to 25.9 at.% Sn [Mas2, V-C]
< 676 Cmcm b = 4777.5
Cu3Sn c = 432.3
, ~Cu6Sn5(h) hP4 a = 419.2 43.5 to 45.5 at.% Sn [Mas2, V-C2]
P63/mmc c = 503.7
NiAs
, ~Cu6Sn5(r) h** a = 2087 44.8 to 45.5 at.% Sn [Mas2]
< 189 c = 2508.1 superstructure of [V-C2]
Nb3Sn cP8 a = 528.5 16.1 to 26.7 at.% Sn [1970Cha],
< 2130 Pm3n Dissolves up to 3 at.% Cu [1987Nei].
Cr3Si Crystal parameter from [1996Sve]
Nb6Sn oI44 a = 565.6 44.9 to 46.4 at.% Sn [1970Cha]
< 930 Immm b = 919.9 Dissolves 3.4 at.% Cu [1987Nei]
Sn5Ti6 c = 1684.3
NbSn2 oF48 a = 986.0 66 to 68.6 at.% Sn [1970Cha]
< 845 Fddd b = 564.77 [V-C2]
CuMg2 c = 1912.7
Landolt-Brnstein
New Series IV/11C2
MSIT
370 CuNbSn

Cu Nb Sn
L + (Nb) (Cu) + Nb3Sn 1075 U1 L 99.8 0.15 0.05
L + (Cu) + Nb3Sn 788 U2 L 84.4 0.1 15.5
L + + Nb3Sn 750 U3 L 80.9 0.1 19
L + Nb3Sn + Nb6Sn5 670 U4 L ~ 70 0.1 ~30
L + Nb6Sn5 + NbSn2 650 U5 L ~ 63 0.1 ~37
L + J + NbSn2 630 U6 L 56.9 0.1 43
L + J + NbSn2 410 U7 L 13.3 0.1 86.6
L + NbSn2 + (Sn) 225 E L 1.3 0.1 98.6
2500
Fig. 1: Cu-Nb-Sn. 2469C
The Nb-Sn binary 2250
system [1970Cha] L+(Nb) L
(Nb)
with vertical sections 2130
2000
at 10 and 20 at.% Cu 9at.% Sn
1750
10at.% Cu
Temperature, C
1500
L+Nb3Sn 20at.% Cu
1250
(Nb)+Nb3Sn
1000
930
845
750
Nb3Sn L+Nb6Sn5 NbSn2+L
500
Nb3Sn+ Nb6Sn5+NbSn2
Nb6Sn5
250
Nb6Sn5 NbSn2 NbSn2+(Sn)
0
Nb 20 40 60 80
Sn
Sn, at.%
New Series IV/11C2
CuNbSn 371
Sn
Fig. 2: Cu-Nb-Sn. (Sn) e3
Melting grooves and e2
fields of primary p3 E
crystallization p7
p2 U7
(schematic)
Nb
Sn 2

Nb 6
Sn
Sn 5
U6 p6
U5
Nb3Sn
Nb3Sn U4
p5
U3 p4
p1
U2 (Cu)
(Nb)
U1
(Nb)
e1
Nb Cu Cu

Fig. 3: Cu-Nb-Sn. Axes: at.%
675C
NbSn2+L
20
80
L
NbSn2
40
60
Nb6Sn5 Nb6Sn5+L
60
40
Nb6Sn5+
Nb3Sn
Nb3Sn+
80
20

+Nb3Sn
Nb3Sn+

20 40 60 80
Nb (Nb) +(Nb) Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
372 CuNbSn

800C
20 NbSn2+L
80
NbSn2
L
Nb6Sn5+L
40
60
Nb6Sn5
60
40
Nb3Sn+L
Nb3Sn
80
20
Nb3Sn+

20 40 60 80
Nb (Nb) (Nb)+ Cu

1000C
20
80
40
60
60
40
Nb3Sn+L
Nb3Sn
80
20
Nb3Sn+

20 40 60 80
Nb +(Nb) Cu
New Series IV/11C2
CuNbSn 373

1100C
20
80
L
40
60
60
40
Nb3Sn+L
Nb3Sn
80
20
20 40 60 80
Nb (Nb) (Nb)+L Cu
Landolt-Brnstein
New Series IV/11C2
MSIT
374 CuNiSi
Copper Nickel Silicon

K.C. Hari Kumar, Armin Kussmaul, Hans Leo Lukas, Gnter Effenberg
Introduction
The phase diagram Cu-Ni-Si is of considerable industrial significance, it contains the Corson alloy, an alloy
of Cu with about 1 mass% Si and 3 mass% Ni, which age-hardens by precipitation of Ni2Si or Ni3Si during
annealing between 450 and 550C. This alloy is produced in large scale for electric switches and plugs. The
Cu-Ni-Si system is relatively complex. Corson [1927Cor1, 1927Cor2, 1930Cor1, 1930Cor2] was first
exploring the system experimentally. Okamoto [1938Oka, 1939Oka1, 1939Oka2, 1939Oka3] investigated
the system by thermal, metallographic, X-ray, dilatometric, and hardness measurements. Several isothermal
and vertical sections were presented. The liquidus projection and coordinates of the corresponding
four-phase equilibria were also reported [1939Oka2]. In the area between 10 and 20 mass% Ni and 12 to 15
mass% Si a ternary phase was reported by [1939Oka2]. For the phase of the Cu-Si system he reported Ni
solubility up to 25 mass%. The ,Cu5Si(r) phase which in the binary Cu-Si system is formed on cooling by
a peritectic reaction + at 730C with more than 10 mass% Ni crystallizes primarily from liquid
containing more than 2 mass% Ni. For the Ni31Si12 and ,Ni2Si phases Okamoto [1939Oka2] reported large
Cu solubilities of 35 and 20 mass%, respectively. [1959Las], however, concluded from X-ray investigations
of the Ni Silicides that Ni2Si, Ni31Si12, and Ni3Si do not dissolve significant amounts of copper. [1973Sok]
report appreciable Cu solubility only for ,Ni2Si, but much less than [1939Oka2]. Other experimental
investigations are restricted to some details. [1957Nov, 1958Nov] gave isotherms of the liquidus and
(Ni,Cu) solvus in the Cu corner. These isotherms, however, show a severe inflection incompatible with the
findings of Corson, Okamoto and Sokolovskaya et al. [1971Sok, 1973Sok], who measured the solubility of
Si in the whole range of the ,(Ni,Cu) solid solution and gave a complete isothermal section at 500C. In
this isothermal section ternary solubilities are shown for the Mn type ,Cu5Si(r) phase (~15 at.% Ni), the
,Cu3Si(h2) phase (~10 at.% Ni) and the ,Ni2Si(h) phase (~10 at.% Cu). [1977Lug] investigated the
vertical section at 10 at.% Si by thermal analysis. [1975Tep] identified the particles precipitating during age
hardening of the Corson alloy to be the orthorhombic Ni2Si ( 1) phase. [2000Wit] measured the partial
enthalpies of liquid by high temperature solution calorimetry at 1627C.
Reviews of the experimental determination of the ternary phase diagram were given by [1949Jae],
[1979Cha], [1979Dri]. The age hardening abilities of Cu-Ni-Si alloys containing 3 and 5% Ni+Si in the
atomic ratio Ni:Si=2:1 were studied by [1935Jen]. Based on microscopic investigations, the authors
proposed a ternary phase on the Cu rich side of the system with a widely variable composition.
Binary Systems
The Cu-Ni and Cu-Si binary systems are accepted from [2002Leb1] and [2002Leb2], respectively. The
transformations between , and were not investigated in the ternary system, therefore these three
phases are not distinguished in this assessment and treated as a single phase called . The Ni-Si system is
accepted from [Mas2].
Solid Phases
The system is dominated by a fcc ,(NixCu1x) solution which dissolves up to 15 mass% Si on the Ni rich
side and 10 mass% Si on the Cu rich side. Corson [1930Cor2] presented solubility limits of Si in (Ni,Cu) of
the whole Cu-Ni range for 975, 825 and below 500C. At a Cu:Ni ratio of 6:1 a solubility minimum of 0.9
mass% Si was reported for 975C. Solubility limits of ,(NixCu1x) were shown in graphs by [1931Jon] for
500 and 900C, by [1939Oka3] for 900 and 450C, [1957Nov, 1958Nov] for 700, 800, 900 and 1000C, by
[1971Sok, 1973Sok] for 500C. Although these solubilities are given in small graphs only, some
disagreement is detectable. On the ternary solubilities of the binary intermediate phases is even more
discrepancy in literature. Okamoto [1939Oka2] reported large solubilities in the binary phase
New Series IV/11C2
CuNiSi 375
(25 mass% Ni), in the !,Ni31Si12 phase (34 mass% Cu) and in the ,Ni2Si(h) phase (30 mass% Cu).
[1959Las], however, at least for !,Ni31Si12 stated the Cu solubility to be small.
A ternary phase with appreciable range of homogeneity around a composition of about Cu3NiSi was
postulated by Okamoto [1939Oka2] without determining structural details. There is no other experimental
verification of this phase. [1949Jae] in his compilation interpreted also the Ni rich part of the ,Cu5Si(r)
phase given by [1939Oka2] as a ternary phase. Also [1957Nov] mentioned it as a ternary phase.
Crystallographic data for all solid phases are given in Table 1.
Quasibinary Systems
Corson [1927Cor1, 1927Cor2] reported the section Cu-Ni2Si to be quasibinary with a eutectic at about
1030C, 9 mass% Ni2Si in the (Cu) solid solution and 12 mass% Ni2Si in the liquid phase (values taken
from graph). In all later publications dealing with this part of the system [1935Jen, 1938Oka, 1939Oka2,
1957Nov, 1959Las] all sections between (Cu) and any of the Ni-silicides were assumed to be not
quasibinary.
[1939Oka2] reported temperatures and liquid compositions of the invariant equilibria containing liquid.
However, these data have to be taken with care, as the homogeneity ranges of some phases of [1939Oka2]
are not commonly accepted. As no better data for coordinates and types of invariant reactions are available
Okamotos table is reproduced here as Table 2.
Liquidus Surface
A liquidus projection of the whole system was reported by [1939Oka2] (reproduced in Fig. 1). The same
problems exist as with the invariant equilibria. The review articles [1949Jae, 1979Cha, 1979Dri] accepted
this liquidus surface.
Isothermal Sections
Isothermal section of the Cu rich corner were given by [1939Oka1] at 450C up to 25 mass% Ni and
20 mass% Si and at 1010, 950 and 800C up to 10 mass% Ni and 7 mass% Si [1939Oka3]. [1957Nov] gave
isothermal sections of the Cu corner up to 8 mass% Ni+Si for 1000, 900, 800 and 700C. [1973Sok] gave
a 500C isothermal section of the whole system. The shapes of the (Cu) solid solution boundary differs
between the three investigators. All three agree on equilibria (Cu)+Ni3Si, (Cu)+Ni31Si12 and
(Cu) + ,Cu5Si(r), the latter assumed to be a ternary phase by [1957Nov]. [1973Sok], however, reports an
equilibrium (Cu)+Ni2Si at 500C between the 2nd and 3rd equilibrium, which was not found by the other
two groups, by [1939Oka3] even not at 450C. [1975Tep] found Ni2Si(r) to be the phase precipitating
during age hardening and that is an argument for Sokolovskaya version [1973Sok]. As there are not
sufficient arguments to solve the disagreements, no critically assessed isothermal section can be given. In
Fig. 2 the 500C section of [1973Sok] is reproduced.

Vertical sections were presented by [1927Cor1, 1927Cor2] (Cu side of Cu-Ni2Si), [1938Oka] (4 complete
and 4 qualitative ones without scaling the composition axis), [1939Oka2] (16 complete and 12 partial ones),
[1957Nov] (six ones restricted to the Cu corner), [1972Che] (30 mass% Cu, 40 mass% Si and 1 mass% Si),
[1973Sok] (one, between Ni2Si and Cu) and [1977Lug] (one, at 10 at.% Si). None of the sections of
different authors is for the same composition line. Comparison of neighboring sections, however, reveals
some disagreement. The Cu side of the section from Cu to Ni2Si from [1927Cor1, 1927Cor2] is reproduced
in Fig. 3. The invariant line, however, has to be interpreted as a narrow normal three-phase field
L+(Cu)+Ni2Si.
Landolt-Brnstein
New Series IV/11C2
MSIT
376 CuNiSi
References
[1927Cor1] Corson, M.G., Copper Hardened by a New Method (In German), Z. Metallkd., 19,
370-371 (1927) (Phase Relations, Experimental, 2)
[1927Cor2] Corson, M.G., Copper Hardened by a New Method, Trans. Amer. Inst. Min. Met. Eng.,
Inst. Metals Div., 421-424 (1927) (Phase Relations, Experimental, 0)
Application for the Copper Hardening, (in French), Rev. Metall., 27, 194-213 (1930)
Application for the Copper Hardening, Fourth Part, (in French), Rev. Metall., 27, 265-281
(1930) (Phase Relations, Experimental, 4)
[1931Jon] Jones, D.G., Pfeil, L.B., Griffiths, W.T., Nickel-Copper Alloys of High Elastic Limit,
J. Inst. Met., 46, 423-442 (1931) (Phase Relations, Experimental, 7)
[1935Jen] Jenkins, C.H.M., Bucknell, E.H., The Inter-Relation of Age-Hardening and Creep
Performance. Part I.-The Age-Hardening of Nickel-Silicon-Copper Alloys, J. Inst. Met.,
57, 141-189 (1935) (Phase Relations, Experimental, 38)
[1938Oka] Okamoto, M., The Investigation of the Equilibrium State of the Whole System
Copper-Nickel-Silicon. Report I (in Japanese), Nippon Kinzoku Gakkai-Shi, 2, 211-238
(1938) (Phase Relations, Experimental, 10)
[1939Oka1] Okamoto, M., The Investigation of the Equilibrium State of the Whole System
Copper-Nickel-Silicon. The II. Report (in Japanese), J. Jpn. Inst. Met., 3, 336-348 (1939)
[1939Oka2] Okamoto, M., The Investigation of the Equilibrium State of the Ternary Whole System
Cu-Ni-Si. III. On the Heterogeneous Equilibrium Relating to Liquid of the Ternary Whole
System Cu-Ni-Si (in Japanese), J. Jpn. Inst. Met., 3, 365-402 (1939) (Phase Relations,
Experimental, 10)
[1939Oka3] Okamoto, M., The Investigation of the Equibrium State of the Whole Ternary System
Cu-Ni-Si. IV. On the Field of the Ternary -Solid Solution(in Japanese), J. Jpn. Inst. Met.,
3(11), 411-420 (1939) (Phase Relations, Experimental)
[1949Jae] Jnecke, E., Cu-Ni-Si in Kurzgefasstes Handbuch Aller Legierungen, Winter,
Heidelberg, 513-517 (1949) (Review)
[1957Nov] Novikov, I.I., Dautova, L.I., Investigation of the Cu corner of the Cu-Ni-Si, Russ. J. Inorg.
Chem., 2, 135-143 (1957) (Phase Relations, Experimental, 4)
[1958Nov] Novikov, I.I., Dautova, L.I., The System Cu-Ni-Si (in Russian), Tr. Inst. Yadernoi Fiz.,
Akad. Nauk, 1, 274-281 (1958) (Phase Relations, Experimental, 4)
[1959Las] Lashko, N.F., Sorokina, K.P., Phase Analysis of the Cu Corner of the Cu-Ni-Si System,
Russ. J. Inorg. Chem., 4(7) 727-728 (1959) (Phase Relations, Experimental, 5)
[1971Sok] Sokolovskaya, E.M., Chechernikova, O.I., Gladyshevsky, E.I., Bodak, O.I.,
Physicochemical Study of the Ni Alloys with Cu and Si, Vestn. Mosk. Univ., Ser. 2:
Khim., 12, (1971) (Phase Relations, Experimental, 7)
[1972Che] Chechernikova, O.I., Sokolovskaya, E.M., Guzei, L.S., A Physicochemical Study of
Alloys of Ni with Cu and Si, Vestn. Mosk. Univ., Ser. 2: Khim, 13, 486-489 (1972) (Phase
[1973Sok] Sokolovskaya, E.M., Chechernikova, O.I., Gladyshevsky, E.I., Bodak, O.I., The Ni-Cu-Si
System, Russ. Metall. (Engl. Transl.), translated from Izv. Akad. Nauk SSSR, Met., (6)
114-119 (1973) (Phase Relations, Phase Diagram, Experimental, 10)
[1975Tep] Teplitskii, M.D., Nikolaev, A.K., Revina, N.I., Rozenberg, V.M., Investigation of the
Dispersed Particles in Ageing Alloys o f Cu-Ni-Si and Cu-Co-Si, Phys. Met. Metallogr.,
40(6), 99-103 (1975) (Phase Relations, Experimental, Crys. Structure, 9)
New Series IV/11C2
CuNiSi 377
[1977Lug] Lugscheider, E., Differential Thermoanalysis of Ternary Nickel-Copper-Metalloid

Alloys, Proc. 5th Int. Conf. Thermal Analysis (ICTA 5), 98-101 (1977) (Phase Relations,
Experimental, 6)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Cu-Ni-Si, in INCRA Monograph
Systems, NSRD, Washington, 597-603 (1979) (Phase Diagram, Crys. Structure,
Review, 13)
[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova, N., Rokhlin, L.L.,
Turkina, N.I., Cu-Ni-Si, in Binary and Multicomponent Copper-Base Systems (in
Russian), Nauka, Moscow, 151-154 (1979) (Phase Relations, Experimental, 11)
[2000Wit] Witusiewicz, V., Arpshofen, I., Siefert, H., Sommer, F., Aldinger, F., Enthaply of Mixing
of Liquid Cu-Ni-Si Alloys, Z. Metallkd., 91(2), 128-142 (2000) (Experimental,
Thermodyn., 35)
[2002Leb1] Lebrun, N., Cu-Ni (Copper-Nickel), MSIT Binary Evaluation Program, in MSIT
Assessment, 51)
[2002Leb2] Lebrun, N., Dobatkina, T., Kuznetsov, V. Li, Ch., Cu-Si (Copper-Silicon), MSIT Binary
Evaluation Program, in MSIT Workplace, Effenberg G. (Ed.), MSI, Materials Science
International Services GmbH, Stuttgart; Document ID 20.12505.1.20 (2002) (Crys.

[C] Prototype
, (NixCu1x) cF4 0x1
Fm3m
(Ni) Cu a = 352.40 pure Ni at 25C [Mas2]
< 1455

< 1084.62
(Si) cF8 a = 543.06 at 25C [Mas2]
< 1414 Fd3m
C (diamond)
, ~Cu7Si hP2 a = 256.05 [V-C2]
842 - 552 P63/mmc c = 418.46
Mg
, ~Cu6Si cI2 a = 285.4 14.6 to 16.7 at.% Si [Mas2]
853 - 787 Im3m
W
, ~Cu5Si(r) cI20 a = 619.8 17.1 to 17.6 at.% Si [Mas2]
< 729 P4132
Mn
, ~Cu5Si(h) t** a = 881.5 17.6 to 19.6 at.% Si [Mas2]
824 - 711 c = 790.3
Landolt-Brnstein
New Series IV/11C2
MSIT
378 CuNiSi

[C] Prototype
J, Cu15Si4 cI76 a = 961.5 21.2 at.% Si [2002Leb2]
< 800 I43d
Cu15Si4
, ~Cu3Si(h2) hR* a = 247 23.4 to 24.9 at.% Si [2002Leb2]
859 - 558 R3m = 109.74
or
t** a = 726.7 [V-C2]
c = 789.2
, ~Cu5Si(h1) hR* a = 472 23.2 to 25.2 at.% Si [Mas2]
620 - 467 R3 = 95.72
, ~Cu5Si(r) o** a = 7676 23.3 to 24.9 at.% Si [Mas2]
< 570 b = 700
c = 2194
3, Ni3Si(h2) oP16 a = 550 [Mas2, V-C2]
1170 - 1115 Pnma b = 650
Fe3C c = 435
2, Ni3Si(h1) cP2 a = 280.8 [Mas2, V-C2]
1115 - 990 Pm3m
CsCl
1, Ni3Si(r) cP4 a = 350.5 [Mas2, V-C2]
< 1035 Pm3m
AuCu3
1, Ni5Si2 hP43 a = 666.7 [V-C2]
< 1242 P321 c = 1227.7
Ni31Si12
a = 667.1 [V-C2]
c = 1228
, Ni2Si(h) hP6 a = 383.6 [V-C2]
1306 - 825 P63/mmc c = 494.8
Ni2In
a = 380.5 [V-C2]
c = 489.0
1, Ni2Si(r) oP12 a = 499 [V-C2]
< 1255 Pnma b = 372
Co2Si c = 706
a = 497.9 [V-C2]
b = 375.4
c = 706.5
, Ni3Si2 oC80 a = 1222.9 [V-C2]
< 830 Cmc21 b = 1080.5
Ni3Si2 c = 692.4
New Series IV/11C2
CuNiSi 379

[C] Prototype
', NiSi oP8 a = 518 [V-C2]
< 992 Pnma b = 334
MnP c = 559
a = 519 [V-C2]
b = 333
c = 562.8
NiSi2 - - -
993 - 981
NiSi2 cF12 a = 538 [V-C2]
< 981 Fm3m a = 538.3
CaF2 a = 540.6
* -, ~Cu3NiSi - - [1939Oka2]

Cu Ni Si
L + 3 + 1 1071 U1 L 47.8 36.6 15.6
NiSi2 NiSi2, L, (Si) 980 D1 L 3 38 59
L + 1 + 940 U2 L 70.1 13.63 16.27
L + 1 + 880 U3 L 47.9 24.1 28.0
L++- 859 P1 L 53.9 18 28.1
L++ 858 U4 L 81.14 2.45 16.41
L++ 835 P2 L 79.8 1.94 18.26
L+J+- 832 U5 L 68.5 6.7 24.8
L ++J 820 E1 L 77.3 2.5 20.2
L+'+- 790 U6 L 42.8 23.16 34.04
L + J - + (Si) 774 U7 L 58.3 8.8 32.9
L ' + NiSi2 + - 770 E2 L 45.56 18.83 35.61
L (Si) + NiSi2 + - 769 E3 L 55.74 11.37 32.89
Landolt-Brnstein
New Series IV/11C2
MSIT
380 CuNiSi

Fig. 1: Cu-Ni-Si. Axes: at.%
Liquidus surface 1400
projection
(Si)
20
80
1300C
1200
40 D1 60
NiSi2 1100
N
iSi
100

2
900 0
900
E2
60 U7 40
E3
110 800
0 10 9
00 00 U6 800
U5
1200 E
1 U3 P1 90 1
80 0 20
U1
P2
3 U4
U2
1100
1300 1200
1400
20 40 60 80
Ni Cu

Fig. 2: Cu-Ni-Si. Axes: at.%
500C
20
80
NiSi2
NiSi2+(Si)+
40
60
NiSi NiSi2+NiSi+
Ni3Si2 60
40
Ni2Si
Ni5Si2
Ni3Si
80
20
Ni S
+ Ni3Si 2 i ++ +
Ni S
5 i +
2

20 40 60 80
Ni Cu
New Series IV/11C2
CuNiSi 381
1100
Fig. 3: Cu-Ni-Si. L
Cu - Ni2Si vertical
section
1000

900
Temperature, C
800
+ Ni2Si
700
600
20
Cu 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0
Ni2Si, mass%
Landolt-Brnstein
New Series IV/11C2
MSIT
382 CuNiZr
Copper Nickel Zirconium

Gautam Ghosh
Introduction
A summary of experimental studies of phase equilibria is given in Table 1.
[1968Fed] investigated the phase equilibria of Cu corner with an emphasis on the solubility of Zr in (Ni,Cu).
The solubility limits were determined at 600, 700, 800 and 900C by metallographic technique and
microhardness measurements. They also determined two isopleths at 0.2 and 0.6 mass% Ni within
0 to 0.49 mass% Zr.
Based on the results of thermal analysis of a number of alloys [1968Tak] constructed the liquidus surface
of Zr rich alloys in the composition range of 20-40 mass% Cu and 15-30 mass% Ni. [1968Vya] investigated
the phase equilibria of Zr corner involving ZrCu2 and ZrNi2 phases, and reported a partial liquidus surface,
four partial isothermal sections at 800, 850, 950 and 1300C, and two isopleths at constant ratios of
Cu:Ni = 4:1 and 1:1. The phase equilibria were determined by dilatometry, thermal analysis, optical
microscopy and hardness measurements.
The solid solubilities of binary intermetallics in the ternary regime have been investigated along the
following composition sections: Zr2Cu-Zr2Ni [1964Ram, 1972Hav1], Zr10Cu7-Zr10Ni7 [1981Gli], and
Zr5Cu-Zr5Ni [1986For]. Besides, investigations of the compounds [1964Ram, 1972Hav1, 1972Hav2,
1981Gli, 1986For, 2000Kov], formation of Zr rich metallic glasses by rapid solidification and their
crystallization kinetics and mechanism [1992Gro, 2002Wan, 2003Liu, 2003Wan1, 2003Wan2, 2003Wan3,
2003Wan4, 2004Wan] were also reported.
Phase relations in the Cu-Ni-Zr have been reviewed by [1979Dri, 2000Gup].
Binary Systems
The Cu-Ni binary system is accepted from [2002Leb]. The Cu-Zr binary phase diagram is accepted from
[2006Sem]. The Ni-Zr binary phase diagram is accepted from [1984Nas] in which the assessed temperature
1170C for invariant reaction L (Ni) + ZrNi5 is replaced by 1196C obtained in recent experiments
[2001Miu].
Solid Phases
The unary, binary and ternary phases of the Cu-Ni-Zr system are presented in Table 2.
The solubilities of Zr in (Ni,Cu) as a function of temperature [1968Fed] are shown in Fig. 1.
Both [1964Ram] and [1972Hav1] reported an incomplete solubility between Zr2Cu and Zr2Ni. However,
[1972Hav1] reported that as-cast Zr2Ni1xCux alloys with x 0.4 have C16 (CuAl2 type) structure, alloys
with x 0.6 have C11b (MoSi2 type) structure, and a two-phase mixture in between. On the other hand, after
annealing the as-cast alloys at 700C for 19 h, [1964Ram] found that the solubility of Cu in Zr2Ni is at least
about 8 at.% and that of Ni in Zr2Cu is negligible.
According to X-ray diffraction investigation of as-cast alloys Cu10Zr7 and Ni10Zr7 form a continuous solid
solution [1981Gli]. However, it is not known if it would be the same after annealing. Even though Zr7Cu10
and Zr7Ni10 are isostructural, [2000Gup] pointed out that a deviation from an isomorphous-type
pseudobinary (complete solid solubility) is expected along Zr7Cu10-Zr7Ni10 section, as Zr7Cu10 melts
congruently while Zr7Ni10 forms by a peritectic reaction. In as-cast alloys, both a and b lattice constants
show a negative deviation while the c lattice constant shows a positive deviation from the ideal behavior.
[1986For] studied Zr(Ni1xCux)5 alloys after annealing them at 840C. The lattice parameters of
Zr(Ni1xCux)5 alloys are listed in Table 2. According to [1986For], in the composition limit of 0 x 0.3
the alloys have cubic AuBe5-type structure, while those with 0.35 x 1 have Zr2Cu9 type tetragonal
structure which is a long-period superstructure derived from AuBe5 type of structure.
New Series IV/11C2
CuNiZr 383
[2000Kov] reported about the ternary phase Zr2NiCu of Heusler type that undergoes martensitic
transformation to two monoclinic structures.
Two studies, [1968Tak] and [1968Vya], reported a ternary eutectic reaction L (Zr)+ZrCu2(r)+Zr2Ni in
the Zr corner; however, the reported invariant temperatures and concentrations of liquid phase are different.
The data of [1968Vya] are preferable because of the large number of experiments performed. A partial
reaction scheme of the system is shown in Fig. 2 based on the results of [1968Vya].
Characteristics of two invariant reactions are listed in Table 3. They are taken from [1968Vya], except for
the compositions of Zr2Cu(r) and Zr2Ni, which are taken after [1964Ram].

Figure 3 shows the liquidus surface in the composition range of Zr2Cu-Zr2Ni-Zr after [1968Vya].
Isothermal Sections
Figures 4, 5, 6 and 7 show the partial isothermal section [1968Vya] at 1300C, 950C, 850C and 800C,
respectively. [1968Vya] constructed these partial isothermal sections using the results of isoplethal sections,
thus, the location of phase boundaries at 950C should be considered as only approximate. At other
temperatures, position of the isoplethal sections enables to draw boundaries between the phase fields with
reasonable accuracy. [1968Vya] did not report the solubility of Cu in Zr2Ni at these temperatures, which is
expected to be significant based on the results of other studies [1964Ram, 1972Hav1]. In accordance with
this, the isothermal sections [1968Vya] are corrected to take into account solubility of Cu in Zr2Ni
[1964Ram].

Figures 8 and 9 show the isopleths [1968Fed] at constant Ni contents of 0.2 mass% and 0.6 mass%,
respectively. In the original publication, [1968Fed] showed the presence of two-phase fields of
(Cu)+ZrCu3; however, according to the accepted binary Cu-Zr [2006Sem] the latter phase most likely to be
ZrCu5. Figures 10 and 11 show the isopleths [1968Vya] at constant ratios xCu:xNi of 4:1 and 1:1,
respectively.
Thermodynamics
[1989Sid] measured the heat of mixing of five Ni rich liquid alloys at 1600C using a high-temperature
calorimeter. Later, [2000Wit] measured the heat of mixing of liquid alloys over a wide composition range
at 1293 and 1295C using a high-temperature isoperibolic calorimeter. They used 99.999% Cu, 99.98% Ni
and 99.8% Zr to prepare the alloys. Figure 12 shows the isoenthalpic contours at 1565 5 K [2000Wit].
Both [1999Zho] and [2000Wit] proposed that a large and negative heat of mixing may imply a tendency for
chemical short range ordering in the liquid phase. [1999Zho] calculated the composition and temperature
dependence of heat of mixing, using a generalized associate solution model [2000Kru] with the assumption
of presence of two binary associates only, Zr1Cu2 and Zr1Ni2, in the liquid phase. They obtained a good
agreement between the calculated and experimental values.

The superconducting critical temperature, magnetic susceptibility and thermoelectric power of Zr2Ni1xCux
(tI12), 0 x 0.17, were measured by [1972Hav2]. Both thermoelectric power and the critical temperature
decreases monotonically as Ni is substituted by Cu [1972Hav2].
The intermetallic compound Zr2NiCu is a promising candidate to develop high-temperature shape memory
materials. [2000Kov] reported that the shape recovery of Zr2NiCu is 90% at a strain level of 0.35%.
Landolt-Brnstein
New Series IV/11C2
MSIT
384 CuNiZr
Miscellaneous
The tracer diffusivity of Cu in amorphous NiZr at 300C was reported to be 2.6#1021 m2#s1 [1986Hah].
Metallic glasses in the composition range of 50 to 70 at.% Zr and up to 25 at.% Cu have been obtained by
rapid solidification [1992Gro, 2002Wan, 2003Liu, 2003Wan1, 2003Wan2, 2003Wan3, 2003Wan4,
2004Wan]. [2003Liu] found that the crystallization of Cu20Ni10Zr70 amorphous alloy took place in two
stages during continuous heating in a differential scanning calorimeter. Nucleation and growth of Zr2Cu
was followed by that of Zr2Ni. The details of crystallization kinetics and associated kinetic parameters, and
microstructure after crystallization have also been discussed [1992Gro, 2002Wan, 2003Liu, 2003Wan1,
2003Wan2, 2003Wan3, 2003Wan4, 2004Wan].
References
[1964Ram] Raman, A., Schubert, K., The I of Zr2Cu- and Cr2Al-Type Intermetallic Compounds (in
German), Z. Metallkd., 55, 798-804 (1964) (Crys. Structure, Experimental, #, *, 23)
[1968Fed] Fedorov, V.N., Zakharov, M.V., Kucherov, V.I., Ivanova, G.S., The Cu Corner of the
Cu-Ni-Zr Phase Diagram. (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall., (5),
74-77 (1968) (Experimental, Phase Diagram, #, *, 14)
[1968Tak] Takeuchi, Y., Watanabe, M., Yamabe, S., Wada, T., Eutectic Titanium- and Zirconium
Solders (in German), Metall, 22, 8-15 (1968) (Experimental, Phase Diagram, #, *, 11)
[1968Vya] Vyal, N.V., Ivanov, O.S., The Zr Corner of the Zr-Cu-Ni Phase Diagram, Fiz. Khim.
Splavov Tsirkoniya, 151-158 (1968) (Experimental, Phase Diagram, #, *, 4)
[1972Hav1] Havinga, E.E., Damsma, H., Hokkeling, P., Compounds and Pseudobinary Alloys with the
CuAl2(C16)-Type Structure. I. Preparation and X-Ray Results, J. Less-Common Met., 27,
169-186 (1972) (Crys. Structure, Experimental, *, 19)
[1972Hav2] Havinga, E.E., Damsma, H., Kanis, J.M., Compounds and Pseudo-Binary Alloys with the
CuAl2(C16)-Type Structure, J. Less-Common Met., 27, 281-291 (1972) (Experimental,
Magn. Prop., 17)
[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova; Rokhlin, L.L., Turkina,
N.I., Cu-Ni-Zr (in Russian) in Binary and Multicomponent Copper-Base Systems,
[1981Gli] Glimois, J.L., Forey, P., Feron, J., Becle, C., Structural Investigations of the Pseudobinary
Compounds Ni10-xCuxZr7, J. Less-Common Met., 78, 45-50 (1981) (Crys. Structure, *, 6)
[1984Nas] Nash, P., Jayanth, C.S., The Ni-Zr (Nickel-Zirconium) System, Bull. Alloy Phase
Diagrams, 5, 144-148 (1984) (Phase Diagram, Phase Relations, Review, #, *, 38)
[1986For] Forey, P., Glimois, J.L., Feron, J.L., Structural Study of the Ternary Alloys (Ni1xCux)6Zr
(in French), J. Less-Common Met., 124, 21-27 (1986) (Crys. Structure, *, 9)
[1986Hah] Hahn, H., Averback, R.S., Rothman, S.J., Diffusivities of Ni, Zr, Au, and Cu in Amorphous
Ni-Zr Alloys, Phys. Rev. B., 33(12), 8825-8828 (1986) (Experimental, 15)
[1989Sid] Sidorov, O.Yu., Esin, Yu.O., Geld, P.V., Enthalpies of Formation of Zirconium Alloys
with Iron, Cobalt, Nickel, and Copper (in Russian), Rasplavy, (3), 28-33 (1989)
(Calculation, Experimental, Thermodyn., *, 22)
[1992Gro] Groma, I., Lendvai, J., Cziraki, A., Gerocs, I., Fogarassy, B., Kovacs, I., Crystallization of
Amorphous Ni50xCuxZr50 Alloys, Scripta Met. Mater., 26(2), 255-260 (1992)
(Experimental, Kinetics, 14)
[1999Zho] Zhou, S.H., Schmid, J., Sommer, F., Thermodynamic Properties of Liquid, Undercooled
Liquid and Amorphous Al-Cu-Zr and Al-Cu-Ni-Zr Alloys, Thermochim. Acta, 339, 1-9
(1999) (Experimental, Theory, Thermodyn., *, 26)
[2000Gup] Gupta, K.P., The Cu-Ni-Zr system (Copper-Nickel-Zirconium), J. Phase Equilib., 21(6),
553-561 (2000) (Assessment, Crys. Structure, Phase Relations, #, *, 13)
New Series IV/11C2
CuNiZr 385
[2000Kru] Krull, H.-G., Singh, R.N., Sommer, F., Generalized Association Model, Z. Metallkd.,
91(5), 356-365 (2000) (Review, Thermodyn., 46)
[2000Wit] Witusiewicz, V.T., Sommer, F., Enthalpy of Mixing of Liquid Ni-Zr and Cu-Ni-Zr
Alloys, Metall. Trans. B, 31B, 277-284 (2000) (Experimental, Thermodyn., *, 18)
[2001Miu] Miura, S., Unno, H., Yamazaki, T., Takizawa, S., Mohri. T., Reinvestigation of Ni-Solid
Solution/Liquid Equilibria in Ni-Al Binary and Ni-Al-Zr Ternary Systems, J. Phase
Equilib., 22, 457-462 (2001) (Phase Diagram, Experimental, #, *, 9)
[2002Leb] Lebrun, N., Cu-Ni (Copper-Nickel), MSIT Binary Evaluation Program, in MSIT
Assessment, 51)
[2002Wan] Wang, H.R., Min, G.H., Hui, X.D., Ye, Y.F., Teng, X.Y., Shi, Z.Q., Zhang, J.Y.,
Decomposition of Metallic Zr-Cu-Ni Glass, J. Mater. Sci. Lett., 21(21), 1705-1707
[2003Liu] Liu, Y., Hui, X.D., Wang, H.R., Effect of Pre-Annealing on Thermal Stability of
Amorphous Zr-Cu-Ni Alloy, Rare Metals, 22(4), 945-948 (2004) (Experimental, 16)
[2003Wan1] Wang, H-R., Gao, Y-L., Hui, X-D., Min, G-H., Chen, Y., Ye, Y-F., Effect of Ni Content
on Crystallization of Metallic Zr-Cu-Ni Glass, J. Alloys Compd., 349(1-2), 129-133 (2003)
(Crys. Structure, Experimental, Kinetics, Phase Relations, 19)
[2003Wan2] Wang, H-R., Gao, Y-L., Min, G-H., Ye, Y.-F., Chen, Y., Shi, Z-Q., Teng, X-Y., High
Stability of Zr2Ni Nanocrystals in Metallic Zr-Cu-Ni Glass, J. Alloys Compd., 349(1-2),
[2003Wan3] Wang, H.R., Deng, Y.F., Gao, Y.L., Hui, X.D., Min, G.H., Ye, Y.F., Chen, Y., HRTEM
Study of Crystallization of Zr-Cu-Ni Metallic Glass, J. Alloys Compd., 350(1-2), 174-177
(2003) (Experimental, Kinetics, 12)
[2003Wan4] Wang, H.R., Gao, Y.L., Ye, Y.F., Min, G.H., Chen, Y; Teng, X.Y., Crystallization Kinetics
of an Amorphous Zr-Cu-Ni Alloy: Calculation of the Activation Energy, J. Alloys Compd.,
353(1-2), 200-206 (2003) (Experimental, Kinetics, 12)
[2004Wan] Wang, H.-R., Gao, Y.-L., Min, G.-H., Chen, Y., Ye, Y.-F., Crystallization Kinetics of an
Amorphous Zr70Cu20Ni10 Alloy, Z. Metallkd., 95(2), 80-83 (2004) (Experimental,
Kinetics, Morphology, Phase Relations, 18)
Assessment, 31)
Table 1: Investigations of the Cu-Ni-Zr Phase Relations, Structures and Thermodynamics

Studied
[1964Ram] XRD 700C; Zr2(Ni,Cu)
[1968Fed] Thermal analysis, metallography, hardness < 1100C; up to 0.6 mass% Ni and 0.6
mass% Zr
[1968Tak] Thermal analysis, soldering characteristics < 1000; Cu: 10-30 mass%, Ni: 10-30
mass%, Zr: balance
[1968Vya] Dilatometry, thermal analysis, XRD, < 1560C; Zr2Cu-Zr2Ni-Zr
optical microscopy, hardness
[1972Hav1] XRD Zr8Ni4xCux, 0 x 1.5
Landolt-Brnstein
New Series IV/11C2
MSIT
386 CuNiZr

Studied
[1972Hav2] Superconductivity, thermo-electric power, Zr8Ni4xCux, 0 x 1.5
magnetic susceptibility
[1981Gli] XRD Zr7(Ni,Cu)10
[1986For] XRD 840C, Zr(Ni1xCux)5, 0 x 1
[1986Hah] Secondary ion mass spectroscopy 300C, ZrNi
[1989Sid] High-temperature calorimetry 1600C; ZrxNi1xCux, 0.015 x 0.075
[1992Gro] Rapid solidification, DSC, XRD, TEM 550C; Zr50Ni50xCux, 0 x 25
[2000Kov] XRD, Resistivity, mechanical testing 250-850C; Zr2NiCu
[2000Wit] Calorimetry 1293-1295C; Zr1xyNiyCux,
0.0102 x 0.9887, 0.0041 y 0.6335
[2002Wan] Rapid solidification, DSC, TEM, XRD 600C; Ni10Cu20
[2003Liu] Rapid solidification, DSC, TEM, XRD 600C; Zr70Ni10Cu20
[2003Wan1] Rapid solidification, DSC, XRD 600C; Zr70NixCu30x, 5 x 15
[2003Wan2] Rapid solidification, DSC, TEM, XRD 600C; Zr70Ni10Cu20
[2004Wan] Rapid solidification, DSC, TEM, XRD 600C; Zr70Ni10Cu20

Temperature Range Space Group / [pm]
[C] Prototype
(Ni,Cu) cF4
Fm3m
(Ni) Cu a = 352.32 pure Ni at 25C [V-C2]
1455
(Cu) a = 361.46 pure Cu at 25C [V-C2]
1084.62
(Zr)(h) cI2 dissolves up to 5.7 at.% Cu [2006Sem]
1855 - 863 Im3m and 2.92 at.% Ni [1984Nas],
W a = 356.8 pure Zr [V-C2]
(Zr)(l) hP2 dissolves up to ~0.2 at.% Cu
< 863 P63/mmc [2006Sem] and 0.2 at.% Ni [1984Nas],
Mg a = 323.2 pure Zr at 25C [V-C2]
c = 514.7
New Series IV/11C2
CuNiZr 387

[C] Prototype
Zr(Ni1xCux)5 cF24 0 x 0.30 [1986For]
F43m
AuBe5 a = 671.2 at x = 0.05 [1986For]
a = 673.6 at x = 0.3 [1986For]
ZrNi5 a = 670.64 to 670.72 at x = 0 [1984Nas]

< 1300
ZrCu5 a = 687.0 at x = 1 [2006Sem]

< 1032
Zr(Ni1xCux)5 t** a = 674.5 at x = 0.35 [1986For]

Zr2Cu9 c = 675.2
(long period
superstructure
derived from
AuBe5 type)
Zr14Cu51 hP68 a = 1124.44 [2006Sem]
1112 P6/m c = 828.15
Gd14Ag51
Zr3Cu8 oP44 a = 786.93 [2006Sem]
1028 Pnma b = 851.47
Hf3Cu8 c = 646.0
Zr24Cu13 o*37 a = 1119.0 [2006Sem]
960 - 915 b = 791.2
c = 998.48
Zr7(Ni1xCux)10 oC68 0 x 1 in cast state [1981Gli]
C2ca a = 1246.8 at x = 0.5 [1981Gli]
Zr7Ni10 b = 923.2
c = 931.5
Zr7Cu10 a = 1267.29 at x = 1, [2006Sem]

< 935 b = 931.63
c = 934/66
Zr7Ni10 a = 1238.6 to 1249.7 at x = 0 and 41.1 to 43.5 at.% Zr

< 1160 b = 915.6 to 921.0 [1984Nas]
c = 921.1 to 932.5
960 - 725 Pm3m
CsCl
Landolt-Brnstein
New Series IV/11C2
MSIT
388 CuNiZr

[C] Prototype
< 140 P21/m b = 414.8
TiNi c = 524.9
= 103.7

Cm b = 856.3
c = 534.5
= 105.6
Zr2Cu(h) tI6 a = 322.04 [2006Sem]
1025 - 950 I4/mmm c = 1183.2
MoSi2
Zr2Cu(r) tP150 a = 1592.4 [2006Sem]
< 950 c = 1132.8
ZrNi5 cF24 a = 670.64 to 670.72 15 to 18 at.% Zr [1984Nas]
1300 F43m
AuBe5
Zr2Ni7 mC36 a = 469.8 [1984Nas]
1440 C2/m b = 823.5
Zr2Ni7 c = 1219.3
= 95.83
ZrNi3 hP8 a = 530.9 24.5 to 26.0 at.% Zr [1984Nas]
920 P63/mmc c = 430.3
Ni3Sn
Zr8Ni21 aP29 a = 647.21 [1984Nas]
< 1180 P1 b = 806.45
Hf8Ni21 c = 858.75
= 75.18
= 68.00
= 75.20
Zr9Ni11 tI40 a = 988.0 [1984Nas]
978 - 1170 I4/m c = 661.0
Zr9Pt11
ZrNi oC8 a = 326.8 [1984Nas]
1260 Cmcm b = 993.0
CrB c = 410.21
New Series IV/11C2
CuNiZr 389

[C] Prototype
Zr2Ni1xCux tI12 0 x 0.24 at 700C [1964Ram]
I4/mcm a = 655.0 at x = 0.24 and 25C [1964Ram]
CuAl2 c = 524.0
Zr2Ni a = 647.7 to 648.3 at x = 0, [V-C2]

1120 c = 524.1 to 526.7
* Zr2NiCu cF16 a = 645.0 [2000Kov]
? Fm3m
MnCu2Al
mP4 a = 333.6 martensite, [2000Kov]

P21/m b = 419.3
TiNi c = 523.6
= 103.1

Cm b = 897.3
c = 530.1
= 103.8

Cu Ni Zr
L (Zr) + Zr2Cu(r) + Zr2Ni ~920 E1 L 15 11 74
(Zr) 2.5 1.7 95.8
Zr2Cu(r) 33 - 67
Zr2Ni ~8 ~25 67
(Zr) (Zr) + Zr2Cu + Zr2Ni 805 E2 (Zr) ~2.5 ~2.5 ~95
(Zr) ~0.1 ~0.1 ~99.8
Zr2Cu 33 - 67
Zr2Ni ~8 ~25 67
Landolt-Brnstein
New Series IV/11C2
MSIT
390 CuNiZr

Fig. 1: Cu-Ni-Zr. Axes: at.%
Solid solutions of Zr
in (Ni,Cu) at different
temperatures
20
80
40
60
600C (Ni,Cu)
60
40
900
700 800
80
20
20 40 60 80
Zr Ni
Cu-Zr Cu-Ni-Zr A-B-C Ni-Zr
995 e1
L (Zr) + Zr2Cu(h)
960 e2
950 d L(Zr) + Zr2Ni
Zr2Cu(h) Zr2Cu(r) L+Zr2Cu(r)+Zr2Ni
~920 L(Zr)+Zr2Cu(r)+Zr2Ni E1
(Zr)+Zr2Cu(r)+Zr2Ni 845 e3
(Zr)(Zr) + Zr2Ni
822 e4
(Zr)(Zr)+Zr2Cu(r)
805 (Zr)(Zr)+Zr2Cu(r)+Zr2Ni E2
Fig. 2: Cu-Ni-Zr. Partial reaction scheme for the solidification of Zr rich alloys
New Series IV/11C2
CuNiZr 391
Zr 50.00
Ni 0.00
Partial liquidus
e
surface
910
60
40
940
950 ZrCu
960
70 970 30
e1 980
990 U?
1000 ?
910
Zr2Cu(h)
920 970
80 960 20
E1
920
930
Zr2Ni
1300C
90
10
1100 950
( Zr)
1200
10 20 e2 30 40
Zr Zr 50.00
Ni 50.00
Cu 0.00
Zr 66.70
Ni 0.00
Partial isothermal
section at 1300C 70
30
80
20
90
10
L+( Zr)
Zr ( Zr) 10 20 30 Zr 66.70
Ni 33.30
Cu 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
392 CuNiZr
Zr 66.70
Ni 0.00
Fig. 5: Cu-Ni-Zr. Zr2Cu(h) Axes: at.%
Partial isothermal
section at 950C 70
30
L+Zr2Cu(h)
80
20
L+Zr2Cu(h)+( Zr) L+
Zr
Zr2Cu(h)+( Zr) 2 Ni
+Z
r2 C
L u(h
)
90
10
L+Zr2Ni
L+( Zr)
L+Zr2Ni+( Zr)
Zr2Ni
( Zr) Zr2Ni+( Zr)
10 20 30
Zr Zr 66.70
Ni 33.30
Cu 0.00
Zr 66.70
Ni 0.00
Fig. 6: Cu-Ni-Zr. Zr2Cu(r) Axes: at.%
Partial isothermal
section at 850C 70
30
80
20
90 ( Zr)+Zr2Ni+Zr2Cu(r)
10
( Zr)+Zr2Cu(r)
Zr2Ni
( Zr) ( Zr)+Zr2Ni
( Zr)
(Zr)+( Zr) 10 20 30
Zr Zr 66.70
Ni 33.30
Cu 0.00
New Series IV/11C2
CuNiZr 393
Zr 66.70
Ni 0.00
Zr2Cu(r)
Partial isothermal
section at 800C 70
30
80
20
(Zr)+Zr2Cu(r)+Zr2Ni
90
10
Zr2Ni
(Zr)
10 20 30
Zr Zr 66.70
Ni 33.30
Cu 0.00
1100
Fig. 8: Cu-Ni-Zr.
Isopleth at a constant L+(Cu)
Ni content of 0.2 1000 L+(Cu)+ZrCu5
mass%, plotted in
at.%
900
(Cu)
Temperature, C
800
(Cu)+ZrCu5
700
600
500
400
Zr 0.49 99.4 99.6 Zr 0.00
Ni 0.22 Ni 0.22
Cu 99.29 Cu, at.% Cu 99.78
Landolt-Brnstein
New Series IV/11C2
MSIT
394 CuNiZr
1100
Fig. 9: Cu-Ni-Zr.
Isopleth at a constant L+(Cu)
Ni content of 0.6 1000
mass%, plotted in
at.% L+(Cu)+ZrCu5
900
(Cu)
Temperature, C
800
(Cu)+ZrCu5
700
600
500
400
Zr 0.49 99.0 99.2 Zr 0.00
Ni 0.65 Ni 0.65
Cu 98.86 Cu, at.% Cu 99.35
2000
Fig. 10: Cu-Ni-Zr.
ratio of Cu:Ni=4:1
1750
L
1500
Temperature, C
L+( Zr)
1250
Zr2Cu+L
( Zr) ( Zr)+Zr2Cu+L Zr2Cu+Zr2Ni+L
1000
( Zr)+( Zr)
( Zr)+Zr2Cu ( Zr)+Zr2Cu+Zr2Ni
805C
750
( Zr)+( Zr)+Zr2Cu
( Zr) ( Zr)+Zr2Cu+Zr2Ni
( Zr)+Zr2Cu
500
Zr 10 20 Zr 65.00
Ni 7.00
Cu, at.% Cu 28.00
New Series IV/11C2
CuNiZr 395
2000
Fig. 11: Cu-Ni-Zr.
ratio of Cu:Ni=1:1
1750
1500
Temperature, C
L+( Zr)
1250
( Zr) ( Zr)+Zr2Ni
L+Zr2Ni
L+( Zr)+Zr2Ni
1000
( Zr)+( Zr) L+Zr2Ni+Zr2Cu

( Zr)+Zr2Ni+Zr2Cu
750
( Zr)+( Zr)+Zr2Ni
( Zr) ( Zr)+Zr2Ni+Zr2Cu
( Zr)+Zr2Ni
500
Zr 2 6 10 14 Zr 65.00
Ni 17.50
Cu, at.% Cu 17.50

Projection of 0
isoenthalpic lines of -5
liquid and
undercooled liquid 20 -10
80
alloys at 1292C, in
kJ#mol1
-15
40
60
60
40
-30
-35
80
-40
20
-45
-25
-20 -46
-15
20 40 60 80
Zr Ni
Landolt-Brnstein
New Series IV/11C2
MSIT
396 CuPbSb
Copper Lead Antimony

Kostyantyn Korniyenko
Introduction
Scientific interest in the phase equilibria in the Cu-Pb-Sb system is due, in particular, to the effect of the
third component on the properties of lead-antimony binary alloys, especially of lead rich alloys in which
dispersion hardening was found [1928Mor]. Copper as the third component forms several compounds with
antimony as well as solid solutions, but with lead it forms a liquid miscibility gap and no appreciable solid
solution. Owing to the compound formation, copper increases the apparent solubility of antimony. The
excess antimony is tied up with the copper and so is not available for dispersion hardening. The constitution
of Cu-Pb-Sb alloys was investigated first by [1899Cha]. Subsequently, the liquidus surface [1923Sch,
1928Mor, 1941Sch, 1963Dav, 1966Kry], reaction scheme, phase equilibria at subsolidus temperatures,
Sb-Cu76.5Pb23.5 vertical section [1941Sch] and isothermal section at 1200C [1990Esp] have been
studied. The existence of a miscibility gap in the system was established. [1941Hof, 1954Sch] investigated
crystal structures of the constituents of the Cu-Pb-Sb alloys. [1972Dee, 1963Dav, 1973Kir, 1974Kir,
1991Esp1, 1991Esp2] studied thermodynamic properties. [1975Heu] studied the process of grain
refinement of hypoeutectic Pb-Sb alloys through the addition of Cu and reported the corresponding phase
relations. The experimental details of studies of phase equilibria are presented in Table 1. However,
information relating to the phase equilibria in the Cu-Pb-Sb system is incomplete, in particular, with respect
to the reaction scheme. Through further study of the system, the possibilities of practical applications of
copper-lead-antimony alloys will be extended.
Binary Systems
The Cu-Pb and Cu-Sb binary systems are accepted from the MSIT Evaluation Program [2006Sch] and
[2006Rok], respectively. The Pb-Sb system is accepted from [Mas2].
Solid Phases
No ternary phases have been reported. Crystallographic data concerning the known unary and binary phases
are listed in Table 2. [1928Mor] studied the effect of Cu on the solid solubility of Sb in (Pb), and found that
the presence of small amounts of copper has a tendency to increase the solubility, at least at higher
temperatures (Table 2).
Table 3 lists temperatures, types of reactions and the compositions of the phases taking place in the invariant
equilibria that have been established unambiguously. Phase compositions from [1941Sch] have been
recalculated from mass to atomic percent. The reaction scheme, with corrections to maintain consistency
with the binary systems, is shown in Fig. 1.
Liquidus Surface
The liquidus surface projection of the system is shown in Figs. 2a, 2b. It is based mainly on the experimental
investigations of [1941Sch]. Constitution in the Pb rich corner was also determined by [1963Dav] and
[1966Kry]. From Fig. 2, it can be seen that the miscibility gap in the ternary system is wider than in the
Cu-Pb binary and extends to lower temperatures - from 980.5C in the binary system to 619C at the critical
point of the ternary. The location of the critical point (c1) is 35.22Cu-35.58Pb-29.2Sb (at.%) [1941Sch].
New Series IV/11C2
CuPbSb 397
Isothermal Sections
The isothermal section at 1200C (Fig. 3) has been constructed by [1990Esp] showing a liquid miscibility
gap. The rest of the section is completely liquid.

The Sb-Cu76.5Pb23.5 vertical section is shown in Fig. 4 after [1941Sch] with corrections to maintain
consistency with the accepted Cu-Pb binary system.
Thermodynamics
Thermodynamic properties of liquid metallic copper-lead-antimony solutions have been investigated for the
first time by [1963Dav] in the Pb rich corner, and by [1972Dee] using emf measurements in the range
1100-1200C. The activity, the activity coefficients of the components and the integral values of the excess
thermodynamic functions for the liquid phase in the ternary system have been calculated. The liquid ternary
alloys exhibit positive-negative deviations from ideality. Thermodynamic analysis of the behavior of the
intermetallides in the ternary system over the temperature interval 627 to 1027C was carried out by
[1973Kir] using their own experimental measurements and those obtained by other authors. The same
authors in [1974Kir] have presented the excess Gibbs energy of liquid alloys at 1027C. The excess entropy
was calculated from the temperature dependence of the Gibbs energy. The method used by [1974Kir] for
the Gibbs energy measurement was not indicated in their work. It should be mentioned that the data of
[1972Dee] and [1973Kir] are in a poor agreement with each other and neither indicate decomposition of the
liquid in the ternary system. Activities of the component elements were determined at 1200C by
[1991Esp1] and [1991Esp2] using the transportation method, based on vapor pressure measurement of Pb
and Sb. Isoactivity curves of antimony and lead determined in [1991Esp2] are shown in Figs. 5 and 6,
respectively. Isoactivity curves of copper were calculated in [1991Esp2] based on data for Sb and Pb
activity. They are shown in Fig. 7. The activity results of Cu, Pb and Sb determined at 1150 C by [1972Dee]
do not show any kinks in the miscibility gap and thus they are not consistent with the results of [1991Esp2].
In the single phase fields, the agreement between these two investigations is also poor. The data of
[1991Esp2] are preferred in the present work because they are consistent with the phase diagram
demonstrating kinks in the activity curves in the region of the miscibility gap. One can see that in the
two-phase L' + L'' region Sb activity is below 0.1, exhibiting a large negative deviation from Raoults law,
while the activity of Pb ranges from 0.75 to 0.95. A high activity of lead is maintained due to the dissolution
of copper in the lead rich liquid which exhibits a tendency for immiscibility in the Cu-Pb binary system.

Lead-antimony castings are used in the electric industry, especially for the production of battery grids
[1975Heu]. Hot tearing can be avoided by suitable grain refinement. Small copper additions to a
Pb95.82Sb4.18 alloy supplies the high grain refining effect. Increasing the copper content above 0.13 at.%
does not further improve the grain refinement. Compression tests of the alloys having a lead content greater
than 41.7 at.% were carried out by [1899Cha]. The maximum load corresponding to compressions of
0.2 and 7.5 mm was found for the Cu29.3Pb46.4Sb24.3 and Cu29.3Pb46.4Sb24.3 alloys, respectively. The effect
of copper (0.22 at.%) on the tensile strength of Pb-Sb alloys (0 to 9.78 at.% Sb) was studied by [1928Mor].
It was concluded that small amounts of copper have the effect of shifting the dispersion hardness peak of
Pb-Sb alloys toward higher antimony contents.
Miscellaneous
The kinetics of nucleation were studied by [1966Kry]. An attempt to explain decoppering in the copper trap
was undertaken through microscopic observation.
Landolt-Brnstein
New Series IV/11C2
MSIT
398 CuPbSb
References
[1899Cha] Charpy, G., Alloys of Lead, Copper and Antimony, Metallographist, 2, 44-46 (1899)
(Morphology, Experimental, Mechan. Prop., 0)
[1923Sch] Schack, H., The Ternary System Copper-Lead-Antimony (in German), Z. Anorg. Chem.,
132, 265-272 (1923) (Morphology, Phase Diagram, Experimental, 4)
[1928Mor] Morgen, R.A., Swenson, L.G., Nix, F.C., Roberts, E.H., The System
Lead-Antimony-Copper, Trans. Amer. Inst. Min. Met Eng., 317-327 (1928) (Morphology,
Phase Diagram, Phase Relations, Experimental, Mechan. Prop., 14)
[1941Hof] Hofmann, W., X-ray Diffraction Analysis Study of the Antimony-Copper and
Antimony-Lead-Copper Alloys (in German), Z. Metallkd., 33(2), 61-62 (1941) (Crys.
[1941Sch] Schrader, A., Hanemann, H., On the System Lead-Antimony-Copper (in German),
Z. Metallkd., 33(2), 49-60 (1941) (Phase Diagram, Experimental, #, 36)
[1954Sch] Schubert, K., Ilschner, M., Investigations in the System Copper-Antimony (in German),
[1958Gue] Gnzel, E., Schubert, K, Structural Investigations in the System Copper-Antimony,
Z. Metallkd., 49, 124-133 (1958) (Crys. Structure, Phase Diagram, Experimental, 21)
[1963Dav] Davey, T.R.A., Phase Systems Concerned with the Copper Drossing of Lead, Bull. Inst.
Min. Met., 72, 553-620 (1963) (Phase Diagram, Thermodyn., Experimental, Review,
Theory)
[1964Pea] Pearson, W.B., Electrical Resistivity, Hall Coefficient and Thermoelectric Power of AuSb2
and Cu2Sb, Canad. J. Phys., 42, 519-525 (1964) (Crys. Structure, Experimental, Electr.
Prop.)
[1966Kry] Krysko, W.W., The Decoppering of Pb: The Parts 5-7 (in German), Z. Erzberg.
Metallhuettenwesen, 19(3), 121-127 (1966) (Morphology, Phase Relations, Experimental,
Kinetics, 17)
[1972Dee] Deev, V. I., Goldobin, V. P., Rybnikov, V. I., Smirnov, V. I., Thermodynamic Properties
of Liquid Ternary Copper-Lead-Antimony Alloys, J. Phys. Chem., 46(6), 811-814 (1972)
(Thermodyn., Experimental, Calculation, 8)
[1973Kir] Kirov, A.S., Boychev, A.P., Neykova, E.A., Denev, D.G., Thermodynamics of the
Intermetallides in the System of Lead-Copper-Antimony, Dokl. Bolg. Akad. Nauk, 26(11),
1505-1508 (1973) (Thermodyn., Experimental, 5)
[1974Kir] Kirov, A.S., Boychev, A.P., Neykova, E.A., Denev, D.G., Thermodynamic Properties of
Alloys from the Ternary System of Lead-Copper-Antimony, Dokl. Bolg. Akad. Nauk,
27(2), 231-233 (1974) (Thermodyn., Experimental, 5)
[1975Heu] Heubner, U., Mueller, I., Ueberschaer, A., Grain Refinement of Hypoeutectic
Lead-Antimony Alloys by Additions of Copper and Sulfur, Z. Metallkd., 66(2), 74-79
(1975) (Morphology, Phase Relations, Experimental, 18)
[1990Esp] Espeleta, A.K., Hino, M., Azakami, T., Phase Separation and Silver and Gold Distribution
in the Pb-Fe-Sb and Pb-Cu-Sb Systems at 1200C, Shigen to Sozai, 106(13), 53-58 (1990)
(Phase Diagram, Phase Relations, Experimental, #, 11)
[1991Esp1] Espeleta, A.K., Hino, M., Azakami, T., Activity Determination in the Pb-Fe-Sb and
Pb-Cu-Sb Ternary Systems by the Transportation Method, Shigen to Sozai, 107(1), 53-59
(1990) (Thermodyn., Experimental, 10)
[1991Esp2] Espeleta, A.K., Hino, M., Azakami, T., Activity of Component Elements in the Pb-Fe-Sb
and Pb-Cu-Sb Ternary Systems, Met. Rev. MMIJ, 8(1), 80-97 (1991) (Phase Relations,
[1991Tep] Teppo, O., Niemelae, J., Taskinen, P., The Copper-Lead Phase Diagram, Thermochim.
Acta, 185(1), 155-169 (1991) (Phase Diagram, Thermodyn., Review, #, 17)
New Series IV/11C2
CuPbSb 399
[2006Rok] Rokhlin, L., Bochvar, N., Cu-Sb (Copper-Antimony), MSIT Binary Evaluation Program,
in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services
GmbH, Stuttgart; to be published, (2006) (Crys. Structure, Phase Diagram,
Assessment, #, *, 19)
[2006Sch] Schmid-Fetzer, R., Shcherban, O., Tomashik, V., Jialin, Y., Cu-Pb (Copper-Lead), MSIT
Science International Services GmbH, Stuttgart, to be published (2006) (Crys. Structure,
Phase Diagram, Assessment, #, 7)
Table 1: Investigations of the Cu-Pb-Sb Phase Relations, Structures and Thermodynamics

[1899Cha] Optical microscopy 41.7 to 100 at.% Pb
[1923Sch] Optical microscopy, thermal analysis 327 - 1084C, whole range of compositions
(cooling curves)
[1928Mor] Optical microscopy, thermal analysis 327 - 1084C, whole range of compositions
(cooling curves), chemical analysis
[1941Hof] X-ray Debye-Scherrer studies Cu alloys with 15.5, 19, 25.4 at.% Sb and Pb
additions
[1941Sch] Thermal analysis, X-ray studies < 1084C, whole range of compositions
[1963Dav] Solubilities of the precipitating phases 327 - 600C, the Pb rich corner
determination
[1966Kry] Optical microscopy, chemical analysis 300 - 900C, the Pb rich corner
[1972Dee] Emf measurements 1100 - 1200C, whole range of compositions
[1973Kir] Copper antimonides stabilities 627 - 1027C
determination
[1974Kir] Excess isobaric-isothermal potential and 627 - 1027C; mole fraction ratios - Cu:Sb =
excess entropy determination 3:1; Pb:Cu = 1:9, 1:1, 9:1
[1975Heu] Optical microscopy, grain refinement 500C, the Pb based alloys with 4.2 at.% Sb and
0.13 at.% Cu
[1990Esp] EMPA 1200C, 30 at.% Sb
[1991Esp1] Transportation method 1200C, whole range of compositions
[1991Esp2] Transportation method 1200C, whole range of compositions
Landolt-Brnstein
New Series IV/11C2
MSIT
400 CuPbSb

[C] Prototype
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m dissolves 5.8 at.% Sb at 645C [Mas2]
Cu and 0.4 at.% Pb at 952.7C [2006Sch]
Cu1xyPbxSby x = 0, 0 y 0.004 at 400C [Mas2]
y = 0, 0 x 0.000046 at 326.5C
[1991Tep]
(Pb) cF4 a = 495.02 at 25C [Mas2]
< 327.502 Fm3m dissolves 5.8 at.% Sb at 251.7C and
Cu 0.02 at.% Cu at 326.5C [2006Sch]
at x = 0, 0 y 0.0344, 238C
CuxPb1xySby [1928Mor]
at x = 0, 0 y 0.0213, 200C
[1928Mor]
at x = 0, 0 y 0.003, 100C [Mas2]
at y = 0, 0 x <0.0002, 326.5C
[1991Tep]
at x = 0.0006, 0 y 0.0456, 238C
[1928Mor]
at x = 0.0006, 0 y 0.0285, 200C
[1928Mor]
(Pb)(I) hP2 a = 326.5 at 25C, 10.3 GPa [Mas2]
P63/mmc c = 538.7
Mg
(Sb) hR6 a = 430.84 at 25C [V-C2]
< 630.755 R3m c = 1127.4
As
CuxPbySb1xy at x = 0, 0 y 0.015 to 0.027, 252C
[H]
at x = 0, 0 y 0.019, 251.7C [Mas2]
(Sb)(II) cP1 a = 299.2 at 25C, 5.0 GPa [Mas2]
Pm3m
Po
(Sb)(III) hP2 a = 337.6 at 25C, 7.5 GPa [Mas2]
P63/mmc c = 534.1
Mg
(Sb)(IV) mP3 a = 556 at 25C, 14.0 GPa [Mas2]
b = 404
c = 422
= 86.0
New Series IV/11C2
CuPbSb 401

[C] Prototype
, Cu1xyPbxSby hP2 x = 0, 0.155 y 0.16 [Mas2]
488 - 400 P63/mmc a = 268.8 x = 0, y = 0.155, 470C [1941Hof]
Mg c = 433.3
Cu11Sb2 a = 271 x = 0, y = 0.155, 460C [1954Sch]

488 - 400 c = 436
, Cu4Sb hP* 0 at.% Pb, 18.5 to 20 at.% Sb [Mas2]
< 462 P63/mmc a = 272.1 at 19.0 at.% Sb, annealed at 350C for
Cu4Sb c = 431.9 48 to 88 h [1954Sch]
, Cu10Sb3 hP26 0 at.% Pb, 21.3 to 21.6 at.% Sb [Mas2]
~ (390 - 260) P3 a = 992.0 at 21.5 at.% Sb [1958Gue]
Cu10Sb3 c = 431.9
J, Cu3Sb oP8 0 at.% Pb, 22.8 to 25.3 at.% Sb [Mas2]
~ 445 - 260 Pmmn a = 550 [E]
TiCu3 b = 476
c = 435
a = 558.2 at 24.9 at.%Sb, 400C [1954Sch]

b = 479.4
c = 438.7
, Cu1xyPbxSby oF16 x = 0, 0.194 y 0.308 [Mas2]
Fm3m
Cu11Sb2 BiF3 a = 601 at x = 0, y = 0.25, 475C [H]
683 - ~440
, Cu2Sb tP6 0 at.% Pb, 32 to 33.3 at.% Sb [Mas2]
< 586 P4/nmm a = 400.0 [H]
Cu2Sb c = 610.3
a = 400.12 at 33 at.% Sb annealed between 550 and

c = 610.39 560C [1964Pea]
Landolt-Brnstein
New Series IV/11C2
MSIT
402 CuPbSb

Cu Pb Sb
L'L'' + 640 e3 L' 5.81 77.51 16.68
L'' 67.02 5.93 27.04
81.37 ~ 0.00 18.63
L' (Cu) + + L'' 623 E1 L' 80.04 2.23 17.72
(Cu) ~ 93.91 ~ 0.00 ~ 6.09
81.37 ~ 0.00 18.63
L'' 3.17 95.18 1.65
L', L'', 619 c1 L', L'' 35.22 35.58 29.20
(crit. point) 81.37 ~ 0.00 18.63
+ (Cu) + L ~ 437 P1 78.81 ~0 21.19
(Cu) 94.92 ~0 5.08
84.5 ~0 15.5
L 0.97 97.86 1.17
L + + ~ 432 U1 L 2.03 91.44 6.53
L + (Cu) + (Pb) 324 U2 L 0.42 99.19 0.39
(Cu) 97.76 ~0 2.24
~ 81.72 ~ 0.004 ~ 18.27
(Pb) ~0 ~ 100 ~0
L + + (Pb) ~ 300 U3 L 1.43 95.16 3.40
~ 76.93 ~ 0.004 ~ 23.07
~ 66.67 ~ 0.004 ~ 33.33
(Pb) 0.03 99.80 0.17
L (Pb) + + (Sb) 248.6 E2 L 0.18 79.57 20.25
(Pb) ~0 ~ 96.98 ~ 3.02
~ 66.67 ~0 ~ 33.33
(Sb) ~0 ~ 1.9 ~ 98.1
New Series IV/11C2
New Series IV/11C2
Landolt-Brnstein
Cu-Pb Cu-Sb Cu-Pb-Sb Pb-Sb
952.7 e1
l' l" + (Cu) 645 e2
640 e3
l (Cu) +
l' l'' +
623 L' (Cu) + + L" E1 L'++L"

586 p1 c1, 619
l+
Cu++L"
526 e4
l + (Sb)
~437 + (Cu) + L P1
+(Cu)+
CuPbSb
++L
~432 L++ U1 (Cu)+L+
++
326.5 e5
l (Cu) + (Pb)
L++
324 L + (Cu) + (Pb) U2
(Cu)++(Pb) L++(Pb)
~300 L + + (Pb) U3
+(Pb)+ L+(Pb)+ 251.7 e6

l (Pb) + (Sb)
248.6 L (Pb) + + (Sb) E2
(Pb)++(Sb)
MSIT
403
Fig. 1: Cu-Pb-Sb. Reaction scheme
404 CuPbSb
Sb Data / Grid: at.%

Fig. 2a: Cu-Pb-Sb. Axes: at.%
Liquidus surface
20
80
(Sb)
e4
40
60
p1
60
40

c1
e"3 E2
e2 80
20
E1 e6
L'+L'' e'3 (Pb)
U1 U
3
(Cu) E"1

e5
Cu
20 40 60 80
(Cu) P1 U2 Pb
e'1 e"1
Cu 0.00
Pb 75.00
Sb 25.00 Data / Grid: at.%
Fig. 2b: Cu-Pb-Sb. Axes: at.%
Pb rich part of the
liquidus surface
(enlargement) E2
20
e6
e'3
10
(Pb)
10
U1
20
U3
E"1

P1 U2
Cu 25.00 80 90
(Cu) e5 Pb
Pb 75.00
Sb 0.00
New Series IV/11C2
CuPbSb 405

Fig. 3: Cu-Pb-Sb. Axes: at.%
1200C
20
80
40
60
L
60
40
80
20
L'+L"
20 40 60 80
Cu Pb
1000
Fig. 4: Cu-Pb-Sb.
The Cu76.5Pb23.5-Sb
vertical section
L'+L" L
750
L'+L"+(Cu)
L'+L"+
Temperature, C
L+ +
L+(Cu) L+
L+(Cu)+ L++ L+(Sb)
500
L+
L++
L+(Cu)+ L+
L+(Pb)+ L+(Sb)+
L+(Pb)+(Cu)
324
(Pb)+ L+(Pb)+
250
(Pb)+(Cu)+ (Pb)+ +
(Pb)+ (Pb)+ (Sb)+(Pb)+
Cu 50.00 20 40 60 80
Sb
Pb 50.00
Sb 0.00 Sb, mass%
Landolt-Brnstein
New Series IV/11C2
MSIT
406 CuPbSb

Isoactivity curves of
Sb at 1200C
0.8
20
80
0.6
40
60
0.4
0.2
60
40
0.1
80
20
0.05
0.03
0.01
20 40 60 80
Cu Pb

Pb at 1200C
20 0.1 80
0.2
40 0.3
60
0.4
0.5
60
0.6 40
0.7
80 0.8
20
0.9
20 40 60 80
Cu Pb
New Series IV/11C2
CuPbSb 407

Cu at 1200C
20
80
0.05
40
60
0.1
60 0.2 40
0.3
0.4
0.5
80 0.6 20
0.7
0.8
20 40 60 80
Cu Pb
Landolt-Brnstein
New Series IV/11C2
MSIT
408 CuPbZn
Copper Lead Zinc

Pierre Perrot
Introduction
Zinc is known since 1850 as an element used to remove copper from lead, so the first extensive studies of
the ternary system were carried out by [1914Par, 1922Nic, 1929Bau1, 1943Dan], then, more precisely by
[1948Hen]. The measurements are in good agreement except for the results of [1922Nic]. The diagram
given by [1914Par], accepted by [1929Bau2] is not fundamentally different from that of [1948Hen] which
is used as a basis for recent thermodynamic assessments of [1998Jan, 2001Her]. Later investigations of
[1955Sei] are in accordance with the previous experimental works. The Calphad assessment made by
[1998Jan] using available information reproduces with a good accuracy the liquidus lines together with the
invariant points experimentally obtained by [1948Hen], the isopleth at 2 mass% Pb drawn by [1929Bau1]
and the isopleth at 10 mass% Cu given by [1955Sei]. A Calphad assessment made by [2001Her],
unfortunately without publishing any optimized value, reproduces with a very good accuracy the liquidus
lines and the isoplethic cut xZn = 3xPb experimentally derived by [1948Hen]. An isoplethic section at 2
mass% Pb, which matches well the experimental work of [1929Bau1] has also been calculated by
[2003Bor]. The existence of a large miscibility gap in the liquid phase which extends from the Cu-Pb to the
Pb-Zn sides was recognized by [1914Par] and confirmed by [1922Nic, 1929Bau2]. The liquidus lines in the
Pb rich corner of the diagram have been experimentally determined by [1948Jol]. The experimental works
made on the Cu-Pb-Zn system are resumed in Table 1.
Binary Systems
The Pb-Zn systems is accepted from [Mas2]. It presents a miscibility gap in the liquid phase with a critical
point at 798C and 28 at.% Pb. The Cu-Pb system accepted from [2006Sch] presents a miscibility gap in
the liquid phase with a critical point at 995C and 35 at.% Pb. The Cu-Zn system is taken from [2006Leb].
Solid Phases
They are given in Table 2. [1929Wer] shows that Pb can be dissolved up to 1.7 mass% in brass and moves
the (+)/ border towards the zinc corner of the binary Cu-Zn diagram, result which is not accepted in a
following discussion by [1929Phi]. [1905Gui] gives a maximum solubility for Pb in and brass of 0.9%.
However, a substantial solubility of Pb in Cu-Zn brasses, as reported by [1969Gue], is doubtful from todays
point of view. A more precise investigation of [1972Leo] shows that, in alloys, Pb is hardly soluble (less
than 0.08 mass% in the alloy with 30 mass% Zn) whereas in alloys, at high temperatures, Pb is soluble
up to a maximum of 0.35 mass%.
They are given in Table 3, mainly from the experimental investigations of [1948Hen, 1955Sei] accepted by
[1979Cha]. The data given in mass% have been converted in at.% and the invariant reaction U5, wrongly
given as a transformation of the E type in [1979Cha] has been corrected.
Liquidus Surface
The liquidus surface, mainly from experimental investigations of [1948Hen, 1955Sei], accepted by
[1979Cha, 1979Dri, 1998Jan] is given in Fig. 1. The Pb rich corner, from [1948Jol, 1979Cha] is shown in
Fig. 2. It is worth to note that the compositions of the liquid L2 given by [1979Cha] match perfectly the
accepted monotectic invariant at 94 at.% Pb and 417.8C in the binary Pb-Zn system. The reaction scheme
is shown in Fig. 3.
New Series IV/11C2
CuPbZn 409
Isothermal Sections
The partial isothermal sections at 700, 800 and 850C, given respectively in Figs. 4a, 4b and 4c [1979Cha],
show that Pb has the effect to move the (+)/ border towards the Zn corner of the diagram [1929Wer].
However, the solubility of Pb in and phases is much lower than that given in [1929Wer] and the slopes
of some lines given by [1979Cha] have been modified for the sake of thermodynamic coherency. The phase
equilibria calculated at 835C [2003Bor], shown in Fig. 5 demonstrate how a Pb rich liquid can form even
at very low Pb content.

Figure 6 shows the isoplethic cut xZn = 3xPb. It is mainly taken from [2001Her], however temperatures of
the invariant reactions U1, U2, U3 have been moved up to the values accepted from [1948Hen, 1955Sei,
1979Cha], therefore some lines in this region are shown dashed. The calculated section by [2001Her] is in
excellent agreement with the experimental result of [1948Hen]. The thermodynamic mistake in the liquidus
slopes drawn by [1948Hen] is corrected by the model. The isoplethic section at 2 mass% Pb measured by
[1929Bau1] and calculated by [1998Jan, 2003Bor], shown in Fig. 7, confirms the formation of a Pb rich
liquid alloy even at very low Pb contents.
Thermodynamics
The zinc isoactivity lines in liquid alloys have been experimentally measured at 802C by [1994Sur] from
an isothermal-isopiestic method, and showed a good agreement with the tie-lines of the miscibility gap
which are given in Fig. 8. The authors propose to describe the excess Gibbs energy of the liquid phase at
802C by a Redlich-Kister development:
Gxs/J#mol1 = XCu XZn [ 21 480 30 (XCu XZn)] + XPb XZn [17 500 2 940 (XPb XZn)]
+ XCu XPb [20 680 + 1 660 (XCu XPb)] + XCu XPb XZn [ 59 420 + 57 730 (XCu XZn)
147 680 (XPb XZn) 95 970 (XCu XPb)].
This development which does not include any term function of T, must be used with caution at other
temperatures. Figure 9 shows the zinc partial pressures calculated above the monophased liquid at 1150C.

A direct application of the Cu-Pb-Zn phase diagram is the use of zinc to remove copper from lead according
to the Parkes process [1948Hen, 1949Jol]. Lead is known to improve the workability of brasses [1905Gui].
However, above 1.5 mass% in brasses, it is no more soluble, is visible under the form of black dots scattered
throughout the crystals [1912Joh, 1972Leo] and has a deleterious effect on the yield strength, the resistance
to impact and the ductility of brasses, while affecting slightly the hardness [1906Gui, 1912Car, 1972Leo].
A copper alloy Cu-36Zn-3Pb (in mass%) prepared by spray deposition shows a Youngs modulus of 99 GPa
and a yield stress of 480 MPa [1999Mor].
Small amounts of Cu added to Pb-Zn liquid alloys increase the value of the viscous flow measured above
the binodal temperatures [2000Neu]. The viscosity of the liquid alloys vary according to an Arrhenius
law: = exp (Ea/RT), where is viscosity at the temperature of infinity, Ea - activation energy. The
viscosity of the Zn95Pb5 alloy, measured at 3.2 mPa#s at 600C with an activation energy of 10.7 kJ#mol1
goes down to 2.2 mPa#s at the same temperature for the Zn90Pb5Cu5 alloy with an activation energy of
14.8 kJ#mol1.
Miscellaneous
Two alloys, Cu-39Zn-3Pb and Cu-40Zn-2Pb (in mass%), produced by melting recycles scraps were shown
to present a high tendency to the formation of hardspots due to the presence of many impurities, even at
concentrations lower than 0.2 mass% [2000Las]. Very difficult to observe due to their small size, their
presence may be recognized by the dimples of the fracture surface after tensile testing.
Landolt-Brnstein
New Series IV/11C2
MSIT
410 CuPbZn
References
[1905Gui] Guillet, M.L., Research on Copper Alloys, Special Brasses and Quenched Bronzes
(in French), Rev. Metall., 2, 97-120 (1905) (Mechan. Prop., Experimental, 0)
[1906Gui] Guillet, M.L., General Investigations on Special Brasses (in French), Rev. Metall., 3,
159-204 (1906) (Mechan. Prop., Experimental, 1)
[1912Car] Carpenter, H.C.H., The Effect of other Metals on the Structure of the -Constitutent in
Copper-Zinc Alloys, J. Inst. Met., 8, 59-73 (1912) (Mechan. Prop., Morphology, 2)
[1912Joh] Johnson, F., The Influence of Tin and Lead on Microstructure of Brass, J. Inst. Met., 7,
201-217 (1912) (Morphology, 4)
[1914Par] Parravano, N., Mazzetti, C., Moretti, R., Gazz. Chim. Ital., 44(11), 475-502 (1914)
(in Italian) (Phase Relations, Experimental, 12)
[1922Nic] Niclassen, H., The System Copper-Zinc-Lead (in German), Forschungsarb. Metallkd., 7,
2-9 (1922) (Experimental, Morphology, Phase Diagram, Phase Relations, 5)
[1929Bau1] Bauer, O., Hansen, M., Influence of a Third Element on the Constitution of Brasses
(in German), Z. Metallkd., 21(5), 145-151 (1929) (Experimental, Phase Diagram, 37)
[1929Bau2] Bauer, O., Hansen, M., Influence of a Third Element on the Constitution of Brasses. I. Lead
Influence (in German), Z. Metallkd., 21(6), 190-196 (1929) (Experimental, Phase
Diagram, Morphology, 49)
[1929Phi] Phillips, A.J., A Discussion of L. R. van Wert`s Paper, The Effect of Lead on the ( + )/
Equilibrium in a 60/40 Brass (Muntz Metal) Published in the November Issue of Metals and
Alloys, 1, 200 (1929), Metals and Alloys, 1(6), 262 (1929) (Experimental)
[1929Wer] van Wert, L.R., The Effect of Lead on the ( + )/ Equilibrium in a 60/40 Brass (Muntz
Metal), Metals and Alloys, 1(5), 200-205 (1929) (Experimental, Morphology, Phase
Relations, 13)
[1943Dan] Dannenmuller, M., Miscibility Gap at the Liquid State in the Alloys, Rev. Metall. (Paris),
40, 85-90 (1943) (Phase Relation, Experimental, 9)
[1948Hen] Henglein, E., Koester, W., About the Application of the Parkes Process on the Basis of
Alloys Systems. The Pb-Zn and Bi-Zn Systems with Ag and Cu (in German), Z. Metallkd.,
39, 391-400 (1948) (Experimental, Phase Diagram, 11)
[1948Jol] Jollivet, L., About Equilibrium of the Lead-Copper-Zinc System in the Lead Corner (in
French), Compt. Rend. Acad. Sci. Paris, 226, 2076-2077 (1948) (Experimental, Phase
Diagram, Phase Relations, 4)
[1949Jol] Jollivet, M.L., On the Equilibrium of the Lead-Rich Complex Systems Containing Some
Zinc and other Elements (in French), Compt. Rend. Acad. Sci. Paris, 228, 1128-1130
[1955Sei] Seith, W., Johnen, H., Wagner, J., Miscibility Gaps in Molten Binary and Ternary Metallic
Systems (in German), Z. Metallkd., 46(11), 773-779 (1955) (Experimental, Phase
Diagram, 20)
[1969Gue] Guertler, W., Guertler, M., Anastasiadias, E., Copper-Zinc-Lead, A Comp. of Const.
Ternary Diagr. Met. Systems, Isr. Pro. Sci. Tr., Jerusalem, 611-613 (1969) (Phase Diagram,
Review, 7)
[1972Leo] Leoni, M., Fortina, G., Investigation on the Solubility of Lead in Alpha and Duplex Brasses
and on the Effects of Small Quaternary Additions on the Properties of these Alloys, Final
Report, INCRA Project 156b/194, Univ. of Missouri-Rolla, 194, 1-26 (1972) (Experimental,
Mechanical Properties, Phase Relations, 8)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Cu-Pb-Zn in INCRA Monograph
Series 6. Phase Diagrams and Thermodynamic Properties of Ternary Copper-Metal
Systems, NSRD, Washington, 643-651 (1979) (Phase Diagram, Review, 13)
N.I., Cu-Pb-Te (in Russian) in Binary and Multicomponent Copper-Base Systems,
Nauka, Moscow, 199 (1979) (Phase Diagram, Review, 3)
New Series IV/11C2
CuPbZn 411
[1994Sur] Surapunt, S., Vasquez, R.R., Itagaki, K., Activity Measurements in Liquid Cu-Zn-X
(X = Pb, Ag, Au) Ternary Alloys (in Japanese), Shigen to Sozai, 110(8), 631-635 (1994)
(Thermodyn., Experimental, 22)
[1998Jan] Jantzen, T., Spencer, P.J., Thermodynamic Assessment of the Cu-Pb-Zn and Cu-Sn-Zn
Systems, Calphad, 22(3), 417-434 (1998) (Assessment, Phase Relations, Thermodyn., 33)
[1999Mor] Morris, D.G., Recent Research on Advanced Copper Alloys: Possibilities for Osprey Spray
Deposition?, Powder Met., 42(1), 20-26 (1999) (Electr. Prop., Experimental, Mechan.
Prop., Phase Relations, Review, 35)
[2000Las] Lassman, S., Hard-spots in Kupfer-Zinc Alloys (in German), Z. Metallkd., 91(10),
868-873 (2000) (Morphology, Experimental, Mechan. Prop., 11)
[2000Neu] Neumann, H., Dong, C., Plevachuk, Yu., The Viscosity of Liquid Immiscible Zn-Pb-Based
Alloys, Z. Metallkd., 91(11), 933-936 (2000) (Experimental, Phys. Prop., Thermodyn., 9)
[2001Her] Hertz, J., What will be done in the Future with O.J. Kleppas Enthalpy Data Set?, J. Alloys
Compd., 321(2), 201-222 (2001) (Phase Relations, Review, Thermodyn., 50)
[2003Bor] Borgrren, U., Selleby, M.,A Thermodynamic Database for Special Brass, J. Phase
Equilib., 22(2), 110-121 (2003) (Phase Relations, Thermodyn., 18)
[2006Leb] Lebrun, N., Cu-Zn (Copper-Zinc), MSIT Binary Evaluation Program, in MSIT
to be published (2006) (Crys. Structure, Phase Diagram, Phase Realtaions, Assessment, 18)
[2006Sch] Schmid-Fetzer, R., Shcerban, O., Tomashik, V., Jialin, Y., Cu-Pb (Copper-Lead), MSIT
Science International Services, GmbH, Stuttgart; to be published (2006) (Crys. Structure,
Phase Diagram, Phase Relations, Assessment, 7)
Table 1: Investigations of the Cu-Pb-Zn Phase Relations, Structures and Thermodynamics

[1914Par] Thermal analysis 425-1043C, the whole diagram, liquidus
[1922Nic] Microscopic observations 599-968C, the whole diagram, miscibility gap in
the liquid phase
[1929Bau1] Microscopic observations, thermal 860-1000C, > 52 mass% Cu, < 2.5 mass% Pb,
analysis isopleth diagram
[1929Bau2] Microscopic observations 420-995C, the whole diagram, miscibility gap in
the liquid phase
[1943Dan] Metallographic observations 400-900C, < 2 mass% Pb, < 10 mass% Cu,
miscibility gap in the liquid phase
[1948Hen] Microscopic observations 327-1084C, the whole diagram, liquidus
[1948Jol] Microscopic observations 326-425C, < 0.1 at.% Cu, < 0.1 at.% Zn, liquidus
[1955Sei] Microscopic observations 500-1050C, < 20 mass% Cu, isoplethic diagram,
miscibility gap in the liquid phase
[1972Leo] Microscopic observations 500-900C, 30-42 mass% Cu, < 1 mass% Pb,
solubility determination
[1994Sur] Zinc activity measurements, isothermal 802C, < 30 at.% Cu (measurement)
isopiestic method 1150C, the whole diagram (estimation)
Landolt-Brnstein
New Series IV/11C2
MSIT
412 CuPbZn

[C] Prototype
, (Cu) cF4 a = 361.46 ( brass) dissolves up to 37.28 at.% Zn
< 1084.62 Fm3m at 454C [Mas2]
Cu a = 361.61 at 300C, 35.84 at.% Zn
, (Zn) hP2 a = 266.50 dissolves up to 2.83 at.% Cu at 425C
< 419.58 P63/mmc c = 494.70
Mg
(Pb) cF4 a = 495.02 [Mas2]
< 327.502 Fm3m
Cu
, CuZn cI2 from 36.1 to 55.8 at.% Zn ( brass)
902 - 454 Im3m a = 295.39 at 47.5 at.% Zn [V-C2]
W
, CuZn cP2 from 44.8 to 48.2 at.% Zn (ordered form
< 468 Pm3m of brass)
CsCl a = 295.9 at 47.5 at.% Zn [V-C2]
, Cu5Zn8 cI52 a = 886.9 from 57 to 70 at.% Zn
< 834 I43m [Mas2, V-C2]
Cu5Zn8
, CuZn3 hP3 a = 427.5 from 72.5 to 76 at.% Zn
700 - 560 P6 c = 259.0 [Mas2, V-C2]
J, CuZn4 hP2 a = 274.18 from 78 to 88 at.% Zn
< 598 P63/mmc c = 429.39 [Mas2, V-C2]
Mg
New Series IV/11C2
CuPbZn 413

Cu Zn Pb
L + (Cu) L + 886 U1 L 57.0 36.2 6.8
(Cu) 68.6 31.4 0
L 6.4 3.3 90.3
63.7 36.3 0
L + L + 825 U2 L 35.3 62.4 2.3
44.7 55.3 0
L 4.9 3.9 91.2
39.7 60.3 0
L + L + 690 U3 L 18.7 80.7 0.6
30.6 69.4 0
L 2.8 4.5 92.7
27.6 72.4 0
L + L2 + J 590 U4 L 10.3 89.4 0.3
24.5 75.5 0
L2 1.56 5.14 93.30
J 21.5 78.5 0
L+ +J 555 U5 L 1.57 3.96 94.47
L + J L + (Zn) 422 U6 L 1.25 98.5 0.25
J 13.3 86.7 0
L 0.62 5.78 93.6
(Zn) 2.78 97.22 0
L + (Cu) + (Pb) 324 U7 L 0.23 0.19 99.58
L + + (Pb) 322 U8 L 0.16 0.47 99.37
L + J + (Pb) 320 U9 L 0.10 1.00 98.90
L J + (Zn) + (Pb) 320 E L 0.06 1.26 98.68
Landolt-Brnstein
New Series IV/11C2
MSIT
414 CuPbZn
Pb Data / Grid: at.%

Fig. 1: Cu-Pb-Zn. Axes: at.%
Liquidus surface e2''
projection
20
80
40
e1'' 60
60
40
850 690 422

e1 '
80 900 886 825 590
20
U1'
1000 (Cu) 950 U2' U6'
U3' U4'
1050C e2 '
20 p1 40 p2 60 p3 80 p5
Cu p4 (Zr) Zn

e3 (Pb)
The liquidus surface U8
U7 U9
projection in the Pb
rich corner
e4

(Zn)
U5
e2''

U6''
U4''
U3''
(Cu) U2''
L1+L2
U1''
Cu 10.00 Cu 0.00
Zn 0.00 Zn 10.00
Pb 90.00 Pb 90.00
New Series IV/11C2
New Series IV/11C2
Landolt-Brnstein
Cu-Zn Cu-Pb-Zn A-B-C Cu-Pb Pb-Zn
955 e1
902 p1 l' (Cu) + l''
l + (Cu) 886 L' + (Cu) L'' + U1
834 p2
l+
825 L' + L'' + U2
700 p3
l+
690 L' + L'' + U3
598 p4
l+
590 L' + L'' + U4
CuPbZn
555 L++ U5
425 p5 ++
l + (Zn)
422 L' + L'' + (Zn) U6
417 e2
326.5 e3 l' (Zn) + l''
l (Cu) + (Pb)
324 L' + (Cu) + (Pb) U7
(Cu)++(Pb)
322 L + + (Pb) U8
++(Pb)
320 L + + (Pb) U9
318 e4
l (Zn) + (Pb)
316 L + (Zn) + (Pb) E
MSIT
+(Zn)+(Pb)
415
Fig. 3: Cu-Pb-Zn. Reaction scheme
416 CuPbZn
0.20
Fig. 4a: Cu-Pb-Zn.
Partial isothermal
section at 700C
0.15
(Cu)+L2 (Cu)++L2
Pb, at %
0.10
+L2
0.05

(Cu)+
(Cu)
0
Cu 74.0 30 34 38 Cu 58.0
Zn 26.0 Zn 42.0
Pb 0.0 Zn, at.% Pb 0.0
0.20
Fig. 4b: Cu-Pb-Zn.
Partial isothermal
section at 800C
0.15
(Cu)+L2
(Cu)++L2
+L2
Pb, at %
0.10
0.05
(Cu)+
(Cu)
0
Cu 74.0 30 34 38 Cu 58.0
Zn 26.0 Zn 42.0
Pb 0.0 Zn, at.% Pb 0.0
New Series IV/11C2
CuPbZn 417
0.20
Fig. 4c: Cu-Pb-Zn.
Partial isothermal
section at 850C
0.15
(Cu)++L
(Cu)+L
+L
Pb, at %
0.10
0.05

(Cu)+
(Cu)
0
Cu 74.0 30 34 38 Cu 58.0
Zn 26.0 Zn 42.0
Pb 0.0 Zn, at.% Pb 0.0

Isothermal section at L2
835C
20
80
40
60
L1+L2
L2+(Cu) L1+L2+
60
40
L2+
80
20
L1
L2+(Cu)+ L1+
20 40 60 80
Cu (Cu) Zn
Landolt-Brnstein
New Series IV/11C2
MSIT
418 CuPbZn
Fig. 6: Cu-Pb-Zn.
Isopleth at a constant L
ratio of Pb:Zn=1:3 1000
(Cu)+L
L1+L2
U1
U2
Temperature, C
750
+L1
(Cu)+L1
+L2 U3 +L1
U4
U5
500
+L1
U6
L1+(Zn)
U7 U8 U9 E (Pb)+(Zn)
(Cu)+(Pb) +(Pb)
250
Cu 20 40 60 Cu 0.00
+(Pb) +(Pb) Zn 75.00
Zn, at.% Pb 25.00
855
Fig. 7: Cu-Pb-Zn.
Isopleth at 2 mass% L+(Cu)
Pb, plotted in at.% 850
L+(Cu)+ L+
L+(Pb)+(Cu)
Temperature, C
L+(Pb)+
(Pb)+
825
(Pb)+(Cu) (Pb)+(Cu)+
815
Cu 67.54 34 36 38 40 Cu 57.48
Zn 31.83 Zn 41.89
Pb 0.63 Zn, at.% Pb 0.63
New Series IV/11C2
CuPbZn 419

Zinc isoactivity lines
at 802C and tie lines L1
in the two liquidus
domain 20
80
40
60
L1+L2
60
40
80
20
0.81
0.88
0.71 L2
0.63
20 40 60 80
Cu Zn

Zinc vapor pressures
above the Cu-Pb-Zn
liquid alloys at
1150C 20
80
40
60
60
5 atm.
40
4
3
2
1
80
20
0.5
0.1
20 40 60 80
Cu Zn
Landolt-Brnstein
New Series IV/11C2
MSIT
420 CuSbSn
Copper Antimony Tin

Gautam Ghosh
Introduction
A summary of experimental studies of phase equilibria is given in Table 1. Early studies [1898Cha,
1913Cam, 1919Tho, 1920Hud] reported the microstructures of as-cast alloys, except that [1913Cam] also
presented a tentative phase diagram of the Sn rich corner. The first systematic study of phase equilibria was
reported by [1927Bon]. They investigated 28 ternary alloys using metallography and thermal analysis, and
determined a partial liquidus surface and an isopleth. [1928Ell] investigated 25 Sn rich alloys using
metallography and thermal analysis, and reported liquidus isotherms in the temperature range of 240 to
400C. [1929Tas] investigated phase equilibria of the entire system, and reported the liquidus surface and
twelve isopleths. There is a good agreement between the results of [1928Ell] and [1929Tas], in the
composition range investigated. [1938Sla] studied solidification process of a Sn-5.5 mass%
Cu-11.5 mass% Sb alloy, and their results are consistent with those reported by [1927Bon].
[1948Har] investigated the phase equilibria of the Sn rich corner, and reported the liquidus and solidus
surfaces, thirteen isopleths, and six isothermal sections between 20 and 240C. They prepared 57 ternary
alloys using 99.99% Sn, 99.9% Cu, 99.7% Sn, and determined the phase equilibria using thermal analysis
and metallography. [1955Sol] correlated the hardness and electrical resistivity properties with the
solid-state phase boundaries in the isopleths of 1 mass% Cu, 2 mass% Sb and 10 mass% Sb reported by
[1948Har].
Phase relations in the Cu-Sb-Sn system have been reviewed by [1969Gue, 1973Bla, 1979Cha, 1979Dri].
Binary Systems
The Cu-Sb binary system is accepted from [1994Sub, 2006Rok]. The Cu-Sn binary system is accepted from
the assessment of [1990Sau] which was later supplemented by thermodynamic modelling [1996Shi,
2000Moo, 2004Liu] within CALPHAD formalism. In the assessment [1990Sau] and in thermodynamic
modeling [1996Shi, 2000Moo] of Cu-Sn system, the 1/1 phase relation is treated as a first-order phase
transformation. In contrast, [2004Liu] reported that a two-stage ordering transition 1 B2 (CsCl
type) 1 takes place in Cu rich alloys. They used diffusion couples in conjunction with high-temperature
electron and X-ray diffraction techniques to study the two-stage ordering transition. However, in the
thermodynamic modeling of Cu-Sn system, [2004Liu] did not consider the 1 phase. Since the two-stage
ordering transition is yet to be verified by others, in this assessment the 1/1 phase relation is treated as a
first-order phase transformation. The phase of Cu-Sn system is believed to be isotypic with B81-NiAs
phase [1990Sau]; however, X-ray and electron diffraction studies have shown that both and phases
have monoclinic symmetry [1994Lar, 1995Lar]. The Sb-Sn binary system is accepted from [Mas2].
Solid Phases
At high temperature, the 1 phase of Cu-Sb and Cu-Sn systems form a continuous solid solution [1929Tas].
The phase dissolves about 18.5 mass% Sb just below the solidus, but it decreases with decreasing
temperature [1929Tas].
[1979Kam] characterized the microstructures of slowly cooled and rapidly solidified Sn-1 mass%
Cu-10.4 mass% Sb alloy, and found that the Cu content is negligible in SbSn phase formed under both
conditions. [1995Sha] studied the microstructure of rapidly solidified Sn-0.5 mass% Cu-8 mass% Sb alloy
using both X-ray and -ray diffraction methods, and found both 1 and phases. The presence of former
implies a metastable state of rapidly solidified microstructure.
[1929Tas] reported that the ternary phase (-1), Cu12Sb3Sn7, forms by a reaction between the J phase of
Cu-Sb and (Sn), but the crystallographic details are presently unknown.
The crystallographic data of all solid phases is listed in Table 2.
New Series IV/11C2
CuSbSn 421
Figure 1 shows the reaction scheme for the solidification of Cu-Sb-Sn alloys [1929Tas], and puts into
evidence seven invariant reactions. The invariant reaction U6 in the Sn corner was first reported by
[1927Bon] and subsequently confirmed by [1929Tas, 1948Har].
The compositions of liquid phase in invariant reactions, taken from [1929Tas], are listed in Table 3.

Figure 2 shows the entire liquidus surface [1929Tas], depicting the melting grooves separating ten different
areas of primary crystallization. A few minor adjustments are made in Fig. 2 to comply with the accepted
binary phase diagrams. In particular, the participation of phase equilibria involving Sb2Sn3 is shown in
Fig. 2, as this phase was not known when the liquidus surface was experimentally determined [1929Tas].
Also, approximate isotherms at 100C interval are superimposed in Fig. 2. [1948Har] made a detailed
investigation of the liquidus surface of Sn corner, and their results are shown in Fig. 3. Figure 4 shows the
phase relations of Cu-Sb-Sn system just below the solidus surface [1929Tas]. The phase fields involving
and Sb2Sn3 are shown dashed as they were not considered by [1929Tas]. In addition, a few minor
adjustments are made to comply with the accepted binary phase diagrams.
Isothermal Sections
Figures 5, 6 and 7 show the isothermal section of Sn corner at 239, 230 and 200C, respectively, based on
a very detailed investigation by [1948Har]. According to the reaction scheme presented in Fig. 1, a
three-phase field (Sn)+Sb2Sn3+ is expected below 240C; however, the stability of Sb2Sn3 below 240C
is unknown and it may transform to SbSn via an yet unknown invariant solid-state reaction just below
240C. Due to this reason, the three-phase field (Sn)+SbSn+ is accepted in three isothermal sections as
originally reported [1948Har].

[1929Tas] reported isopleths at 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70 mass% Sb, and [1948Har]
reported isolpeths at 0.5, 0.75, 1, 1.25, 2, 3 mass% Cu and also at 2, 4, 6, 8, 10, 12, 14 mass% Sb. Figures
8, 9, 10 and 11 show the isopleths at 0.5, 0.75, 1.25 and 3 mass% Cu, respectively. [1948Har] reported a
liquidus minima in the isopleth at 1.25 mass% Cu. However, this is judged to be unlikely considering the
trend of isopleths as a function of Cu content. Therefore, in Fig. 10, the liquidus in the composition range
of less than 10 mass% Sb is shown dashed. Figures 12, 13, 14, 15, 16 and 17 show the isopleths at 2, 4, 6,
8, 10 and 14 mass% Sb, respectively. Once again, a few minor adjustments are made in the isopleths to
comply with the accepted binary phase diagrams.
Thermodynamics
[1956Kle] measured the heat of mixing of three Sn rich liquid alloys at 450C by mixing appropriate
amounts of Cu-Sb and Cu-Sn liquids. Later, [1993Lee] measured the heat of mixing of liquid alloys over a
wide composition range at 727C using a high-temperature calorimeter. Figure 18 shows the isoenthalpy
(mixing) contours in ternary alloys [1993Lee]. The experimental data show that the enthalpy of mixing of
ternary alloys is positive in the Sb corner, and it gradually becomes negative in the Sn corner with increasing
Cu concentration. A negative heat of mixing may imply the tendency for chemical short range ordering in
the liquid phase. [1993Lee] calculated the composition dependence of heat of mixing, using an associate
solution model [1982Som1, 1982Som2], with the assumption of the presence of five binary associates,
Cu3Sb1, Cu1Sb1, Cu3Sn1, Sb1Sn2 and Sb1Sn1 in liquid alloy. They obtained a good agreement between
calculated and experimental results.
[1973Gri] measured the activity of Sn at 389C in liquid alloys containing less than 12 at.% solute
(xCu+xSb). Their data indicate a slight positive deviation from Raults law in the ternary alloys. [1984Sze]
determined the activity of Sb in liquid alloys in the temperature range of 788 to 1163C. [1989Cho]
Landolt-Brnstein
New Series IV/11C2
MSIT
422 CuSbSn
determined the activity of Sb at 1150C in liquid alloys in the entire composition range by
isothermal-isopiestic method. Both measurements show a negative deviation from Raults law; however,
the data of [1984Sze] exhibit a large scatter.

Hardness of ternary alloys have been measured by several authors [1919Tho, 1928Ell, 1929Tas, 1995Sha,
2003Elb]. In addition, [1928Ell] measured hardness at high temperature (up to 125C), and yield strength
and ultimate strength under compression. They also established several cross-property relationships in Sn
rich alloys, such as hardness vs yield strength, hardness vs ultimate strength and hardness vs Youngs
modulus. [1929Tas] also reported mechanical properties of Sn rich alloys under compression. [1955Sol]
determined the hardness and electrical resistivity of alloys along the isopleths of 1 mass% Cu, 2 mass% Sb
and 10 mass% Sb. [2003Elb] measured the isotropic elastic moduli (bulk, shear and Youngs), internal
friction and electrical resistivity of rapidly solidified Sn-1Cu-10Sb (mass%) alloy. The addition of
1 mass% Cu in Sn-10 mass% Sb alloy increases the elastic moduli, but decreases hardness and internal
friction while the resistivity remains unchanged.
The phase alloyed with Sb is age-hardenable, because the solubility of Sb varies with temperature
[1929Tas].
Miscellaneous
[1995Sha] demonstrated the advantage of using -ray diffraction technique over X-ray diffraction for
structural studies of Cu-Sb-Sn alloys.
References
[1898Cha] Charpy, G., Inorganic Chemistry- on the Constitution of the Ternary Alloys (in French),
Compt. Rend. Acad. Sci. Paris, 126, 1645-1648 (1898) (Experimental, 1)
[1913Cam] Campbell, W., Lead-Tin-Antimony and Tin-Antimony-Copper Alloys, Proc. Amer. Soc.
Test. Mater., 13, 630-668 (1913) (Experimental, Phase Diagram, 58)
[1919Tho] Thompson, F.G., Orme, F., Some Notes on the Constitution and Metallurgy of
Britannia-Metal, J. Inst. Met., 22, 203-216 (1919) (Experimental, Phys. Prop., 5)
[1920Hud] Hudson, O.F., Darley, J.H., The Constitution and Structure of Certain
Tin-Antimony-Copper Alloys, J. Inst. Met., 24(2), 361-370 (1920) (Experimental, Phase
Diagram, 9)
[1927Bon] Bonsack, W., About Tin-Copper-Antimony System (in German), Z. Metallkd., 19,
[1928Ell] Ellis, O.W., Karelitz, G.B., A Study of Tin-Base Bearing Metals, Trans. Amer. Soc. Mech.
Eng., 50(11), 13-28 (1928) (Experimental, Mechan. Prop., Phase Diagram, Phase
Relations, 8)
[1929Tas] Tasaki, M., On the Cu-Sn-Sb Ternary System (in German), Mem. Coll. Eng. Kyoto Imp.
Univ., (A)12, 227-255 (1929) (Experimental, Morphology, Phase Diagram, Phase
Relations, Phys. Prop., 0)
[1938Sla] Slavinskiy, M.P., Kleiman, N.L., (in Russian), Metallurg, (12), 68 (1938) (Experimetal,
Phase Diagram, *, 7)
[1948Har] Harding, J.V., Pell-Walpole, W.T, The Constitution of Tin-Rich Tin-Antimony-Copper
Alloys, J. Inst. Met., 75, 115-130 (1948-49) (Experimental, Phase Diagram, 6)
[1955Sol] Solodennikov, A.I., The Determination of Phase Region Boundaries in Ternary Alloy
Systems by the Hardness Method (in Russian), Uchen. Zap., Kirov. Pedagog. Inst., 8,
[1956Kle] Kleppa, O.J., A Calorimetric Investigation of Some Binary and Ternary Liquid Alloys
Rich in Tin, J. Phys. Chem., 60, 842 (1956) (Experimental, Thermodyn., 15)
New Series IV/11C2
CuSbSn 423
[1969Gue] Guertler, W., Guertler, M., Anastasiadias, E., Copper-Antimony-Tin, A Comp. of Const.
Ternary Diagr. Met. Systems, Isr. Pro. Sci. Tr., Jerusalem, 626-628 (1969) (Phase Diagram,
Phase Relations, Review, 7)
[1973Bla] Blalock, J.M., Harding, J.V., Pell-Walpole, W.T., Cu-Sb-Sn (Cooper-Antimpny-Tin) in
Met. Handbook. Metallogr., Struct. Phase Diagr., 8, 428-430 (1973) (Phase Diagram,
Review, Phase, Diagram, 5)
[1973Gri] Griffiths, D.A., Braithwaite, J., Beckstead, L.W., Elliott, G.R.B., Tin Solvent Activity
Equations for Cu-Sb-Sn Liquid Alloys by Stirred H-Cell EMF Measurements,
J. Electrochem. Soc., 120(2), 301-303 (1973) (Experimental, Thermodyn. 16)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Cu-Sb-Sn, INCRA Monograph
Series 6. Phase Diagrams and Thermodynamic Properties of Ternary Copper-Metall
Systems, NSRD, Washington, 659-664 (1979) (Review, Phase Diagram, 11)
N.I., Cu-Sn-Sb (in Russian) in Binary and Multicomponent Copper-Base Systems,
Nauka Moscow, 190-191 (1979) (Review, Phase Diagram, 1)
[1979Kam] Kamal, M., Pieri, J.C., Jouty, R., The Intermatallic Compound in Alloys Sn-10.4 wt.% with
Various Additions (in French), Ann. Chim. (Paris), 4(4), 305-311 (1979) (Crys. Structure,
Experimental, 16)
[1981Ros] Rose, D., New Data for Stistaite and Antimony-Bearing Cu6Sn5 from Rio Tamana,
Colombia, Neues Jahrb. Mineral., Monatsh., (3), 117-126 (1981) (Crys. Structure,
Experimental, 15)
[1982Som1] Sommer, F., Association Model for the Description of Thermodynamic Functions of
Liquid Alloys. 2. Basic Concepts, Z. Metallkd., 73(2), 72-76 (1982) (Theory, 24)
[1982Som2] Sommer, F., Association Model for the Description of Thermodynamic Functions of
Liquid Alloys. 2. Numerical Treatment and Results, Z. Metallkd., 73(2), 77-86 (1982)
(Theory, 74)
[1984Sze] Szemla, G., Dziewidek, L., Norwisz, J., Determination of Antimony Activity in
Antimony-Copper-Tin-Lead Alloys by Mass Spectrometry. Part II, Metal. Odlew., 10(3),
259-279 (1984) (Experimental, Thermodyn., 4)
[1989Cho] Chon, I.H., Lee, Y.H, Thermodynamics of the Sb-Sn-Cu Ternary System, J. Korean Inst.
Met., 27(10), 939-941 (1989) (Experimental, Thermodyn., 7)
[1990Sau] Saunders, N., Miodownik, A.P., The Cu-Sn (Copper-Tin) System, Bull. Alloy Phase
Diagrams, 11, 278-287 (1990) (Phase Diagram, Review, #, *, 57)
[1993Lee] Lee, J.J., Kim, B.J., Min, W.S., Calorimetric Investigations of Liquid Cu-Sb, Cu-Sn and
Cu-Sn-Sb Alloys, J. Alloys Compd., 202, 237-242 (1993) (Calculation, Thermodyn., 13)
[1994Lar] Larsson, A.K., Stenberg, L., Lidin, S., The Superstructure of Domain-twinned -Cu6Sn5,
Acta Crystallogr., B50, 636-643 (1994) (Crys. Structure, Experimental, 14)
[1994Sub] Subramanian, P.R., Laughlin, D.E., Cu-Sb (Copper-Antimony), in Phase Diagrams of
Binary Copper Alloys, ASM, Materials Park, OH, 372-383 (1994) (Crys. Structure, Phase
Diagram, Review, #, *, 54)
[1995Lar] Larsson, A.K., Stenberg, L., Lidin, S., Crystal Structure Modulations in -Cu5Sn4,
Z. Krystallogr., 210, 832-837 (1995) (Crys. Structure, Experimental, 15)
[1995Sha] Shaban, A.M., Gamma-Ray Investigations of Intermetallic Compounds in SnSb8Cu0.5
Melt-Spun Alloy, Rad. Eff. Def. Solids, 133, 51-61 (1995) (Crys. Structure, Experimental,
Mechan. Prop. Phase Diagram, Phase Relations, 15)
[1996Shi] Shim, J.-H., Oh, C.-S., Lee, B.-J., Lee, D.N., Thermodynamic Assessment of the Cu-Sn
System, Z. Metallkd., 87, 205-212 (1996) (Phase Diagram, Thermodyn., Calculation, 36)
[2000Moo] Moon, K.-W., Boenttinger, W.J., Kattner, U.R., Biancaniello, F.S., Handwerker, C.A.,
Experimental and Thermodynamic Assessment Sn-Ag-Cu Solder Alloys, J. Electron.
Mater., 29, 1122-1136 (2000) (Phase Diagram, Thermodyn., Calculation, 24)
Landolt-Brnstein
New Series IV/11C2
MSIT
424 CuSbSn
[2003Elb] El-Bediwi, A.B., Effects of Micro-Additions on Structures and Properties of Rapidly

Solidified Sn-10% Sb Alloy, Rad. Eff. Def. Solids, 158, 475-479 (2003) (Phase Diagram,
Thermodyn., Calculation, 12)
[2004Liu] Liu, X.-J., Wang, C.P., Ohnuma, I., Kainuma, R., Ishida, K., Experimental Investigation
and Thermodynamic Calculation of the Phase Equilibria in the Cu-Sn and Cu-Sn-Mn
System, Metall. Mater. Trans. A, 35A, 1641-1654 (2004) (Experimental, Phase
Diagram, 55)
Table 1: Investigations of the Cu-Sb-Sn Phase Relations, Structures and Thermodynamics

[1898Cha] Metallography
[1913Cam] Metallography, thermal analysis 0.0 wCu 0.3, 0.0 wSb 0.3, wSn = balance
[1919Tho] Metallography, thermal analysis, hardness wCu = 0.0451, xSb = 0.0876, wSn = balance
[1920Hud] Metallography, thermal analysis 0.023 wCu 0.034, 0.084 wSb 0.087,
wSn = balance
[1927Bon] Metallography, thermal analysis 0.0 wCu 0.3, 0.0 wSb 0.58, wSn = balance
[1928Ell] Metallography, thermal analysis, hardness 0.005 wCu 0.0842, 0.021 wSb 0.11,
wSn = balance
[1929Tas] Metallography, thermal analysis, hardness 0.025 wCu 0.95, 0.05 wSb 0.79,
wSn = balance
[1938Sla] Infiltration, XRD wCu = 0.055, wSb = 0.115, wSn = balance
[1948Har] Metallography, thermal analysis 0.0025 wCu 0.03, 0.01 wSb 0.14,
wSn = balance
[1955Sol] Hardness, electrical resistivity 0.0025 wCu 0.03, 0.01 wSb 0.14,
wSn = balance
[1956Kle] Calorimetry 450C; 0.1012 xCu 0.1073 and
0.0588 xSb 0.0688; liquid
[1973Gri] EMF 389 2C; 0.01 xCu + xSb 0.125; liquid
[1979Kam] Rapid solidification, SEM, TEM wCu = 0.01, 0.118 wSb 0.124, wSn = balance
[1981Ros] XRD Cu10Sb1Sn9
[1984Sze] Secondary ion mass spectroscopy 788 - 1163C; 0.193 xCu 0.762 and 0.048
xSb 0.4
[1989Cho] Isothermal-isopiestic 1150C; xCu < 0.9 and xSb > 0.1
[1993Lee] High-temperature calorimetry 723C; 0.05 xCu 0.62 and
0.05 xSb 0.665; liquid
[1995Sha] Rapid solidification, Dynamic resonance, 25C; wCu = 0.005, wSb = 0.08, wSn = balance
XRD, -ray diffraction
[2003Elb] Dynamic resonance, resistivity, hardness, 25C; wCu = 0.01, wSb = 0.10, wSn = balance
XRD
New Series IV/11C2
CuSbSn 425

[C] Prototype
, (Cu) cF4 a = 361.46 pure Cu at 25C [V-C2]
1084.62 Fm3m
Cu
(Sb) hR6 a = 450.67 pure Sb at 25C[V-C2]
< 630.755 R3m = 57.11
As
(Sn) tI4 a = 583.18 pure Sn at 25C [V-C2]
231.5 - 13 I41/amd c = 318.18
Sn
(Sn) cF8 a = 648.92 pure Sn [V-C2]
< 13 Fd3m
C (diamond)
1, Cu17Sn3 cI2 a = 297.81 0.131 xSn 0.158 [V-C2]
586 - 798 Im3m to 298.71
W
, Cu11Sb2 hP2 a = 270 to271.7 0.155 xSb 0.16 [Mas2] [1994Sub]
488 - 400 P63/mcm c = 435 to 437.4
Mg
1, cF16
Cu3Sb Fm3m a = 592.6 to 601 0.194 xSb 0.308 [Mas2] [1994Sub]
683 - 440 BiF3
Cu3Sn(h) a = 606.05 to 611.76 0.165 xSn 0.279 [V-C2]

755 - 520
, Cu9Sb2 hP2 a = 272.1 to 272.9 0.185 xSb 0.20 [Mas2] [1994Sub]
< 462 P63/mcm c = 431.9 to 433.1
Mg
J, Cu3Sb oP8 a = 548.6 to 557.6 0.245 xSb 0.259 [Mas2]
445 - 360 Pmmn b = 476.8 to 480.5 [1994Sub]
Cu3Ti c = 435.2 to 439.8
, Cu10Sb3 hP26 a = 992.0 0.213 xSb 0.216 [V-C2],
390 - 260 P3 c = 432.0 [1994Sub]
Cu10Sb3
', Cu2Sb tP6 a = 398.8 to 403.7 0.32 xSb 0.33 [V-C2],
< 526 P4/nmn c = 608.7 to 615.2 [1994Sub]
Cu2Sb
J1, Cu3Sn(r) oC80 a = 552.9 0.245 xSn 0.259 [V-C2]
< 676 Cmcm b = 4775.0 at 25 at.% Sn [V-C2]
Cu3Sn c = 432.3
, Cu41Sn11 cF416 a = 1798 0.203 xSn 0.208 [V-C2],
590 - 350 F43m a = 1801 at 20.5 at.% Sn
Cu41Sn11
Landolt-Brnstein
New Series IV/11C2
MSIT
426 CuSbSn

[C] Prototype
1, Cu10Sn3 hP26 a = 733.0 0.209 xSn 0.225 [V-C2],
640 - 582 P63 c = 784.0 at 23.1 at.% Sn [V-C2]
, Cu6Sn5(h) mP36 a = 983.0 0.435 xSn 0.445 [Mas2],
415 - 186 P21/c b = 727.0 superstructure of B81-NiAs type, at
Cu5Sn4 c = 983.0 44.44 at.% Sn [1995Lar]
= 62.5
mC54 a = 1260.0 superstructure of B81-NiAs type, at

C2 b = 727.0 44.44 at.% Sn [1995Lar]
Cu5Sn4 c = 1020.0
= 90
, Cu6Sn5(r) mP44 a = 1103.6 0.435 xSn 0.445 [Mas2],
< 186 C2/c b = 728.8 superstructure of B81-NiAs type, at
Cu6Sn5 c = 984.0 44.44 at.% Sn [1994Lar]
= 98.81
SbSn cF8 0.348 xSn 0.57 [V-C2],
< 425 Fm3m a = 588.0 at 50 at.% Sn [V-C2]
NaCl
hR8 a = 864.8 mineral at 56.2 at.% Sn [1981Ros]

c = 1067.5
Sb2Sn3 - - [V-C2]
324 - 242
-, Cu12Sb3Sn7 - - [1929Tas]

Cu Sb Sn
L (Cu) + + 1 643 E1 L 79.5 18.0 2.5
L + 1 ' + J 470 U1 L 34.8 29.7 35.5
L + J '+ 405 U2 L 18.9 30.5 50.6
L + (Sb) SbSn + ' 386 U3 L 14.1 42.4 43.5
L + ' SbSn + 372 U4 L 10.8 37.4 51.8

L + SbSn Sb2Sn3 + 319 U5 L 3.7 20.2 76.1
L + Sb2Sn3 (Sn) + 319 U6 L 1.8 7.4 90.8
New Series IV/11C2
New Series IV/11C2
Landolt-Brnstein
Cu-Sb Cu-Sb-Sn A-B-C Cu-Sn Sb-Sn

798 p1
l + (Cu)
755 p2
645 e1 l + 1
L (Cu) + 1
643 L (Cu) + + 1 E1 640 e2
586 p3 (Cu)++1 1 L +
L + 1
526 e3
L (Sb) + 470 L + 1 + U1 425 p4
L + (Sb) SbSn
L+ + 1++ 415 p5
L+
CuSbSn
405 L++ U2
++
L++
386 L + (Sb) + SbSn U3
L++SbSn (Sb)++SbSn
372 L + + SbSn U4
++SbSn L++SbSn 324 p6

L + SbSn Sb2Sn3
319 L + SbSn + Sb2Sn3 U5
L++Sb2Sn3 SbSn++Sb2Sn3
250 p7
240 L+ Sb2Sn3 + (Sn) U6 L + Sb2Sn3 (Sn)
227 e4
Sb2Sn3++(Sn) L++Sn
L (Sn) +
MSIT
Fig. 1: Cu-Sb-Sn. Reaction scheme for the solidification of Cu-Sb-Sn alloys
427
428 CuSbSn

Fig. 2: Cu-Sb-Sn. Axes: at.%
Liquidus surface
600C
20
80
(Sb)
e3
40
60
p4
p3 U3
60
Cu2Sb
40
U4
U1
max, 683C 500 400
U2
E1 1 p6
e180 600 20
650 U5
800 650 Sb2Sn3
Cu3Sn
900 U6
1000 (Cu) 700 p7
300 (Sn)
Cu p1 20 p2 40 e
2
60 80 p5 e4 Sn
3.0
Fig. 3: Cu-Sb-Sn. 310C
Liquidus surface of
Sn corner 300C
290C

2.0 280C
Cu, mass%
260C
250C
240C
1.0 235C
U6
0C
(Sn)
C
Sb2Sn3
C
25
270
e4
275
C
C

35
0
C
C
2 0
23
24
260
C
285
C
5
24
0
Sn 2.0 4.0 6.0 p7 8.0 10.0 12.0 14.0
Sb, mass%
New Series IV/11C2
CuSbSn 429

Phase relations just (Sb)
below the solidus
20
80
(Sb)+SbSn+Cu2Sb
40
60
SbSn
Sb2Sn3
60
40

n 3+
Cu2Sb +Cu2Sb+SbSn Sb 2S
+
1+Cu3Sn+Cu2Sb Sn
Sb
80
20
(Cu)+ 1+ 1 Cu3Sn+
+Cu2Sb+ +( Sn)+Sb2Sn3
( Sn)
Cu (Cu) 20 Cu3Sn 40 60 80
Sn
14.0
Fig. 5: Cu-Sb-Sn.
Isothermal section of (Sn) + Sb
Sn corner at 239C 12.0
(Sn) + SbSn +
(Sn) +
Sb, mass%
8.0
(Sn) L + (Sn) +
L + (Sn)
6.0
L+
4.0
L
2.0
0
Sn 1.0 2.0 3.0
Cu, mass%
Landolt-Brnstein
New Series IV/11C2
MSIT
430 CuSbSn
14.0
Fig. 6: Cu-Sb-Sn.
Isothermal section of
(Sn) + Sb
10.0
(Sn) + SbSn+
Sb, mass%
8.0
6.0
(Sn) (Sn) +
4.0
L + (Sn) +
2.0
L + (Sn)
L+
L
0
Sn 1.0 2.0 3.0
Cu, mass%
14.0
Fig. 7: Cu-Sb-Sn.
Isothermal section of (Sn) + Sb
(Sn) + SbSn+
10.0
Sb, mass%
8.0
6.0
4.0
2.0
(Sn)
(Sn) +
0
Sn 1.0 2.0 3.0
Cu, mass%
New Series IV/11C2
CuSbSn 431
Fig. 8: Cu-Sb-Sn.
Cu content of 0.5 275
mass%, plotted in L
at.%
L+Sb2Sn3
Temperature, C
250
L+(Sn) L+Sb2Sn3+
240
(Sn)+Sb2Sn3+
L+(Sn)+
225
(Sn)+
Sn+SbSn+
200
Cu 0.93 95 90 Cu 0.93
Sn 99.07 Sn 85.43
Sb 0.00 Sn, at.% Sb 13.64
Fig. 9: Cu-Sb-Sn.
275
Cu content of 0.75
mass%, plotted in L
at.%
250
L+Sb2Sn3
Temperature, C
L+(Sn) 240
L+ (Sn)+Sb2Sn3+
L+(Sn)+
225
(Sn)+
(Sn)+SbSn+
200
Cu 1.39 95 90 Cu 1.40
Sn 98.61 Sn 88.89
Sb 0.00 Sn, at.% Sb 9.71
Landolt-Brnstein
New Series IV/11C2
MSIT
432 CuSbSn
Fig. 10: Cu-Sb-Sn.

Cu content of 1.25 275
mass%, plotted in L
at.%
L+Sb2Sn3
Temperature, C
250
L+ L+Sb2Sn3+
L+(Sn)+ 240
(Sn)+Sb2Sn3+
225
(Sn)+
(Sn)+SbSn+
200
Cu 2.31 95 90 85 Cu 2.32
Sn 97.69 Sn 84.13
Sb 0.00 Sn, at.% Sb 13.55
Fig. 11: Cu-Sb-Sn.

L
Cu content of 3 300
mass%, plotted in L+
at.%
275
Temperature, C
L+Sb2Sn3+
250
240
L+(Sn)+
(Sb)+Sb2Sn3+
225
(Sn)+
(Sn)+SbSn+
200
Cu 5.46 90 85 Cu 5.48
Sn 94.54 Sn 81.17
Sb 0.00 Sn, at.% Sb 13.35
New Series IV/11C2
CuSbSn 433
350
Fig. 12: Cu-Sb-Sn.
Sb content of 2
at.%
L
Temperature, C
300
L+
275
250
L+(Sn)+
L+(Sn)
(Sn)
225
(Sn)+
Cu 5.46 93 95 97 Cu 0.00
Sn 92.63 Sn 98.05
Sb 1.90 Sn, at.% Sb 1.95
Fig. 13: Cu-Sb-Sn.

Sb content of 4 300
mass%, plotted in
at.%
L
Temperature, C
275
L+
250
L+(Sn)
L+(Sn)+
225
(Sn)
(Sn)+
Cu 5.47 91 93 95 Cu 0.00
Sn 90.73 Sn 96.10
Sb 3.80 Sn, at.% Sb 3.90
Landolt-Brnstein
New Series IV/11C2
MSIT
434 CuSbSn
Fig. 14: Cu-Sb-Sn.

Sb content of 6
300
mass%, plotted in
at.%
L
Temperature, C
275
L+
250
L+(Sn)
L+(Sn)+
(Sn)
225
(Sn)+
Cu 5.47 90 92 94 Cu 0.00
Sn 88.82 Sn 94.14
Sb 5.71 Sn, at.% Sb 5.86
Fig. 15: Cu-Sb-Sn.

Sb content of 8 L
at.%
Temperature, C
L+
275
L+Sb2Sn3
L+(Sn)+Sb2Sn3
250
L+Sb2Sn3+ L+(Sn)
240
(Sn)+Sb2Sn3+ (Sn)+SbSn+ (Sn)
Cu 5.47 88 90 92 Cu 0.00
Sn 86.91 Sn 92.18
Sb 7.62 Sn, at.% Sb 7.82
New Series IV/11C2
CuSbSn 435
Fig. 16: Cu-Sb-Sn.

Sb content of 10
at.%
L
Temperature, C
L+
275
L+Sb2Sn3+ L+Sb2Sn3
250
(Sn)+Sb2Sn
(Sn)+Sb2Sn3+
(Sn)+SbSn+ L+(Sn)+Sb2Sn3 (Sn)+SbSn

230
Cu 5.48 86 88 90 Cu 0.00
Sn 85.00 Sn 90.23
Sb 9.53 Sn, at.% Sb 9.77
Fig. 17: Cu-Sb-Sn.

Sb content of 14 L
at.%
L+
Temperature, C
L+Sb2Sn3
275
L+Sb2Sn3+
L+(Sn)+Sb2Sn3
250
(Sn)+Sb2Sn3+ (Sn)+Sb2Sn
240
(Sn)+SbSn+ (Sn)+SbSn
230
Cu 5.48 83 85 Cu 0.00
Sn 81.17 Sn 86.30
Sb 13.35 Sn, at.% Sb 13.70
Landolt-Brnstein
New Series IV/11C2
MSIT
436 CuSbSn

Integral enthalpy of
mixing of liquid
alloys at 727C, in 0
kJ#mol1 20
80
40
60
-1
60
40
-4 -3 -2
-1.5
80 -4.5 20
-5
-1
-4.5
-4
0
20 40 60 80
Cu Sn
New Series IV/11C2
CuSbZn 437
Copper Antimony Zinc

Nathalie Lebrun, Christian Btzner, Riccardo Ferro, Lazar Rokhlin, Jean-Claude Tedenac,
updated by Pierre Perrot
Introduction
Phase equilibria data on the Cu-Sb-Zn system are very sparse. Mainly physical and mechanical properties
have been investigated by [1906Gui, 1912Car]. They suggested a solubility of Sb in and brasses of about
0.5 at.%. This solubility was later investigated by [1946McL] by thermal analysis, metallographic
observations and mechanical properties measurements on the alloys. Samples have been prepared from
electrolytic Cu, Zn of comparably high purity and Sb containing Pb, Fe and S as impurities. The charges,
melted under a glass cover were water quenched or slowly cooled from 450 to 200C in 6 h. The solubility
of Sb in brass (Cu0.7Zn0.3) was found to decrease from 0.6 at.% at 550C to 0.01 at.% at 200C. The
solubility of Sb in (Cu) at 200C is thus reduced from 2 at.% to 0.01 at.% when the Zn content of the alloy
goes from 0 to 30 at.%. This agrees with the results of [1906Gui, 1912Car] but disagrees with the statement
of [1956Gla] which reports without giving any experimental details a solubility of 1 at.% Sb in brass at
400C, which may increases up to 2 at.% at 550C.
[1936Kee] gave some indications about the phase equilibria at room temperature. He found seven
pseudobinary sections for the triangulation of the ternary system by the clear-cross method: CuZn-Cu3Sb,
CuZn-Cu2Sb, CuZn-Sb, Cu2Zn3-Sb, Cu2Zn3-ZnSb, Cu2Sb3-Zn4Sb3 and Cu2Zn3-Zn3Sb2. Unfortunately,
only metallographic methods have been applied and the binary phases described in this work are no more
in agreement with the widely accepted binary phase diagrams. The binary compound Cu2Zn does not exists
and the Zn3Sb2 phase does not crystallize at room temperature. The results have thus to be considered as
doubtful and are not reported here.
The thermodynamic properties of the liquid Cu-Sb-Zn alloys were measured with an electromotive force
method at four cross sections characterized by a Cu:Sb ratio of 2, 1, 0.5 and 0.33 [1995Pen] and integral
quantities were derived by Gibbs-Duhem integration. The set of data obtained have then been compared
with the result of calculation using four different models [1996Pen, 1996Qia].
Binary Systems
The Cu-Sb and Cu-Zn and Sb-Zn binary systems are respectively accepted from [2006Rok], [2006Leb] and
[Mas2]. These systems are thermodynamically well known. The most complete Calphad assessments are
from [2000Liu] for the Cu-Sb and Sb-Zn systems, and [2003Dav] for the Cu-Zn system.
Solid Phases
Unary and binary phases are presented in Table 1. No ternary compound is known.

Figure 1 presents the partial vertical section at 30 at.% Zn as suggested by [1946McL]. The liquidus was
determined by thermal analysis and the solids mainly by micrography. The results illustrate the low
solubility of Sb in the Cu-Zn phases. For a final judgment on the correctness of the figure, further
experiments including annealing and X-ray analysis are necessary.
Thermodynamics
The partial Gibbs energy of mixing of zinc in the ternary liquid alloy has been determined at 600 and 700C
by means of a galvanic cell: Zn(l)/LiCl KCl + 0.5 % ZnCl2(l)/alloy(l). The integral Gibbs energy of
mixture and the integral enthalpy of mixture in the liquid phase at 700C are respectively shown in Figs. 2
and 3. The diagrams show clearly that the chemical short range order observed in Sb-Zn liquid alloys is
Landolt-Brnstein
New Series IV/11C2
MSIT
438 CuSbZn
suppressed by addition of copper. Since the thermodynamic properties of the three binary systems are well
known, four different models were used to calculate the Gibbs energy of mixing and the enthalpy of mixing
of the ternary alloys from the three binary systems [1996Pen]. The asymmetric models of Toop and Hillert
with Cu as the asymmetric component gave an almost perfect agreement with experimental results.
[1996Qia] pointed out the importance of the choice of the asymmetric component in asymmetric models of
solutions.

Microstructure, microhardness, density, line broadening, electrical and thermoelectric properties have been
investigated by [1962Yur]. According to his conclusion, the alloys between: CuZn3?, Cu5Zn8, CuZn and
Zn3Sb2 (actually Zn58Sb42 at low temperatures) are mechanical mixtures of pure binary phases. Zn3Sb2
(h1 and h2) are high temperature modifications of Zn58Sb42 and cannot remain stable at low temperatures
after the slow cooling applied by [1962Yur]. The electrical and thermoelectric properties of the alloys were
non linear functions of composition. A short review of the published data is given in [1979Dri].
References
[1906Gui] Guillet, M.L., General Study of Special Brasses (in French), Rev. Metall., 3, 159-204
[1912Car] Carpenter, H.C., The Effect of Other Metals on the Structure of Constituent in
Copper-Zinc Alloys, J. Inst. Met., 8, 59-73 (1912) (Experimental, 4)
[1936Kee] Keese, W., About the Exchange of Tin in the Cast Brasses Rg5 and Rg9, Especially by
Antimony (in German), Z. Metallkd., 28, 58-63 (1936) (Experimental, Phase Diagram, 16)
[1946McL] McLean, D., Northcott, L., Antimonial 70:30 Brass, J. Inst. Met., 72, 583-616 (1946)
(Mechan. Prop., Experimental, Phase Diagram, 37)
[1956Gla] Gladyshevsky, E.I., Cherkashin, E.E, Solid Solutions Based on Metallic Compounds,
Russ. J. Inorg.Chem., 1(6), 288-295 (1956) translated from Zh. Neorg. Khim., 1(6),
[1962Yur] Yurkov, V.A., Physical Properties of Cu-Zn-Sb Alloys, Phys. Met. Metallogr., 14(2),
11-16 (1962) translated from Fiz. Met. Metalloved., 14(2), 172-181 (1962) (Experimental,
Phase Diagram, Phys. Properties, 20)
Turkina, N.I., Cu-Sb-Zn (in Russian) in Binary and Multicomponent Copper-Base
Systems, Nauka, Moscow, 207-208 (1979) (Phase Diagram, 2)
[1994Sub] Subramanian, P.R., Laughlin, D.E., Cu-Sb (Copper-Antimony), in Phase Diagram of
Binary Copper Alloys, ASM, Materials Park, OH), 372-383 (1994) (Review, Crys.
Structure, Thermodyn., #, 54)
[1995Pen] Peng, M., Mikula, A., Emf Measurements of Liquid Cu-Sb-Zn Alloys, Z. Metallkd.,
86(4), 228-233 (1995) (Experimental, Phase Diagram, Thermodyn., 11)
[1996Pen] Peng, M., Qiao, Z., Mikula, A., Comparison Between Measured and Calculated
Thermodynamic Data for Ternary Liquid Alloys, Calphad, 20(1), 69-78 (1996)
(Calculation, Thermodyn., 20)
[1996Qia] Qiao, Z.Y., Xing, X., Peng, M., Mikula, A., Thermodynamic Criterion for Judging the
Symmetry of Ternary Systems and Criterion Applications, J. Phase Equilib., 17(2),
502-507 (1996) (Assessment, Thermodyn., 33)
[2000Liu] Liu, X.J., Wang, C.P., Ohnuma, I., Kainuma, R., Ishida, K., Thermodynamic Assessment
of the Phase Diagrams of the Cu-Sb and Sb-Zn Systems, J. Phase Equilib., 21(5), 432-442
(2000) (Assessment, Thermodyn., #, 33)
[2003Dav] David, N., Fiorani, J.M., Vilasi, M., Herz, J., Thermodynamic Reevalation of the Cu-Zn
System by Electromotive Force Measurements in the Zinc-Rich Part, J. Phase Equilib.,
23(3), 240-248 (2003) (Experimental, Assessment, Thermodyn., #, 39)
New Series IV/11C2
CuSbZn 439

[C] Prototype
, (Cu) cF4 a = 361.46 Dissolves up to 5.8 at.% Sb at 645C and
< 1084.62 Fm3m 38.27 at.% Zn at 454C [Mas2]
Cu
(Sb) hR6 a = 450.67 [Mas2]
< 630.755 R3m = 5711
As
(Zn) hP2 a = 266.50 Dissolves up to 2.83 at.% Cu at 425C
< 419.58 P63/mmc c = 494.70 [Mas2]
Mg
, CuZn cI2 a = 295.39 36.1 to 55.8 at.% Zn [Mas2]
902 - 454 Im3m at 47.5 at.% Zn [V-C2]
W
, CuZn cP2 a = 295.9 44.8 to 48.2 at.% Zn [Mas2]
< 468 Pm3m at 49.5 at.% Zn [V-C2]
CsCl
, Cu5Zn8 cI52 a = 887.8 57 to 70 at.% Zn [Mas2]
< 834 I43m lattice parameter from [V-C2]
Cu5Zn8
, CuZn3 hP3 a = 427.5 72.45 to 76 at.% Zn [Mas2]
700 - 560 P6 c = 259.0 lattice parameters from [V-C2]
CuZn3
J, CuZn4 hP2 a = 274.18 78 to 88 at.% Zn [Mas2]
< 598 P63/mmc c = 429.39 lattice parameters from [V-C2]
Mg
CuSb5 hP2 - 15.5 to 16 at.% Sb [Mas2]
488 - 400 P63/mmc
Mg
CuSb4 hP* - 18.5 to 20 at.% Sb [Mas2]
< 462 P63/mmc
Mg
Cu3Sb(h3) oF16 a = 601 19.4 to 30.8 at.% Sb [Mas2]
683 - 440 Fm3m From high temperature X-ray diffraction
BiF3 [1994Sub]
Landolt-Brnstein
New Series IV/11C2
MSIT
440 CuSbZn

[C] Prototype
Cu3Sb(h2) oP8 a = 550.4 22.8 to 25.3 at.% Sb
445 - 360 Pmmn b = 435.3 at 24 at.% Sb, annealed 8 d at 425C
Cu3Ti c = 476.8 [1994Sub]
Cu3Sb(h1) hP26 a = 992.0 21.3 to 21.6 at.% Sb
390 - 260 P3 c = 432.0 at 24 at.% Sb, annealed 8 d at 425C
Cu10Sb3 [1994Sub]
Cu2Sb tP6 a = 403.7 32.0 to 33.3 at.% Sb [Mas2]
< 586 P4/nmm c = 615.2 at 33.3 at.% Sb [1994Sub]
Cu2Sb
ZnSb oP16 - 50 to 53 at.% Zn [Mas2]
< 546 Pbca
CdSb
Zn11Sb9 - - 54 to 56 at.% Zn [Mas2]
527 - 493
Zn4Sb3(h) - - 57 to 58.5 at.% Zn [Mas2]
564 - 492
Zn4Sb3(r) - - 57 to 58 at.% Zn [Mas2]
< 494
Zn3Sb2(h2) oI* a = 1516 60 to 61 at.% Zn [Mas2]
566 - 440 b = 2442
c = 721
Zn3Sb2(h1) oP30 a = 803.2 60 to 61 at.% Zn [Mas2]
455 - 409 Pmmn b = 732.2
? c = 1134
New Series IV/11C2
CuSbZn 441
1000
Fig. 1: Cu-Sb-Zn. L
Partial vertical section
at 30 at.% Zn
900
800
L+
Temperature, C
700

L+ +Cu3Sb(h1)
600
+Cu3Sb(h1)
500
+Cu3Sb(h1)+Cu3Sb(h2)
400
+Cu3Sb(h2)
Cu 67.00 68 69 Cu 70.00
Zn 30.00 Zn 30.00
Pb 3.00 Cu, at.% Pb 0.00

Fig. 2: Cu-Sb-Zn. Axes: at.%
Integral Gibbs energy
of mixing in liquid -4
alloys at 700C, in
kJ#mol1 -6
20
80
-8
40
60
60
40
-14
80 -12 20
-10
-8
-6 -10
-8
-4 -6 -4
20 40 60 80
Cu Zn
Landolt-Brnstein
New Series IV/11C2
MSIT
442 CuSbZn

Fig. 3: Cu-Sb-Zn. Axes: at.%
Integral enthalpy of
mixing in liquid
alloys at 700C, in
kJ#mol1 20
80
-1
40 -2 60
-3
60 -2 40
-4
-1
80 -6 20
-8
-6
-4
-2
20 40 60 80
Cu Zn
New Series IV/11C2
CuSiZr 443
Copper Silicon Zirconium

Suray Bhan, Nataliya Bochvar, Boris Kasper, Ortrud Kubaschewski,
Hari Kumar, Peter Rogl, Svitlana Ilyenko
Introduction
Information on the ternary system is rather limited. [1965Smi] showed three isothermal sections of the
copper corner at 700, 1000 and 1050C investigated by metallography. Also shown is a vertical section from
Cu to Zr6Si5 including a eutectic maximum at 1045C and 97.28 at.% Cu, 1.36 at.% Zr and 1.36 at.% Si
obtained by thermal analysis and metallographic methods. [1970Nic] reported this eutectic reaction at a
temperature of 1055C and at the composition 95.6 at.% Cu and 2.2 at.% Si using metallography and DTA.
An isothermal section at 800C was presented by [1974Spr1] based on 168 alloys revealing seven ternary
compounds. The experimental techniques used were X-ray powder diffraction, electron microprobe
analysis and chemical analysis. A projection of the liquidus surface for the Cu corner is due to [1974Spr1,
1974Spr2].
[1979Dri] reviewed the ternary system citing the work of [1965Smi] and [1974Spr1]. Crystal structures of
the ternary compounds have been examined by [1967Gan, 1967Nic, 1972Spr, 1974Spr1, 1975And,
1983Thi]. The majority of the alloys were prepared by argon arc melting metal ingots of 99.5% min. purity
[1972Spr, 1974Spr2]. A floating zone technique has been employed for some alloys in the region of the
pseudobinary eutectic [1970Nic, 1974Spr1]. Some of the ternary compounds have been synthesized by
reaction sintering of powder compacts [1967Gan, 1983Thi]. [1965Smi] used a Tamann induction furnace
in graphite or alumina crucible and a protective melt of equal proportions of NaF, CaF2 and SiO2. After
casting in metallic moulds the samples were annealed (800C), cold worked (50%) and homogenized up to
240 h.
Binary Systems
The binary system Si-Zr have been accepted in the version of [Mas2]. The binary systems Cu-Si and Cu-Zr
are taken from the MSIT Binary Evaluation Program [2002Leb], [2006Sem].
Solid Phases
Seven ternary compounds are established. All unary, binary and ternary solid phases are summarized in
Table 1.
Quasibinary Systems
[1965Smi] investigated the copper rich part of the vertical section Cu-Zr6Si5. [1974Spr2] confirmed the
quasibinary eutectic behavior and corrected the diagram replacing Zr6Si5 with the phase ZrCuSi established
by [1967Nic, 1974Spr1]. Figure 1 shows the vertical section from [1974Spr2] with the inclusion of the
homogeneity range (Cu) from [1965Smi]. The temperature for the eutectic reaction e1(max) was given by
[1965Smi] at 1045C in agreement with that of [1970Nic] 1055C and [1974Spr2] 1045C. The
composition of the eutectic reaction suggested by [1974Spr2] 95.1 at.% Cu, 2.45 at.% Zr and 2.45 at.% Si
is in good agreement with [1970Nic] given at of 95.6 at.% Cu, 2.2 at.% Zr and 2.2 at.% Si. With respect to
the much larger solid solubility of Si in (Cu) than that of Zr in (Cu), a reinvestigation of the precise location
of the e1(max) is recommended.
In the copper corner there are two invariant reactions, one three-phase reaction e1(max) (see above) and one
four-phase reaction E. The partial reaction scheme is given in Fig. 2.
The temperature and the composition of the ternary eutectic E has not been established yet.
ZrCuSi is reported by [1974Spr2] to form peritectically at a temperature of 1610 50C.
Landolt-Brnstein
New Series IV/11C2
MSIT
444 CuSiZr
Liquidus Surface
Figure 3 shows the copper corner of the liquidus projection accepted from [1974Spr2]. The regions of
primary crystallization of (Cu), ZrCu5 and ZrCuSi are added to the diagram. The isotherms of the liquidus
projection given by [1974Spr2] were omitted since these were rough estimates without experimental
measurements.
Isothermal Sections
Figure 4 shows the isothermal section of the copper corner at 1000C accepted from [1965Smi]. The solid
solubility of Zr in (Cu) was adjusted to make it consistent with the accepted binary phase diagram. Figure 5
shows the modified version of the isothermal section for 800C accepted mainly from [1974Spr1]. The
authors showed small homogeneity ranges for the binary and ternary phases. However, all solid phases in
the two binary sub-systems Cu-Zr and Si-Zr are shown as line compounds in the accepted binary phase
diagrams. As no detailed information is available on the extension of the ternary compounds, these phases
are considered without ranges of homogeneity. Thus the two-phase regions presented in the diagram
[1974Spr1] are degenerated into single lines.
The two binary phases ,Cu5Si and ZrCu5 were found later than the report by [1974Spr1] and are included
in the present version.
The region of existence for Zr3Si2(Cu) was corrected assuming Cu-Si exchange at constant Zr content. The
position of the compound -7 was reinterpreted keeping its location at a constant Zr-content of 50 at.% (as
suggested in the text of [1974Spr1]) but accepting the higher Cu-content of ~3 at.% as shown in the original
publication.
The location of the ternary compounds drawn in the isothermal section at 800C by [1974Spr1] do not
correspond to the chemical formulae. Assuming lattice vacancies, the positions for -1, -2 and -3 have been
adjusted according to the experimentally determined compositions [1974Spr1].
Miscellaneous
[1955Rob] carried out investigations of reactions between molten copper and various disilicides including
ZrSi2 and observed the formation of complex phases of low melting points. [1986McR] investigated the
electrical properties of the ternary compounds ZrCuxSi (x = 0, 0.5, 1.33) between 4.2 and 300 K.
References
[1955Rob] Robinson, D.A., Jenkins, I., The Stability of Some Metal Silicides of Potential Value in
High-Temperature Materials, Plansee Proc., Reutte, Tyrol, 187-198 (1955)
(Experimental, 9)
[1965Smi] Smiryagin, A.P., Kvurt, O.S., The Cu Corner of the Cu-Si-Zr System (in Russian), Trudy
Gosudarst. Nauch. Issledovatel. i Proekt. Inst. po Obrabotke Tsvetn. Met., 26(24) (1965)
(Phase Diagram, Experimental, *, 10)
[1967Gan] Ganglberger; E., Nowotny; H., Benesovsky; F., Some New E-Phases (in German),
Monatsh. Chem., 98, 95-99 (1967) (Crys. Structure, Experimental, 3)
[1967Nic] Nickl, J.J., Sprenger, H., Single Crystals of the Ternary Compounds TiCuSi and ZrCuSi
(in German), Naturwissenschaften, 54, 18 (1967) (Experimental, Crys. Structure, 1)
[1970Nic] Nickl, J.J., Sprenger, H., Unidirectional Solidification in the System Cu-ZrCuSi (in
German), Z. Metallkd., 61, 229 (1970) (Experimental, 6)
[1972Spr] Sprenger, H., Nickl, J.J., New Ternary Transition Metal Silicides and Germanides of the
Fe2P-Type (in German), J. Less-Common Met., 27, 163-168 (1972) (Experimental, Crys.
Structure, 13)
[1974Spr1] Sprenger, H., The Ternary Systems (Ti, Zr, Hf)-Cu-Si (in German), J. Less-Common
Met., 34, 39-71 (1974) (Experimental, Crys. Structure, Phase Diagram, #, *, 79)
New Series IV/11C2
CuSiZr 445
[1974Spr2] Sprenger, H., Nickl, J.J., Unidirectional Solidification of the Cu/E-Phase Pseudobinary
Eutectic (in German), J. Less-Common Met., 34, 73 (1974) (Experimental, Phase Diagram,
#, *, 11)
[1975And] Andrukhiv, L.S., Lysenko, L.O., Yarmolyuk, Ya.P., Hladyshevsky, E.I., On Structure of
the Compounds HfCuSi2, HfCuGe2, ZrCuSi2 and ZrCuGe2 (in Ukrainian), Dop. Akad.
Nauk Ukrain. RSR, Ser. A, Fiz-Mat. Tekh. Nauki, (7), 645-648 (1975) (Experimental, Crys.
Structure, 6)
Turkina, N.I., Binary and Multicomponent Copper-Base Systems (in Russian), Nauka,
Moscow, 158-161 (1979) (Review, Phase Diagram, Crys. Structure, 2)
[1983Thi] Thirion, F., Venturini, G., Malaman, B., Steinmetz, J., Roques, B., Crystal Structures of
Zr6Cu8Si12 and Hf2CuGe4 and Characterisation of a Family of Semimetallic
Pseudolamellar Compounds with the Formula ZrCuxSi2 for x = 0.5, 1 and 1.33 (in French),
J. Less-Common Met., 95(1), 47-54 (1983) (Exprimental, Crys. Structure, 11)
[1986McR] McRae, E., Mareche, J. F., Steinmetz, J., Francois, M., Electrical Properties of Certain
Pseudo-lamellar Phases of Formula Zr(Hf)CuxSi(Ge)2 (x = 0, 0.5, 1.33) and ZrSiS,
J. Less-Common Met., 115(1), 9-15 (1986) (Experimental, 10)
[2002Leb] Lebrun, N., Dobatkina T., Kuznetsov V., Li, C., Cu-Si (Copper - Silicon), MSIT Binary
Assessment, 31)

Phase / Pearson Symbol/ Lattice Parameters Comments/References
[C] Prototype
(Cu) cF4 a = 361.46 at 25C [Mas2]
< 1084.62 Fm3m
Cu
(Si) cF8 a = 543.06 [Mas2] 0 to 0.002 at.% Cu
< 1414 Fd3m
C-diamond
(Zr) cI2 dissolves up to 5.7 at.% Cu [2006Sem]
1855 - 863 Im3m a = 356.8 pure Zr [V-C2]
W
(Zr) hP2 dissolves up to ~0.2 at.% Cu [2006Sem]
< 863 P63/mmc a = 323.2 pure Zr at 25C [V-C2]
Mg c = 514.7
Landolt-Brnstein
New Series IV/11C2
MSIT
446 CuSiZr

[C] Prototype
ZrCu5 cF24 a = 687.0 [2006Sem]
< 1032 F43m
AuBe5
or
t** long period superstructure derived from
Zr2Cu9 AuBe5 type
Zr14Cu51 hP68 a = 1124.44 [2006Sem]
1112 P6/m c = 828.15
Gd14Ag51
Zr3Cu8 oP44 a = 786.93 [2006Sem]
1028 Pnma b = 851.47
Hf3Cu8 c = 646.0
Zr24Cu13 o*37 a = 1119.0 [2006Sem]
960 - 915 b = 791.2
c = 998.48
Zr7Cu10 oC68 a = 1267.29 [2006Sem]
< 935 C2ca b = 931.63
Zr7Ni10 c = 934/66
960 - 725 Pm3m
CsCl
< 140 P21/m b = 414.8
TiNi c = 524.9
= 103.7
Cm b = 856.3
c = 534.5
= 105.6
Zr2Cu(h) tI6 a = 322.04 [2006Sem]
1025 - 950 I4/mmm c = 1183.2
MoSi2
Zr2Cu(r) tP150 a = 1592.4 [2006Sem]
< 950 c = 1132.8
, Cu7Si hP2 11.05 to 14.5 at.% Si
842 - 552 P63/mmc a = 256.06 at 12.75 at.% Si [2002Leb]
Mg c = 418.46
, ~Cu6Si cI2 14.2 to 16.2 at.% Si
853 - 787 Im3m a = 285.4 at 14.9 at.% Si [2002Leb]
W
, Cu5Si(h) t** a = 881.5 17.6 to 19.6 at.% Si
[2002Leb]
< 729 P4132
New Series IV/11C2
CuSiZr 447

[C] Prototype
< 800 I43d
Cu15Si4
859 - 558 R3m = 109.74
or
t** a = 726.7 [V-C2]
c = 789.2
620 - 647 R3 = 95.72
< 570 b = 700
c = 2194
ZrSi2 oC12 a = 373 [V-C2]
< 1620 Cmcm b = 1472
ZrSi2 c = 367
ZrSi(r) oP8 a = 699.5 [V-C2]
1460 Pnma b = 378.6
FeB c = 529.6
Zr5Si4(r) tP36 a = 712.25 [V-C2]
< 1860 P41212 c = 1300.0
Zr5Si4
Zr3Si2 tP10 a = 708.2 [V-C2]
2215 P4/mbm c = 371.5
U3Si2
Zr2Si tI12 a = 660.9 [V-C2]
< 1925 I4/mcm c = 529.8
CuAl2
ZrSi1xCux oC8 [Mas2]
Cmcm a = 376.3 x = 0.06 [V-C2]
CrB b = 994.4 stabilized to low temperature
c = 374.7 -7, [1974Spr1]
ZrSi(h) a = 375.7 x = 0.0 [V-C2]

2210 - 1460 b = 991.5
c = 374.0
* -1, Zr3Cu4Si6 tI26 a = 373.8 [V-C2]
I4/mmm c = 2822.3 Zr2Cu3Si4, [1974Spr1]
Zr3Cu4Si6
* -2, ZrCuSi2 tP8 a = 372.4 [V-C2]
P4/nmm c = 902.9
ZrCuSi2
Landolt-Brnstein
New Series IV/11C2
MSIT
448 CuSiZr

[C] Prototype
* -3, Zr2CuSi4 oC28 a = 370.4 [V-C2]
Cmcm b = 3291.0
Hf2CuGe4 c = 368.1
* -4, Zr3Cu4Si4 oI22 a = 1309.0 [V-C2]
Immm b = 639.3
Gd3Cu4Ge4 c = 393.4
* -5, ZrCuSi oP12 a = 650.6 [V-C2]
Pnma b = 392.1
Co2Si c = 727.8
(TiNiSi)
* -6, Zr3Cu4Si2 hP9 a = 637.2 [V-C2]
P62m c = 389.0
Fe2P
* -7, ~Zr50Cu3Si47 oC8 a = 376.3 [V-C2], [1974Spr1]
Cmcm b = 994.4
CrB c = 374.7
1200
Fig. 1: Cu-Si-Zr.
Part of the
quasibinary section
-5 - Cu L
Temperature, C
L+5
1100
1084.62C
L+(Cu)
1045C
(Cu)+5
1000
Zr 10.00 90
Cu
Cu 80.00
Si 10.00 Cu, at.%
New Series IV/11C2
CuSiZr 449
Cu-Si-Zr Cu-Zr
1045 e1 (max) 1032 p

L (Cu) + 5 L + Zr14Cu51 ZrCu5
?
?
1000 e2
L+ZrCu5+5
L (Cu) + ZrCu5
<1000 L (Cu) + ZrCu5 + 5 E
(Cu)+ZrCu5+5
Fig. 2: Cu-Si-Zr. Partial reaction scheme
Zr 0.00
Cu 85.00
Fig. 3: Cu-Si-Zr. Axes: at.%
Schematic liquidus
projection of the Cu
corner
10
10
5
1045, e1(max)
E (Cu)
ZrCu5
Zr 15.00 90 e2,1000C
Cu
Cu 85.00
Si 0.00
Landolt-Brnstein
New Series IV/11C2
MSIT
450 CuSiZr
Zr 0.00
Cu 96.00
1000C
(Cu)+ 5
L+(Cu)+ 5
L+(Cu) (Cu)
Zr 4.00 Cu
Cu 96.00
Si 0.00

800C
20
80
ZrSi2
3
40
60
ZrSi 2
Zr5Si4(r) 7
60 1
Zr3Si2 4
40
Zr2Si
5

80
20
6

(Cu)
Zr
20 40 60 Zr3Cu8 80
ZrCu5 Cu
Zr14Cu51
New Series IV/11C2
CuTiZn 451
Copper Titanium Zinc

Julius C. Schuster, Pierre Perrot
Introduction
Phase equilibria (liquidus surface, reaction scheme and isothermal section at room temperature) for alloys
containing up to 25 mass% Ti were investigated in detail by [1962Hei1]. The alloys were prepared by
melting under Ar or air pure Cu, pure Zn and a Zn-3mass% Ti alloy. Phase analysis were done by optical
microscopy and XRD. This work was later reviewed by [1979Cha, 1979Dri]. A more recent study of the
zinc rich corner of the system has been carried out by [1996Zer]. The interactions between Cu-Zn brasses
and Ti has been investigated by [2001Soa].
Binary Systems
The Cu-Ti and Cu-Zn systems are respectively taken from [2002Ans, 2006Leb]. The Ti-Zn accepted by
[Mas2] is taken from the review of [1984Mur]. Later investigation [1997Glo] showed that the phases TiZn5
and TiZn10 whose structure was unknown were probably the same phase TiZn7 whose composition,
according to [1995Che] would be close to Ti3Zn22. The existence of this phase was confirmed by [2004Vas]
who does not exclude a non stoichiometry between the compositions TiZn7 and TiZn8. An indication about
the presence of a formerly unknown phase Ti2Zn3 has been found by [2004Vas].
Solid Phases
Two ternary phases have been reported, namely -1,Cu2TiZn [1962Hei2, 1967Hof] and -2,Cu2TiZn22
[1996Zer]. Lattice parameters change indicates a Cu solubility in Ti2Zn [1964Ram]. [1959Bis] determined
metallographically a Ti solubility between 0.68 and 1.22 mass% in the binary compound Cu70Zn30. This
result was confirmed by [1966Zwi], who reports that zinc content has little effect on the Ti solubility in
copper base alloys containing up to 10 mass% Zn. It should be noted however that [1959Bis], as well as
[1964Ram] encountered oxidation phenomena in their alloys. The solubility of Ti in Zn-0.6 mass% Cu is
less than 0.06 mass% [1961Pel]. Crystal structure data for Cu2TiZn are given in Table 1 together with the
data on binary boundary phases.
The invariant reactions are given in Table 2 which come mainly from the experimental work of [1962Hei1]
and the review of [1979Cha]. However, they have been modified because the reactions E1, E2, and E3
presented as E type in Table 2 were wrongly labelled U type in [1979Cha]. These reactions can not be
of the U type because the composition of the liquid is situated inside the triangle formed by the three solid
phases.
Liquidus Surface
The liquidus surface, shown in Figs. 1a and 1b is mainly derived from the experimental works of [1962Hei1,
2001Soa]. However, the maxima e2, e3 and e4 missed by [1962Hei] have been introduced according to the
Alkemades rule which states that the border line separating two crystallization fields is crossed by the
straight line linking the compositions of the two phases in a point which must be a maximum. As a
consequence, the invariant equilibria are coherent with elemental geometric considerations reminded
above. The domain labelled Ti2Cu3 is actually crossed by a border between Ti2Cu3 and TiCu2.
However, the exact shape of the TiCu2 domain is unknown. It must be very small because TiCu2 crystallizes
from the liquid phase only between 870 and 875C. The reaction scheme is shown in Fig. 2.
Landolt-Brnstein
New Series IV/11C2
MSIT
452 CuTiZn
Isothermal Sections
The isothermal section at room temperature, shown in Fig. 3 for alloys containing up to 25 mass% Ti
[1962Hei1], is dominated by equilibria surrounding the ternary phase -1,Cu2TiZn. This compound presents
a small homogeneity range. The solubility of the respective third element in either of the binary compounds
is small, except for Cu5Zn8, which dissolves nearly 8 mass% Ti.

Titanium additions in amount as low as 0.06 mass% have a marked effect on grain refining in Zn-0.6 mass%
Cu alloys. The microstructure is stable in annealing 12 h at 350C [1961Pel]. Improved recrystallization
resistance is reported for the Cu70Zn30 alloy having dissolved Ti [1959Bis]. By transmission electron
microscopy (TEM) observations on rapidly solidified Cu rich alloys, precipitation of orthorhombic Cu4Ti
was observed [1980Psh]. Cu-Ti-Zn alloys (15 mass% Ti) were used as a filler alloy in nitride ceramics
[2004Zha] because Ti gives copper the same white color as nickel [2003Yos] without skin irritations
resulting from the presence of Ni. The hardness of Cu58Zn10Ti5 (at.%) alloy increases from 135 to 253
Vickers after ageing 30 min at 500C. Zn-0.1% Cu-0.12% Ti alloys present an improved bendability
[1984Weg] which depends on the ductile-brittle transition temperature.
References
[1959Bis] Biswas, S.K., Gupta, S.C., Effect of Ti addition in alpha-Brass, Trans. Indian Inst. Met.,
12, 175-184 (1959) (Experimental, 3)
[1961Pel] Pelzel, E., The Structure of Zn-Cu-Ti Alloys (in German), Metall, 15, 881-883 (1961)
(Experimental, 5)
[1962Hei1] Heine, W., Zwicker, U., Contribution on the Constitution of Zn-Cu-Ti Alloys (in
German), Z. Metallkd., 53, 386-388 (1962) (Experimental, Phase Diagram, 9)
[1962Hei2] Heine, W., Zwicker, U., Phases of the B-2 Type (CsCl) in Ternary Systems Containing Cu
and Ni (in German), Naturwissenschaften, 49(17), 391 (1962) (Crys. Structure,
Experimental, 1)
[1964Ram] Raman, A., Schubert, K., The Occurence of Zr2Cu- and Cr2Al-Type Intermetallic
Compounds, Z. Metallkde., 55, 798-804 (1964) (Experimental, 23)
[1966Zwi] Zwicker, U., Kalsch, E., Nishimura, T., Ott, D., Seilstorfer, H., The Effect of Additions on
the Equilibria of Cu-Rich Cu-Ti Alloys (in German), Metall, 20(12), 1252-1255 (1966)
[1967Hof] Hofer, G., Stadelmaier, H.H., Co, Ni and Cu Phases of the Ternary MnCu2Al-Type (in
German), Monatsh. Chem., 98, 408-411 (1967) (Crys. Structure, Experimental, 9)
[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., Cu-Ti-Zn, in INCRA
Copper-Metall Systems, NSRD, Washington, 685-689 (1979) (Crys. Structure, Phase
Diagram, 3)
[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padeshnova, E.M., Rokhlin, L.L.,
Turkina, N.I., Cu-Ti-Zn in Binary and Multicomponent Copper-Base Systems (in
Russian), Nauka, Moscow, 209-210 (1979) (Phase Diagram, Review, 1)
[1980Psh] Pshenina, L.S., Korotaev, A.D., Influence of Alloying on the Development of Precipitation
in Cu-Ti Alloys, Sov. Phys. J., 23(4), 293-299 (1980) (Experimental, 23)
[1984Mur] Murray, J.L. The Ti-Zn (Titanium-Zinc) System Bull. Alloy Phase Diagrams, 5(1), 52-56
(1984) (Phase Diagram, Review, 16)
[1984Weg] Wegria, J., Foct, J., Structural Aspects of the Bendability of Zinc-Copper-Titanium
Alloys, Mem. Sci. Rev. Metall., 81(3), 145-155 (1984) (in French) (Mechan. Prop.,
Experimental, 33)
New Series IV/11C2
CuTiZn 453
[1995Che] Chen, X.-A., Jeitschko, W., Danebrock, M.E., Evers, C.B.H., Wagner, K., Preparation,
Properties and Crystal Structure of Ti3Zn22 and TiZn16, J. Solid State Chem., 118, 219-226
[1996Zer] Zermout Z., Durand-Charre M., Kapelski G., Baudelet B., Phase Equilibria in the Zn-rich
Corner of the Zn-Cu-Ti System, Z. Metallkd., 87(4), 274-279 (1996) (Crys. Structure,
Experimental, Phase Diagram, 15)
[1997Glo] Gloriant, T., Reumont, G., Perrot, P., The Fe-Zn-Ti System at 450C, Z. Metallkd., 88(7),
[2001Soa] Soares, D.F., Vilarinho, C., Castro, F., Contribution to the Knowledge of the Cu-Zn-Ti
System for Compositions Close to Brass Alloys, Scand. J. Metall., 30(4), 254-257 (2001)
(Crys. Structure, Experimental, Phase Diagram, 4)
[2002Ans] Ansara, I., Ivanchenko, V., Cu-Ti (Copper-Titanium), MSIT Binary Evaluation Program,
in MSIT Workplace, Effenberg, G. (Ed.), Materials Science International Services GmbH,
Stuttgart; Document ID: 20.11457.1.20, (2002) (Phase Diagram, Crys. Structure,
Assessment, 26)
[2003Yos] Yoshimura, Y., Kita, K., Inoue, A., Mechanical Properties and Microstructure of New Ni
Free White Cu Alloy, Mater. Sci. Forum, 426(4), 3359-3364 (2003) (Mechan. Prop.,
Experimental, 6)
[2004Vas] Vassilev, G.P., Liu, X.J., Ishida, K., Reaction Kinetics and Phase Diagram Studies in the
Ti-Zn System, J. Alloys Compd., 375, 162-170 (2004) (Phase Diagram, Experimental, 34)
[2004Zha] Zhang, J., Liu, C.F., Naka, M., Meng, Q.C., Zhou, Y., A TEM Analysis of the Si3N4/TiN
Joint with a Cu-Zn-Ti Filler Metal, J. Mater. Sci., 39(14), 4587-4591 (2004) (Mechan.

[C] Prototype
(Cu) cF4 a = 361.46 Dissolves up to 38.27 at.% Zn at 454C
< 1084.62 Fm3m and up to 9 at.% Ti at 985C.
Cu
(Ti) cI2 a = 330.65 Dissolves up to 10 at.% Cu at 1005C
1670 - 790 Im3m [Mas2]
W
(Ti) hP2 a = 295.06 Dissolves up to 1.5 at.% Cu at 790C
< 882 P63/mmc c = 468.35 [Mas2]
Mg
(Zn) hP2 a = 266.50 at 22C [Mas2]
< 419.6 P63/mmc c = 494.61
Mg
TiCu4 oP20 a = 452.5 [2002Ans];78 - 80.9 at.% Cu
885 - ~400 Pnma b = 434.1
Au4Zr c = 1295.3
Landolt-Brnstein
New Series IV/11C2
MSIT
454 CuTiZn

[C] Prototype
TiCu4 tI10 - [2002Ans]; 78 - 80.9 at.% Cu
500 I4/m
MoNi4
TiCu2 oC12 a = 436.3 [2002Ans]
890 - 870 Amm2 b = 797.7
Au2V c = 447.8
Ti2Cu3 tP10 a = 313 [2002Ans]
< 875 P4/nmm c = 1395
Cu3Ti2
Ti3Cu4 tI14 a = 313.0 [2002Ans]
< 925 I4/mmm c = 1994
Cu4Ti3
TiCu tP4 a = 310.8 to 311.8 [2002Ans]
< 982 P4/nmm c = 588.7 to 592.1 Range from 48 to 52 at.% Cu
CuTi
Ti2Cu tI6 a = 295.3 [2002Ans]
< 1005 I4/mmm c = 1073.4
MoSi2
, CuZn(h) cI2 a = 295.39 at 47.5 at.% Zn [2006Leb]
902 - 454 Im3m Range from 36.1 to 55.8 at.% Zn
W
', CuZn(r) cP2 a = 295.9 at 49.5 at.% Zn [2006Leb]
< 468 Pm3m Range from 44.8 to 50 at.% Zn
CsCl
, Cu5Zn8 cI52 a = 885.9 to 888.7 [2006Leb]
< 835 I43m Range from 57 to 70 at.% Zn
Cu5Zn8
, CuZn3 hP3 a = 427.5 [2006Leb]
700 - 560 P6 c = 259.0 Range from 72.5 to 76.0 at.% Zn
CuZn3
J, CuZn4 hP2 a = 274.18 [2006Leb]
< 574 P63/mmc c = 429.39 Range from 78.0 to 88.0 at.% Zn
Mg
TiZn15 oC68 a = 769.8 93.75 to 94.1 at.% Zn [1995Che,
< 445 Cmcm b = 1141.4 1996Zer, 2004Vas]
TiZn15 c = 1180.0
TiZn7 tP100 a = 1152.3 Exactly Zn2.842Ti22.160
< 468 P42/mbc c = 1145.6 [1995Che]
TiZn3 cP4 a = 393.22 [1984Mur]
< 650 Pm3m
AuCu3
New Series IV/11C2
CuTiZn 455

[C] Prototype
TiZn2 hP12 a = 506.4 [1962Hei1, 1984Mur]
< 950 P63/mmc c = 821.0
MgZn2
TiZn cP2 a = 314.6 [1962Hei1, 1984Mur]
< 1050 Pm3m
CsCl
Ti2Zn tI6 a = 303.6 [1984Mur]
< 664.6 I4/mmm c = 1067.8
MoSi2
* -1, Cu2TiZn cP2 a = 296 [1962Hei2]
< 950 Pm3m
CsCl
* -2, Cu2TiZn22 cF* a = 1386 2 [1996Zer]
Fd3 or Fd3m
C (diamond)

Ti Cu Zn
L + TiCu4 (Cu) + Ti2Cu3 < 875 U1 L 23.8 72.4 3.8
L (Cu) + Ti2Cu3 + -1 < 875 E1 L 20.2 69.6 10.2
L + (Cu) + -1 < 875 U2 L 14.2 48.8 37.0
L + + -1 < 834 U3 L 14.3 31.4 54.3
L + (Zn) TiZn15 + J < 425 U4 L 0.7 0.5 98.8
L + TiZn15 TiZn7 + J < 425 U5 L 1.4 1.0 97.6
L + TiZn7 TiZn3 + J < 425 U6 L 2.8 6.4 90.8
L TiZn3 + + J < 425 E2 L 4.0 11.2 84.8
L TiZn3 + + < 425 E3 L 5.4 18.2 76.4
L + TiZn3 TiZn2 + < 425 U7 L 14.3 26.5 59.2
L TiZn2 + + -1 < 425 E4 L 14.3 30.4 65.3
Landolt-Brnstein
New Series IV/11C2
MSIT
456 CuTiZn

Fig. 1a: Cu-Ti-Zn. p8 d p9 Axes: at.%
Partial liquidus p7 U5

projection up to 30 p6
at.% Ti U6
20 E2 p4
p5 80
e4
TiZn3 E3
e3
40 TiZn U7
60
p3
TiZn2 E4
U3

60
40
U2 p1
1 e2
80
20
E1 (Cu)
U1
Ti2Cu3
TiCu4
20 40 60 e1 p2 80
Ti Cu

Fig. 1b: Cu-Ti-Zn. d (Zn) Axes: at.%
TiZn15
Enlarged Zn rich part p9
p8
of the liquidus U4
projection p7
(schematic) U5
TiZn7
p6
U6
10
90
TiZn3
Ti 15.00 10 Ti 0.00
Cu 0.00 Cu 15.00
Zn 85.00 Zn 85.00
New Series IV/11C2
New Series IV/11C2
Landolt-Brnstein
Cu-Zn Cu-Ti-Zn Cu-Ti Ti-Zn
903 p1 885 p2
l + (Cu) l + (Cu) TiCu4
875 e1
l TiCu2 + TiCu4
ca.870 e2(max) 870 e
L (Cu) + 1 TiCu2Ti2Cu3+TiCu4
<870 L+TiCu4Ti2Cu3+(Cu) U1
?
835 p3
l+ ca.817 L Ti2Cu3 + (Cu) + 1 E1 TiCu4+Ti2Cu3+(Cu)
650 p5
665 p4 Ti2Cu3+(Cu)+1 l + TiZn2 TiZn3
l+ L + (Cu) + 1 U2
486 p7
574 p6 (Cu)++1 l + TiZn3 TiZn7
l+ 468 p8
L + + 1 U3
l + TiZn7 TiZn15
CuTiZn
424 p9
l + (Zn) ++1 419 d
l (Zn) + TiZn15
<419 L + (Zn) + TiZn15 U4
(Zn)++TiZn15
L + TiZn15 + TiZn7 U5
TiZn15++TiZn7
L + TiZn7 + TiZn3 U6
TiZn7++TiZn3 e3(max)
e4(max)
L TiZn3 +
L TiZn3 +
L + + TiZn3 E2
++TiZn3
L + + TiZn3 E3
++TiZn3
L + TiZn3 1 + TiZn2 U7 ?
TiZn3+1+TiZn2
L + 1 + TiZn2 E4
+1+TiZn2
MSIT
457
Fig. 2: Cu-Ti-Zn. Partial reaction scheme
458 CuTiZn

Fig. 3: Cu-Ti-Zn. (Zn) Axes: at.%
Phase equilibria in the TiZn15 2,TiCu2Zn22
solid state TiZn7

20
80
TiZn3
TiZn2

40
60
60
40
1,TiCu2Zn
80
20
(Cu)
20 40 60 80
Ti Ti2Cu3 TiCu4 Cu
New Series IV/11C2

Non-Ferrous Metal Systems. Part 2 Selected Copper Systems

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Landolt-Brnstein

Numerical Data and Functional Relationships in Science and Technology

Group IV: Physical Chemistry

Ternary Alloy Systems

ISBN 978-3-540-25776-9 Springer Berlin Heidelberg New York

Library of Congress Cataloging in Publication Data

Springer is a part of Springer Science+Business Media

Cover layout: Erich Kirchner, Heidelberg

SPIN: 10916001 63/3020 - 5 4 3 2 1 0 Printed on acid-free paper

MSI, Materials Science International Services GmbH

Authors: Materials Science International Team, MSIT

Christian Btzner, Stuttgart, Germany Viktor Kuznetsov, Moscow, Russia

The Baikov Institute of Metallurgy, Academy of National University of L'viv, Cathedra of

Donbass State Mechanical Engineering Academy, RWTH Aachen, Germany

I.M. Frantsevich Institute for Problems of Materials Technische Universitt Clausthal,

Indian Institute of Technology Madras, Department Universit di Genova, Dipartimento di Chimica,

Institute for Semiconductor Physics, National Universit de Lille I, Laboratoire de Mtallurgie

G.V. Kurdyumov Institute for Metal Physics, University of Cambridge, Department of

Laboratoire de Physicochimie de la Matire Condense, University of Florida, Gainesville, USA

Materials Science International Services GmbH, University of Leeds, Department of Materials,

Max-Planck-Institut fr Metallforschung, Institut fr Universiti Sains Malaysia, School of Materials

Gnter Effenberg and Svitlana Ilyenko Stuttgart, December 2005

IV/11 Ternary Alloy Systems

Subvolume C: Non-Ferrous Metal Systems

Part 2: Selected Copper Systems

Free WEB Access to update information and more.

Links to Literature (up-to-date bibliographic data base)

Structure of a System Report

Fig. 1: Structure of a system report

Liquidus, Solidus, Solvus Surfaces

Temperature Composition Sections

Notes on Materials Properties and Applications

Ag-Tl Tl-Bi Ag-Tl-Bi Bi-Ag

289 e4 (min) (Ag) + (Tl)(h) + Tl3Bi

New Series IV/11C2

C Data / Grid: at.%

limit of known region

C Data / Grid: mass%

phase field notation

estimated phase boundary

L phase field notation

Ternary Systems Al - Ternary Systems Be - Ternary Systems Ce -

Ternary Systems Co - Ternary Systems Cr - Ternary Systems Cu -

Aluminium Copper Lithium

Temperature Composition Sections

Notes on Materials Properties and Applications

Table 1: Investigations of the Al-Cu-Li Phase Relations, Structure and Thermodynamics

Reference Method/Experimental Technique Temperature/Composition/Phase

Reference Method/Experimental Technique Temperature/Composition/Phase

Table 2: Crystallographic Data of Solid Phases

Phase/ Pearson Symbol/ Lattice Parameters Comments/References

Phase/ Pearson Symbol/ Lattice Parameters Comments/References

Table 3: Invariant Equilibria

Reaction T [C] Type Phase Composition (at.%)

Reaction T [C] Type Phase Composition (at.%)

Table 4: Investigations of the Al-Cu-Li Materials Properties

Reference Method/Experimental Technique Type of Property Comments

Reference Method/Experimental Technique Type of Property Comments

LiAl + 1 + 3 L+LiAl+3 625 p4

596 e4 3+2+1 597 L' + 2 + 1 U5 596 p5

Fig. 2a: Al-Cu-Li. Reaction scheme, part 1

L+(Al)+1 524 L + (Al) + B U9

313 L + 1 L9Al4 + 1 U11

Fig. 2b: Al-Cu-Li. Reaction scheme, part 2

CuBe a = 270.2 0.3 46.2 to 49 at.% Be at 850C [2006Wat]