(Landolt-Börnstein - Group IV Physical Chemistry 19B5 _ Physical Chemistry) P. Franke, D. Neuschütz (Auth.), P. Franke, D. Neuschütz (Eds.) - Binary Systems. Part 5_ Binary Systems Supplement 1_ Phase
(Landolt-Börnstein - Group IV Physical Chemistry 19B5 _ Physical Chemistry) P. Franke, D. Neuschütz (Auth.), P. Franke, D. Neuschütz (Eds.) - Binary Systems. Part 5_ Binary Systems Supplement 1_ Phase
(Landolt-Börnstein - Group IV Physical Chemistry 19B5 _ Physical Chemistry) P. Franke, D. Neuschütz (Auth.), P. Franke, D. Neuschütz (Eds.) - Binary Systems. Part 5_ Binary Systems Supplement 1_ Phase
Thermodynamic Properties of
Inorganic Materials
compiled by SGTE
Subvolume B
Binary Systems
Phase Diagrams, Phase Transition Data,
Integral and Partial Quantities of Alloys
Part 5
Binary Systems Supplement 1
Editor
Lehrstuhl für Werkstoffchemie,
Rheinisch-Westfälische Technische Hochschule Aachen
Authors
Scientific Group Thermodata Europe (SGTE)
ISSN 1615-2018 (Physical Chemistry)
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Dedication to Ibrahim Ansara
This series of volumes, presenting thermodynamic properties of binary alloys, is dedicated to the memory
of Ibrahim Ansara – better known to his friends as Himo. Himo was a member of SGTE from the time of
its origin as a CNRS research project in 1967, through the time of its constitution as a European, non-profit-
making company under French law in 1979, until his sudden, unexpected death in 2001.
Through all those years, Himo missed scarcely a single SGTE meeting and his continual cheerfulness
and enthusiasm, as well as his scientific understanding, were an inspiration to his colleagues both in their
joint work of SGTE database development as well as in their individual research projects in their home
laboratories. He was a friend to everyone in SGTE, and it is the spirit of friendship and warmth that he
promoted that has been largely responsible for the continued close collaboration and achievements of this
diverse international group as a whole.
It is very appropriate to dedicate the Landolt-Börnstein handbooks on binary alloy systems to Himo. In
the preparation of the previous volumes on pure substances, Himo made substantial contributions both as
database manager and as advisor. The present series of volumes on binary alloys has benefited considerably
from his contributions to the review and selection of available assessments during the initial stages of the
work. It is a sad coincidence that it was during a meeting to prepare the first of these volumes that Himo
died.
Philip Spencer
Preface
Thermodynamic data, in conjunction with appropriate software for calculation of complex chemical equi-
libria, are finding wide application in many areas of materials design and development. In particular, the last
25 years have seen enormous advances in the thermodynamic modelling of alloy solution phases, whereby
a knowledge of the underlying crystallographic structure of each phase is fundamental to a reliable rep-
resentation of the thermodynamic properties and phase equilibria of a particular system of interest. With
the aid of thermodynamic calculations, considerable time and costs can and are being saved in producing a
material of the required composition and phase constitution required for a particular application.
SGTE has been at the forefront in providing critically assessed thermodynamic data for alloy systems and
has provided guidelines for the modelling of alloy phases of different types. Major advantages of the SGTE
data are their self-consistency, the fact that they are produced with careful attention to a well-defined quality
procedure and that the expertise of SGTE members in various areas of inorganic chemistry and materials
science allows review of the numbers by highly qualified scientists in the fields concerned.
Following the publication of a first set of four volumes of SGTE compiled thermodynamic properties of
inorganic substances, which dealt with pure substances (Subvolume A), this second set of four volumes
presents selected thermodynamic data for binary alloy systems (Subvolume B). The possibility to continue
to ternary and multi-component systems is also foreseen. The data in the latter would be so presented as to
correspond to potential application themes (steels, light alloys, nickel-base alloys, etc.). The fundamental
equations used in evaluating the data are given in the introduction to the volumes and the models used in
representing the data are also described.
Each book in this binary alloys series is accompanied by a CD, which allows computer calculation of a range
of solution properties for selected temperature and phase composition ranges for the systems presented in
that particular volume. Graphical representations, including the calculated phase diagram for each system,
are also possible. Information on more comprehensive software, allowing complex equilibrium calculations
involving both pure substances and solution phases of different types (e.g. slags, salt systems, aqueous
solutions, etc.), can be obtained from SGTE members. A list of the SGTE membership is presented in the
cover pages of this volume.
Very many scientists, in addition to those currently participating in SGTE activities, have contributed to the
development of the SGTE databases. Their names have become too numerous to list and we respectfully
ask them to accept this acknowledgement of their efforts. However, special recognition is given here to the
late Himo Ansara, who was SGTE Pure Substances Database manager from the beginning and who made
major contributions to these binary alloy volumes. His dedicated work and friendship were an inspiration
to all of his colleagues. We remember him with deep affection and gratitude.
Introduction XV
Assessment and selection procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XV
Thermodynamic Modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XVII
Description of the Tables and Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . XXI
Description of the Software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XXIII
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XXVII
Binary Systems 1
Ag – B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Ag – Ba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Ag – Be . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Ag – C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Ag – Ca . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Ag – Cd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Ag – Ce . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Ag – Cr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Ag – Cu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Ag – Fe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Ag – Mo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Ag – Nb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Ag – O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Ag – Te . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Ag – V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Ag – W . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Al – Be . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Al – Dy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Al – Gd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Al – Ho . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Al – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Al – Sc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Al – Sn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Al – Sr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Au – B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Au – Co . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Au – Hf . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Au – Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Au – Pb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Au – Ti . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Au – Zr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
B – Zr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Ba – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Bi – Pd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
C – Ir . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
C – Os . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
C – Pd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
C – Pt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
C – Rh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
C – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
C – Zn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Ca – Li . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Ca – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Cd – Y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
Ce – Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
Co – Gd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Co – Ge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Co – O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
Co – Pd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
Co – Y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Co – Zn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Cr – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Cu – Ir . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
Dy – Mg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Eu – Pd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
Eu – Sn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Fe – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
Fe – Sb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Ga – Mg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Ga – Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Ga – Ti . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
Gd – Li . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
Gd – Mg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
Gd – Mn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Gd – Mo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
Gd – Zr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Hf – Mo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
Hf – Nb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
Hf – Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
Hf – W . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
Hg – Sn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Hg – Te . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Hg – Zn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Ho – Mg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
In – La . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
In – Pd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
Ir – Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Ir – Pt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
Ir – Rh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Ir – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
Ir – Zr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
La – Mg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Li – N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
Li – Na . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Li – Sn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
Mg – Tm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
Mg – Yb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
Mn – Sc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
Mo – V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Mo – Zr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
N – Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
Nb – Ta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
Ni – Pb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
Ni – Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Ni – Zn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Os – Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Pd – Rh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
Pd – Sm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
Pd – Tb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Ru – Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Ru – Zr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Sn – V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
V–W . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
W – Zr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
CD-ROM: Software for the calculation of phase diagrams and thermodynamic data of binary systems
Survey of volume IV/19
Introduction XV
Introduction
The first 4 volumes of this series, under the general heading Thermodynamic Properties of Inorganic Ma-
terials, presents SGTE-compiled thermodynamic data for pure substances, including the elements in their
stable states. The series now continues with a further 4 volumes of SGTE selected and compiled data – this
time for binary alloy systems. For thermodynamic calculations involving alloy solution phases, Gibbs en-
ergies of the pure elements in different stable and metastable states are required. Such data have been
compiled on behalf of SGTE by Dinsdale [91Din] and have recently been updated [02Din]. The values
have found wide use internationally as the basis for thermodynamic assessments of higher order systems.
As with the pure element values, the binary alloy descriptions contained in the present 4-volume series are
not only complete in themselves, but also extend the basis for thermodynamic assessments and calculations
relating to multicomponent alloys.
Members of SGTE have played a principle role in promoting the concept of “computational thermochem-
istry” as a time and cost-saving basis for guiding materials development and processing in many different
areas of technology. At the same time, through organisation of workshops and participation in CODATA
Task Groups, SGTE members have contributed significantly to the broader international effort to unify
thermodynamic data and assessment methods.
The SGTE data can be obtained via members and their agents world-wide for use with commercially avail-
able software developed by some of the members, to enable users to undertake calculations of complex
chemical equilibria efficiently and reliably.
Landolt-Börnstein SGTE
New Series IV/19B
XVI Introduction
As an example, the relations between the Gibbs energy curves and the phase diagram for the Bi-Sn system
are demonstrated in Figs. 1 and 2, respectively. In Fig. 1 the Gibbs energy curves for the phases in the
Bi-Sn system are given as a function of the mole fraction of Sn, xSn , at T = 450 K. At fixed pressure,
temperature and composition, the equilibrium of the system is determined by the state with the lowest Gibbs
energy. All equilibrium states are located on the convex hull of the set of G-curves which is constructed
by applying double-tangents to the curves. The tangent points denote the boundaries between one- and
two-phase regions. In Fig. 2, these points are marked on the selected isotherm of T = 450 K. If this
construction is repeated for other temperatures the complete phase diagram of the system is obtained.
Fig. 1. Gibbs energy functions for the phases in the Bi-Sn Fig. 2. Phase diagram for the system Bi-Sn.
system at 450 K.
If several published assessments are available for a particular system, selection has been made following an
analysis of how well the available experimental data are reproduced by the description. Compatibility of
the modelling used with respect to assembly of a data set for higher order systems has also been taken into
account.
There are many different phases present in binary systems and, in order to combine their thermodynamic
descriptions in higher order systems, it is important to know their crystal structures as well as the solubilities
of alloyed elements in them. In these volumes, the naming of phases has been carried out as consistently as
possible so as to facilitate identification of the same phase appearing in different binary systems.
The main characteristics of each system are presented in individual reports which generally include
– the calculated phase diagram
– an abstract summarising the main features of the system
– a summary of the various stable and metastable phases defined in the system together with crys-
tallographic information, the phase name used in the database and the thermodynamic model used,
including the occupation of the sublattices
– a table of the invariant reactions
– tables and diagrams with integral quantities
– tables and diagrams with partial quantities
– plots of calculated thermodynamic functions
SGTE Landolt-Börnstein
New Series IV/19B
Introduction XVII
Thermodynamic Modelling
Elements
The Gibbs energy of the pure element i, ◦ Gφi (T ), referred to the enthalpy for its stable state φ at 298.15 K,
◦ φ
Hi (298.15 K), is denoted by GHSERi . This quantity is described as a function of temperature by the
following equation:
A number of temperature ranges may be used. The first and second derivatives of this quantity with respect
to temperature are related to the absolute entropy and heat capacity of the compound at the same temper-
ature. Experimental values for heat capacities can thus be directly used in the optimisation and will be
related to the coefficients c, d, e, f, g and h.
For elements which have a magnetic ordering, e.g. Co, Cr, Fe, Ni and Mn, the term GHSER is referred to
a para-magnetic state. An additional term is thus added to the molar Gibbs energy of the magnetic phase.
For elements as well as for solutions, this term is equal to:
where τ is T /T ∗ , T ∗ being the critical temperature for magnetic ordering (Curie temperature TC for
ferromagnetic materials or the Néel temperature TN for antiferromagnetic materials), and β the average
magnetic moment per atom of the alloy expressed in Bohr magnetons.
These equations were derived by Hillert et al. [78Hil] from an expression of the magnetic heat capacity
CPmag described by Inden [81Ind].
The value of p depends on the crystal structure. For example, p is equal to 0.28 for fcc and hcp metals and
0.40 for bcc metals [81Ind]. For anti-ferromagnetic alloys the T ∗ and β are modelled as negative and they
are divided by an anti-ferromagnetic factor of -1 for bcc and -3 for fcc and hcp before the values are used
in equation (2).
For each element, equation (1) is taken from the SGTE unary database. These data have been published
previously as the SGTE data for the pure elements by Dinsdale [91Din, 02Din].
Landolt-Börnstein SGTE
New Series IV/19B
XVIII Introduction
The function GHSERi is also often used to express the thermodynamic functions of metastable structures
ϕ, different from the stable structure of the pure element. The expression ◦ Gϕ ◦ φ
i (T ) − Hi (298.15 K) is
equivalent to ◦ Gϕ ◦ φ ◦ ϕ ◦ φ
i (T ) − Gi (T ) + GHSERi . The term Gi (T ) − Gi (T ) is often called the lattice
stability of element i in phase ϕ.
Binary compounds
where a and b are stoichiometric numbers. The expression for f (T ) is identical to that given by equation (1).
Equation (3) can be transformed by applying equation (1) for each component
The term ∆f GAa Bb (T ) is the Gibbs energy of formation of the compound referred to the stable elements at
temperature T . It can often be taken as a linear function of T .
Gaseous species
An expression identical to equation (1) may be used to describe the Gibbs energy of the gaseous species
with the additional RT ln(P/P0 ) term, where P is the total pressure and P0 the reference pressure, usually
0.1 MPa. The species in the gas phase are assumed to form an ideal solution. The reference state for each
vapour species is taken to be the pure components at 0.1 MPa pressure. The thermodynamic properties of
the gas species are normally obtained from vapour pressure measurements coupled to spectroscopic data.
Data for gaseous substances are covered in more detail in subvolume (A) for pure substances.
Many species, i.e. molecules, may exist in the gas phase and each has a Gibbs energy of formation. The
equilibrium within a gas for a given composition at a given temperature and pressure is calculated by min-
imising the Gibbs energy varying the fraction of the species. As the Gibbs energy is used as the modelling
function in most solution databases it is not possible to calculate the critical point for gas/liquid. The models
used for the different liquids are also not compatible with the ideal model for the gas.
Condensed phases
1: Substitutional solutions
For the substitutional solution φ, the molar Gibbs energy is expressed as follows:
Gφm = Gφ,srf
m + Gφ,id φ,E
m + Gm (5)
with
Gφ,srf
m = xi o Gφ (6)
i
Gφ,id
m = RT xi ln xi (7)
i
xi is the molar fraction of component i with i xi = 1. The term Gφ,srf m is the Gibbs energy of the phase
relative to the reference state for the components and Gφ,id
m is the contribution of ideal mixing entropy.
SGTE Landolt-Börnstein
New Series IV/19B
Introduction XIX
The Redlich - Kister equation [48Red], a power series expansion, is used to express the excess Gibbs energy,
Gφ,E
m , for the interaction between the two elements i and j as follows:
ν φ
Gφ,E
m = xi xj Lij (xi − xj )ν (8)
ν=0
If experimental information for ternary solutions is available then an extra term can be added to equation (8).
For a ternary system A–B–C, this term is equal to:
xA xB xC LABC (9)
The liquid is in most cases treated as a substitutional solution. For liquids with very strong short range order
the associate model [78Som] or the ionic liquid model [85Hil] has sometimes been used.
For magnetic alloys, the composition dependence of T ∗ and β are expressed by:
T ∗ (x) = xi ◦ Ti∗ + T ∗,E (10)
i
β(x) = xi ◦ βi + β E (11)
i
where T ∗,E and β E are both represented by an expression similar to equation (8).
2: Ordered Phases
The use of the sublattice model, developed by Hillert and Staffansson [70Hil] based on Temkin’s model for
ionic solutions [45Tem] and extended by Sundman and Ågren [81Sun], allows a variety of solution phases
to be treated, for example interstitial solutions, intermediate phases, carbides etc. All of these represent an
ordering of the constituents on different sublattices.
As non-stoichiometric phases are formed by several sublattices, they can be schematically described as
follows:
(A, B, ...)p (A, B, ...)q ...
where the constituents A, B, ... can be atoms, vacancies, molecules or ions on the different sublattices .... p,
q, ... are the number of sites. If p + q + ... = 1, then the thermodynamic quantities are referred to one mole
of sites. Most often p and q are selected to be the smallest set of integers.
For each sublattice s, the site fraction of the species i, yis , is equal to
ns ns
yis = i s = is with yis = 1 and ns = n (12)
j nj n i s
where nsi is the number of species i in sublattice s, ns the number of sites in sublattice s, and n the total
number of sites. ns is related to n by ns = n · p/(p + q + ...). The number of sublattices and the species
occupying them, is generally obtained from crystallographical information. The mole fraction of an element
is obtained by s s
n yi
xi = ss s ) (13)
s n (1 − yVa
s
where yVa is the fraction of vacant sites on sublattice s.
This model also describes stoichiometric phases, in which case the sublattices are occupied only by a single
species, and substitutional phases which have a single lattice.
Landolt-Börnstein SGTE
New Series IV/19B
XX Introduction
The molar Gibbs energy for a phase φ expressed by the sublattice model is equal to
Gφm = Gφ,srf
m + Gφ,id φ,E
m + Gm (14)
As an example, a two sublattice phase with two elements A and B in each of the sublattices is considered.
Denoting the sublattices with primes at the symbols, the surface of reference for the Gibbs energy is
Gsrf = yA yA o GA:A + yA yB o GA:B + yB yA o GB:A + yB yB o GB:B (15)
o o
The terms GA:A and GB:B represent the Gibbs energies of the phase φ for the constituent elements A
and B. The colon separates the different sublattices. The terms o GA:B and o GB:A represent the Gibbs
energies of the stoichiometric compounds Ap Bq and Bp Aq , which may be stable or metastable. o GA:A ,
o
GB:B , o GA:B and o GB:A are numerically given by equations (3) and (1).
Gid
m = R T [p(yA ln yA + yB ln yB ) + q(yA ln yA + yB ln yB )] (16)
Finally, the excess Gibbs energy GE
m is equal to
GE
m = yA yB [yA LA,B:A + yB LA,B:B ]
+yA yB [yA LA:A,B + yB LB:A,B ]
+yA yB yA yB LA,B:A,B (17)
The terms Li,j:i and Li:i,j represent the interaction parameters between the atoms on one sublattice for a
given occupancy of the other, and can be described by a Redlich - Kister polynomial, as follows:
Li,j:i = (yi − yj )ν ν Li,j:i (18)
ν=0
ν
The parameters Li,j:i can be temperature dependent. The term Li,j:i,j is known as the reciprocal parame-
ter which may be related to the exchange reaction of A and B between the sublattices. It is usually assumed
to be composition independent but may depend on temperature.
The above equations can easily be extended to ternary and higher order systems.
Phases with order-disorder transformation, like A2/B2 and A1/L12 can also be described with the sublattice
method although this disregards any explicit short range order contributions. A single Gibbs energy function
may be used to describe the thermodynamic properties of both the ordered and disordered phases as follows:
ord s
Gm = Gdis
m (xi ) + ∆Gm (yi ) (19)
ord s
where Gdis
m (xi ) is the molar Gibbs energy of the disordered phase, given by equation (5) and ∆G m (yi ) is
the ordering energy given by:
subl s subl s
m = Gm (yi ) − Gm (yi = xi )
∆Gord (20)
s
where Gsublm (yi ) is given by equation (14). This must be calculated twice, once with the original site
s
fractions yi and once with these site fractions replaced by the mole fractions. If the phase is disordered the
site fractions and mole fractions are equal and thus ∆Gord
m equal to zero.
SGTE Landolt-Börnstein
New Series IV/19B
Introduction XXI
The diagrams and tables which are presented for the binary systems provide an overview of the major
thermodynamic properties and the mixing behaviour of these systems. Depending on the nature of the
respective system, the number and the type of the presented diagrams and tables varies. For all systems, a
calculated phase diagram, a short abstract and a table listing the condensed phases are provided. Additional
tables and diagrams present data for invariant reactions, integral and partial quantities of the liquid and solid
phases, and standard reaction quantities of intermetallic compounds in the system.
The following list gives on overview of the quantities in the tables and diagrams and their designations. The
definition of these quantities is provided in the following paragraphs.
The first diagram shows the phase diagram of the system. The single-phase fields and the compounds
are marked with labels which are used in the tables to refer to the respective phases. All boundaries be-
tween phases which transform into each other by first-order transformations are drawn with solid lines.
Second-order phase transformations and magnetic transformations are denoted by dashed and dotted lines,
respectively.
The table “phases, structures and models”, contains crystallographic data and information on the thermo-
dynamic model in the database. The designations of the phases according to Strukturbericht, prototype,
Pearson symbol and the space group have been collected from various sources, including the original pub-
lication of the assessment and the reference books of Pearson [85Vil], Massalski [90Mas] and Smithells
[92Bra]. The SGTE name is used by the accompanying software on the CD-ROM. The last column of
this table denotes how the sublattices of the crystals have been mapped into a thermodynamic model. The
species which dissolve in a common sublattice are enclosed in parentheses. The indices denote the stoi-
Landolt-Börnstein SGTE
New Series IV/19B
XXII Introduction
chiometric coefficients of the respective sublattices. If a sublattice is occupied by a single species only, the
parentheses have been omitted. Vacancies are denoted by a box (2).
The table of “invariant reactions” provides detailed data for the invariant equilibria and special transition
points shown in the phase diagram. For each of these reactions the temperature and the phase compositions
are provided. The compositions of the participating phases are listed in the same sequence as given by the
symbolic equation. The last column gives the reaction enthalpy on cooling for one mole of atoms according
to the respective transformation.
The thermodynamic quantities for the liquid and solid solutions are provided by a set of three tables which
are denoted by a suffix a–c after the Roman number. The first of these tables lists the integral quantities
as well as the change of the molar heat capacity. The other two tables give the partial quantities for the
respective two components.
The integral and partial quantities can often be obtained easily from experiments. Partial molar quantities
are used to describe the thermodynamic behaviour of the individual components. In a binary system, the
partial molar Gibbs energy GA of component A can be calculated from the molar Gibbs energy, Gm , at
constant temperature and pressure by the well-known relation:
GA is also known as the chemical potential of component A and denoted by the symbol µ A . Similar
relations hold for the partial molar enthalpy, HA , and the partial molar entropy, SA .
Partial quantities provide the difference between the values of thermodynamic functions of a component in
a solution and the corresponding values for the pure components. Thus, the partial Gibbs energy ∆G A of
component A is calculated from GA in the solution and G◦A in the pure substance by:
Usually, the values of the pure components are given for their most stable modification at the respective
temperature and pressure. But in order to avoid ambiguities the reference states for each component are
given at the tables. The quantities ∆HA and ∆SA are defined accordingly.
The thermodynamic activity aA of a component A is closely related to the partial Gibbs energy by:
Therefore, the activity is 1 for pure components in the chosen reference state.
The integral Gibbs energy, ∆Gm is equal to the difference between the Gibbs energy of one mole of a
solution Gm and the sum of the molar Gibbs energies of the pure components G◦i at the same temperature
and pressure. For a binary system the integral Gibbs energy is:
If the reference state of the components is the same phase as the mixture, ∆Gm is also called the Gibbs
energy of mixing. If the reference state of at least one component is different from the phase of the mixture
then ∆Gm contains the difference in Gibbs energies for the pure components between two phases. In these
cases ∆Gm is called the Gibbs energy of formation of the mixture. The quantities ∆Hm and ∆Sm are
defined accordingly.
The excess quantities describe the deviation of the mixture from the ideal mixing behaviour. The molar
excess Gibbs energy, GEm , is given by the difference of the integral Gibbs energy and the Gibbs energy of
mixing for an ideal mixture:
GEm = ∆Gm − Gm
id
(25)
SGTE Landolt-Börnstein
New Series IV/19B
Introduction XXIII
The partial excess quantities can be derived from the integral excess functions by relations similar to those
between partial and integral quantities. Thus, analogous to equation (21), the partial excess Gibbs energy
of component A is given by:
E
GEA = Gm + (1 − xA )(∂Gm /∂xA )P,T
E
(26)
Since the heat of mixing is zero for an ideal mixture, the excess enthalpy is identical to the heat of mixing
and the partial excess enthalpy of a component is equal to its partial enthalpy. Therefore, the partial ex-
cess entropy can be calculated from the partial excess Gibbs energy by a temperature derivative or by the
difference from the partial enthalpy:
E
SA = −(∂GE
A /∂T )P,xA = (∆HA − GA )/T
E
(27)
The activity coefficient is related to the partial excess Gibbs energy by an expression analogous to equa-
tion (23):
γA = exp(GE A /RT ) (28)
For the case of simple substitutional solutions the activity of a component A is related to its mole fraction
by: aA = γA xA .
The preceding equations describe the thermodynamic behaviour of a single phase. In an unconstrained
equilibrium between two phases each component has the same chemical potential and the same activity in
each phase and the integral quantities are linear functions of the composition in a two-phase region. In the
diagrams, the functions are drawn with dashed lines in these regions.
Special considerations apply to stoichiometric compounds. Here, the partial quantities cannot be defined
by the expression given in equation (21) because the composition cannot be varied. Instead, the chemical
potentials are defined by the equilibrium with the next adjacent stable phase.
The table of “standard reaction quantities” provides the Gibbs energy, the enthalpy, and the entropy of
formation for the given compounds from the pure elements in their most stable state at 298.15 K and
0.1 MPa. Phosphorus deviates from this rule since here the white modification is conventionally chosen as
a reference state instead of the more stable red form. All values in this table are given for the reaction of a
total amount of 1 mole of atoms.
Phase Names
The phase names are the same as used in the volumes. If the phase has a miscibility gap or could appear as
both ordered and disordered in the same system, a ”COMPOSITION SET” number is appended to the name
after a hash sign. For example LIQUID and LIQUID#2 may appear as phase names if there is a miscibility
gap in the liquid phase. Normally the composition set 1 is not identified explicitly. As both phases are
thermodynamically identical the assignment of a specific composition set number is arbitrary. For ordering
in the Au-Cu system for example there are four different composition sets for the FCC phase.
Landolt-Börnstein SGTE
New Series IV/19B
XXIV Introduction
Diagram Selection
The two basic windows for SGTEbin are shown in Fig. 3. In the text area of the base window references
for data and other key textual information may appear. For the selection of a system press any two of the
elements highlighted in bold print. The four buttons at the bottom of the window will become available.
Four basic types of diagrams can be generated by use of specific buttons. These are,
The basic diagrams are obtained by just selecting two elements and the specific button. From these four
calculations an infinite number of modified diagrams can be generated. Some of these will be discussed
below.
In addition to selecting the two elements one can also select the set of phases. The folder tagged ”PHASE”
gives the default selection of stable phases for the selected system. By changing this selection various
metastable diagrams can be calculated.
Phase Diagram
This button will generate a standard temperature - composition phase diagram with the axes in mole frac-
tions and degrees Celsius, see the example in Fig. 4a and 4b. Magnifications and phase labels can be
obtained using specific buttons in the graphical window. The REDEFINE button provides a menu, which
will allow a change of the axes as shown in Fig. 5. Fig. 6 is equivalent to Fig. 4 but now plotted with
activity and temperature in Celsius as axes variables.
SGTE Landolt-Börnstein
New Series IV/19B
Introduction XXV
Fig. 4a. The periodic chart window shows the selected Fig. 4b. A binary phase diagram, here Al-Cu.
elements in red. Note that the buttons in the lower area
are activated.
There are a number of different possible choices for the axis variable, some will be more sensible than
others for a particular phase diagram. You may find it instructive to try a few on your own.
Fig. 5. The REDEFINE window for Al-Cu. Fig. 6. The calculated Al-Cu system using the activity of
Al and the Celsius temperature as axis variables.
G-Curves
In this diagram the Gibbs energies for each phase will be plotted vs composition at a given temperature.
This diagram is related to the phase diagram in that the stable combination of phases is given by the lowest
Gibbs energy at each composition. An example is given in Fig. 7. The number listed to the right of the
diagram identifies each curve. Some phases have limited ranges of existence and stoichiometric phases
appear with a small + sign. It is possible to change the axis to plot any integral quantity such as the enthalpy
or entropy of the phases. In most cases the default for the reference phase for each element is the stable
phase at 298.15 K.
Landolt-Börnstein SGTE
New Series IV/19B
XXVI Introduction
A-Curves
In this diagram the activities of the two elements are plotted vs composition at a given temperature as shown
in Fig. 8. The horizontal lines represent two-phase equilibria. It may be useful to change the activity axis to
a logarithmic scale in the REDEFINE window or to plot the chemical potential instead. In most cases the
default for the reference phase for each element is the stable phase at 298.15 K.
Note the difference between A-CURVES and G-CURVES. In the latter all phases are calculated for their
range of composition. In the A-CURVES diagram the phases are included only where they are stable.
Fig. 7. The diagram calculated by pressing the G curves Fig. 8. The diagram calculated by pressing the A curves
button. The Gibbs energy curves are shown for all phases button. The component activities in the system Al-Cu are
of the Al-Cu system at 1273 K. shown at 1000 K.
Phase Fraction
This diagram gives the amount of the stable phases as a function of temperature for a given composition
as shown in Fig. 9. The amount is given as mass fraction of phase. If one is interested to know how the
amount of the phases varies with composition for a given temperature one can use the A-CURVES button
and then change the axis with REDEFINE.
SGTE Landolt-Börnstein
New Series IV/19B
Introduction XXVII
References
[45Tem] M. Temkin: Acta Phys. Chim. 20 (1945) 411–420.
[48Red] O. Redlich, A. Kister: Ind. Eng. Chem. 40 (1948) 345–348.
[70Hil] M. Hillert, L.-I. Staffanson: Acta Chem. Scand. 24 (1970) 3618–3626.
[78Hil] M. Hillert, M. Jarl: Calphad 2 (1978) 227–238.
[78Som] F. Sommer: Calphad 2 (1978) 319–324.
[81Ind] G. Inden: Physica 103B (1981) 82–100.
[81Sun] B. Sundman, J. Ågren: J. Phys. Chem. Solids 42 (1981) 297–301.
[85Hil] M. Hillert, B. Jansson, B. Sundman, Ågren: Metall. Trans. A 16A (1985) 261–266.
[85Vil] P. Villars, L.D. Calvert: “Pearson’s Handbook of Crystallographic Data for Intermetallic
Phases”, Vol. 1–3, ASM, Metals Park, Ohio, USA, 1985.
[88Ans] I. Ansara, P. Willemin, B. Sundman: Acta metall. 36 (1988) 977–982.
[90Mas] T.B. Massalski, H. Okamoto, P.R. Subramanian, L. Kacprzak: “Binary Alloy Phase Diagrams”,
2nd ed., ASM International, Materials Park, Ohio, USA, 1990.
[91Din] A.T. Dinsdale: Calphad 15 (1991) 317–425.
[92Bra] E.A. Brandes, G.B. Brook (eds.): “Smithells Metals Reference Book”, 7th ed., Butterworth-
Heinemann Ltd., Oxford, 1992.
[97Ans] I. Ansara, N. Dupin, H.L. Lukas, B. Sundman: J. Alloys Compd. 247 (1997) 20–30.
[98Sau] N. Saunders, A.P. Miodownik: “CALPHAD Calculation of Phase Diagrams”, Elsevier Science
Ltd., Oxford, 1998.
[02Din] A.T. Dinsdale: to be published (2002).
Landolt-Börnstein SGTE
New Series IV/19B
LANDOLT-BÖRNSTEIN
GROUP IV: Physical Chemistry
VOLUME 19: Thermodynamic Properties of Inorganic Materials
SUBVOLUME B: Binary Systems
PART 5: Binary Systems Supplement 1
Frontmatter
Introduction
Ag – B (Silver – Boron)
2900
2700 liquid′ + liquid″
2500
2300
2100
1900
T / K
1700 βB
1500
1300
1100
900 fcc
700
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag xB B
No phase diagram data are available for the Ag-B system, except for the invariant equilibrium at 1235 K
reported by Wald and Stormont [1970Wal]. Ag and B are immiscible in both the liquid and solid state
[1965Wal]. This is consistent with the reported insolubility of B in liquid Ag even at 1873 K [1915Gie].
However, reliable information on the extent of minor solubilities is not available. The compound AgB 2 was
obtained by direct synthesis at an unspecified temperature and identified as having a hexagonal structure
[1961Obr]. However, X-ray results of alloys with 66.6 at.% B [1965Wal] annealed for two months at
1173 K did not confirm the existence of AgB2 [1990Kar]. The thermodynamic assessment of the Ag-
B system was carried out by Korb [2004Kor]. The calculated phase diagram is in good agreement with
available experimental information.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – B
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Ba 1
Ag – Ba (Silver – Barium)
1300
1200
liquid
1100
1000
900
T / K
800
700
600
Ag 2 Ba 3
Ag 5 Ba
Ag 2 Ba
500
AgBa
fcc bcc
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag xBa Ba
The Ag-Ba binary system contains two components interesting in the nuclear field, silver being part of
AIC control rods (Ag-In-Cd). The phase diagram reported in the compilation of Okamoto [1992Oka] is
mainly based on the experimental work of Bruzzone et al. [1987Bru] using DTA, X-ray and metallography.
The older work of Weibke [1930Wei] using DTA has been discarded. Four intermetallic phases have been
identified: Ag5 Ba, with a wide non-stoichiometry range, and three stoichiometric compounds, Ag 2 Ba,
AgBa, and Ag2 Ba3 . The first two melt congruently at 988 K and 1043 K, the two others decompose
peritectically at 833 K and 633 K. There are two eutectic reactions located at 973 K on the silver side and
at 513 K on the barium side. There is no reported mutual solubility of both elements in the solid state, and
a complete miscibility in the liquid state. The enthalpy of mixing of liquid alloys of silver with barium
and rare earth metals (La, Ce, Sm, Eu, Gd, Dy and Yb) have been measured by Ivanov and Witusiewicz
[1992Iva] using isoperibolic calorimetry. No experimental data are available for thermodynamic properties
of the intermetallic solid phases. This system was assessed by Chevalier and Fischer [1995Che]. The
excess Gibbs energy of the liquid and the Gibbs energy of the intermetallic compounds which are all treated
as stoichiometric were optimised from selected data for the phase diagram [1987Bru] and the enthalpy of
mixing in the melt [1992Iva]. A sub-regular substitution model was used for the liquid. The heat capacity
versus temperature and the entropy at 298.15 K of the compounds were estimated from the pure elements
by using the Neumann-Kopp rule. The enthalpy of formation was optimised in consistency with other data.
The calculations are in very satisfactory agreement with the selected experimental data.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Ba
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Ba 3
8 1.0
T∆Sm
4
0.8
0
Energies / (kJ/mol)
−4 0.6 a Ag a Ba
Activities
−8
−12 0.4
∆Hm
−16
0.2
−20 ∆Gm
−24 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Ba Ba Ag x Ba Ba
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1273 K.
T =1273 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ag – Ba
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xBa ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ag5 Ba1 0.167 −11206 −11205 0.001 0.000
Ag2 Ba1 0.333 −18356 −18356 0.001 0.000
Ag1 Ba1 0.500 −17045 −17045 0.001 0.000
Ag2 Ba3 0.600 −13868 −13868 0.001 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Be 1
Ag – Be (Silver – Beryllium)
1600
bcc
1500 liquid
1400
1300
T / K
Ag 3 Be 8
1200
1100
1000
fcc hcp
900
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag xBe Be
The equilibrium phases of the Ag-Be system are the liquid, the Ag-based fcc solid solution, the Be-based
bcc and the hcp solid solution phases, as well as the high-temperature intermetallic compound Ag 3 Be8
which exists only within a limited temperature range between 1033 K and 1283 K [1973Gol, 1979Ald].
The compound is a Laves phase of the Cu2 Mg type but it has been represented by the formula Ag3 Be8
since it exists only in a very narrow range at the off-stoichiometric composition of about 73 at.% Be. The
Ag-Be system was critically assessed by Korb [2004Kor]. The calculated Ag-Be phase diagram compares
well with the data compilation in [1987Oka].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Be
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Be 3
10 1.0
T∆Sm
8
0.8
Energies / (kJ/mol)
6
∆Hm 0.6 a Be a Ag
Activities
4
2
0.4
0
0.2
−2
∆Gm
−4 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Be Be Ag x Be Be
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1600 K.
T =1600 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xBe ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ag3 Be8 0.730 1838 2569 2.452 0.000
References
[1973Gol] O. von Goldbeck in: Beryllium: Physico-Chemical Properties of Its Compounds and Al-
loys, O. Kubaschewski, ed., Atomic Energy Review Special Issue No. 4, International
Atomic Energy Agency, Vienna, 1973, pp.45–46.
[1979Ald] F. Aldinger, G. Petzow in: “Beryllium Science and Technology”, vol. 1, D. Webster, G.J.
London, eds., Plenum Press, New York, 1979, 235–305.
[1987Oka] H. Okamoto, L.E. Tanner in: “Phase Diagrams of Binary Beryllium Alloys”, H. Okamoto,
L.E. Tanner, eds., ASM, Metals Park, 1987, 4–8.
[2004Kor] J. Korb, unpublished assessment, GTT-Technologies, 2004.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ag – C 1
Ag – C (Silver – Carbon)
2000
liquid
1500
T / K
fcc
1000
fcc + graphite
500
0.0000 0.0001 0.0002 0.0003 0.0004
Ag xC
The Ag-C phase diagram has been studied by various experimental techniques [1919Ruf, 1949Ves,
1959Sne, 1969McL]. The Ag-C system displays the liquid, fcc and graphite phases. This system exhibits
immiscibility to a very high degree [1988Kar]. The solubility of Ag in graphite is extremely low, but not
known precisely [1988Kar]. The solid solubility of graphite in fcc-Ag has been studied by a vapour trans-
port technique [1969McL] in the range from 1058 to 1230 K. The solubility of carbon in solid silver at its
melting point has been found to be 0.036 at.% C. The solubility of carbon in liquid silver is much lower and
has been reported in [1919Ruf]. Some compounds of Ag and C have been reported, such as Ag 4 C and AgC
[1959Sne] and Ag2 C2 [1949Ves, 1959Sne]. Their existence has not been confirmed by other investigations.
The data for the Ag-C system were critically assessed by Korb [2004Kor]. The calculated phase diagram is
in good agreement with the data compilation in [1988Kar].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – C
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Ca 1
Ag – Ca (Silver – Calcium)
1300
1200
liquid
1100
1000
900
T / K
bcc
800
700
600
Ag 9 Ca 2
Ag 7 Ca 2
Ag 3 Ca 5
Ag 2 Ca
AgCa 3
500
AgCa
fcc fcc
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Ca Ca
The Ag-Ca binary system contains two components interesting the nuclear field, silver being part of
AIC control rods (Ag-In-Cd) and calcium being a major component of the concrete basemat in its ox-
ide form (CaO). The phase diagram reported in the compilation of Moffatt [1981Mof] and reported by
Baren [1988Bar] is based on investigations of Alexander et al. [1969Ale] using DTA, X-ray and metal-
lography, and Pascal et al. [1970Pas] using DTA. Baar’s results from thermal analysis [1911Baa] were
reported by Hansen and Anderko [1958Han]. Six intermetallic stoichiometric compounds were clearly
identified, Ag9 Ca2 , Ag7 Ca2 , Ag2 Ca, AgCa, Ag3 Ca5 , and AgCa3 . In addition, Calvert and Rand [1964Cal]
identified Ag8 Ca3 by X-ray analysis, but it was not confirmed by thermal analysis. Ag7 Ca2 and AgCa melt
congruently at 1004 K and 938 K, respectively, while the four others decompose peritectically. There is
no reported mutual solubility of both elements in the solid state, and a complete miscibility in the liquid
state. The thermodynamic properties of liquid alloys were electrochemically determined by Delcet and
Egan [1978Del] and by Fischbach [1985Fis] using the Knudsen effusion technique. The enthalpy of forma-
tion of the compounds was measured potentiometrically [1981Not]. No experimental data are available for
the thermodynamic properties of the other compounds. This system was assessed by Chevalier and Fischer
[1996Che]. The excess Gibbs energy of the liquid and the Gibbs energy of the intermetallic compounds con-
sidered as stoichiometric ones were optimised from the selected experimental information. A sub-regular
substitution model was used for the liquid. The enthalpy of formation was optimised in consistency with
other data. The agreement with the experimental phase diagram information [1969Ale, 1970Pas] is quite
satisfactory. The calculated activity of calcium at 1073 K is in satisfactory agreement with the experiments.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Ca
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Ca 3
10 1.0
5 T∆Sm
0.8
0
Energies / (kJ/mol)
−5 0.6 a Ag a Ca
Activities
−10
−15 0.4
∆Hm
−20
0.2
−25
∆Gm
−30 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Ca Ca Ag x Ca Ca
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1273 K.
T =1273 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ag – Ca
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xCa ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ag9 Ca2 0.182 −16462 −16583 −0.407 0.175
Ag7 Ca2 0.222 −19522 −19671 −0.498 0.214
Ag2 Ca1 0.333 −22563 −22786 −0.748 0.321
Ag1 Ca1 0.500 −25291 −25626 −1.122 0.481
Ag3 Ca5 0.625 −21322 −21740 −1.403 0.601
Ag1 Ca3 0.750 −15106 −15608 −1.684 0.722
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Cd 1
Ag – Cd (Silver – Cadmium)
1300
1200
liquid
1100
1000
900
bcc
T / K
800
fcc
700
ζAgCd
600
Ag 2 Cd 3
AgCd
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Cd Cd
The Ag-Cd binary system contains two components interesting in the nuclear field, silver and cadmium
being part of AIC control rods (Ag-In-Cd). The phase diagram has been reported in several compilations
of binary systems [1958Han, 1965Ell, 1969Shu]. It is mainly based on the investigation of phase equilib-
ria by [1905Ros, 1910Bru, 1911Pet, 1937Hum, 1939Owe] with additional results of [1896Gau, 1928Ast,
1928Nat, 1931Dur, 1935Dur, 1957Ray, 1959Pya, 1960Qua, 1962Mas]. The Ag-Cd system is a typical
representative for the formation of intermetallic electron phases which are characterised by certain ratios
of valence electrons to atoms. Among them are the β-, γ- and -brasses which are here denoted as the
bcc, Ag2 Cd3 and hcp phases, respectively. The latter hexagonal phase and the terminal Cd-rich solid so-
lution (hcp ) have been modelled as a single hexagonal phase with a miscibility gap. A third hexagonal
solid solution, ζAgCd, has been described as a separate phase. The intermetallic compounds AgCd and
Ag2 Cd3 have been approximated with stoichiometric descriptions. Ag2 Cd3 has the γ-brass structure at
higher temperature and a related superstructure at lower temperature but it has been described as a single
phase only. The thermodynamic properties of liquid and solid alloys have been compiled from the liter-
ature in [1973Des] based on the measured activities of cadmium [1933Öla, 1942Sch, 1949Bir, 1956Her,
1956Sca, 1963Fil, 1969Con, 1970Mas, 1984Hou] and on calorimetric investigations [1956Kle, 1958And,
1958Orr, 1958Hul, 1969Wal]. This system has been assessed by Chevalier [2004Che]. A simple substitu-
tion model has been used for all solution phases (liquid, fcc, bcc, ζAgCd, and hcp) the excess interaction
parameters being described by a Redlich-Kister polynomial of maximal second order. The heat capacity
of the compounds was estimated from the pure solid components by using the Neumann-Kopp rule. The
enthalpy and entropy of formation were optimised in consistency with other data. The agreement with
the experimental information is quite satisfactory, as well for phase diagram [1905Ros, 1910Bru, 1911Pet,
1958Han, 1937Hum, 1939Owe] as thermodynamic data of solid and liquid phases (partial Gibbs energy
and enthalpy of formation).
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Cd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Cd 3
4 1.0
2
T∆Sm
0.8
0
Energies / (kJ/mol)
−2 0.6 a Ag a Cd
Activities
−4
−6 0.4
∆Hm
−8
∆Gm 0.2
−10
−12 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Cd Cd Ag x Cd Cd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1273 K.
T =1273 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ag – Cd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Cd 5
4 1.0
2
T∆Sm 0.8
Energies / (kJ/mol)
0.6 a Ag a Cd
Activities
−2
−4
0.4
−6
∆Hm 0.2
−8
∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Cd Cd Ag x Cd Cd
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =573 K.
T =573 K.
Table V. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xCd ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ag1 Cd1 0.500 −8005 −7325 2.279 0.000
Ag2 Cd3 0.600 −7413 −6277 3.811 0.000
Landolt-Börnstein SGTE
New Series IV/19B
6 2 Binary Systems: Ag – Cd
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Ce 1
Ag – Ce (Silver – Cerium)
1400
1300 liquid
1200
1100
1000
T / K
bcc
900
800
700
Ag 51 Ce 14
Ag 2 Ce
AgCe
500
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Ce Ce
Ag-rare earth binary alloys are potential electronic materials and amorphous materials. They attract the
interest of theoretical research and industrial purposes.
The phase diagram of the the Ag-Ce system has been studied in several investigations [1943Rol, 1970McM,
1975Del, 1980Heu, 1983Sta, 1984Sta] with some disagreement on the number of the intermetallic phases,
their stoichiometry and the data of the invariant reactions. A review on the the literature of the Ag-Ce
system has been given in [1985Gsc] and the existence of four stable intermetallic compounds has been
accepted: Ag4 Ce, Ag51 Ce14 , Ag2 Ce and AgCe. [1980Heu] reported the maximum solubility of Ce in
Ag and the solubility of Ag in Ce has been reported by [1975Del, 1983Sta]. [1987Iva] measured the
thermodynamic activity of liquid phase at 1090◦ C by means of the Knudsen effusion method and found a
large deviation from ideal behaviour. [1992Iva] determined the heats of mixing of liquid alloys of the Ag-
Ce system by means of isoperibolic calorimetry. [1993Fit] measured the standard enthalpies of formation
of AgCe, Ag51 Ce14 and the enthalpies of mixing of the liquid, which agreed well with that of [1992Iva].
The measured standard enthalpy of formation of AgCe is abnormally less negative compared to that of
equi-atomic compounds in other Ag-rare earth systems.
The thermodynamic assessment of the Ag-Ce system is from [2002Yin]. The terminal solid solutions fcc,
bcc, hcp and the liquid phase were described by a substitutional solution model using the Redlich-Kister
equation. The intermetallic compounds AgCe, Ag2 Ce, Ag51 Ce14 , and Ag4 Ce are treated as stoichiometric
phases. Due to a lack of data the high and low temperature modifications of Ag2 Ce and AgCe have not
been distinguished.
The calculated phase diagram is in excellent agreement with that reported by [1975Del, 1983Sta, 1984Sta].
The assessed enthalpy of formation of Ag51 Ce14 agree very well with experimental results, the assessed
value for AgCe is more negative. The agreement of optimised results with the experimental activities at
1090◦ C and with the experimental enthalpies of mixing is good.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Ce
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Ce 3
10 1.0
5 T∆Sm
0.8
Energies / (kJ/mol)
0.6 a Ag a Ce
Activities
−5
−10
0.4
−15
∆Hm
0.2
−20
∆Gm
−25 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Ce Ce Ag x Ce Ce
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1323 K.
T =1323 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ag – Ce
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xCe ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ag4 Ce1 0.200 −17765 −17863 −0.329 0.000
Ag51 Ce14 0.215 −18949 −18998 −0.166 0.000
Ag2 Ce1 0.333 −20412 −20194 0.734 0.000
Ag1 Ce1 0.500 −22272 −22331 −0.197 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Cr 1
Ag – Cr (Silver – Chromium)
3000
2500
liquid′ + liquid″
2000
T / K
bcc
1500
1000
fcc
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Cr Cr
The Ag-Cr system shows a wide range of immiscibility in the liquid phase. A monotectic reaction according
to Allen [1967All] occurs at about 1723 K, where the Ag-rich liquid contains about 3 at.% Cr [1990Ven].
The assessed equilibrium Ag-Cr phase diagram is based on the studies of Hindrichs [1908Hin], Grigorev
et al. [1954Gri], and Allen [1967All]. The boundaries of the liquid miscibility gap above the monotectic
temperature have not been established. The absence of intermediate phases was confirmed by the thin-film
studies of Simic and Marinkovic [1978Sim]. The solubility of Cr in liquid Ag was measured by Allen
[1967All]. Neumann et al. [1981Neu] determined the solubility of Cr in solid Ag in the temperature
range 973 K to 1233 K. Formation of a metastable solid solution of Cr in Ag beyond the equilibrium
concentration was observed by Ning [1983Nin], who quenched liquid Ag-rich alloys at cooling rates of 105
to 106 K/s. The observed metastable solid solubility limit corresponds to the solubility of Cr in liquid Ag at
the monotectic temperature. The thermodynamic assessment of the Ag-Cr system was carried out by Korb
[2004Kor]. The melting point of pure Cr at 2136 K reported in [1990Ven] does not correspond with the
value of 2180 K given by SGTE [1991Din]. The calculated monotectic temperature using the SGTE data is
about 2058 K. The experimental data are well represented by the calculated phase equilibria.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Cr
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Cu 1
Ag – Cu (Silver – Copper)
1400
1300 liquid
1200
1100
fcc′
1000
fcc″
900
T / K
800
700
600
500
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Cu Cu
The combination of silver and copper is encountered in gold alloys for dental applications, jewelry and
coinage. Copper-Silver alloys with high contents of phosphorus are used for brazing. The thermodynamics
of the binary Ag-Cu system has been re-assessed recently in [2004Wit] in the course of the optimisation of
the ternary Ag-Al-Cu system. The phase diagram of the Ag-Cu binary is a simple eutectic with appreciable
solid solubilities of the metallic elements. The evaluation takes into account literature data for the phase
boundaries in the phase diagram from many experimental investigations. For the description of the liquid
phase, several experimental studies of the mixing enthalpy have been taken into account. The evaluated
dataset of [2004Wit] is preferred over that of [2002Kus] because more recent calorimetric data for the
mixing properties of the liquid [1999Fit] have been included.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Cu
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Cu 3
9 1.0
T∆Sm
6 0.8
Energies / (kJ/mol)
3 0.6
Activities
∆Hm a Cu a Ag
0 0.4
−3 0.2
∆Gm
−6 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Cu Cu Ag x Cu Cu
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1373 K.
T =1373 K.
References
[1999Fit] K. Fitzner, Q. Guo, J. Wang, O.J. Kleppa: J. Alloys Comp. 291 (1999) 190–200.
[2002Kus] A. Kusoffsky: Acta Mater. 50 (2002) 5139–5145.
[2004Wit] V.T. Witusiewicz, U. Hecht, S.G. Fries, S. Rex: J. Alloys Comp. 385 (2004) 133–143.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ag – Fe 1
Ag – Fe (Silver – Iron)
2600
2200
2000
1800
T / K
bcc
1600
1400 fcc″
1200
fcc′ bcc
1000 TC
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Fe Fe
The Ag-Fe system has been reviewed in [1984Swa] and a critical thermodynamic assessment has been done
by Korb [2004Kor]. The equilibrium phases of the Ag-Fe system are the liquid, the bcc solid solution based
on low-temperature α-Fe as well as high-temperature δ-Fe, and the fcc phase with a large miscibility gap
between the Ag- and γ-Fe-based terminal solutions. The mutual solubility of Ag and Fe is indeed very low
in both the solid and the liquid state. According to [1973Wri] the solubility of Ag in solid γ-Fe reaches
a maximum of approximately 0.022 at.% at 1671 K. Data on the Fe-rich side for the solubility of Ag in
the fcc phase were taken from [1973Wri]. On the Ag-rich side, the data of [1969Ber] were used for the
solubility of Fe between 923 and 1185 K. The assessed phase diagram is based on the results of [1930Tam,
1955Chi, 1958Gib].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Fe
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Mo 1
Ag – Mo (Silver – Molybdenum)
3000
liquid
2500
2000
T / K
1500 bcc
1000
fcc
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Mo Mo
The experimental information on the Ag-Mo system is limited [1990Bar]. The Ag-Mo system is charac-
terised by the liquid, the fcc phase based on Ag and the bcc phase based on Mo with very small solubility
for Ag. The experimental studies [1924Dre, 1948Lin] indicate the insolubility of Mo in solid silver as deter-
mined by X-ray investigations and microscopy. According to Dreibholz [1924Dre] liquid Ag can dissolve
at least 5.6 at.% Mo at about 1873 K. Linel [1948Lin] observed that several percent of Mo are soluble in
liquid Ag at 1673 K. An assessment for the Ag-Mo system has been provided by Korb [2004Kor]. The
invariant at 1231 K reported by Baren in [1990Bar] can be reproduced well by the calculations.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Mo
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Mo 3
1.0
12
T∆Sm
0.8
8
Energies / (kJ/mol)
0.6
Activities
4 ∆Hm a Mo a Ag
0.4
0
−4 0.2
∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Mo Mo Ag x Mo Mo
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2900 K.
T =2900 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ag – Nb 1
Ag – Nb (Silver – Niobium)
2500
2000
liquid
bcc
T / K
1500
1000
fcc
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Nb Nb
A review on the scarce information about the Ag-Nb system has been given by [1989Bar]. Results of X-ray
diffraction, electrical conductivity, and metallographic studies [1963Kie] showed that the solubility of Nb in
liquid Ag is extremely small. No intermediate compounds have been reported for the Ag-Nb system, which
apparently is similar to the Ag-W, Ag-Mo, and Ag-V systems. Based on the information of the systems
mentioned above the thermodynamic descriptions for all the stable phases (liquid, fcc, bcc) in the Ag-Nb
system have been estimated by Korb [2004Kor].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Nb
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – O 1
Ag – O (Silver – Oxygen)
1500
1400
liquid liquid + gas
1300
1200
1100
1000
T / K
700
Ag 2 O
600
500
400
300
0.0 0.1 0.2 0.3 0.4
Ag xO
The silver-oxygen system has been reviewed and a thermodynamic assessment has been given by
[1997Ass]. The stable phases in the system are the liquid, solid silver (fcc) with limited solubility for
oxygen and at higher oxygen activities Ag2 O. The optimisation of the dataset is based on the evaluation
of a large amount of experimental data from the literature. It includes the solubility and the activities of
oxygen in the liquid phase, the solubility of oxygen in solid silver, the oxygen activities in the 2-phase
equilibria of the condensed phases, and data for the heat capacity of Ag2 O as well as formation energies
for this oxide. In a recent update [2003Hal] the description of the oxygen solubility in solid silver has been
switched to an interstitial model.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – O
gas gas
Ag 2 O
−1
−2
log 10 a O2
liquid fcc
−3
−4
Fig. 2. Calculated temperature-
activity phase diagram. Reference
−5 state: 12 O2 (gas, 0.1 MPa).
0.5 1.0 1.5 2.0 2.5 3.0
1000 K / T
Table III. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xO ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ag2 O 0.333 −3599 −10228 −22.233 0.279
References
[1997Ass] J. Assal, B. Hallstedt, L. Gauckler: J. Am. Ceram. Soc. 80 (1997) 3054–3060; J. Am.
Ceram. Soc. 81 (1998) 450–451.
[2003Hal] B. Hallstedt, L.J. Gauckler: Calphad 27 (2003) 177–191.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Te 1
Ag – Te (Silver – Tellurium)
1500
liquid liquid + gas
1400
1300
1200
1100
1000
Ag 19 Te 10
T / K
900
800
700
600
Ag 5 Te 3
500
Ag 2 Te
fcc A8
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag x Te Te
The data for the Ag-Te system were critically assessed by Korb [2004Kor]. The condensed phases of the
Ag-Te system are the liquid, with a miscibility gap and the solid phases fcc and hcp and three compounds,
Ag2 Te, Ag1.9 Te, and Ag5 Te3 [1991Kar]. The experimental investigations of the near-stoichiometric com-
pounds Ag2 Te and Ag5 Te3 were reported by [1964Hon]. With the exception of the miscibility gap, the
phase boundaries for the liquid field were established from cooling curves [1910Pel, 1916Chi]. The pres-
ence of a miscibility gap was established by [1940Kra, 1966Kra]. The mutual solid solubilities of the
elements in each other are negligible [1939Koe]. The calculated phase diagram agrees well with available
experimental data. All three intermetallic compounds are known to have polymorphic modifications but
they are not modelled in the assessment.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – Te
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – Te 3
15 1.0
T∆Sm
0.8
5
Energies / (kJ/mol)
0.6 a Ag a Te
Activities
−5
∆Hm
0.4
−15
0.2
∆Gm
−25 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag x Te Te Ag x Te Te
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1281 K.
T =1281 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xTe ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ag2 Te1 0.333 −14104 −12117 6.662 2.830
Ag19 Te10 0.345 −13542 −9839 12.418 0.000
Ag5 Te3 0.379 −13942 −12236 5.721 3.630
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ag – Te
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – V 1
Ag – V (Silver – Vanadium)
3400
liquid
3000
2600
2200
T / K
1800
bcc
1400
1000
fcc
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag xV V
Ag-V is a simple system involving one eutectic and one monotectic invariant reaction. The system exhibits
the liquid as well as two solid solutions, based on fcc-Ag and bcc-V, respectively. Experimental studies
[1915Gie, 1954Ros] reported the existence of a miscibility gap in the liquid phase. With increasing tem-
perature the solubility of Ag in bcc-V increases reaching a composition near 3.2 at.% Ag at the monotectic
temperature 2124 K [1989Smi]. The solubility of V in fcc-Ag is negligible.
The Ag-V system has been critically assessed by Korb [2004Kor]. The calculated phase diagram is in good
agreement with the experimental thermodynamic data. The small solubility of Ag in solid vanadium is
reproduced well by the calculations.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – V
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ag – V 3
20 1.0
T∆Sm
15
0.8
Energies / (kJ/mol)
10 ∆Hm
0.6
Activities
aV a Ag
5
0.4
0
∆Gm 0.2
−5
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ag xV V Ag xV V
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3200 K.
T =3200 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ag – W 1
Ag – W (Silver – Tungsten)
6000
5500 gas
5000
4500 liquid
4000
3500
T / K
gas bcc
3000
2500
2000
liquid bcc
1500
1000 fcc
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ag xW W
A review on the very limited information of the Ag-W system has been given in [1991Nag] and a thermo-
dynamic dataset has been assessed by Korb [2004Kor]. Only three condensed phases are stable: the liquid,
Ag-based fcc and the W-based bcc phases. According to experimental investigations [1860Ber, 1929Sch]
the Ag-W system exhibits nearly complete immiscibility in both the liquid and the solid states.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ag – W
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Be 1
Al – Be (Aluminium – Beryllium)
1600
bcc
1500 liquid
1400
1300
1200
T / K
hcp
1100
1000
900
800
fcc
700
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al xBe Be
The Al–Be system has been reviewed in [1987Mur, 2004Pan] and a thermodynamic assessment has been
given in [2004Pan]. The phase diagram shows a simple eutectic with the melting minimum close to the
Al-side and with only small mutual solid solubility of the elements. The thermodynamic optimisation is
based on experimental data from the literature as well as on new experiments reported in [2004Pan]. Data
for the liquidus and for the solubility of beryllium in aluminium from several investigations are taken into
account. In addition, activity data for the elements in the liquid have been included in the assessment.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Be
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Be 3
1.0
20
T∆Sm
16 0.8
Energies / (kJ/mol)
12 ∆Hm
0.6
Activities
8 a Be a Al
4 0.4
0
0.2
−4 ∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Be Be Al x Be Be
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1600 K.
T =1600 K.
References
[1987Mur] J.L. Murray, D.J. Kahan in: “Phase Diagrams of Binary Beryllium Alloys”, H. Okamoto,
L.E. Tanner, Eds., ASM Int., Metals Park, OH, 1987, pp. 9–14.
[2004Pan] Z. Pan, Y. Du, B.Y. Huang, Y. Liu, R.C. Wang: Calphad 28 (2004) 371–378.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Al – Dy 1
Al – Dy (Aluminium – Dysprosium)
2000
liquid
1800
bcc
βAl 3 Dy
1600
1400 C15
T / K
1200
1000
800
αAl 3 Dy
Al 2 Dy 3
AlDy 2
AlDy
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al x Dy Dy
The rare earth elements have attracted some attention as additives to light metal alloys in the aerospace
and automotive industry due to the improvement of mechanical properties of Al- and Mg-alloys at high
temperatures. Cacciamani et al. [2003Cac] prepared a thermodynamic optimisation of the complete Al-Dy
system, which is based on a review of the Al-rich part [1988Gsc] and an experimental investigation of the
phase equilibria in the range from 0 to 67 at.% Al [2000Sac]. Except for the standard enthalpy of formation
of the Al2 Dy phase [1985Col] no other thermodynamic data for the intermetallic compounds have been
available. Despite this lack of data, the assessment [2003Cac] can be considered as quite reasonable since
other similar systems (Al-Gd, Al-Ho) have been evaluated simultaneously and data have been estimated
taking advantage of the close relations between the involved rare earth elements. The dataset should not be
used at too high temperatures because an artificial inverse miscibility gap opens in the liquid above 3500 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Dy
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Dy 3
0 1.0
0.8
T∆Sm
Energies / (kJ/mol)
−15
0.6 a Al a Dy
Activities
∆Gm
0.4
−30
∆Hm 0.2
−45 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Dy Dy Al x Dy Dy
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xDy ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
αAl3 Dy1 0.250 −39408 −42486 −10.324 −0.192
βAl3 Dy1 0.250 −35571 −37486 −6.422 −0.192
C15 0.333 −49997 −53981 −13.362 −0.256
AlDy 0.500 −45439 −49471 −13.523 −0.385
Al2 Dy3 0.600 −40130 −43966 −12.864 −0.462
Al1 Dy2 0.667 −35022 −38462 −11.538 −0.513
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Al – Dy
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Gd 1
Al – Gd (Aluminium – Gadolinium)
2000
liquid
1800
1600 bcc
1400
T / K
1200
1000
800
Al 2 Gd 3
Al 3 Gd
AlGd 2
AlGd
600
C15
fcc hcp
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al x Gd Gd
The rare earth elements have attracted some attention as additives to light metal alloys in the aerospace
and automotive industry due to the improvement of mechanical properties of Al- and Mg-alloys at high
temperatures. For the Al-Gd system two thermodynamic optimisations have been reported in the literature
[2001Grö, 2003Cac], however, no parameters have been given in [2001Grö]. The optimisation of Caccia-
mani et al. [2003Cac] is based on an experimental revision of the phase equilibria in the concentration
range from 0 to 67 at.% Al [2000Sac] and for the Al-rich part on the review [1988Gsc]. In addition, the
assessment takes into account the standard enthalpies of formation for the five intermetallic compounds
from the literature [1987Som, 1988Col]. The dataset should not be used at too high temperatures because
an artificial inverse miscibility gap opens in the liquid above 3900 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Gd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Gd 3
0 1.0
T∆Sm 0.8
Energies / (kJ/mol)
−15
0.6 a Al a Gd
Activities
∆Gm
0.4
−30
0.2
∆Hm
−45 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Gd Gd Al x Gd Gd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xGd ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Al3 Gd 0.250 −39008 −41063 −6.892 −3.243
C15 0.333 −50043 −53084 −10.200 −4.326
AlGd 0.500 −45501 −48626 −10.480 −6.489
Al2 Gd3 0.600 −40583 −43551 −9.953 −7.786
Al1 Gd2 0.667 −35386 −38001 −8.773 −8.652
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Al – Gd
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Ho 1
Al – Ho (Aluminium – Holmium)
2000
liquid
1800
1600
1400
T / K
1200
1000
800
Al 2 Ho 3
Al 3 Ho
AlHo 2
AlHo
600
C15
fcc hcp
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al x Ho Ho
The rare earth elements have attracted some attention as additives to light metal alloys in the aerospace
and automotive industry due to the improvement of mechanical properties of Al- and Mg-alloys at high
temperatures. Cacciamani et al. [2003Cac] prepared a thermodynamic optimisation of the Al-Ho system,
which is based on an experimental investigation of the phase equilibria involving the liquid [1966Mey]
and one datum for the standard enthalpy of formation of the Al2 Ho phase [1985Col]. Although no other
thermodynamic data for the system are available, the assessment [2003Cac] can be still considered as rea-
sonable since other similar systems (Al-Dy, Al-Gd) have been evaluated simultaneously and data have been
estimated taking advantage of the close relations between the involved rare earth elements.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Ho
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Ho 3
0 1.0
−10 0.8
T∆Sm
Energies / (kJ/mol)
−20 0.6 a Al a Ho
Activities
∆Gm
−30 0.4
−40 0.2
∆Hm
−50 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Ho Ho Al x Ho Ho
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xHo ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Al3 Ho 0.250 −40754 −43000 −7.532 0.000
C15 0.333 −52687 −56000 −11.113 0.000
AlHo 0.500 −47389 −50500 −10.435 0.000
Al2 Ho3 0.600 −41638 −44500 −9.600 0.000
Al1 Ho2 0.667 −37302 −40000 −9.050 0.000
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Al – Ru 1
Al – Ru (Aluminium – Ruthenium)
2800
2600 liquid
2400
2200
2000
1800
Al 3 Ru 2
T / K
1600 hcp
1400
1200
1000
Al 13 Ru 4
800
Al 6 Ru
Al 2 Ru
AlRu
600 fcc
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al x Ru Ru
The Al-Ru system contains two components interesting for the nuclear field, aluminium being a major
component of the concrete basemat in its oxide form (Al2 O3 ) and Ru being one selected component rep-
resentative of a family of non volatile fission products. The system has been thermodynamically optimised
by Chevalier and Fischer [1996Che] and Prins et al. [2003Pri] but the latter work is not recommended
due to the modelling of the imprecise non-stoichiometry range of Al 13 Ru, Al2 Ru, Al3 Ru2 and AlRu lead-
ing to different temperatures of decomposition of these compounds. The phase diagram reported in the
compilation of Moffatt [1981Mof] is based on the phase diagram of Obrowski [1963Obr] which has been
obtained from microscopy, X-ray, and DTA experiments, and the investigation of Al-rich alloys by Anlage
et al. [1988Anl] using scanning electron microscopy, X-ray, and thermal analysis. Five intermetallic com-
pounds were identified, Al6 Ru, Al13 Ru4 , Al2 Ru, Al3 Ru2 and AlRu. The three last show a non-negligible
stoichiometry range. AlRu melts congruently at about 2323 K. The standard molar enthalpy of formation
of AlRu has been determined calorimetrically by Jung and Kleppa [1992Jun]. The excess Gibbs energy of
the liquid and hcp solution phases and the Gibbs energy of the intermetallics which have been described
as stoichiometric compounds were optimised from the selected experimental information. A sub-regular
substitution model was used for the liquid and a regular solution for the hcp phase. The enthalpy of for-
mation was optimised in consistency with other data. The agreement with the experimental information
[1963Obr, 1988Anl, 1992Jun] is quite satisfactory. However, a revised phase diagram for Al-rich alloys
has been published in [2003Mi] which presents different equilibria at higher temperatures and an additional
high-temperature compound, Al5 Ru2 .
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Ru 3
20 1.0
T∆Sm
10
0.8
Energies / (kJ/mol)
0
0.6 a Al a Ru
Activities
−10
0.4
−20 ∆Hm
0.2
−30
∆Gm
−40 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Ru Ru Al x Ru Ru
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2700 K.
T =2700 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Al – Ru
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xRu ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Al6 Ru1 0.143 −26312 −28000 −5.660 0.000
Al13 Ru4 0.235 −40494 −42300 −6.056 0.000
Al2 Ru1 0.333 −48062 −51000 −9.854 4.971
Al3 Ru2 0.400 −50011 −52245 −7.494 4.474
Al1 Ru1 0.500 −59012 −62050 −10.188 3.728
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Sc 1
Al – Sc (Aluminium – Scandium)
1900
liquid
1700
1500 bcc
1300
hcp
T / K
1100
900
700
Al 3 Sc
Al 2 Sc
AlSc 2
AlSc
fcc
500
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al x Sc Sc
Additions of Sc to Al- and Mg-alloys are of potential interest for the aerospace and automotive industry
because the mechanical properties of the alloys can be improved at higher temperatures. Thermodynamic
assessments and reviews of the literature of the Al-Sc system have been reported in [1998Mur, 1999Cac].
The assessment of [1999Cac] is selected here, because it includes a set of additional experimental data
which are reported in that paper. The optimisation takes into account data for the phase equilibria from
several literature sources as well as new DTA investigations [1999Cac]. According to these results, the
solubility of Al in bcc-Sc and hcp-Sc is much higher than in previous reports. Furthermore, the assessment
takes account of investigations of mixing enthalpies in the liquid [1986Lit] and heats of formation for the
intermetallic compounds from the literature as well as from new experiments [1999Cac].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Sc
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Sc 3
5 1.0
0 T∆Sm
0.8
−5
Energies / (kJ/mol)
−10 0.6 a Al a Sc
Activities
−15
−20 0.4
−25
0.2
∆Hm
−30
∆Gm
−35 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Sc Sc Al x Sc Sc
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1873 K.
T =1873 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSc ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Al3 Sc1 0.250 −39855 −42000 −7.193 0.000
Al2 Sc1 0.333 −45764 −48000 −7.500 0.000
Al1 Sc1 0.500 −43932 −46000 −6.937 0.000
Al1 Sc2 0.667 −35887 −37000 −3.733 0.000
References
[1986Lit] V.V. Litovskii, M.G. Valishev, Yu.O. Esin, P.V. Geld, M.S. Petrushevskii: Russ. J. Phys.
Chem. 60 (1986) 1385–1386.
[1998Mur] J.L. Murray: J. Phase Equilibria 19 (1998) 380–384.
[1999Cac] G. Cacciamani, P. Riani, G. Borzone, N. Parodi, A. Saccone, R. Ferro, A. Pisch, R. Schmid-
Fetzer: Intermetallics 7 (1999) 101–108.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Al – Sn 1
Al – Sn (Aluminium – Tin)
1000
liquid
900
800
700
fcc
T / K
600
500
bct
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al x Sn Sn
The Al-Sn is a simple eutectic system with the eutectic point close to the tin side. The mutual solubility
in the solid metals is quite low. An optimised dataset for the Al-Sn system has been reported by [1998Fri]
which has been corrected recently [2003Luk]. A review of the system has been given in [1983McA]. Since
then no additional experimental investigations on the thermodynamics of Al-Sn have been reported. The
liquidus has been measured across the whole composition range in several investigations using various
techniques [1906Gwy, 1949Sul, 1964Bon]. The mixing enthalpy in the liquid has been determined at
different temperatures [1930Kaw, 1958Oel, 1963Wit] and measurements of the activities of Al in the liquid
are reported in [1964Bon, 1966Tik, 1968Bat, 1969Lee]. The solubility of Sn in fcc-Al has been determined
by [1976Dor].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Sn
1000
900
800 fcc
T / K
700
fcc + liquid
600
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Sn 3
7 1.0
T∆Sm
5 0.8
Energies / (kJ/mol)
∆Hm
3 0.6
Activities
a Sn a Al
1 0.4
−1 0.2
∆Gm
−3 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Sn Sn Al x Sn Sn
Fig. 3. Integral quantities of the liquid phase at T =973 K. Fig. 4. Activities in the liquid phase at T =973 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Al – Sn
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Sr 1
Al – Sr (Aluminium – Strontium)
1400
1300 liquid
1200
1100
1000
T / K
bcc
900
800
700
Al 7 Sr 8
600
Al 4 Sr
Al 2 Sr
fcc fcc
500
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Al x Sr Sr
Small amounts of strontium are added to Al-Si alloys in order to improve their eutectic microstructure.
For this purpose, aluminium-strontium master alloys are used with Sr-concentrations up to 90%. Reviews
and thermodynamical assessments for the Al-Sr system have been prepared by [1989Gsc, 2003Wan] the
latter dataset being selected here. The optimisation is based on investigations of the phase diagram from
the literature which are well reproduced within the scatter of data between the various literature sources.
The thermodynamics of the liquid has been evaluated throughout the whole composition range using data
for the mixing enthalpy and the activity of Sr at several temperatures. In lack of experimental data for
the thermodynamics of the three intermetallic compounds, results for the enthalpy of formation from first-
principle calculations have been used in the optimisation. The dataset should not be used at too high
temperatures because an artificial inverse miscibility gap opens in the liquid above 3100 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Al – Sr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Al – Sr 3
4 1.0
0
0.8
Energies / (kJ/mol)
−4 T∆Sm
0.6 a Al a Sr
Activities
−8
0.4
−12 ∆Gm
0.2
−16
∆Hm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Al x Sr Sr Al x Sr Sr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1400 K.
T =1400 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSr ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Al4 Sr1 0.200 −23484 −26069 −8.670 0.000
Al2 Sr1 0.333 −27361 −30903 −11.880 0.000
Al7 Sr8 0.533 −19291 −21385 −7.020 0.000
References
[1989Gsc] K.A. Gschneidner Jr., F.W. Calderwood: Bull. Alloy Phase Diagrams 10 (1989) 34–36.
[2003Wan] C. Wang, Z. Jin, Y. Du: J. Alloys Comp. 358 (2003) 288–293.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Au – B 1
Au – B (Gold – Boron)
3600
3200
2400
T / K
2000
βB
1600
1200
800 fcc
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Au xB B
The Au-B binary system was assessed by Chevalier [1998Che]. The phase diagram reported in the com-
pilation of Moffatt [1981Mof] is based on the investigations of Wald and Stormont [1965Wal] using X-ray
analysis, optical metallography, and thermal analysis. The compound AuB2 previously reported by Elliott
[1965Ell] could not be confirmed. An eutectic reaction deported on the gold side, was determined at 1329 K
and less than 5 at.% B. A liquid miscibility gap is believed to exist at compositions of more than 50 at.% B,
with a monotectic reaction at about 15 K below the melting point of boron, which has been given at 2498 K
[1981Mof]. However, in the optimisation [1998Che] the recommended melting temperature for boron of
2348 K [91Din] has been used and consequently the calculated monotectic temperature is located 15 K
lower at 2333 K. No mutual solubility of both elements is known in the solid state and no thermodynamic
properties are available for that system.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Au – B
20 1.0
a Au
15 T∆Sm 0.8
Energies / (kJ/mol)
10 0.6 aB
Activities
∆Hm
5 0.4
0 0.2
∆Gm
−5 0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.00 0.05 0.10 0.15 0.20 0.25 0.30
Au xB Au xB
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2000 K.
T =2000 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – B 3
References
[1965Ell] R.P. Elliott, “Constitution of Binary Alloys”, 1st Suppl., McGraw-Hill, New-York, 1965.
[1965Wal] F. Wald, R. W. Stormont: J. Less-Common Met. 9 (1965) 423–433.
[1981Mof] W.G. Moffatt, “The Handbook of Binary Phase Diagrams”, General Electric Corp. (1981).
[1991Din] A.T. Dinsdale: Calphad 15 (1991) 317–425.
[1998Che] P.-Y. Chevalier, unpublished work, 1998.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Au – Co 1
Au – Co (Gold – Cobalt)
1800
liquid
1600
1400 TC
1200 fcc′
T / K
fcc″
1000
800
600 hcp
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Au x Co Co
The equilibrium phases of the Au-Co system are: the liquid, the fcc solid solution which is separated by
a large miscibility gap into a gold-rich phase dissolving up to 22 at.% Co and a Co-rich phase with an
Au-solubility of less than 2 at.%, and the hcp-Co based phase containing less than 0.05 at.% Au. The
thermodynamic descriptions for the Au-Co system has been obtained by Korb [2004Kor]. The assessed
phase boundaries are based mainly on the experimental data of [1950Rau] and [1984Tas]. The liquidus
boundary in equilibrium with Co-rich alloys is based on the results of [1984Tas]. The calculated phase
diagram is in good agreement with the critical review of [1987Oka].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Au – Co
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Co 3
12 1.0
T∆Sm
8 0.8
Energies / (kJ/mol)
4 0.6
Activities
∆Hm
a Co a Au
0 0.4
−4 0.2
∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Co Co Au x Co Co
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IVa. Integral quantities for the stable phases at 1270 K.
Phase xCo ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −1838 6193 6.323 1595 3.620 −1.404
0.200 −2067 10445 9.852 3217 5.692 −2.806
0.222 −2027 11142 10.369 3562 5.968 −3.113
fcc 0.981 −225 925 0.905 782 0.113 1.395
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Au – Co
1.0
12
T∆Sm
0.8
a Au
Energies / (kJ/mol)
8 ∆Hm
0.6
Activities
a Co
4
0.4
0 ∆Gm 0.2
−4 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Co Co Au x Co Co
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1270 K.
T =1270 K.
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Hf 1
Au – Hf (Gold – Hafnium)
2600
2400 liquid
2200
bcc
2000
1800
T / K
βAuHf
1600
1400
1200 fcc
1000
Au 10 Hf 7
hcp
Au 5 Hf
Au 4 Hf
Au 3 Hf
Au 2 Hf
αAuHf
AuHf 2
800
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Au x Hf Hf
The Au-Hf system has been reviewed in [1984Oka, 2000Oka, 2003Du] and a thermodynamic dataset has
been optimised in [2003Du]. The assessment is based mainly on investigations of the phase diagram by
[2000Lom] using differential thermal analysis, x-ray diffraction, and electron microprobe analysis. Seven
intermetallic compounds have been identified in agreement with previous studies of the phase diagram by
[1962Sto]. The enthalpies of formation of the compounds Au3 Hf, Au2 Hf, AuHf and AuHf2 have been
determined by [1992Fit]. The terminal solid solutions bcc, hcp, fcc and the liquid phase were described
by substitutional solution models using Redlich-Kister polynomials. The three intermetallic compounds
Au5 Hf, Au2 Hf, αAuHf and βAuHf with certain homogeneity ranges were treated by two-sublattice models
with Au and Hf in one sublattice and the other filled with Au only. The four other compounds Au4 Hf,
Au3 Hf, Au10 Hf7 , AuHf2 were considered as stoichiometric. Satisfactory agreement is obtained between
the calculated and experimental data.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Au – Hf
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Hf 3
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Au – Hf
10 1.0
0
0.8
−10
Energies / (kJ/mol)
T∆Sm
−20 0.6 a Au a Hf
Activities
−30
−50
0.2
−60 ∆Hm
−70 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Hf Hf Au x Hf Hf
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2573 K.
T =2573 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xHf ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Au5 Hf 0.167 −44927 −49061 −13.867 0.000
Au4 Hf1 0.200 −47656 −51155 −11.738 0.000
Au3 Hf1 0.250 −51314 −54301 −10.020 0.000
Au2 Hf 0.333 −56382 −59453 −10.299 0.000
Au10 Hf7 0.412 −60171 −63666 −11.719 0.000
αAuHf 0.500 −58264 −61203 −9.858 0.000
βAuHf 0.500 −57386 −60085 −9.052 0.000
Au1 Hf2 0.667 −39665 −40794 −3.784 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Ni 1
Au – Ni (Gold – Nickel)
1800
liquid
1600
1400
1200
T / K
fcc
1000
800
600
TC
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Au x Ni Ni
Nickel is a common addition for improving the strength of gold alloys and these materials are frequently
encountered in jewellery. A thorough review on the thermodynamics of the gold-nickel system has been
given in [1991Oka] and a thermodynamic optimisation has been reported in [2005Wan]. The phase diagram
consists of only two phases, the liquid and the the fcc solid solution phase which hosts a broad miscibility
gap. The optimisation is based on many experimental investigations of Au-Ni alloys from the literature
including phase equilibrium studies, calorimetric and EMF investigations of liquid and solid alloys, and
experiments using Knudsen techniques.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Au – Ni
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Ni 3
16 1.0
12 T∆Sm
0.8
Energies / (kJ/mol)
0.6
Activities
4
0 ∆Hm
0.4 a Ni a Au
−4
0.2
−8
∆Gm
−12 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Ni Ni Au x Ni Ni
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1820 K.
T =1820 K.
Table IVa. Integral quantities for the stable phases at 1150 K.
Phase xNi ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −1825 1944 3.277 1283 0.575 −0.015
0.200 −2492 3694 5.380 2292 1.219 −0.030
0.300 −2775 5204 6.939 3066 1.860 −0.045
0.400 −2818 6403 8.018 3617 2.422 −0.060
0.500 −2691 7196 8.597 3937 2.833 −0.075
0.600 −2445 7462 8.615 3990 3.019 −0.089
0.700 −2122 7059 7.984 3719 2.905 −0.100
0.800 −1745 5817 6.576 3039 2.415 −0.103
0.900 −1264 3539 4.177 1844 1.474 −0.081
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Au – Ni
10 1.0
T∆Sm
8
0.8
∆Hm
Energies / (kJ/mol)
0.6
Activities
4
a Ni a Au
2
0.4
0
0.2
−2 ∆Gm
−4 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Ni Ni Au x Ni Ni
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1150 K.
T =1150 K.
References
[1991Oka] H. Okamoto, T.B. Massalski in: Phase Diagrams of Binary Nickel Alloys, P. Nash, Ed.,
ASM Intl., Materials Park, 1991, pp. 16–30.
[2005Wan] J. Wang, X.-G. Lu, B. Sundman, X. Su: Calphad 29 (2005) 263–268.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Pb 1
Au – Pb (Gold – Lead)
1400
1300
liquid
1200
1100
1000
900
T / K
800
700
600
Au 2 Pb
500 fcc
AuPb 2
AuPb 3
400
fcc
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Au x Pb Pb
The knowledge of the Au-Pb system is required for an understanding of the interactions between Sn-Pb
solder and gold-plated contacts of electronic components. An old thermodynamic assessment of this system
has been presented in the first volume of this series [2002SGTE]. Since then several additional investigations
of Au-Pb have been published which have been incorporated in a recent optimisation [2004Wan]. The
assessment takes into account several experimental investigations on the phase diagram from the literature,
measurements of the enthalpy of mixing in the liquid at different temperatures and determination of the Pb
activities in the liquid from several sources. In addition the assessment takes account of the experimental
standard enthalpies of formation of the compounds. The mixing properties of the melt seem to be very
temperature dependent and there are pronounced discrepancies between the various experimental datasets
in the literature.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Au – Pb
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Pb 3
15 1.0
10 T∆Sm
0.8
Energies / (kJ/mol)
5
0.6 a Au a Pb
Activities
0
∆Hm
0.4
−5
∆Gm 0.2
−10
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Pb Pb Au x Pb Pb
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1373 K.
T =1373 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xPb ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Au2 Pb1 0.333 −2861 −3010 −0.500 0.000
Au1 Pb2 0.667 −2368 −2800 −1.450 0.000
Au1 Pb3 0.750 −1733 −1900 −0.560 0.000
References
[2002SGTE] SGTE in: Landolt-Börnstein, New Series, IV/19 B1, Springer-Verlag, Berlin Heidelberg,
2002, pp. 280–282.
[2004Wan] J. Wang, H.S. Liu, Z.P. Jin: Calphad 28 (2004) 91–95.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Au – Ti 1
Au – Ti (Gold – Titanium)
2000
liquid
1800
1600
AuTi bcc
1400
T / K
1200 fcc
1000 hcp
Au 4 Ti
Au 2 Ti
AuTi 3
800
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Au x Ti Ti
Alloys of gold and titanium as well as gold platings on titanium are encountered in jewelry and also in
dental applications. A thorough review of the literature on the thermodynamics of the Au-Ti system has
been given in [1987Mur] and a thermodynamic optimised dataset has been reported by [2001Luo]. The
optimisation takes into account 5 experimental datasets for the phase diagram from the literature, a calori-
metric investigation of the mixing enthalpy in Au-rich melts and reported standard enthalpies of formation
for three of the intermetallic compounds, AuTi3 , AuTi, and Au2 Ti which have been obtained from direct
synthesis calorimetry. The low-temperature modifications of the AuTi compound have not been included in
the optimisation due to a lack of data.
References
[1987Mur] J.L. Murray in: Phase Diagrams of Binary Titanium Alloys, J.L. Murray, Ed., ASM Intl.,
Metals Park, OH, 1987, pp. 27–32.
[2001Luo] W. Luo, Z. Jin, H. Liu, T. Wang: Calphad 25 (2001) 19–26.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Au – Ti
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Ti 3
20 1.0
10 T∆Sm
0.8
Energies / (kJ/mol)
0.6 a Au a Ti
Activities
−10
−20
∆Hm 0.4
−30
0.2
−40 ∆Gm
−50 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Ti Ti Au x Ti Ti
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2000 K.
T =2000 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Au – Ti
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Ti 5
10 1.0
0 T∆Sm
0.8
Energies / (kJ/mol)
−10
0.6 a Au a Ti
Activities
−20
−30
0.4
−40 ∆Gm
0.2
−50
∆Hm
−60 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Ti Ti Au x Ti Ti
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1300 K.
T =1300 K.
Table V. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xTi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Au4 Ti 0.200 −37730 −39855 −7.125 0.000
Au2 Ti1 0.333 −55074 −57889 −9.443 0.000
AuTi 0.500 −44914 −45242 −1.098 0.013
Au1 Ti3 0.750 −29128 −29281 −0.514 0.000
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Au – Zr 1
Au – Zr (Gold – Zirconium)
2200
liquid
2000
1800
1600
bcc
1400
T / K
1200 fcc
1000
Au 2 Zr 3
Au 10 Zr 7
Au 4 Zr
Au 3 Zr
Au 2 Zr
AuZr 2
AuZr 3
800 AuZr
hcp
600
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Au x Zr Zr
The alloy systems or intermetallic compounds composed of Zr and Au have attracted much attention for
the theoretical study of the solid state and for many industrial purposes such as the use of amorphous Au-Zr
alloys as catalysts for CO hydrogenation and oxidation. The Au-rich side of the Au-Zr phase diagram was
studied by [1948Rau]. [1997Lom] reexamined this system by means of differential thermal analysis, x-ray
diffraction and electron probe microanalysis, and established the phase diagram in its present form. He
suggested that the compounds AuZr3 , AuZr, Au2 Zr and Au3 Zr melt congruently. AuZr2 and Au4 Zr form
peritectically. Au2 Zr3 and Au10 Zr7 are formed by peritectoid reactions. The maximum solid solubility of
Au in βZr is 16 at.% Au. The αZr has a narrow homogeneity range. The maximum solid solubility of
Zr in Au is about 8 at.% Zr. This value agrees with that of [1948Rau]. A literature review was presented
by [1999Oka]. According to [1999Oka], Au4 Zr5 does not exist. The experimental standard enthalpies
of formation of the congruently melting compounds AuZr2 , Au4 Zr5 , Au2 Zr, Au3 Zr were determined by
[1992Fit], those of the compounds AuZr3 , AuZr2 , Au4 Zr5 , AuZr, Au10 Zr7 , Au2 Zr, Au3 Zr, Au4 Zr were
determined by [1998Lom]. The enthalpies of mixing of solid Zr in liquid Au and the enthalpies of mixing
for the liquid alloys were also measured by [1998Lom] and [1992Fit], respectively. The thermodynamic
evaluation of the Au-Zr system was made by [2000Su]. The terminal solid solutions bcc, hcp, fcc and
the liquid phase were described by a substitutional solution model using the Redlich-Kister equation. The
intermetallic compounds AuZr3 , AuZr2 , Au2 Zr3 , AuZr, Au10 Zr7 , Au2 Zr, Au3 Zr, Au4 Zr are modelled as
stoichiometric phases. The calculated phase diagram is in good agreement with the experiments reported by
[1998Lom]. All invariant equilibria in the system are reproduced well. The assessed terminal solubilities
of Zr in Au, and of Au in Zr do not agree well with the experimental data, but the review of [1999Oka]
showed a thermodynamic improbability. The assessed enthalpies of formation agree well with experimental
data. The calculated partial and integral molar enthalpies of mixing of solid Zr in liquid is good below 11
at.% Zr; above this composition, the measurements of the enthalpies of mixing are not accurate due to the
occurrence of solid Au4 Zr at the experimental temperature. More experimental work on the liquid/βZr and
βZr/αZr boundaries may be necessary to improve the description.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Au – Zr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Au – Zr 3
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Au – Zr
10 1.0
0 T∆Sm
0.8
Energies / (kJ/mol)
−10
0.6 a Au a Zr
Activities
−20
0.4
−30
0.2
−40 ∆Gm
∆Hm
−50 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Au x Zr Zr Au x Zr Zr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2200 K.
T =2200 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZr ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Au4 Zr1 0.200 −40169 −41759 −5.335 0.000
Au3 Zr1 0.250 −49395 −51453 −6.903 0.000
Au2 Zr1 0.333 −57045 −59445 −8.050 0.000
Au10 Zr7 0.412 −57473 −59624 −7.217 0.000
Au1 Zr1 0.500 −57951 −59823 −6.278 0.000
Au2 Zr3 0.600 −51184 −53114 −6.472 −0.063
Au1 Zr2 0.667 −46730 −48743 −6.754 0.000
Au1 Zr3 0.750 −35657 −36536 −2.950 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: B – Zr 1
B – Zr (Boron – Zirconium)
3800
liquid
3200
2600
T / K
2000
bcc
ZrB 2
ZrB 12
1400
βB
hcp
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
B x Zr Zr
A review and a thermodynamic assessment for the system B-Zr has been published in [1988Rog] which
has been revised later [1998Dus]. The data for the phase diagram are based mostly on the results from
[1966Rud] and from [1970Por]. The liquidus data show a very high scatter due to the aggressive attack of
the B-melt on the crucible materials. Thermodynamic properties have been determined only for ZrB 2 . The
experimental data for this compound have been reviewed by [1976Alc] and recommended values have been
given which are used in the assessment [1998Dus].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: B – Zr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: B – Zr 3
10 1.0
0 T∆Sm
0.8
−10
Energies / (kJ/mol)
−20 0.6 aB a Zr
Activities
−30
−40 0.4
−50
∆Gm 0.2
−60
∆Hm
−70 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
B x Zr Zr B x Zr Zr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3600 K.
T =3600 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZr ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Zr1 B12 0.077 −18871 −18306 1.897 0.000
Zr1 B2 0.333 −107409 −108899 −5.000 0.142
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: B – Zr
References
[1966Rud] E. Rudy, St. Windisch: Techn. Rept. AFML-TR-65-2, pt. I, vol. VIII, Wright Patterson
AFB, Ohio, 1966, 1–33.
[1970Por] K.P. Portnoi, V.M. Romashov, L.I. Vyroshina: Poroshkov. Metall. 91 (1970) 68–71.
[1976Alc] C.B. Alcock, K.T. Jacob, S. Zador in: “Zirconium: physoco-chemical properties of its
compounds and alloys”, Atomic Energy Review, Spec. Issue No. 6, O. Kubaschewski, Ed.,
IAEA, Vienna, 1976, pp. 7–65.
[1988Rog] P. Rogl, P.E. Potter: Calphad 12 (1988) 191–204.
[1993Oka] H. Okamoto: J. Phase Equilibria 14 (1993) 261–262.
[1998Dus] H. Duschanek, P. Rogl in: “Phase Diagrams of Ternary Metal-Boron-Carbon Systems”, P.
Rogl, ASM, Materials Park, 1998, pp. 445–485.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ba – Ru 1
Ba – Ru (Barium – Ruthenium)
3000
2800 liquid′ + liquid″
2600
2400
2200
2000
T / K
1800 hcp
1600
1400
1200
1000
800 bcc
600
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ba x Ru Ru
The Ba-Ru binary system contains two components of interest in the nuclear field, selected as representative
of families of non volatile fission products. The classical compilations of binary phase diagrams, give no
information at all on this system. Consequently, it has been supposed that there is a negligible mutual
solubility of the elements barium and ruthenium in the solid state, and a wide miscibility gap in the liquid
state, the mutual solubility increasing at high temperature. Thus, the assessed diagram is only qualitative,
and solubilities may only be estimated. No thermodynamic properties are available for that system. The
system was assessed by Chevalier and Fischer [1995Che]. The excess Gibbs energy of the liquid was
estimated to be highly positive, to produce a small mutual solubility of pure components at low temperature
and a large miscibility gap at high temperature. Similarly, highly positive interaction parameters in the bcc
and hcp phases allow to produce a negligible mutual solubility of the components. No experimental data
are available for comparison with the calculated phase diagram.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ba – Ru
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Bi – Pd 1
Bi – Pd (Bismuth – Palladium)
1900
1700 liquid
1500
1300
fcc
T / K
1100
900
Bi 3 Pd 5
700
Bi 2 Pd
BiPd 3
BiPd
500
A7
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Bi x Pd Pd
This system was assessed by Vřešt’ál et al. [2006Vre], from the available experimental information, and
ab-initio calculations of the total energies of BiPd and Bi2 Pd. Bismuth is an important component both as
a solvent of uranium in nuclear metallurgy, and also in lead-free solder materials, the substrates of which
often containing palladium. The phase diagram is based on the experimental work of Zhuravlev and Zh-
danov[1953], Zhuravlev [1957Zhu], Brasier and Hume-Rothery [1959Bra], using cooling curve analysis,
Schweitzer and Weeks [1961Sch] who analysed the liquidus after equilibrating annealing. The experimental
Bi-Pd phase diagram was assessed by Okamoto [1994Oka]. It presents three solution phases, the liquid with
a complete miscibility range, the palladium rich terminal solid solution (fcc), and the intermediate solution
phase Bi3 Pd5 (62-71 at.%Pd). The following intermediate compounds have been identified with a very nar-
row non-stoichiometry range and two allotropic forms, αBi2 Pd, βBi2 Pd (1.5 at.%, 653 K), αBiPd, βBiPd
(1 at.%, 483 K), αBiPd3 , βBiPd3 (1073 K). The structures of the intermetallic phases were experimentally
studied by Schubert et al. [1953Sch], Zhuravlev and Zhdanov [1953Zhu], Kheiker et al. [1953Khe], Levin
et al. [1953Lev], Zhdanov [1954Zhd], Zhuravlev [1958Zhu] and Bhatt and Schubert [1979Bat]. Two other
compounds, Bi2 Pd5 and Bi12 Pd31 , were put in evidence by Sarah and Schubert [1979Sar], the second one
in a very limited temperature range (823 K - 878 K). However, in diffusion couple experiments using BiPd
and pure Pd [2001Obe] only the formation of BiPd3 and Bi3 Pd5 has been observed but neither Bi2 Pd5 nor
Bi12 Pd31 have been detected. Therefore, only three stoichiometric compounds, Bi 2 Pd, BiPd and BiPd3
without structural transformation were modelled by the assessor [2006Vre]. There is no reported solubility
of palladium in rhombohedral bismuth. In addition, the solubility of bismuth in palladium at lower temper-
ature has been determined [2001Obe] and the integral enthalpy of mixing of liquid Bi-Pd alloys has been
measured by high temperature solution calorimetry in the range of 0-50 at.% Pd at 1028 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Bi – Pd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Bi – Pd 3
5 1.0
T∆Sm
0
0.8
Energies / (kJ/mol)
−5
0.6 a Bi a Pd
Activities
−10
−15
0.4
−20
0.2
−25 ∆Gm
∆Hm
−30 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Bi x Pd Pd Bi x Pd Pd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1828 K.
T =1828 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Bi – Pd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Bi – Pd 5
5 1.0
0 T∆Sm
0.8
Energies / (kJ/mol)
−5
0.6 a Bi a Pd
Activities
−10
−15
0.4
∆Hm
−20
0.2
−25
∆Gm
−30 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Bi x Pd Pd Bi x Pd Pd
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1028 K.
T =1028 K.
Table V. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xPd ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Bi2 Pd1 0.333 −24355 −25100 −2.500 0.000
Bi1 Pd1 0.500 −31319 −33600 −7.650 0.000
Bi1 Pd3 0.750 −22181 −22300 −0.400 0.000
Landolt-Börnstein SGTE
New Series IV/19B
6 2 Binary Systems: Bi – Pd
References
[1953Khe] D.M. Kheiker, G.S. Zhdanov, N.N. Zhuravlev: Zh. Eksp. Teoret. Fiz. 25 (1953) 621–627.
[1953Lev] L.S. Levin, G.S. Zhdanov, N.N. Zhuravlev: Zh. Eksp. Teoret. Fiz. 25 (1953) 751–754.
[1953Sch] K. Schubert, K. Anderko, M. Kluge, H. Beeskov, M. Ilschner, E. Dorre, P. Esslinger: Natur-
wiss. 40 (1953) 269.
[1953Zhu] N.N. Zhuravlev, G.S. Zhdanov: Zh. Eksp. Teoret. Fiz. 25 (1953) 485–490.
[1954Zhd] G.S. Zhdanov: Tr. Inst. Kristallogr. Akad. Nauk SSSR 10 (1954) 99–116.
[1957Zhu] N.N. Zhuravlev: Zh. Eksp. Teoret. Fiz. 32 (1957) 1305–1312; transl.: Sov. Phys. JETP 5
(1957) 1064–1072.
[1958Zhu] N.N. Zhuravlev: Kristallogr. 3 (1958) 503–504; transl.: Sov. Phys. Crystallogr. 3 (1958)
506.
[1959Bra] J. Brasier, W. Hume-Rothery: J. Less-Common Met. 1 (1959) 157–164.
[1961Sch] D.G. Schweitzer, J.R. Weeks: Trans. Q. ASM 54 (1961) 185-200.
[1979Bat] Y.C. Bhatt, K. Schubert: J. Less-Common Met. 64 (1979) P17–P24.
[1979Sar] N. Sarah, K. Schubert: J. Less-Common Met. 63 (1979) 75–82.
[1994Oka] H. Okamoto: J. Phase Equilibria 15 (1994) 191–194.
[2001Obe] P. Oberndorff: Ph.D. Thesis, TU Eindhoven, 2001.
[2006Vre] J. Vřešt’ál, J. Pinkas, A. Watson, A. Scott, J. Houserová, A. Kroupa: Calphad 30 (2006)
14–17.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: C – Ir 1
C – Ir (Carbon – Iridium)
3000
liquid
2500 fcc
2000
T / K
1500
graphite + fcc
1000
500
0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Ir Ir
The C-Ir phase diagram displays the liquid phase, the fcc phase based on Ir with quite small solubility of
C and the graphite phase. Burylev [1967Bur, 1969Bur] estimated the solubility of C in liquid Ir assuming
systematic changes with atomic number in the interaction between the elements. Vol and Kagan [1976Vol]
constructed the Ir-C phase diagram based on the above information [1990Mas]. The C-Ir system has been
critically assessed by Korb [2004Kor]. The eutectic was experimentally determined by Nadler and Kempter
[1960Nad], and later confirmed by the experimental investigations carried out by Dinsdale [2004Din]. The
calculated eutectic temperature agrees well the experimental value [2004Din].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: C – Ir
1.0
12 a Ir
0.8
Energies / (kJ/mol)
T∆Sm
8
0.6 aC
Activities
4
∆Hm 0.4
0 0.2
∆Gm
−4 0.0
0.75 0.80 0.85 0.90 0.95 1.00 0.75 0.80 0.85 0.90 0.95 1.00
x Ir Ir x Ir Ir
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: C – Ir 3
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: C – Os 1
C – Os (Carbon – Osmium)
3500
liquid
3000
hcp
2500
T / K
2000
1500
graphite + hcp
1000
500
0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Os Os
The C-Os phase diagram is eutectic and includes the liquid phase, the hcp phase based on Os and graphite
[1990Mas]. Experimental data on the C-Os system are limited and as the basis for the optimisation the phase
diagram data given in [1976Mof] are used. OsC does not exist, according to [1964Rau]. The thermody-
namic assessment of the C-Os system was carried out by Korb and Jantzen [2004Kor]. The experimentally
determined invariant equilibria [1960Nad] agree satisfactorily with the calculations.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: C – Os
1.0
40
0.8 a Os
30
Energies / (kJ/mol)
T∆Sm
0.6
Activities
20
aC
∆Hm 0.4
10
0 0.2
∆Gm
−10 0.0
0.70 0.75 0.80 0.85 0.90 0.95 1.00 0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Os Os x Os Os
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3350 K.
T =3350 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: C – Os 3
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: C – Pd 1
C – Pd (Carbon – Palladium)
2000
liquid
fcc
1500
graphite + fcc
T / K
1000
500
0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Pd Pd
The C-Pd phase diagram is eutectic and includes the liquid phase, the fcc phase based on Pd and graphite
[1990Mas]. Experimental data on the C-Pd system are limited and as the basis for the optimisation the
phase diagram data given by [1996Mas, 2004Din] are used. The solid solubility of C in Pd was determined
by Siller and Oates [1968Sil] in the temperature range 1173 to 1473 K. The eutectic reaction was studied by
different authors using various methods. Nadler and Kempter [1960Nad] reported the eutectic temperature
at about 1777 K, Bhatt and Venkataramani [1987Bha] at about 1783 K. Later investigations carried out
by Dinsdale [2004Din] pointed out the temperature 1765 K, which has been used for the data assessment.
The thermodynamic assessment of the C-Pd system was carried out by Korb [2004Kor]. The most recent
experimental [2004Din] and the calculated invariant equilibria agree well.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: C – Pd
14 1.0
12 a Pd
T∆Sm 0.8
10
Energies / (kJ/mol)
8
0.6
Activities
6
∆Hm
4 aC
0.4
2
0 0.2
∆Gm
−2
−4 0.0
0.80 0.85 0.90 0.95 1.00 0.80 0.85 0.90 0.95 1.00
x Pd Pd x Pd Pd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1900 K.
T =1900 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: C – Pd 3
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: C – Pt 1
C – Pt (Carbon – Platinum)
2500
liquid
2000
fcc
T / K
1500
graphite + fcc
1000
500
0.80 0.85 0.90 0.95 1.00
x Pt Pt
The C-Pt phase diagram has been studied by [1960Har, 1966Rhe, 1968Shi] using various experimental
techniques. The system consists of the liquid, the fcc phase with very small solubility of C in Pt and the
graphite phase with practically no solubility for Pt. No compounds were found to form at 65 kbar and
2973 K [1960Har]. The solid solubility of C in Pt was determined by [1968Sil] in the range from 1149
to 1518 K. According to [1996Mas] the solubility of C in Pt is less than 3 at.% C. This behaviour can be
reproduced well by the calculations. Earlier investigations of the eutectic reaction at about 1978 K in the
C-Pt system were carried out by Rhee [1966Rhe]. Later measurements done by Bhatt and Venkataramani
[1987Bha], Park and Yamada [1999Par], and Dinsdale [2004Din] do not confirm previous experimental
work. These investigations are however in good accord with each other and report the eutectic reaction
between 2010 and 2011 K. The thermodynamic assessment of the C-Pt system was carried out by Korb
and Jantzen [2004Kor]. The calculated eutectic temperature agrees very well with the experimental values
[1987Bha, 2000Par, 2004Din].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: C – Pt
6 1.0
a Pt
5
0.8
T∆Sm
Energies / (kJ/mol)
0.6
Activities
2 ∆Hm 0.4 aC
1
0.2
0
∆Gm
−1 0.0
0.95 0.96 0.97 0.98 0.99 1.00 0.95 0.96 0.97 0.98 0.99 1.00
x Pt Pt x Pt Pt
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2100 K.
T =2100 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: C – Pt 3
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: C – Rh 1
C – Rh (Carbon – Rhodium)
2500
liquid
2000
fcc
T / K
1500
500
0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Rh Rh
The C-Rh phase diagram is eutectic and includes the liquid phase, the fcc phase based on Rh and graphite
[1990Mas]. Experimental data on the C-Rh system are limited and as the basis for the optimisation the phase
diagram data given in [1990Mas] and the experimental data about the eutectic temperature [2004Din] are
used. The solubility ranges for C in fcc-Rh were investigated by Barabash and Koval [1986Bar] in the tem-
perature range from 1073 to 1523 K. The invariant equilibrium experimental data have been determined by
Nadler and Kempter [1960Nad] who reported the eutectic temperature 1967±17 K, by Bhatt and Venkatara-
mani (1947 K) [1987Bha] and by Dinsdale (1930 K) [2004Din]. The experimental investigations are in
reasonable agreement, except for the eutectic temperature. The most recent measurement [2004Din] was
used in the data assessment. The C-Rh system has been critically assessed by Korb and Jantzen [2004Kor].
The calculated and experimental [1967Gie, 2004Din] phase diagram are in good agreement.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: C – Rh
20 1.0
16
T∆Sm 0.8 a Rh
Energies / (kJ/mol)
12
0.6
Activities
8
∆Hm
4
0.4 aC
0
∆Gm 0.2
−4
−8 0.0
0.75 0.80 0.85 0.90 0.95 1.00 0.75 0.80 0.85 0.90 0.95 1.00
x Pd Rh x Rh Rh
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2250 K.
T =2250 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: C – Rh 3
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: C – Ru 1
C – Ru (Carbon – Ruthenium)
3000
liquid
2500
hcp
2000
T / K
1500
500
0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Ru Ru
The C-Ru phase diagram is eutectic and includes the liquid phase, the hcp phase based on Ru and graphite
[1990Mas]. The solubility range of C in hcp-Ru was investigated by Barabash and Koval [1986Bar] in the
temperature range from 1073 to 1523 K. Experimental data on the C-Ru system are limited. The assessment
is based on the phase diagram data given in [1990Mas] which have been measured by Fromm and Gebhardt
[1978Fro]. The experimental data for the eutectic temperature are consistent and do not contradict each
other. According to Fromm and Gebhardt [1978Fro] the invariant reaction occurs at 2213 K, Bhatt and
Venkatarami [1987Bha] reported the temperature 2231 K, while Park and Yamada [2000Par] as well as
Dinsdale [2004Din] found the eutectic temperature to be 2225 K. The latter value was used in the data
assessment. The C-Ru system has been critically assessed by Korb and Jantzen [2004Kor]. The calculated
and experimentally determined phase diagram agree well.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: C – Ru
35 1.0
30 a Ru
25 0.8
T∆Sm
20
0.6
Activities
15
10
∆Hm 0.4
5 aC
0 0.2
−5 ∆Gm
−10 0.0
0.70 0.75 0.80 0.85 0.90 0.95 1.00 0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Ru Ru x Ru Ru
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2700 K.
T =2700 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: C – Ru 3
References
[1978Fro] E. Fromm, T.E. Gebhardt: “Gasses and Carbon in Metals”, Metallurgiya, Moscow, 1978.
[1986Bar] O.M. Barabash, Yu.N. Koval: “Crystal Structure of Metals and Alloys”, Naukova Dumka,
Kiev, (1986) 209–210.
[1987Bha] Y.J. Bhatt, R. Venkataramani, S.P. Garg: J. Less-Common Met. 132 (1987) L21–L24.
[1990Mas] T.B. Massalski (Ed.): “Binary Alloy Phase Diagrams”, 2nd Ed., ASM Int., Materials Park,
OH, 1990.
[2000Par] S.N. Park, Y. Yamada: SAE Mulli 40 (2000) 322–328.
[2004Din] A.T. Dinsdale, NPL, Teddington, U.K., private communication, 2004.
[2004Kor] J. Korb, T. Jantzen, unpublished assessment, GTT-Technologies, 2004.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: C – Zn 1
C – Zn (Carbon – Zinc)
3000
liquid
2500
2000
T / K
b.p. Zn
1000
graphite + hex
500
0.70 0.75 0.80 0.85 0.90 0.95 1.00
x Zn Zn
Only minor information is available on the carbon-zinc system. The solubility of C in liquid Zn at the
boiling point of Zn is only small but no reliable value has been measured [1919Ruf]. The solubility of C in
solid Zn is unknown. In an assessment of the ternary system C-Co-Zn, Hämäläinen and Isomäki [2005Häm]
evaluated the interaction between carbon and zinc in the melt which allows the calculation of the binary C-
Zn phase diagram. This result compares well with the phase diagram given by [2000Tur] which has been
calculated with different preconditions. The boiling point of Zn is indicated in the phase diagram although
the gas phase has been suppressed in the calculation.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: C – Zn
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ca – Li 1
Ca – Li (Calcium – Lithium)
1200
1100
liquid
1000
900
800
T / K
bcc
700
600
500 fcc
CaLi 2
400
bcc
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ca x Li Li
Calcium and lithium are both important alloying elements for magnesium. Calcium acts as a grain refiner
and it improves the creep resistance while Li decreases the density of the alloys. The literature on the Ca-
Li system has been reviewed in [1987Bal, 2002Grö] and a thermodynamic assessment has been given in
[2002Grö]. The phase diagram has been thoroughly investigated by [1966Car]. The enthalpy of formation
of CaLi2 has been measured by drop solution calorimetry [2002Grö]. Based on these data, the critical
recommendations for the phase diagram and the invariants given in [1987Bal] and using the SGTE element
data the thermodynamic description for Ca-Li has been optimised.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ca – Li
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ca – Li 3
8 1.0
6 T∆Sm
4 0.8
Energies / (kJ/mol)
2
0.6 a Ca a Li
Activities
0 ∆Hm
−2
0.4
−4
−6 0.2
−8 ∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ca x Li Li Ca x Li Li
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1200 K.
T =1200 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xLi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ca1 Li2 0.667 −3258 −3894 −2.132 0.000
References
[1966Car] D.G. Carfagno, Ph.D. Thesis, Syracuse Univ., Syracuse, NY, 1966.
[1987Bal] C.W. Bale, A.D. Pelton: Bull. Alloy Phase Diagrams 8 (1987) 125–127.
[2002Grö] J. Gröbner, R. Schmid-Fetzer, A. Pisch, C. Colinet, V.V. Pavlyuk, G.S. Dmytriv, D.G.
Kevorkov, O.I. Bodak: Thermochim. Acta 389 (2002) 85–94.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ca – Ru 1
Ca – Ru (Calcium – Ruthenium)
3000
2800 liquid′ + liquid″
2600
2400
2200
2000
T / K
1800 hcp
1600
1400
1200
1000
bcc
800
600 fcc
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ca x Ru Ru
The Ca-Ru binary system contains two components of interest in the nuclear field, calcium being a major
component of the concrete basemat in its oxide form (CaO) and Ru selected as representative of a family of
non-volatile fission products.
The classical compilations of binary phase diagrams, give no information at all on this system. Conse-
quently, it has been supposed that there is a negligible mutual solid solubility of calcium and ruthenium
in each other, and a wide miscibility gap in the liquid state, the mutual solubility increasing at high tem-
perature. Thus, the assessed diagram is only qualitative and the solid and liquid solubilities are entirely
estimated. No thermodynamic property is available for that system. The system was assessed by Chevalier
and Fischer [1996Che].
The excess Gibbs energy of the liquid was estimated to be highly positive, to produce a small solubility of
components at low temperature and a large miscibility gap at high temperature. Similarly, highly positive
interaction parameters in the bcc, fcc and hcp phases allow to produce a negligible mutual solubility. No
comparison of the calculated phase diagram with experimental data is possible.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ca – Ru
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Cd – Y 1
Cd – Y (Cadmium – Yttrium)
1900
liquid bcc
1700
1500
1300
T / K
1100
900
Cd 58 Y 13
Cd 6 Y
700
Cd 45 Y 11
hcp
Cd 3 Y
Cd 2 Y
CdY
500 hcp
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Cd xY Y
The design of pyrometallurgically reprocessing for recycling nuclear reactor fuels needs thermodynamic
information on multicomponent systems of actinides and rare earths solute with cadmium.
The experimental data for the Cd-Y system are relatively limited. There are no information on the mutual
solubility of cadmium and yttrium in the solid state. Only the partial phase diagram covering the range
63 to 100 at.% Cd was reported by [1969Ryb]. Phase boundaries were determined by differential thermal
analysis, metallography and x-ray diffraction methods. The Cd-richest compound is Cd 6 Y which decom-
poses peritectically. [1988Gsc] reviewed this system. [1995Sak] determined the activity of yttrium using
electromotive force measurements. The thermodynamic assessment of the Cd-Y system is from [2001Kur].
The liquid phase was described by a substitutional solution model using the Redlich-Kister equation. The
intermetallic compounds Cd6 Y, Cd58 Y13 , Cd45 Y11 , Cd3 Y, Cd2 Y and CdY are treated as stoichiometric
compounds. The calculated phase diagram presents slight differences with experimental data. These differ-
ences may be due to a lack of experimental solubility data. The activities are well reproduced.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Cd – Y
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Cd – Y 3
5 1.0
0
0.8
−5
Energies / (kJ/mol)
T∆Sm
−10 0.6 a Cd aY
Activities
−15
0.4
−20 ∆Gm
−25
0.2
−30 ∆Hm
−35 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Cd xY Y Cd xY Y
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xY ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Cd6 Y1 0.143 −19674 −20876 −4.031 0.000
Cd58 Y13 0.183 −23837 −25529 −5.673 0.000
Cd45 Y11 0.196 −25033 −26825 −6.011 0.000
Cd3 Y1 0.250 −29083 −31104 −6.777 0.000
Cd2 Y1 0.333 −35289 −37814 −8.469 0.000
Cd1 Y1 0.500 −47210 −51936 −15.852 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Cd – Y
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ce – Ni 1
Ce – Ni (Cerium – Nickel)
1800
1700
liquid
1600
1500
1400
1300
1200
T / K
1100 bcc
1000
900 fcc
800
700
fcc
Ce 7 Ni 3
Ce 2 Ni 7
600 TC
CeNi 2
CeNi 3
CeNi 5
CeNi
500
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ce x Ni Ni
The interest in the Ce-Ni system is related to its potential use in hydrogen storage materials or in perma-
nent magnets. A review on the thermodynamic literature of the Ce-Ni system has been given by Nash and
Tung [1991Nas] and a thermodynamic optimisation has been prepared by Du et al. [2004Du]. The opti-
misation is based mainly on experimental information on the phase diagram [1947Vog, 1964Dus, 1965Per,
1967Geb]. No thermodynamic data are available for the melt. Calorimetric data for the standard enthalpy
of formation for intermetallic compounds have been reported only for CeNi 5 [1983Col, 1998Guo] and for
CeNi [1998Guo].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ce – Ni
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ce – Ni 3
20 1.0
10 T∆Sm
0.8
Energies / (kJ/mol)
0.6 a Ce a Ni
Activities
−10
−20
0.4
∆Hm
−30
0.2
−40
∆Gm
−50 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ce x Ni Ni Ce x Ni Ni
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xNi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ce7 Ni3 0.300 −24116 −25508 −4.667 −0.229
Ce1 Ni1 0.500 −31122 −30422 2.345 −0.382
Ce1 Ni2 0.667 −30676 −29654 3.427 −0.510
Ce1 Ni3 0.750 −29610 −28955 2.198 −0.573
Ce2 Ni7 0.778 −29044 −28532 1.717 −0.595
Ce1 Ni5 0.833 −27602 −27521 0.274 −0.637
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ce – Ni
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Gd 1
Co – Gd (Cobalt – Gadolinium)
1900
1700 liquid
bcc
1500
TC
1300
T / K
1100
fcc
Co 5 Gd
900 hcp
700
Co 17 Gd 2
Co 7 Gd 2
Co 3 Gd 4
Co 3 Gd
Co 2 Gd
hcp
CoGd 3
500
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Co x Gd Gd
Intermetallic compounds formed between rare earth and transition metals, especially 3d elements are of
particular interest regarding their magnetic properties and their reversible absorption of hydrogen gas at
room temperature and nearly atmospheric pressure. The phase diagram of the Co-Gd system was measured
by [1961Nov, 1969Bus, 1992Ge]. [1992Oka] reviewed this system. The results of [1961Nov] are quite
different from those of the studies of [1969Bus, 1992Ge] and are discarded. The last two investigations gave
the same kind of relationships, i.e. two eutectic reactions, congruent melting of Co 17 Gd2 and incongruent
melting of all other compounds. Co5 Gd is unstable at low temperatures. Both Co5 Gd and Co17 Gd2 were
reported to have a certain homogeneity region at high temperatures. Co 17 Gd2 and Co7 Gd2 are dimorphic,
but their transformation temperatures are unknown. The heat of mixing in the liquid phase at 1823 K was
measured by [1989Nik] for the entire composition range. The enthalpies of formation of the compounds
were measured by various authors [1976Deo, 1986Sch, 1987Col1] with the most complete set being that by
[1987Col1, 1987Col2]. The heat capacities of Co5 Gd and Co2 Gd were measured by [1974Kel, 1989Leg] in
the temperature ranges 5-300 K and 300-473 K, respectively. [1987Bar] measured the heat capacity at the
composition 63.2 at.% Gd in the temperature range 800-980 K. Magnetic measurements of the compounds
are reported by [1966Lem1, 1966Lem2, 1972Bur]. The thermodynamic assessment of the Co-Gd system
is from [1995Liu]. The fcc, hcp, bcc, and the liquid phases were described by a substitutional solution
model using the Redlich-Kister equation. A magnetic contribution is added for the fcc, hcp and bcc phases,
and no solubility range is assumed for these phases. The seven intermetallic compounds Co 17 Gd2 , Co5 Gd,
Co7 Gd2 , Co3 Gd, Co2 Gd, Co3 Gd4 , and CoGd3 are all treated as stoichiometric compounds because of
limited information. Good agreement is obtained between the calculation and the experimental results.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Co – Gd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Gd 3
4 1.0
0
0.8
T∆Sm
Energies / (kJ/mol)
−4
0.6 a Co a Gd
Activities
−8
0.4
−12 ∆Gm
0.2
−16 ∆Hm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Co x Gd Gd Co x Gd Gd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1823 K.
T =1823 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Co – Gd
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xGd ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Co17 Gd2 0.105 −7717 −7229 1.637 −0.130
Co5 Gd1 0.167 −11347 −11449 −0.345 1.594
Co7 Gd2 0.222 −15390 −15925 −1.793 −0.113
Co3 Gd1 0.250 −16463 −17141 −2.274 −0.109
Co2 Gd1 0.333 −15798 −16270 −1.584 −0.097
Co3 Gd4 0.571 −12787 −13930 −3.833 1.546
Co1 Gd3 0.750 −8984 −9906 −3.094 1.572
References
[1961Nov] V.F. Novy, R.C. Vickery, E.V. Kleber: Trans. Metall. Soc. AIME 221 (1961) 588–590.
[1966Lem1] R. Lemaire: Cobalt 32 (1966) 132–140.
[1966Lem2] R. Lemaire: Cobalt 33 (1966) 201–211.
[1969Bus] K.H.J. Buschow, A.S. van der Goot: J. Less-Common Met. 17 (1969) 249–255.
[1972Bur] E. Burzo: Phys. Rev. B 6B (1972) 2882–2887.
[1974Kel] D.A. Keller, S.G. Sankar, R.S. Craig, W.E. Wallace: Am. Inst. Phys. Conf. Proc. 18 (1974)
1207–1211.
[1976Deo] S.S. Deodhar, P.J. Ficalora: High Temp. Sci. 8 (1976) 185–193.
[1986Sch] J. Schott, F. Sommer: J. Less-Common Met. 119 (1986) 307–317.
[1987Bar] M. Barrico, C. Antonions and L. Battezzati: Scr. Metall. 21 (1987) 849–852.
[1987Col1] C. Colinet, A. Pasturel, K.H.J. Buschow: Metall. Trans. A 18A (1987) 903–907.
[1987Col2] C. Colinet, A. Pasturel: Calphad 11 (1987) 323–324.
[1989Nik] I.V. Nikolaenko, M.A. Turchanin: Rasplavy 5 (1989) 77–79.
[1989Leg] S.B.K. Leghari: J. Nat. Sci. Math. 29 (1989) 69–85.
[1992Ge] W.Q. Ge, C.H. Wu, Y.C. Chuang: Z. Metallkd. 83 (1992) 300–303.
[1992Oka] H. Okamoto: J. Phase Equilibria 13 (1992) 673–674.
[1995Liu] Z.-K. Liu, W. Zhang, B. Sundman: J. Alloys Comp. 226 (1995) 33–45.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Ge 1
Co – Ge (Cobalt – Germanium)
1900
1700 liquid
1500 fcc
1300
TC Co 3 Ge
T / K
1100
900
700
Co 5 Ge 3
Co 5 Ge 7
hcp
CoGe 2
500 A4
CoGe
Co 5 Ge 2
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Co x Ge Ge
The equilibrium phases are the liquid, the Co-rich fcc solid solution, the Co-rich hcp solid solution, the
Ge-rich solid solution, with negligible solid solubility of Co and 6 near-stoichiometric compounds Co 3 Ge,
Co5 Ge2 , Co5 Ge3 , CoGe, Co5 Ge7 and CoGe2 . Two compounds, CoGe and CoGe2 , decompose peritecti-
cally at 1258 and 1105 K, respectively. CoGe has a narrow homogeneity range of about 2.5 at.% with a
stoichiometric composition at the peritectic temperature. The compound Co5 Ge7 is stable up to the peritec-
toid temperature of 1079 K. Co3 Ge is formed below about 1043 K, the hexagonal phase Co5 Ge2 is stable
between 655 and 909 K. The phase Co5 Ge3 which exhibits a fairly wide homogeneity range of almost 10
at.% melts congruently at 1483 K. The thermodynamic assessment of the Co-Ge system carried out by
Korb [2004Kor] is based on [1949Pfi, 1980Day, 1990Eno], with review of the data of [1952Kös, 1973Aga,
1976Bal]. All compounds have been treated as stoichiometric, including Co 5 Ge3 and CoGe. Taking into
account this simplification the calculated and the published [1991Ish] phase diagram agree well.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Co – Ge
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Ge 3
60 1.0
40 T∆Sm
0.8
Energies / (kJ/mol)
20
0.6 a Co a Ge
Activities
0
∆Hm
−20
0.4
−40
0.2
−60 ∆Gm
−80 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Co x Ge Ge Co x Ge Ge
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1823 K.
T =1823 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Co – Ge
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xGe ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Co3 Ge1 0.250 −41387 −39698 5.668 −0.109
Co5 Ge2 0.286 −47219 −46188 3.458 −0.104
Co5 Ge3 0.375 −60000 −60000 0.001 −0.287
Co1 Ge1 0.500 −51800 −51800 0.001 −0.228
Co5 Ge7 0.583 −44163 −44167 −0.015 −0.060
Co1 Ge2 0.667 −36403 −37120 −2.405 −0.149
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – O 1
Co – O (Cobalt – Oxygen)
2900
2700 liquid
liquid
2500 + gas
2300
2100
1900
T / K
1700
CoO + gas
fcc
1500
1300 TC
1100
Co 3 O 4
CoO
900
700
hcp
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Co xO
A thorough review on the cobalt-oxygen system and a thermodynamic assessment has been given by
[2003Che]. The stable phases in the system are the liquid, metallic cobalt (hcp and fcc) with limited
solubility for oxygen and two oxides, CoO and Co3 O4 , which are described as stoichiometric compounds.
The optimisation of the dataset is based on the evaluation of a large amount of experimental data from the
literature. It includes the solubility and the activities of oxygen in the liquid phase, the solubility of oxy-
gen in Co metal, the oxygen activities in the 2-phase equilibria of the condensed phases, data for the heat
capacity and the heat content of both oxides as well as the enthalpies of formation and the entropy of these
oxides at 298.15 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Co – O
−5 gas
Co 3 O 4
−10
−15 liquid
CoO
log 10 a O2
−20
−25 fcc
−30
Table III. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xO ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Co1 O1 0.500 −106765 −118430 −39.123 7.567
Co3 O4 0.571 −114126 −130769 −55.822 −1.712
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Pd 1
Co – Pd (Cobalt – Palladium)
1900
liquid
1700
1500
1300
fcc
T / K
TC
1100
900
700
500
hcp + fcc
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Co x Pd Pd
The Co-Pd phase diagram is quite simple, consisting only of the melt, a broad fcc solution phase and at
lower temperature the Co-based hcp phase. The present thermochemical optimisation of the Co-Pd system
has been done by [2004Fra]. The phase diagram of the Co-Pd system and the T C curve of fcc alloys have
been determined essentially by Grube and Kästner [1936Gru]. The mixing enthalpy in the melt has been
measured calorimetrically at 1873 K [1977Vat] and the excess properties of mixing have been determined by
Knudsen mass spectrometry for the melt [1994Tom] as well as for solid solutions [1995Wan]. The activity
of Co in fcc solid solutions has been measured in gas equilibration experiments [1965Sch] and by EMF
methods [1965Sch, 1970Bid]. The experimental results of Vatolin and Kozlov [1977Vat] are in conflict
with the results of Tomiska et al. [1994Tom]. [1977Vat] obtained slightly positive mixing enthalpies in
the liquid whereas [1994Tom] found considerable negative mixing enthalpies. However, the same group
investigated also the solid solutions [1995Wan] and both of their datasets are in accord with the phase
diagram. Therefore, the results of [1977Vat] have been excluded from the present assessment. Another
assessment for Co-Pd has been reported in [1999Gho] but the results of [1977Vat] have been adopted and
the dataset predicts the presence of a miscibility gap in the fcc phase below 846 K at 17 at.% Pd which is
not supported by experiments.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Co – Pd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Pd 3
5 1.0
T∆Sm
0 0.8
Energies / (kJ/mol)
−5 0.6 a Co a Pd
Activities
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Co x Pd Pd Co x Pd Pd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1850 K.
T =1850 K.
Table IVa. Integral quantities for the stable phases at 1473 K.
Phase xPd ∆Gm ∆Hm ∆Sm GEm Sm
E
∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −4321 −1872 1.662 −339 −1.041 −1.600
0.200 −7231 −4160 2.085 −1102 −2.076 −2.216
0.300 −9574 −6488 2.095 −2093 −2.984 −2.422
0.400 −11364 −8544 1.915 −3122 −3.681 −2.425
0.500 −12497 −10049 1.662 −4008 −4.101 −2.296
0.600 −12814 −10738 1.409 −4572 −4.186 −2.043
0.700 −12116 −10353 1.197 −4634 −3.882 −1.657
0.800 −10144 −8623 1.032 −4016 −3.128 −1.155
0.900 −6513 −5267 0.846 −2532 −1.857 −0.585
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Co – Pd
4 1.0
2
T∆Sm
0 0.8
Energies / (kJ/mol)
−2
0.6 a Co a Pd
Activities
−4
−6
0.4
−8
−10 ∆Hm
0.2
−12
∆Gm
−14 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Co x Pd Pd Co x Pd Pd
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1473 K.
T =1473 K.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Y 1
Co – Y (Cobalt – Yttrium)
1900
bcc
1700 liquid
1500
TC
1300
T / K
1100 TC
Co 5 Y
900 hcp
fcc Co 7 Y 6
700 TC CoY
Co 17 Y 2
hcp
Co 7 Y 2
Co 3 Y 2
Co 3 Y 4
Co 5 Y 8
500
Co 3 Y
Co 2 Y
CoY 3
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Co xY Y
The Co-Y system is of interest for permanent magnets (Co17 Y2 ) and for its potential use as hydrogen
storage materials. A survey on the literature of the Co-Y system and a thermodynamic assessment has
been been given by [2004Du]. The optimisation is based on experimental data on the phase diagram which
are taken mainly from [1974Kha, 1991Wu] and on thermochemical data for the intermetallic compounds
[1985Sub, 1987Col, 1987Mey]. For the liquid, no data have been available. A polymorphic transformation
between αCo17 Y2 and βCo17 Y2 at about 1573 K has been omitted in the assessment. At higher temperature
the compounds Co17 Y2 and Co5 Y deviate from their stoichiometric compositions due to an excess of Y in
Co17 Y2 and excess Co in Co5 Y. Since their crystal structures are closely related, [2004Du] have described
both compounds as a single phase with a miscibility gap. However, since both structures are different, the
phases are still denoted as different compounds in the present diagrams and tables. The dataset should
not be used at too high temperatures because an artificial inverse miscibility gap opens in the liquid above
3800 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Co – Y
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Y 3
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Co – Y
20 1.0
15
10 T∆Sm 0.8
5
Energies / (kJ/mol)
0 a Co aY
0.6
Activities
−5
−10
0.4
−15
−20
∆Hm 0.2
−25
−30 ∆Gm
−35 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Co xY Y Co xY Y
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xY ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Co17 Y2 0.105 −10488 −10226 −0.878 −0.078
Co7 Y2 0.222 −19841 −19935 −0.314 0.307
Co3 Y1 0.250 −21765 −21643 0.407 5.028
Co2 Y1 0.333 −27238 −27815 −1.935 −0.097
Co3 Y2 0.400 −30600 −32522 −6.446 −0.087
Co7 Y6 0.462 −33450 −36853 −11.412 −0.078
Co1 Y1 0.500 −32365 −35553 −10.693 −0.072
Co3 Y4 0.571 −29319 −32133 −9.437 −0.062
Co5 Y8 0.615 −26768 −29066 −7.708 −0.056
Co1 Y3 0.750 −18245 −18892 −2.171 −0.036
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Zn 1
Co – Zn (Cobalt – Zinc)
1900
1700 liquid
1500
1100
CoZn
900
Co 5 Zn 21
700
CoZn 13
CoZn 7
500 hcp
hex
TC
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Co x Zn Zn
The Co-Zn system has been reviewed and a thermodynamic dataset has been optimised in [2004Vas]. The
Co-Zn system has been studied thoroughly by Schramm using metallographic and thermal analyses, x-ray
diffraction and magnetic methods [1938Sch1, 1938Sch2, 1938Sch3, 1938Sch4, 1941Sch]. Later, various
parts of the phase diagram have been re-investigated [1955Kös, 1955Lih, 1976Bud1, 1995Tak]. Thermo-
dynamic properties of Co-Zn solutions have been reported for solid alloys [1976Bud2, 1977Bud, 1981Ali,
1982Cöm] as well as more limited data for the melt [1982Cöm]. The assessed dataset which is shown here
[2004Vas] provides a good representation of the experimental data. The dataset should not be used at too
high temperatures because an artificial inverse miscibility gap opens in the liquid above 2600 K. Another
assessment for Co-Zn has been reported by [2004Iso] but here the phase diagram has been modelled with
less detail.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Co – Zn
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Co – Zn 3
10 1.0
T∆Sm
0.8
5
Energies / (kJ/mol)
0.6
Activities
0
∆Hm 0.4 a Zn a Co
−5
0.2
∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Co x Zn Zn Co x Zn Zn
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZn ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Co1 Zn7 0.875 −9901 −10986 −3.638 −0.018
Co2 Zn15 0.882 −6739 −6491 0.830 −0.017
Co1 Zn13 0.929 −5795 −6101 −1.029 −0.010
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Co – Zn
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Cr – Ru 1
Cr – Ru (Chromium – Ruthenium)
2700
liquid
2300
1900
T / K
Cr 2 Ru
1500
bcc hcp
1100
Cr 3 Ru
700
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Cr x Ru Ru
The Cr-Ru binary system contains two components interesting for the nuclear field, chromium being a major
component of stainless steel structures of the vessel, and ruthenium being selected as representative of a
family of non-volatile fission products. Experimental information on the phase diagram has been reported
in several compilations of binary systems [1958Han, 1965Ell, 1969Shu, 1981Mof] and in the review of
Venkatraman and Neumann [1987Ven]. Raub and Mahler [1955Rau] and Greenfield and Beck [1956Gre]
firstly put in evidence the existence of the bcc and hcp terminal solid solutions, and intermetallic phases,
Cr4 Ru, Cr3 Ru and Cr2 Ru (σ). The diagram constructed by Savitskii et al. [1961Sav] by classical methods is
in poor agreement with the selected one. Shurin and Dmitrieva [1964Shu] determined liquidus and solidus
data. Cr4 Ru was not confirmed. The high temperature data are in agreement with [1961Sav] and [1964Shu],
the low temperature transitions of Cr3 Ru were determined by Wopersnow and Raub [1979Wop]. The
solubility of Ru in bcc was determined by Waterstrat [1981Wat] at 1373 K and 1073 K. No thermodynamic
properties are available for that system.
The system was assessed by Chevalier and Fischer [1998Che]. The excess Gibbs energy of the liquid,
bcc, hcp and the Gibbs energy of the intermetallic compounds, Cr3 Ru and σ which are considered as
stoichiometric was optimised from the selected phase diagram experimental information. A sub-regular
substitution model was used for solution phases. The heat capacity of the compounds was estimated from
the pure solid components by using the Neumann-Kopp rule. The enthalpy and entropy of formation was
optimised in consistency with other data. The agreement with the experimental information [1961Sav,
1964Shu, 1979Wop, 1981Wat, 1987Ven] is satisfactory.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Cr – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Cr – Ru 3
20 1.0
T∆Sm
10 0.8
Energies / (kJ/mol)
0 0.6 a Cr a Ru
Activities
−20 0.2
∆Gm
−30 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Cr x Ru Ru Cr x Ru Ru
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2700 K.
T =2700 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Cr – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Cr – Ru 5
10 1.0
T∆Sm
5
0.8
Energies / (kJ/mol)
0
a Cr a Ru
0.6
Activities
−5
∆Hm 0.4
−10
0.2
−15 ∆Gm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Cr x Ru Ru Cr x Ru Ru
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1600 K.
T =1600 K.
Table V. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xRu ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Cr3 R1 0.250 −3237 −1604 5.476 −0.110
Cr2 Ru 0.333 −4596 −2800 6.024 −0.098
Landolt-Börnstein SGTE
New Series IV/19B
6 2 Binary Systems: Cr – Ru
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Cu – Ir 1
Cu – Ir (Copper – Iridium)
2800
2600 liquid
2400
2200
2000
T / K
1800
1600
1400
1200
fcc′ fcc″
1000
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Cu x Ir Ir
The thermodynamic description of the Cu-Ir system is based on the only reported phase diagram study
below 1473 K [1969Rau]. The higher temperature part of the diagram (above 1473 K) was estimated from
calculations based on thermodynamic modelling of the experimental phase diagram data. The equilibrium
phases of the Cu-Ir system are the liquid, miscible in all proportions and stable down to the melting point of
Cu, the fcc solid solution based on Cu, which has a maximum solubility of about 8 at.% Ir at the peritectic
temperature and the fcc solid solution based on Ir, which has a maximum solubility of 6.3 at.% Cu at
2123 K [1987Cha]. According to [1969Rau] the peritectic temperature is 1411±5 K, and the corresponding
compositions of the liquid, fcc’, and fcc” phases are 4, 8, 97 at.% Ir, respectively. This behaviour can be
reproduced well by the calculations. The calculated Cu-Ir phase diagram indicates a good agreement with
published experimental data [1987Cha].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Cu – Ir
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Cu – Ir 3
15 1.0
10 T∆Sm 0.8
Energies / (kJ/mol)
5 0.6
Activities
a Ir a Cu
∆Hm
0 0.4
−5 0.2
∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Cu x Ir Ir Cu x Ir Ir
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Dy – Mg 1
Dy – Mg (Dysprosium – Magnesium)
1800
liquid
1600
1400
1200
bcc
T / K
1000
hcp B2
800
Mg 24 Dy 5
hcp
Mg 3 Dy
C14
600
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Dy x Mg Mg
The rare earth elements have attracted some attention as additives to light metal alloys in the aerospace
and automotive industry due to the improvement of mechanical properties of Al- and Mg-alloys at high
temperatures. Cacciamani et al. [2003Cac] prepared a thermodynamic optimisation of the complete Dy-
Mg system, which is primarily based on an experimental investigation of the phase equilibria at elevated
temperatures throughout the whole composition range [1991Sac]. The solid solubilities have been measured
by [1965Jos] for Mg in hcp-Dy and by [1978Rok] for Dy in magnesium. Since no thermodynamic data have
been available for the Dy-Mg system the assessors estimated the values based on other systems of Mg with
rare-earth metals which have been evaluated in the same publication.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Dy – Mg
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Dy – Mg 3
5 0.8
Energies / (kJ/mol)
0 0.6 a Dy a Mg
Activities
∆Hm
−5 0.4
−10 0.2
∆Gm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Dy x Mg Mg Dy x Mg Mg
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xMg ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
B2 0.500 −12298 −13952 −5.550 −0.383
C14 0.667 −12142 −13981 −6.167 −0.241
Mg3 Dy 0.750 −10504 −12386 −6.312 −0.192
Mg24 Dy5 0.828 −8790 −10680 −6.339 −0.133
References
[1965Jos] R.R. Joseph, K.A. Gschneidner jr.: Trans. Metall. Soc. AIME 233 (1965) 2063–2069.
[1978Rok] L.L. Rokhlin in: “Probl. Metalloved. Tsvetn. Splavov”, N.M. Zhavoronkov (Ed.), Izd.
Nauka, Moscow, 1978, pp. 59–70.
[1991Sac] A. Saccone, S. Delfino, D. Macció, R. Ferro: Z. Metallkd. 82 (1991) 568–573.
[2003Cac] G. Cacciamani, S. de Negri, A. Saccone, R. Ferro: Intermetallics 11 (2003) 1135–1151.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Eu – Pd 1
Eu – Pd (Europium – Palladium)
2000
1800 liquid
1600
1400
T / K
1200 fcc
EuPd 7
1000
800
Eu 5 Pd 2
Eu 3 Pd 2
EuPd 2
EuPd 3
EuPd 5
EuPd
600 bcc
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Eu x Pd Pd
Intermetallic compounds of palladium with rare earth metals are of interest due to their potential use in
hydrogen diffusion membranes for purification and isotope enrichment. A review of the Eu-Pd system and a
thermodynamic assessment has been given by [2001Du]. The optimisation is based on data on the the phase
diagram which have been reported in [1974Ian] for equilibria with the liquid across the whole composition
range and in addition results for equilibria involving the compound EuPd 7 which have been reported by
[1990Tak]. No thermodynamic data have been available for the melt or the intermetallic compounds. Due to
the close chemical relationships among the rare earth metals, [2001Du] have considered in the optimisation
of the intermetallic compounds the corresponding enthalpies of formation in the systems Gd-Pd and Pd-Sm
which have been available in the literature. The dataset should not be used at too high temperatures because
an artificial inverse miscibility gap opens in the liquid above 3550 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Eu – Pd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Eu – Pd 3
60 1.0
40
20 T∆Sm 0.8
Energies / (kJ/mol)
0
0.6 a Eu a Pd
Activities
−20
−40
∆Hm 0.4
−60
−80 0.2
∆Gm
−100
−120 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Eu x Pd Pd Eu x Pd Pd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1900 K.
T =1900 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xPd ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Eu5 Pd2 0.286 −48926 −44766 13.953 0.000
Eu3 Pd2 0.400 −67389 −62722 15.652 0.000
Eu1 Pd1 0.500 −81068 −78545 8.461 0.000
Eu1 Pd2 0.667 −101882 −104636 −9.236 0.000
Eu1 Pd3 0.750 −92103 −95334 −10.836 0.000
Eu1 Pd5 0.833 −63717 −65892 −7.294 0.000
Eu1 Pd7 0.875 −49326 −51176 −6.207 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Eu – Pd
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Eu – Sn 1
Eu – Sn (Europium – Tin)
1800
liquid
1600
1400
1200
T / K
1000
800
Eu 5 Sn 3
Eu 3 Sn 5
Eu 2 Sn
EuSn 3
EuSn
600 bcc
bct
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Eu x Sn Sn
A review on the Eu-Sn system and a thermodynamic assessment has been given by [2004Liu]. The opti-
misation is based mostly on data for the phase diagram which have been reported in [1998Pal] throughout
the whole composition range. Some additional thermodynamic data have been available from the literature.
Bacha et al. [1973Bac] have obtained by EMF experiments the enthalpy of formation of EuSn 3 as well as
the partial enthalpy of Eu in Sn-melts at low concentrations of Eu. Using also EMF techniques Kober et al.
[1987Kob] have reported activities of Eu in Sn-melts at low Eu contents.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Eu – Sn
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Eu – Sn 3
10 1.0
T∆Sm
0
0.8
Energies / (kJ/mol)
−10
0.6 a Eu a Sn
Activities
−20
0.4
−30
∆Hm 0.2
−40
∆Gm
−50 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Eu x Sn Sn Eu x Sn Sn
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSn ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Eu2 Sn1 0.333 −38759 −37010 5.867 0.000
Eu5 Sn3 0.375 −42913 −41643 4.260 0.000
Eu1 Sn1 0.500 −55167 −55544 −1.265 0.000
Eu3 Sn5 0.625 −54359 −55526 −3.912 0.000
Eu1 Sn3 0.750 −51517 −54877 −11.271 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Eu – Sn
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Fe – Ru 1
Fe – Ru (Iron – Ruthenium)
2700
2500 liquid
2300
2100
1900
1700
bcc hcp
T / K
1500
fcc
1300
1100 TC
900
700
bcc
500
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Fe x Ru Ru
The Fe-Ru binary system contains two components interesting for the nuclear field, iron being a major
component of stainless steel structures of the vessel, and ruthenium being selected as representative of a
family of non-volatile fission products. Experimental information on the phase diagram has been reported
in several compilations of binary systems [1958Han, 1965Ell, 1969Shu]. The components are completely
miscible in the liquid state. The maximal solubility of ruthenium reaches 5 at.% at 1809 K and 4.8 at.% at
773 K in iron-rich bcc terminal solid solutions, and varies from 9.3 at.% at 773 K to 29.5 at.% at 1863 K
in the iron-rich fcc terminal solid solution. The solubility of iron in ruthenium-rich hcp terminal solid solu-
tions varies from 76.5 at.% at 773 K to 64.5 at.% at 1863 K. The transition temperatures fcc/bcc have been
studied by Fallot [1938Fal] and Martelly [1938Mar] using X-ray and magnetic analysis. The iron-rich side
at high temperature was determined by Gibson and Hume-Rothery [1958Gib] by thermal analysis. Raub
and Plate [1960Rau] determined monophasic and diphasic domains between fcc, hcp and bcc in the range
from 673 K to 1473 K. The activity of iron in the fcc and hcp domains was determined by Stepakoff and
Kaufman [1968Ste] from vapour pressure measurements at 1600 K. The system was assessed by Cheva-
lier and Fischer [2004Che]. The excess Gibbs energy of the liquid, bcc, fcc and hcp solution phases was
optimised based on selected experimental information for the phase diagram and thermodynamic proper-
ties. A regular substitution model was used for all solution phases. The agreement with the experimental
information is satisfactory, but however the vertical shape of the fcc/hcp region [1960Rau] cannot be easily
reproduced to be compatible with the peritectic determined by Obrowski [1959Obr]. This point should be
re-analysed.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Fe – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Fe – Ru 3
16 1.0
T∆Sm
8 0.8
Energies / (kJ/mol)
0 0.6 a Fe a Ru
Activities
∆Hm
−8 0.4
−16 0.2
∆Gm
−24 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Fe x Ru Ru Fe x Ru Ru
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2700 K.
T =2700 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Fe – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Fe – Ru 5
8 1.0
6
T∆Sm
4 0.8
2
Energies / (kJ/mol)
0 a Fe a Ru
0.6
Activities
−2
−4
∆Hm 0.4
−6
−8
−10 0.2
∆Gm
−12
−14 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Fe x Ru Ru Fe x Ru Ru
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1600 K.
T =1600 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Fe – Sb 1
Fe – Sb (Iron – Antimony)
2000
liquid
1800
1600
1400 fcc
T / K
1200
bcc
FeSb
1000
TC
800
FeSb 2
600 A7
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Fe x Sb Sb
Iron and antimony are often found as substitutional elements in copper arsenide and sulfide minerals which
are used in copper smelting processes. A thermodynamic optimisation of the Fe-Sb system has been re-
ported by [1995Pei]. For the assessment a large number of reports has been evaluated which determine
the phase diagram over the complete composition range and temperatures up to the liquidus. In addition,
enthalpies of mixing and the activities of both elements have been available for Sb-rich melts as well as in
the sub-solidus region across the whole composition range. In the assessment of the phases FeSb and FeSb 2
their magnetic properties have not been considered.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Fe – Sb
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Fe – Sb 3
6 1.0
4
T∆Sm
0.8
2
Energies / (kJ/mol)
0 0.6
Activities
−2 a Sb a Fe
−4 0.4
∆Hm
−6
∆Gm 0.2
−8
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Fe x Sb Sb Fe x Sb Sb
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1823 K.
T =1823 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSb ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Fe1 Sb2 0.667 −7055 −7012 0.145 −0.139
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ga – Mg 1
Ga – Mg (Gallium – Magnesium)
1000
liquid
900
800
700
T / K
600
hcp
500
Mg 2 Ga 5
400
Mg 5 Ga 2
Mg 2 Ga
MgGa 2
MgGa
300
A11
200
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ga x Mg Mg
Magnesium is the major p-type dopant for GaN semiconductors and Ga-Mg melts can be used for this
purpose in ion implantation processes. Another interesting applications is the potential use of Ga-based
pastes for brazing and soldering Mg-alloys. The Ga-Mg system has been reviewed in [1986Nay] and a new
experimental investigation and a thermodynamic optimisation has been reported by [1991Not]. Although
this dataset seems to be a good assessment it has not been based on the SGTE description for the element
data. Therefore, the system has been re-optimised [2005Fra] using the SGTE element data. For this adjust-
ment the the same selection of experimental data has been used and the same invariant points of the phase
diagram as recommended by [1991Not].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ga – Mg
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ga – Mg 3
4 1.0
2
T∆Sm
0 0.8
Energies / (kJ/mol)
−2
0.6
Activities
−4
a Ga a Mg
−6
0.4
−8
−10 ∆Hm 0.2
−12
∆Gm
−14 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ga x Mg Mg Ga x Mg Mg
Fig. 2. Integral quantities of the liquid phase at T =973 K. Fig. 3. Activities in the liquid phase at T =973 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xMg ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Mg2 Ga5 0.286 −10766 −9695 3.594 0.000
Mg1 Ga2 0.333 −11783 −10388 4.680 0.000
Mg1 Ga1 0.500 −14015 −13183 2.790 0.000
Mg2 Ga1 0.667 −12293 −11463 2.785 0.000
Mg5 Ga2 0.714 −11508 −10927 1.950 0.000
References
[1988Nay] A.A. Nayeb-Hashemi, J.B. Clark in: “Phase Diagrams of Binary Magnesium Alloys”, A.A.
Nayeb-Hashemi, J.B. Clark, Eds., ASM Intl., Metals Park, OH, 1988, pp. 122–128.
[1991Not] M. Notin, E. Belbacha, J. Charles, J. Hertz: J. Alloys Comp. 176 (1991) 25–38.
[2005Fra] P. Franke: unpublished optimisation, 2005.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ga – Si 1
Ga – Si (Gallium – Silicon)
1800
liquid
1600
1400
1200
T / K
1000
A4
800
600
400
A11
200
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ga x Si Si
The system Ga-Si is of interest for the semiconductor industry. Ga can be used as a p-type dopant in Si
and furthermore, thin films of silicon can be grown from its solution in Ga melts by liquid phase epitaxy.
A thorough review on the gallium-silicon system has been given by Olesinski et al. [1985Ole]. Since then,
it seems that only one major thermodynamic investigation has been published for this system [2004Sud].
The selected dataset has been optimised by [2005Fra]. The phase diagram of Ga-Si is simple eutectic and
almost degenerate on the Ga-side. For the optimisation of the liquidus curve, data from 3 experimental
investigations have been selected which are in good mutual agreement [1948Kle, 1953Kec, 1977Gir]. For
the solid solubility of gallium in crystalline silicon the data of [1960Tru, 1977Gir] have been chosen. In
a recent investigation mixing enthalpies for the melt have been reported [2004Sud] across the whole com-
position range. These data compare well with the partial enthalpy of Si in Ga-rich melts which have been
given in [1983Tma].
References
[1948Kle] W. Klemm, L. Klemm, F. Hohmann, H. Volk, E. Orlamünder, H.A. Klein: Z. Anorg. Allg.
Chem. 256 (1948) 239–252.
[1953Kec] P.H. Keck, J. Broder: Phys. Rev. Lett. 90 (1953) 521–522.
[1960Tru] F.A. Trumbore: Bell. Sys. Tech. J. 39 (1960) 205–233.
[1977Gir] B. Girault, F. Chevrier, A. Joullie, G. Bougnot: J. Cryst. Growth 37 (1977) 169–177.
[1983Tma] M. Tmar, A. Pasturel, C. Colinet: J. Chem. Thermodyn. 15 (1983) 1037–1040.
[1985Ole] R.W. Olesinski, N. Kanani, G.J. Abbaschian: Bull. Alloy Phase Diagrams 6 (1985) 362–
364.
[2004Sud] V.S. Sudavtsova, T.N. Zinevich, N.V. Kotova, E.A. Beloborodova: Zh. Fiz. Khim. 78 (2004)
957–960.
[2005Fra] P. Franke: unpublished optimisation, 2005.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ga – Si
1800
1600
1400 A4
T / K
1200
1000 liquid + A4
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ga – Si 3
15 1.0
T∆Sm
10 0.8
Energies / (kJ/mol)
5 0.6 a Ga a Si
Activities
∆Hm
0 0.4
−5 0.2
∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ga x Si Si Ga x Si Si
Fig. 3. Integral quantities of the liquid phase at Fig. 4. Activities in the liquid phase at T =1750 K.
T =1750 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ga – Ti 1
Ga – Ti (Gallium – Titanium)
2000
liquid
1800
1600
bcc
1400
TiGa
T / K
1200
1000
hcp
Ti 2 Ga 3
Ti 5 Ga 4
Ti 5 Ga 3
Ti 2 Ga
Ti 3 Ga
TiGa 3
TiGa 2
800
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ga x Ti Ti
A review and a thermodynamically optimised dataset for the complete Ga-Ti system has been given by Li
et al. [2003Li]. In a previous overview by Murray [1985Mur] a phase diagram has been assessed only for
the Ti-rich part of the phase diagram because at that time only one experimental investigation [1962Pot]
on almost the complete composition range of the phase diagram has been available but various questions
remained open in that report. This investigation, a 2nd extended study of the phase diagram from the liter-
ature [2001Ant] and other partial evaluations of the phase diagram as well as additional own experiments
have been used in [2003Li] to establish a complete phase diagram and an optimised thermodynamic dataset
for the Ga-Ti system. The mixing enthalpy in the liquid has been measured by [1974Esi], however the cal-
culated curve from the evaluated dataset shows significant deviations. The partial enthalpies of solution for
Ti in Ga-rich melts [1985Nik] are in good agreement with the calculation within the experimental scatter.
The experimental chemical potential differences between Ga and Ti in bcc alloys reported by [1973Geg] are
in good agreement with the calculation. Except for the standard enthalpy of formation of GaTi 2 [1999Mes]
no other thermodynamic data for the intermetallic compounds have been available. In order to estimate the
respective values of the other compounds Li et al. [2003Li] used enthalpies of formation for Ti-Al alloys
from the literature as a guide.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ga – Ti
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ga – Ti 3
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ga – Ti
5 1.0
0
0.8
−5
Energies / (kJ/mol)
−10 T∆Sm a Ga a Ti
0.6
Activities
−15
∆Gm 0.4
−20
−25
0.2
−30 ∆Hm
−35 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ga x Ti Ti Ga x Ti Ti
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2000 K.
T =2000 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xTi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ti1 Ga3 0.250 −33809 −35130 −4.429 0.000
Ti1 Ga2 0.333 −38427 −39867 −4.827 0.000
Ti2 Ga3 0.400 −38795 −40064 −4.257 0.000
Ti5 Ga4 0.556 −38491 −39500 −3.384 0.000
Ti5 Ga3 0.625 −37787 −39125 −4.487 0.000
Ti2 Ga1 0.667 −37056 −38667 −5.403 0.000
Ti3 Ga 0.750 −32028 −34127 −7.040 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Gd – Li 1
Gd – Li (Gadolinium – Lithium)
1700
bcc liquid
1500
1300
1100
T / K
hcp
900
700
500
bcc
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Gd x Li Li
Lithium is a common addition for magnesium alloys in order to decrease their density and to improve
the ductility. Rare Earth metals can enable precipitation hardening of magnesium alloys and enhance the
castability. Only very few data have been reported about the Gd-Li system. At 473 K no mutual solubility of
the elements could be observed [1989Pav]. In DTA experiments [1998Gan] only two invariant temperatures
have been detected, a eutectic almost degenerate on the Li-side, and a monotectic at higher temperatures.
The existence of the miscibility gap has been verified experimentally [2001Kev] and in the course of an
assessment of the ternary system Gd-Li-Mg, the dataset for the binary Gd-Li has been optimised as well
[2001Kev].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Gd – Li
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Gd – Li 3
10 1.0
8 T∆Sm
0.8
6
Energies / (kJ/mol)
4 ∆Hm
0.6
Activities
a Li a Gd
2
0 0.4
−2
0.2
−4 ∆Gm
−6 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Gd x Li Li Gd x Li Li
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1600 K.
T =1600 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Gd – Mg 1
Gd – Mg (Gadolinium – Magnesium)
1700
liquid
1500
1300
bcc
1100
T / K
hcp B2
900
700 hcp
Mg 3 Gd
Mg 5 Gd
C15
500
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Gd x Mg Mg
The rare earth elements have attracted some attention as additives to light metal alloys in the aerospace and
automotive industry due to the improvement of mechanical properties of Al- and Mg-alloys at high tem-
peratures. Cacciamani et al. [2003Cac] prepared a thermodynamic optimisation of the complete Gd-Mg
system, which is mostly based on an experimental investigation of the phase equilibria at elevated temper-
atures throughout the whole composition range [1986Man]. The solid solubilities have been measured by
[1965Jos] for Mg in hcp-Gd and by [1978Rok] for Gd in magnesium. Except for the standard enthalpy
of formation of the GdMg phase no other thermodynamic data for the Gd-Mg system have been available.
Despite this lack of data, the assessment [2003Cac] can be considered as quite reasonable since other sim-
ilar systems (Dy-Mg, Ho-Mg) have been evaluated simultaneously and data have been estimated taking
advantage of the close relations between the involved rare earth elements.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Gd – Mg
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Gd – Mg 3
15 1.0
10
T∆Sm 0.8
Energies / (kJ/mol)
0.6 a Gd a Mg
Activities
−5 ∆Hm
0.4
−10
0.2
−15 ∆Gm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Gd x Mg Mg Gd x Mg Mg
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xMg ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
B2 0.500 −14191 −15138 −3.176 −6.456
C15 0.667 −13962 −14750 −2.643 −4.322
Mg3 Gd1 0.750 −11732 −12313 −1.949 −3.244
Mg5 Gd1 0.833 −8274 −8659 −1.290 −2.163
References
[1965Jos] R.R. Joseph, K.A. Gschneidner jr.: Trans. Metall. Soc. AIME 233 (1965) 2063–2069.
[1978Rok] L.L. Rokhlin in: “Probl. Metalloved. Tsvetn. Splavov”, N.M. Zhavoronkov (Ed.), Izd.
Nauka, Moscow, 1978, pp. 59–70.
[2003Cac] G. Cacciamani, S. de Negri, A. Saccone, R. Ferro: Intermetallics 11 (2003) 1135–1151.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Gd – Mn 1
Gd – Mn (Gadolinium – Manganese)
1700
bcc
1500
1400 fcc
1300
T / K
1200
cub
1100
1000
hcp
Mn 23 Gd 6
Mn 12 Gd
900
Mn 2 Gd
cbcc
800
700
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Gd x Mn Mn
Manganese and rare earth metals are added to magnesium alloys in order to improve their creep resistance
and strength. A review and a thermodynamic optimisation of the Gd-Mn system has been prepared by
[2001Grö]. The phase diagram of the system Gd-Mn has been determined by Kirchmayr and Lugscheider
[1967Kir]. The partial enthalpies of the components in molten Gd-Mn alloys have been measured calori-
metrically by Nikolaenko and Nosova [1989Nik]. However, their data have a large range of scatter and
they are not used in the optimisation [2001Grö]. Enthalpies of formation of the intermetallic compounds
have been estimated from the corresponding values of the Mn-Y system which been assessed in the same
publication [2001Grö].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Gd – Mn
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Gd – Mn 3
6 1.0
4 T∆Sm
0.8
2
Energies / (kJ/mol)
0 0.6
Activities
−2
∆Hm
0.4 a Mn a Gd
−4
−6
0.2
−8 ∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Gd x Mn Mn Gd x Mn Mn
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1600 K.
T =1600 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xMn ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Mn2 Gd1 0.667 −6111 −6408 −0.996 −4.329
Mn23 Gd6 0.793 −6026 −6371 −1.158 −2.689
Mn12 Gd1 0.923 −3720 −4027 −1.031 −1.003
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Gd – Mo 1
Gd – Mo (Gadolinium – Molybdenum)
3200
3000 liquid
2800
2600
2400
2200
T / K
bcc″
2000
1800
1600
bcc′
1400
1200 hcp
1000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Gd x Mo Mo
In the solid state Gd and Mo are almost insoluble in each other and no binary compounds are formed by
them. The interest in this system is related to ternary and higher systems where intermetallic compounds
are formed with interesting magnetic properties. The combination of gadolinium and molybdenum can also
be encountered in Mo-containing stainless steel repositories for nuclear waste where Gd is added due to
its high absorption cross section for thermal neutrons. The few experimental data on the Gd-Mo system
consist of the temperature of the Gd-rich eutectic, the temperature and composition of the monotectic and
the solubility of Gd in Mo [1966Chu]. Based on these data an optimised thermodynamic dataset of the
Gd-Mo system has been reported in [2001Zin].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Gd – Mo
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Gd – Mo 3
20 1.0
T∆Sm
15
0.8
Energies / (kJ/mol)
10 ∆Hm
0.6
Activities
a Mo a Gd
5
0.4
0
∆Gm 0.2
−5
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Gd x Mo Mo Gd x Mo Mo
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3200 K.
T =3200 K.
References
[1966Chu] Y.-C. Chuang, C.-W. Li, H.-L. Chuang, L.-M. Kao: Acta Metall. Sinica 9 (1966) 110–112.
[2001Zin] M. Zinkevich, N. Mattern, H.J. Seifert: J. Phase Equilibria 22 (2001) 43–50.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Gd – Zr 1
Gd – Zr (Gadolinium – Zirconium)
2200
liquid
2000
1800
bcc″
bcc′
1600
T / K
1400
hcp′
1200
1000
hcp″
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Gd x Zr Zr
The interest in the Gd-Zr system is related to ternary and higher systems, e.g.. with iron, where intermetallic
compounds with interesting magnetic properties are found. The presence of Zr enables also the formation
of metallic glasses. The phase diagram of the Gd-Zr systems is of eutectic type with no intermetallic
phases and limited mutual solubility in the terminal phases. The phase diagram has been investigated by
Copeland and co-workers [1961Cop, 1964Cop]. No investigations of the thermodynamic mixing proper-
ties are known. Based on these limited data, a thermodynamic dataset for Gd-Zr has been optimised by
[2001Zin].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Gd – Zr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Gd – Zr 3
12 1.0
T∆Sm
8 0.8
Energies / (kJ/mol)
4 ∆Hm 0.6
Activities
a Zr a Gd
0 0.4
−4 0.2
∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Gd x Zr Zr Gd x Zr Zr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2200 K.
T =2200 K.
References
[1961Cop] M. Copeland, G. Kato, in: “Rare Earth Research”, J.F. Nachman, C.E. Lundin (eds.),
Plenum Press, New York, 1961, p 133.
[1964Cop] M. Copeland, H. Kato, in: “Physics and Material Problems of Reactor Control Rods”,
IAEA, Vienna, 1964, 295–317.
[2001Zin] M. Zinkevich, N. Mattern, H.J. Seifert: J. Phase Equilibria 22 (2001) 43–50.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Hf – Mo 1
Hf – Mo (Hafnium – Molybdenum)
3000
liquid
2800
2600
2400
C36
2200
bcc
2000
T / K
bcc
1800 C15
1600
1400
hcp
1200
1000
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Hf x Mo Mo
Hf, Mo and W are useful elements for developing refractory intermetallic alloys of high modulus and creep
resistance at high temperatures. The experimental phase diagram of the Hf-Mo system is largely based
on the early work of [1961Tay] and [1969Rud]. There was good agreement on the Mo-rich side, though
discrepancy existed about phase equilibria on the Hf-rich part. [1969Rud] found a shallow minimum with
congruent melting of the bcc solid solution as well as a peritectic reaction (liq + C36
bcc) instead of
the eutectic reaction proposed by [1961Tay]. [1977Gar] proposed a less detailed phase diagram, obtained
by gravimetric and pyrometric methods, in reasonable agreement with [1961Tay]. [1980Bre] presented a
critical review of this system. The thermodynamic evaluation of the Hf-Mo system was made by [2002Sha],
guided by the work of [1980Bre]. The bcc, hcp and liquid phases were described by a substitutional solution
model using the Redlich-Kister equation, and the Laves phases C15 and C36 were described by a two-
sublattice model. There is good overall agreement between the calculated phase diagram and experimental
phase boundaries, particularly on the phase fields of the two Laves phases.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Hf – Mo
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hf – Mo 3
1.0
20 T∆Sm
0.8
10
Energies / (kJ/mol)
0.6 a Hf a Mo
Activities
0
∆Hm
0.4
−10
−20 0.2
∆Gm
−30 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hf x Mo Mo Hf x Mo Mo
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2900 K.
T =2900 K.
Table IVa. Integral quantities for the stable phases at 2050 K.
Phase xMo ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
bcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −6470 3447 4.838 −929 2.135 0.000
0.200 −9735 4259 6.826 −1205 2.666 0.000
0.300 −11588 3112 7.171 −1176 2.092 0.000
0.400 −12556 696 6.465 −1085 0.869 0.000
0.448 −12787 −702 5.895 −1066 0.178 0.000
C15 0.641 −13451 −11144 1.125 −2325 −4.302 2.374
0.662 −13315 −12317 0.487 −2413 −4.831 2.248
bcc 0.800 −9926 −7354 1.255 −1407 −2.901 0.000
0.900 −6621 −5265 0.662 −1081 −2.041 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Hf – Mo
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hf – Mo 5
15 1.0
T∆Sm
10
0.8
Energies / (kJ/mol)
5
0.6 a Hf a Mo
Activities
∆Hm
0
0.4
−5
0.2
−10
∆Gm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hf x Mo Mo Hf x Mo Mo
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =2050 K.
T =2050 K.
Table V. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xMo ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
C15 0.667 −11058 −10700 1.200 0.000
References
[1961Tay] A. Taylor, N.J. Doyle, B.J. Kagle: J. Less-Common Met. 3 (1961) 265–280.
[1969Rud] E. Rudy: Compendium of Phase Diagram Data, AFML, Wright-Patterson AFB, Ohio, Rep.
No. AFML-TR-65-2, Part 5, 1969.
[1977Gar] S.P. Garg, R.J. Ackermann: Metall. Trans. A 8A (1977) 239–244.
[1980Bre] L. Brewer, R.H. Lamoreaux in: “Molybdenum: Physico-Chemical Properties of its Com-
pounds and Alloys”, L. Brewer (ed.), Atomic Energy Rev. Spec. Issue 7, IAEA, Vienna,
1980.
[2002Sha] G. Shao: Intermetallics 10 (2002) 429–434.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Hf – Nb 1
Hf – Nb (Hafnium – Niobium)
2900 liquid
2700
2500
2300
2100
1900 bcc
T / K
1700
1500
1300 hcp
1100
900
700
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Hf x Nb Nb
The Hf-Nb system has been reviewed and a thermodynamic dataset has been optimised in [1996Fer]. The
phase diagram consists of three phases only, the liquid and bcc phases with complete miscibility and the hcp
phase which has only limited solubility for Nb. The selected data for the assessment determine the melting
equilibria [1964Tyl, 1969Rud] and the solid phase equilibria between bcc and hcp [1964Sie, 1964Tyl,
1971Car]. Since no experimental data for the thermodynamic mixing properties have been available various
calculations and estimates from the literature have been used to approximate the mixing enthalpy for the
liquid and solid alloys.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Hf – Nb
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hf – Nb 3
20 1.0
15
T∆Sm 0.8
Energies / (kJ/mol)
10
0.6
Activities
5
0 ∆Hm
0.4 a Nb a Hf
−5
0.2
−10
∆Gm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hf x Nb Nb Hf x Nb Nb
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
Table IVa. Integral quantities for the stable phases at 2200 K.
Phase xNb ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
bcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −3889 2057 2.703 2057 0.000 0.000
0.200 −5501 3652 4.161 3652 0.000 0.000
0.300 −6389 4785 5.079 4785 0.000 0.000
0.400 −6851 5460 5.596 5460 0.000 0.000
0.500 −7001 5678 5.763 5678 0.000 0.000
0.600 −6868 5442 5.596 5442 0.000 0.000
0.700 −6420 4754 5.079 4754 0.000 0.000
0.800 −5537 3616 4.161 3616 0.000 0.000
0.900 −3915 2031 2.703 2031 0.000 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Hf – Nb
1.0
12
T∆Sm
0.8
8
Energies / (kJ/mol)
0.6 a Nb a Hf
Activities
4 ∆Hm
0.4
0
−4 0.2
∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hf x Nb Nb Hf x Nb Nb
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =2200 K.
T =2200 K.
References
[1964Sie] R.E. Siemens, H.R. Babitzke, H. Kato: U.S. Bur. Mines Rep. Invest. 6492, Washington
DC., 1964
[1964Tyl] M.A. Tylkina, I.A. Tsyganova, E.M. Savitskii: Zh. Neorg. Khim. 9 (1964) 1650–1652;
Russ. J. Inorg. Chem. 9 (1964) 893–895 (engl. transl.)
[1969Rud] E. Rudy: Tech. Rep. AFML-TR-65-2, Part V, Wright-Patterson AFB, OH, 1969, pp. 95–96.
[1971Car] R.W. Carpenter, C.T. Liu, P.G. Mardon: Metall. Trans. 2 (1971) 125–131.
[1996Fer] A. Fernandez Guillermet: J. Alloys Comp. 234 (1996) 111-118.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hf – Ni 1
Hf – Ni (Hafnium – Nickel)
2600
liquid
2400
2200
Hf 8 Ni 21
bcc
βHfNi 3
2000
1800
βHfNi
T / K
1600
1400
fcc
1200
Hf 3 Ni 7
1000 hcp
Hf 9 Ni 11
Hf 7 Ni 10
Hf 2 Ni 7
Hf 2 Ni
αHfNi
αHfNi 3
HfNi 5
800
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Hf x Ni Ni
The Hf-Ni system attracts attention because Hf is a common addition to certain Ni-based superalloys where
it can enhance the scale adhesion and lead to substantial gain refinement, and improve the oxidation re-
sistance. A review on the Hf-Ni system has been given by [1983Nas] where the phase diagram has been
based mainly on the results of[1967Sve, 1979Bse]. The Hf-rich part has been re-investigated by [1993Yer],
the solubility of Hf in fcc-Ni has been derived from X-ray measurements of the lattice parameter [1998Haj]
and sub-solidus equilibria have been investigated by [2001Wan] at two temperatures using diffusion couples
which have been analysed by an electron microprobe. [1992Sel] studied the Ni-rich liquid phase by disso-
lution of Hf in the liquid alloy at 1743 and 1633 K, and measured the integral enthalpy of formation and the
partial enthalpy of hafnium by calorimetry. Using direct reaction calorimetry, the enthalpies of formation of
five compounds HfNi5 , Hf2 Ni7 , Hf9 Ni11 , HfNi, Hf2 Ni were measured [1992Sel]. [1996Ben] measured the
equilibrium vapour pressure of Ni over all intermediate compounds by the Knudsen-effusion technique, and
the enthalpies of formation of compounds were determined by means of the second and third law methods.
[1995Guo, 1998Guo] determined the standard enthalpies of formation of Hf2 Ni7 , HfNi11 , HfNi3 , HfNi by
high-temperature direct synthesis calorimetry. The present assessment of [2001Wan] is based mainly on the
selected phase equilibrium data from [1993Yer] for the Hf-rich part and from [1967Sve] and [1979Bse] for
other regions. The terminal solid solutions bcc, hcp, fcc and the liquid phase were described by substitu-
tional solution models using the Redlich-Kister equation. The Hf2 Ni has a finite range of homogeneity and
a two-sublattice model is used to described this phase with the C16 structure. The eight stable intermediate
compounds HfNi5 , Hf2 Ni7 , αHfNi3 and βHfNi3 , Hf8 Ni21 , Hf3 Ni7 , Hf7 Ni10 , Hf9 Ni11 , αHfNi and βHfNi
show very restricted homogeneity range and are considered as stoichiometric in this assessment. There
is good agreement between the calculated phase diagram and experimental phase boundaries, although the
range of the bcc phase is different from that suggested by [1983Nas]. The proposed solubility by [1983Nas]
cause a very steep slope which is thermodynamically improbable [1991Oka]. The calculated quantities are
consistent with most of the experimental data.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Hf – Ni
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hf – Ni 3
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Hf – Ni
10 1.0
T∆Sm
0
0.8
Energies / (kJ/mol)
−10
0.6 a Hf a Ni
Activities
−20
−30
0.4
−40
0.2
−50 ∆Gm
∆Hm
−60 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hf x Ni Ni Hf x Ni Ni
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2600 K.
T =2600 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xNi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Hf2 Ni 0.333 −37387 −36488 3.016 −0.025
αHfNi 0.500 −51478 −51198 0.939 −0.382
βHfNi 0.500 −49107 −48198 3.047 −0.382
Hf9 Ni11 0.550 −50577 −50232 1.160 −0.420
Hf7 Ni10 0.588 −49417 −49072 1.157 −0.450
Hf3 Ni7 0.700 −43521 −43098 1.420 −0.535
Hf8 Ni21 0.724 −41897 −41430 1.565 −0.554
αHfNi3 0.750 −44110 −44622 −1.718 −0.573
βHfNi3 0.750 −41717 −41622 0.319 −0.573
Hf2 Ni7 0.778 −41715 −42096 −1.278 −0.595
Hf1 Ni5 0.833 −36034 −37169 −3.807 −0.637
References
[1967Sve] V.N. Svechnikov, A.K. Shurin, G.P. Dmitriyeva: Izv. Akad. Nauk SSSR, Met., No. 6 (1967)
176–179; transl.: Russ. Met. 6 (1967) 95–96.
[1979Bse] L. Bsenko: J. Less-Common Met. 63 (1979) 171–179.
[1983Nas] P. Nash, A. Nash: Bull. Alloy Phase Diagrams 4 (1983) 250–253.
[1991Oka] H. Okamoto: J. Phase Equilibria 12 (1991) 393.
[1992Sel] N. Selhaoui, J.C. Gachon, J. Hertz: Metall. Trans. B 23B (1992) 815–819.
[1993Yer] V.N. Yeremenko, E.L. Semenova, L.A. Tretyachenko, V.M. Petyukh: J. Alloys Comp. 191
(1993) 117–119.
[1995Guo] Q. Guo, O.J. Kleppa: J. Phys. Chem. 99 (1995) 2854–2856.
[1996Ben] L. Bencze, K. Hilpert: Metall. Mater. Trans. A 27A (1996) 3576–3590.
[1998Guo] Q. Guo, O.J. Kleppa: J. Alloys Comp. 269 (1998) 181–186.
[1998Haj] M. Hajjaji: J. Alloys Comp. 274 (1998) 185–188.
[2001Wan] T. Wang, Z. Jin, J.-C. Zhao: Z. Metallkd. 92 (2001) 441–446.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hf – W 1
Hf – W (Hafnium – Tungsten)
4000
liquid
3500
3000
bcc
T / K
2500
2000 bcc
C15
1500 hcp
1000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Hf xW W
Hafnium and carbon are typically added in small amounts to tungsten alloys in order to improve their high-
temperature creep strength. The literature on the Hf-W system has been reviewed in [1981Spe, 1991Nag]
and thermodynamic optimised datasets have been reported by [1986Lee, 2002Sha]. The phase diagram
is based mostly on the results of Rudy and co-workers [1960Bra, 1969Rud]. The eutectic reaction and
part of the liquidus curve have been investigated by Ackermann and Rauh [1972Ack] using samples of
high purity. No experimental investigations of thermodynamic mixing properties have been reported. The
assessed dataset of Shao [2002Sha] is preferred over that of Lee and Lee [1986Lee] because it is based on
the SGTE recommended element data. However, the calculated invariant points differ to some extent from
the values which have been recommended in previous reviews [1981Spe, 1991Nag].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Hf – W
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hf – W 3
20 1.0
15 T∆Sm
10 0.8
Energies / (kJ/mol)
5
0.6 a Hf aW
Activities
0
∆Hm
−5
0.4
−10
−15 0.2
−20 ∆Gm
−25 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hf xW W Hf xW W
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3700 K.
T =3700 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xW ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
C15 0.667 −13677 −14109 1.450 0.000
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Hg – Sn 1
Hg – Sn (Mercury – Tin)
550
500 liquid
450
HgSn 38
400
HgSn 12
T / K
350
bct
HgSn 7
300
250 A4
HgSn 4
200
A10
150
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Hg x Sn Sn
Mercury-tin alloys are of considerable interest since more than hundred years because traditional den-
tal amalgams are based on the Ag-Hg-Sn system. More recently, tin amalgams have been developed for
application in compact fluorescent lamp amalgams. According to the importance of Hg-Sn alloys many
experimental investigations of the phase equilibria and their thermodynamic properties are available. The
literature has been reviewed by [1993Zab, 2003Yen] and a thermodynamic dataset for Hg-Sn has been op-
timised in [2003Yen] which describes the phase diagram as well as the mixing properties and the vapour
pressure. In the optimisation the liquidus has been optimised to fit the data of about 20 selected investi-
gations from the literature which have been obtained by several techniques such as thermal and chemical
analysis and electrochemical methods. The enthalpy of mixing has been reported in several investigations
and for different temperatures. These data are mostly in agreement for Hg-rich liquids but they differ in
the Sn-rich part. Within these limitations the calculations provide a good description of the experimental
results. The activities of Hg and Sn have been determined in many investigations at different temperatures
for the homogeneous melt as well as across 2-phase regions and again the calculations provide a good
representation of the data within the range of deviation between different authors.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Hg – Sn
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hg – Sn 3
4 1.0
3
T∆Sm 0.8
Energies / (kJ/mol)
0.6
Activities
1
∆Hm
0 a Sn a Hg
0.4
−1
∆Gm 0.2
−2
−3 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hg x Sn Sn Hg x Sn Sn
Fig. 2. Integral quantities of the liquid phase at T =523 K. Fig. 3. Activities in the liquid phase at T =523 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Hg – Sn
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSn ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Hg1 Sn4 0.800 459 −3109 −11.966 0.183
Hg1 Sn7 0.875 −237 442 2.278 0.114
Hg1 Sn38 0.974 530 1767 4.151 0.023
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hg – Te 1
Hg – Te (Mercury – Tellurium)
1000
liquid
900
800
700
600
T / K
500
HgTe
400
A8
300
200
A10
100
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Hg x Te Te
The Hg-Te system is of interest because of the semimetallic compound HgTe which forms continuous solid
solutions with the semiconducting compound CdTe. The resulting Cd-Hg tellurides are infrared sensitive
semiconductors with wavelengths which can be tailored by means of the Cd-Hg composition ratio. Reviews
and thermodynamic datasets for the Hg-Te system have been prepared by [1995Sha, 1995Yan] and the
assessment of [1995Yan] is selected here because it is based on the SGTE element data. The data for
the phase equilibria which have been used in the optimisation are based mainly on [1965Bre, 1967Str,
1971Dzi, 1980Har]. Partial pressure data for Hg [1963Gol, 1965Bre, 1981Su, 1989Sha] and Te [1965Bre]
in the equilibrium of the liquid with the HgTe compound have been included in the assessment. Except
for these partial pressure data no other thermodynamic data have been available for the liquid. The partial
pressures and in addition results from EMF experiments [1964Ter] have been used to determine the Gibbs
energy of formation of the HgTe compound. The terminal phases as well as the the HgTe compound have
been modelled as stoichiometric since no solubility data have been available. The liquid has been described
with an associate model using the species Hg, Te and HgTe.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Hg – Te
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hg – Te 3
3 1.0
0
T∆Sm 0.8
Energies / (kJ/mol)
−3
0.6 a Hg a Te
Activities
−6
0.4
−9 ∆Gm
0.2
−12
∆Hm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hg x Te Te Hg x Te Te
Fig. 2. Integral quantities of the liquid phase at T =950 K. Fig. 3. Activities in the liquid phase at T =950 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xTe ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Hg1 Te1 0.500 −18594 −21769 −10.648 0.925
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Hg – Te
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hg – Zn 1
Hg – Zn (Mercury – Zinc)
750
700 liquid
650
600
550
500
T / K
450
400
hex
350
300
Hg 3 Zn
HgZn 2
HgZn 3
250
A10
200
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Hg x Zn Zn
The Hg-Zn system is of interest for the semiconductor industry because of the infrared sensitive tellurides
which form a continuous solid solution between HgTe and ZnTe. Reviews on the literature of the Hg-
Zn system have been given in [1995Zab, 1998Han] and a thermodynamic dataset has been optimised by
[1998Han] which is based on the SGTE recommended element data. The liquidus has been determined
throughout the whole composition range already long ago [1903Pus]. More investigations of the liquidus in
the Hg-rich region have been reported by [1910Coh] and [1946Pes] who investigated especially the eutectic
close to pure mercury. Many other contributions to the liquidus have been reported in the literature and a
compilation of these data can be found in the review of [1995Zab]. A wide range of scattered data has been
reported in the literature for the solubility of mercury in solid zinc probably due to problems in attaining
equilibrium. The most reliable data seem to be given by [1967Tan] since the samples have been equilibrated
for up to one year. The solubility of Zn in solid Hg is small and not precisely known. Three intermetallic
phases have been found which are all described as stoichiometric compounds in the assessment [1998Han].
Two of them , HgZn2 and HgZn3 , seem to have a wider solubility range. From calorimetric investigations
of liquid alloys enthalpies of mixing have been reported [1960Kle, 1960Wit]. The assessment takes also
into account activity data for Hg in liquid alloys reported in [1912Hil, 1933Ped, 1971Koz].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Hg – Zn
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Hg – Zn 3
4 1.0
3 T∆Sm
0.8
2
Energies / (kJ/mol)
1 0.6
Activities
0 ∆Hm
0.4 a Zn a Hg
−1
−2
0.2
∆Gm
−3
−4 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Hg x Zn Zn Hg x Zn Zn
Fig. 2. Integral quantities of the liquid phase at T =700 K. Fig. 3. Activities in the liquid phase at T =700 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZn ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Hg3 Zn1 0.250 −111 −1255 −3.835 0.003
Hg1 Zn2 0.667 −149 −1455 −4.380 0.007
Hg1 Zn3 0.750 −158 −1354 −4.013 0.008
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Hg – Zn
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ho – Mg 1
Ho – Mg (Holmium – Magnesium)
1800
liquid
1600
1400
1200 hcp
T / K
bcc
1000
B2
800
hcp
Mg 24 Ho 5
C14
600
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ho x Mg Mg
The rare earth elements have attracted some attention as additives to light metal alloys in the aerospace
and automotive industry due to the improvement of mechanical properties of Al- and Mg-alloys at high
temperatures. Cacciamani et al. [2003Cac] prepared a thermodynamic optimisation of the complete Ho-
Mg system, which is primarily based on an experimental investigation of the phase equilibria at elevated
temperatures throughout the whole composition range [1993Sac]. The solid solubility of Ho in magnesium
has been measured by [1978Rok]. Since no thermodynamic data have been available for the Ho-Mg system
the assessors estimated the values based on other systems of Mg with rare-earth metals which have been
evaluated in the same publication.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ho – Mg
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ho – Mg 3
10 1.0
T∆Sm
5 0.8
Energies / (kJ/mol)
0 0.6 a Ho a Mg
Activities
∆Hm
−5 0.4
−10 0.2
∆Gm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ho x Mg Mg Ho x Mg Mg
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xMg ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
B2 0.500 −11784 −13537 −5.882 0.000
C14 0.667 −11803 −13667 −6.250 0.001
Mg24 Ho5 0.828 −8516 −10342 −6.124 0.000
References
[1978Roc] L.L. Rokhlin in: “Probl. Metalloved. Tsvetn. Splavov”, N.M. Zhavoronkov (Ed.), Izd.
Nauka, Moscow, 1978, pp. 59–70.
[1993Sac] A. Saccone, S. Delfino, D. Macció, R. Ferro: J. Phase Equilibria 14 (1993) 280–287.
[2003Cac] G. Cacciamani, S. de Negri, A. Saccone, R. Ferro: Intermetallics 11 (2003) 1135–1151.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: In – La 1
In – La (Indium – Lanthanum)
1500 liquid
1300
bcc
1100
In 57 La 43
T / K
900
700 fcc
In 5 La 3
In 3 La
In 2 La
InLa 2
InLa 3
InLa
500
dhcp
A6
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
In x La La
Most of the interest in the In-La system has probably been attracted by the superconducting compound
InLa3 which has one of the highest transition temperatures among the superconducting intermetallics of
lanthanum. Variations in the reported transition temperatures between 8 and 10 K have been attributed to
impurities and prompted for investigations on the solubility range and the phase diagram. The literature
on the In-La system has been reviewed by [1992Pal] and a thermodynamic dataset has been optimised in
[2002Wei] which is presented here. The phase diagram for the In-La system has been essentially worked
out by [1974McM] and in addition the liquidus of In-rich melts with up to 10 at.% La has been investigated
by [1971Deg]. Seven intermetallic compounds have been established and only for In 5 La3 a small range
of solid solubility has been indicated but not quantified. Therefore, the assessment [2002Wei] describes
all of them as stoichiometric. Enthalpies of formation have been measured by [1977Bor] across the whole
composition range. For In3 La several other measurements of the enthalpy of formation have been reported
and also EMF measurements of the Gibbs energy of formation [1971Deg].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: In – La
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: In – La 3
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: In – La
5 1.0
0
−5 T∆Sm 0.8
Energies / (kJ/mol)
−10
−15 0.6 a In a La
Activities
−20
−25 0.4
−30 ∆Gm
−35 0.2
−40 ∆Hm
−45 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
In x La La In x La La
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1500 K.
T =1500 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xLa ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
In3 La1 0.250 −52657 −57092 −14.876 0.000
In2 La1 0.333 −53128 −56759 −12.181 0.000
In5 La3 0.375 −53323 −56714 −11.374 0.000
In57 La43 0.430 −53434 −57105 −12.314 −0.002
In1 La1 0.500 −53577 −57607 −13.518 0.000
In1 La2 0.667 −35950 −37692 −5.843 0.000
In1 La3 0.750 −27021 −28087 −3.574 0.000
References
[1974McM] O.D. McMasters, K.A. Gschneidner, Jr.: J. Less-Common Met. 38 (1974) 137–148.
[1971Deg] V.A. Degtyar, A.P. Bayanov, L.A. Vnuchkova, V.V. Serebrennikov: Izv. Akad. Nauk SSSR,
Met. 4 (1971) 149–153.
[1977Bor] A. Borsese, A. Calabretta, S. Delfino, R. Ferro: J. Less-Common Met. 51 (1977) 45–49.
[1992Pal] A. Palenzona, S. Cirafici in: “Phase Diagrams of Indium Alloys and Their Engineering
Applications”, C.E.T. White, H. Okamoto (eds.), ASM Intl., Materials Park, OH, 1992, pp.
145–151.
[2002Wei] Y. Wei, X. Su, F. Yin, Z. Li, X. Wu, C. Chen: J. Alloys Comp. 333 (2002) 118–121.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: In – Pd 1
In – Pd (Indium – Palladium)
1900
liquid
1700
βInPd 3
1500
βInPd 2
fcc
1300
InPd
T / K
1100
900
700
In 7 Pd 3
In 3 Pd 2
In 3 Pd 5
αInPd 2
αInPd 3
500
A6
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
In x Pd Pd
Palladium alloys with small amounts of indium are used for certain dental applications where In lowers the
melting point of the alloys and causes the formation of an oxide layer which promotes the bonding between
the alloy and ceramic materials. Furthermore, the In-Pd is of interest for the manufacturing of certain
semiconductor devices when Pd-containing contacts are used on In-containing semiconductors, such as
InSb or InP. The In-Pd system has been reviewed in [1992Oka] but since then new experimental work
required a revision in the In-rich part. An updated review including an optimised thermodynamic dataset
has been given by [2002Jia] which is presented here. The phase diagram has been determined by [1959Kni]
and it has been modified later in the Pd-rich part [1988Sch] and recently in the In-rich part [2002Fla]. The
enthalpy of mixing has been investigated for the melt in the range 0-65 at.% Pd at several temperatures
and it has been found to be independent of temperature [1995ElA]. Enthalpies of formation for the solid
phases have been determined in several investigations across the whole composition range and they are well
represented by the calculation [2002Jia] within the deviations among the different datasets. Activities of In
across the whole composition range have been reported from 873 K [1975Bir] up to 1273 K [1978Sch]. The
heat capacities of the intermetallic compounds have been measured up to about 1000 K by [1975, 2001Per].
The dataset should not be used at too high temperatures because an artificial inverse miscibility gap opens
in the liquid above 3100 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: In – Pd
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: In – Pd 3
10 1.0
0
0.8
Energies / (kJ/mol)
−10
0.6 a In a Pd
Activities
−20 T∆Sm
−30
0.4
∆Gm
−40
0.2
−50
∆Hm
−60 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
In x Pd Pd In x Pd Pd
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1900 K.
T =1900 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: In – Pd
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xPd ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
In7 Pd3 0.290 −38518 −41122 −8.733 −1.067
In3 Pd2 0.400 −52041 −56456 −14.811 −2.415
In3 Pd5 0.625 −56502 −60537 −13.534 −1.768
βInPd2 0.660 −54590 −58730 −13.885 0.000
αInPd2 0.667 −55055 −58941 −13.032 −1.677
βInPd3 0.740 −48986 −52801 −12.796 0.000
αInPd3 0.750 −49942 −54212 −14.320 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Ni 1
Ir – Ni (Iridium – Nickel)
3000
2800 liquid
2600
2400
T / K
2200
2000
1800
fcc
1600
1400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ir x Ni Ni
The thermodynamic description of the Ir-Ni system was established by Korb [2004Kor]. The equilibrium
phases of the Ir-Ni system are the liquid and the fcc continuous solid solution. The Ir-Ni system was
determined by [1970Rau] using X-ray diffraction (XRD) and optical microscopy. A continuous series of
solid solutions was found, and no decomposition reaction or formation of superlattice phase was detected
[1991Yan]. The same conclusion was confirmed by [1970Buc] on the basis of XRD, specific heat, magnetic
susceptibility, and Debye temperature measurements. No changes in structure occurred after annealing
alloys for several days in the temperature range from 773 to 1373 K [1970Buc]. The Curie temperatures
of the fcc alloys were determined by [1960Cra]. The data show a linear dependence of Curie temperature
on composition. The calculated phase diagram shows good agreement with published experimental data
[1991Yan].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ir – Ni
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Ni 3
20 1.0
15
T∆Sm
0.8
10
Energies / (kJ/mol)
5 0.6
Activities
∆Hm
0
0.4 a Ni a Ir
−5
−10
0.2
∆Gm
−15
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Ni Ni Ir x Ni Ni
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
Table IIIa. Integral quantities for the stable phases at 1600 K.
Phase xNi ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −4193 133 2.703 132 0.001 −0.003
0.200 −6423 236 4.162 234 0.001 −0.006
0.300 −7819 310 5.081 307 0.002 −0.009
0.400 −8602 355 5.598 351 0.002 −0.011
0.500 −8855 371 5.766 366 0.003 −0.014
0.600 −8602 357 5.599 352 0.003 −0.016
0.700 −7819 313 5.082 308 0.003 −0.017
0.800 −6422 240 4.164 235 0.003 −0.015
0.900 −4192 136 2.705 132 0.002 −0.010
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ir – Ni
10 1.0
8 T∆Sm
6 0.8
Energies / (kJ/mol)
4
2 0.6
Activities
∆Hm
0
−2 0.4 a Ni a Ir
−4
−6 0.2
−8 ∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Ni Ni Ir x Ni Ni
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1600 K.
T =1600 K.
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Pt 1
Ir – Pt (Iridium – Platinum)
3000
2800 liquid
2600
2400
2200
2000
T / K
1800
fcc
1600
1400
1200
1000
800
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ir x Pt Pt
The equilibrium phases in the Ir-Pt system are the liquid phase and the fcc phase, exhibiting a miscibility
gap. Experimental data on the Ir-Pt system are limited, the liquid and fcc phase boundaries were studied
by [1930Mül], the miscibility gap in the fcc phase was investigated by [1956Rau]. The thermodynamic
descriptions for all the stable phases in the Ir-Pt system were obtained by Korb and Jantzen [2004Kor]
using available experimental data [1930Mül, 1956Rau]. The calculated phase diagram compares well with
experimental data from the literature as collected in [1990Mas].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ir – Pt
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Pt 3
40 1.0
T∆Sm
30
0.8
Energies / (kJ/mol)
20
0.6
Activities
10
∆Hm a Ir a Pt
0
0.4
−10
0.2
−20
∆Gm
−30 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Pt Pt Ir x Pt Pt
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
Table IVa. Integral quantities for the stable phases at 1400 K.
Phase xPt ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −3247 8899 8.676 537 5.973 0.000
0.200 −4557 14443 13.571 1268 9.410 0.000
0.300 −5035 17147 15.844 2076 10.765 0.000
0.400 −4992 17529 16.086 2842 10.491 0.000
0.500 −4618 16106 14.803 3450 9.040 0.000
0.600 −4052 13394 12.461 3782 6.866 0.000
0.700 −3390 9911 9.501 3720 4.422 0.000
0.800 −2677 6173 6.321 3148 2.160 0.000
0.900 −1837 2697 3.239 1947 0.536 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ir – Pt
25 1.0
20 T∆Sm
0.8
∆Hm
Energies / (kJ/mol)
15
0.6
Activities
10 a Pt a Ir
5
0.4
0
0.2
−5
∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Pt Pt Ir x Pt Pt
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1400 K.
T =1400 K.
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Rh 1
Ir – Rh (Iridium – Rhodium)
3000
2800 liquid
2600
2400
2200
2000 fcc
T / K
1800
1600
1400
1200
1000
800
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ir x Rh Rh
The equilibrium phases in the Ir-Rh system are the liquid phase and fcc phase, the latter exhibiting a misci-
bility gap at lower temperatures. [1959Rau] concluded that Ir forms a continuous series of solid solutions
with Rh at high temperatures and empirically estimated the critical temperature of the miscibility gap from
the difference in the melting points of the elements. The miscibility gap in the fcc phase at lower tempera-
tures was evaluated on the basis of thermodynamic data [1983Tri]. The thermodynamic description of the
Ir-Rh system was obtained by Korb and Jantzen [2004Kor] using available experimental data reported in
[1991Tri]. The calculated phase diagram compares well with the diagram from the literature.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ir – Rh
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Rh 3
6 1.0
4 T∆Sm
0.8
Energies / (kJ/mol)
0.6
Activities
0
∆Hm
−2 a Rh a Ir
0.4
−4
0.2
−6 ∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Rh Rh Ir x Rh Rh
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
Table IVa. Integral quantities for the stable phases at 1800 K.
Phase xRh ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −2191 1030 1.789 2675 −0.914 0.000
0.200 −2782 1784 2.537 4707 −1.624 0.000
0.300 −3026 2279 2.948 6116 −2.131 0.000
0.400 −3154 2534 3.160 6919 −2.436 0.000
0.500 −3241 2565 3.226 7133 −2.538 0.000
0.600 −3296 2391 3.160 6776 −2.436 0.000
0.700 −3275 2030 2.948 5867 −2.131 0.000
0.800 −3067 1499 2.537 4422 −1.624 0.000
0.900 −2404 817 1.789 2461 −0.913 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ir – Rh
6 1.0
T∆Sm
4 0.8
Energies / (kJ/mol)
2 0.6
Activities
∆Hm
a Rh a Ir
0 0.4
−2 0.2
∆Gm
−4 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Rh Rh Ir x Rh Rh
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1800 K.
T =1800 K.
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Ru 1
Ir – Ru (Iridium – Ruthenium)
3000
2800 liquid
2600
2400
2200
T / K
2000
1600
1400
1200
1000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ir x Ru Ru
The Ir-Ru system exhibits the equilibrium phases liquid, Ir-rich fcc and Ru-rich hcp. The phase diagram
was experimentally studied by [1964Rau] and [1988Ere] using thermal, X-ray, and metallographic investi-
gations. Both studies are in good agreement. The fcc and hcp solvus boundaries as experimentally deter-
mined by Raub [1964Rau] and Eremenko et al. [1988Ere] are reproduced satisfactorily by the calculations.
The solubility limit of Ir in hcp-Ru is 49 at.% at 2668 K [1988Ere]. The thermodynamic description of
the Ir-Ru system was obtained by Korb [2004Kor]. The agreement between experimentally determined
[1990Oka] and calculated phase diagrams is good for the solid-liquid range but at low temperature the two
phase field between fcc and hcp appears a little wide.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ir – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Ru 3
70 1.0
60 T∆Sm
50 0.8
Energies / (kJ/mol)
40
∆Hm 0.6 a Ir a Ru
Activities
30
20
0.4
10
0 0.2
−10
∆Gm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Ru Ru Ir x Ru Ru
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
Table IVa. Integral quantities for the stable phases at 2000 K.
Phase xRu ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −6202 −1073 2.565 −796 −0.138 0.000
0.200 −9566 −1629 3.968 −1245 −0.192 0.000
0.300 −11503 −1669 4.917 −1345 −0.162 0.000
0.400 −12289 −1193 5.548 −1097 −0.048 0.000
0.418 −12317 −1054 5.632 −1016 −0.019 0.000
hcp 0.525 −12389 −896 5.746 −884 −0.006 0.000
0.600 −12201 −1090 5.556 −1010 −0.040 0.000
0.700 −11182 −1154 5.014 −1024 −0.065 0.000
0.800 −9181 −993 4.094 −860 −0.067 0.000
0.900 −5924 −609 2.658 −519 −0.045 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ir – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Ru 5
12 1.0
T∆Sm
8
0.8
Energies / (kJ/mol)
∆Hm 0.6
Activities
0
−4 a Ru a Ir
0.4
−8
∆Gm 0.2
−12
−16 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Ru Ru Ir x Ru Ru
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =2000 K.
T =2000 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ir – Zr 1
Ir – Zr (Iridium – Zirconium)
3000
liquid
2500
Ir 3 Zr
fcc
2000
T / K
βIrZr
1500 bcc
1000
Ir 3 Zr 5
Ir 2 Zr
αIrZr
IrZr 2
IrZr 3
hcp
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ir x Zr Zr
This system was assessed by Ran and Du [2006Ran], from the available experimental information on the
phase diagram and thermodynamics. Iridium alloys are new materials with higher melting temperatures
and superior oxidation resistance than Ni-based superalloys. The phase diagram was experimentally deter-
mined by Kuprina and Kuryachava [1974Kup], Eremenko et al. [1974Ere, 1978Ere1, 1978Ere2, 1980Ere].
The experimental phase diagram was assessed by Okamoto [1992Oka]. It presents four solution phases,
the liquid with a complete miscibility range, the iridium based fcc phase and the zirconium rich terminal
solution phases, bcc and hcp. There are three non-stoichiometric intermetallic compounds, Ir 3 Zr, αIrZr and
βIrZr, and four stoichiometric compounds, Ir2 Zr, Ir3 Zr5 , IrZr2 and IrZr3 . The Ir3 Zr homogeneity range is
equal to 19-30 at.% Zr at 2393 K [1980Ere]. βIrZr extends from 47 to 52 at.% Zr at 2143 K and from 49
to 50 at.% Zr below 1500 K. The crystal structures of the compounds were reported by Dwight and Beck
[1959Dwi, 1961Dwi], Raman and Schubert [1964Ram], Schubert et al. [1964Sch], Biswas and Schubert
[1967Bis], McCarthy [1971McC], Eremenko et al. [1978Ere2, 1980Ere], Matthias et al. [1961Mat], Cen-
zul and Parthe [1985Cen]. The enthalpy of formation of IrZr has been measured by Topor and Kleppa
[1989Top].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ir – Zr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ir – Zr 3
60 1.0
40
20 T∆Sm 0.8
Energies / (kJ/mol)
0
−20 0.6 a Ir a Zr
Activities
−40
−60 ∆Hm 0.4
−80
−100 0.2
∆Gm
−120
−140 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ir x Zr Zr Ir x Zr Zr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2800 K.
T =2800 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ir – Zr
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZr ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ir3 Zr 0.250 −81038 −80773 0.892 0.000
Ir2 Zr1 0.333 −87313 −85827 4.982 0.000
αIrZr 0.500 −92448 −89893 8.568 0.000
βIrZr 0.500 −90393 −87162 10.837 −0.231
Ir3 Zr5 0.625 −93849 −92893 3.207 0.000
Ir1 Zr2 0.667 −88518 −88473 0.150 0.000
Ir1 Zr3 0.750 −69264 −69236 0.095 0.000
References
[1959Dwi] A.E. Dwight, P.A. Beck: Trans. Metall. Soc. AIME 215 (1959) 976–979.
[1961Dwi] A.E. Dwight: Trans. ASM 53 (1961) 479–500.
[1961Mat] B.T. Matthias, V.B. Compton, E. Corenzwit: J. Phys. Chem. Solids 19 (1961) 130–133.
[1964Ram] A. Raman, K. Schubert: Z. Metallkd. 55 (1964) 704–710.
[1964Sch] K. Schubert, A. Raman, W. Rosseteutscher: Naturwiss. 51 (1964) 506–507.
[1967Bis] T.K. Biswas, K. Schubert: Z. Metallkd. 58 (1967) 558–559.
[1971McC] S.L. McCarthy: J. Low Temp. Phys. 4 (1971) 489–501.
[1974Kup] V.V. Kuprina, G.I. Kuryachaya: Vestn. MGU, Ser. 2, Khim. 15 (1974) 371–373 ;transl.:
Moscow Univ. Chem. Bull. 29 (1974) 88.
[1974Ere] V.N. Eremenko, T.D. Shtepa, E.L. Semenova in: R. Rykhal, M. L’vov (Eds.), “Tezisy Dokl.
Vses. Konf. Kristallokhim. Intermet. Soedin.”, 2nd ed., Inst. Probl. Materialoved, Kiev,
1974, 28.
[1978Ere1] V.N. Eremenko, E.L. Semenova, T.D. Shtepa: Izv. Akad. Nauk SSSR, Met. 2 (1978) 200–
203; transl.: Russ. Metall. 2 (1978) 158.
[1978Ere2] V.N. Eremenko, E.L. Semenova, T.D. Shtepa, Yu.V. Kudryavtsev: Dop. Akad. Nauk. Ukr.
RSR, Ser. A, Fiz.-Mat. Tekn., No. 10 (1978) 943–945.
[1980Ere] V.N. Eremenko, E.L. Semenova, T.D. Shtepa: Izv. Akad. Nauk SSSR, Met. 5 (1980) 237–
241; transl.: Russ. Metall. 5 (1978) 210.
[1985Cen] K. Cenzual, O.J. Parthe: Acta Cryst. C 41C (1985) 820–823.
[1989Top] L. Topor, O.J. Kleppa: J. Less-Common Met. 155 (1988) 61–73.
[1992Oka] H. Okamoto: J. Phase Equilibria 13 (1992) 653–656.
[2006Ran] H. Ran, Z. Du: J. Alloys Comp. 413 (2006) 101–105.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: La – Mg 1
La – Mg (Lanthanum – Magnesium)
1300
1200 liquid
1100
1000
bcc
900
LaMg 2
T / K
fcc
800
hcp
700
600
La 2 Mg 17
500
LaMg 12
LaMg 3
LaMg
dhcp
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
La x Mg Mg
The addition of rare-earth metals to magnesium alloys retains their strength at elevated temperatures and
improves their creep resistance over a wide range of temperature. The literature on the La-Mg system
has been reviewed in [1988Nay] and a thermodynamic dataset has been optimised by [2004Guo]. For the
assessment [2004Guo] have selected literature data on the phase diagram [1931Can, 1940Wei, 1947Vog,
1965Jos, 1986Man], activities of Mg in the melt at 1133 K [1973Afa], and enthapies of mixing in the melt
for various temperatures and composition ranges [1995Aga]. Data for the intermetallic compounds have
not been available.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: La – Mg
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: La – Mg 3
8 1.0
6
T∆Sm
4 0.8
2
Energies / (kJ/mol)
0 a La a Mg
0.6
Activities
−2
−4
0.4
−6 ∆Hm
−8
−10 0.2
∆Gm
−12
−14 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
La x Mg Mg La x Mg Mg
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1200 K.
T =1200 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xMg ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
La1 Mg1 0.500 −15331 −16701 −4.594 0.000
LaMg3 0.750 −17520 −19698 −7.303 0.000
La1 Mg2 0.667 −9946 −8938 3.379 0.000
La2 Mg17 0.895 −8046 −8663 −2.070 0.000
LaMg12 0.923 −6009 −6398 −1.304 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: La – Mg
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Li – N 1
Li – N (Lithium – Nitrogen)
1300
1100 liquid
1000
900
T / K
800 Li 3N + gas
700
600
Li 3 N
500
400
bcc
300
0.0 0.1 0.2 0.3 0.4
Li xN
Lithium nitride, LiN, can store more than 11% of its own weight in hydrogen which is considerably more
than any other hydrogen storage material so far. Although there are still problems to solve for releasing the
hydrogen from the storage the Li-N system will continue to be of high interest. The Li-N system has been
reviewed by [1992San] and a thermodynamic optimisation has been reported in [2003Wan]. However the
dataset of [2003Wan] leads to the formation of the liquid phase in the region where only LiN 3 +gas should
be stable and therefore, it has been re-assessed for the SGTE collection of binary systems [2005Fra]. The
system Li-N includes 5 stable phases: gas, liquid, bcc-Li, Li3 N, and LiN3 . For the latter compound, lithium
azide, no quantitative thermodynamic information seem to be available, except that under atmospheric
pressure it does not melt but decomposes between 388 and 571 K. Therefore, it has not been included in
the assessment. The solubility of nitrogen in solid lithium seems to be very small although no data have
been reported. Therefore, bcc-Li has been treated as a pure substance. Similarly, Li 3 N is described as a
stoichiometric compound. The data for Li3 N are based on the SGTE substance database but with adjusted
enthalpy and entropy. The solubility of nitrogen in molten Li has been measured in several investigations. A
survey of these results is given in [2001Bor]. For the present optimisation a set of 3 investigations with the
best agreement among them has been selected [1959Bol, 1975Ada, 1975Yon]. Since at lower temperatures
the data of [1959Bol] deviate a bit too much from the other two sets the results of [1959Bol] have been used
only for optimising the liquidus line above 800 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Li – N
−5 gas
−10
−15 Li 3 N
−20
log 10 a N2
−25 liquid
−30
−35
−40
Fig. 2. Calculated temperature-
−45 bcc
activity phase diagram. Reference
−50 state: 12 N2 (gas, 0.1 MPa).
0.5 1.0 1.5 2.0 2.5 3.0
1000 K / T
Table III. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xN ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Li3 N1 0.250 −32402 −41391 −30.149 −2.903
References
[1959Bol] K.A. Bolshakov, P.I Fedorov, L.A. Stepina: Izv. V. U. Z., Tsvet. Metall. 4 (1959) 52–53.
[1975Ada] P.F. Adams, M.G. Down, P. Hubberstey, R.J. Pulham: J. Less-Common Met. 42 (1975)
325–334.
[1975Yon] R.M. Yonco, E. Veleckis, V.A. Maroni: J. Nucl. Mater. 57 (1975) 317–324.
[1992San] J. Sangster, A.D. Pelton: J. Phase Equilibria 13 (1992) 291–296.
[2001Bor] H.U. Borgstedt, C. Guminsky: J. Phys. Chem. Ref. Data 30 (2001) 835–1158.
[2003Wan] W.J. Wang, W.X. Yuan, Y.T. Song, X.L. Chen: J. Alloys Comp. 352 (2003) 103–105.
[2005Fra] P. Franke, unpublished optimisation, 2005.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Li – Na 1
Li – Na (Lithium – Sodium)
600
liquid
550
500
T / K
450
400
350
bcc′ bcc″
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Li x Na Na
The literature on the Li-Na system has been reviewed by Bale [1989Bal] and a thermodynamic dataset has
been optimised in [2003Zha] based on the element data recommended by SGTE. The system is charac-
terised by dominant miscibility gaps in the liquid as well as in the solid (bcc) phase. For the optimisation
Zhang et al. [2003Zha] have selected data for the phase equilibria from several experimental reports which
are in general agreement with each other [1956Sal, 1957How, 1968Kan, 1971Sch, 1975Dow1, 1975Dow2,
1975Fei, 1975Wu, 1979End]. In most of these investigations the liquid-liquid equilibria have been deter-
mined. No data on the thermodynamics of mixing have been available.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Li – Na
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Li – Na 3
4 1.0
T∆Sm
3 0.8
Energies / (kJ/mol)
∆Hm
2 0.6
Activities
a Na a Li
1 0.4
0 0.2
∆Gm
−1 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Li x Na Na Li x Na Na
Fig. 2. Integral quantities of the liquid phase at T =600 K. Fig. 3. Activities in the liquid phase at T =600 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Li – Sn 1
Li – Sn (Lithium – Tin)
1100
liquid
1000
Li 13 Sn 5
Li 5 Sn 2
900
800
T / K
700
600
500
Li 7 Sn 2
Li 7 Sn 3
Li 2 Sn 5
Li 22 Sn 5
400
LiSn
bcc bct
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Li x Sn Sn
Tin based materials are promising candidates for replacing conventional graphite anodes in Li-ion batteries.
Compared with the intercalation compound LiC6 which is formed with graphite the intermetallic lithium tin
compounds can reach much higher storage capacities of Li per mass, especially in Li 22 Sn5 . The literature
on the Li-Sn system has been reviewed in [1998San] and a thermodynamic dataset has been optimised by
[2005Yin]. The assessment is based on literature data on the phase diagram and on thermodynamic mea-
surements. The selected phase equilibria have been reported by [1910Mas, 1932Bar, 1934Gru, 1964Fos,
1979Bai, 1982Dad]. Enthalpies of formation in the liquid and in two-phase regions with intermetallic com-
pounds have been investigated at several temperatures in [1986Mos]. The activities of Li in the liquid have
been measured at 1473 K by [1972Fis] and activities of Sn at 688 K have been reported in [1981Wen].
For their assessment [2005Yin] have selected enthalpies and entropies of formation for the intermetallic
compounds at 688 K reported by [1981Wen] and enthalpies of formation at 298 K which have been given
in [1938Kub].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Li – Sn
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Li – Sn 3
10 1.0
5
T∆Sm 0.8
0
Energies / (kJ/mol)
−5
0.6 a Li a Sn
Activities
−10
−15
0.4
−20
−25 0.2
∆Hm
−30
∆Gm
−35 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Li x Sn Sn Li x Sn Sn
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1100 K.
T =1100 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Li – Sn
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSn ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Li22 Sn5 0.185 −39617 −43314 −12.399 0.000
Li7 Sn2 0.222 −39321 −41722 −8.051 0.000
Li13 Sn5 0.278 −38604 −39897 −4.335 0.000
Li5 Sn2 0.286 −38497 −39652 −3.875 0.000
Li7 Sn3 0.300 −38272 −39382 −3.725 0.000
Li1 Sn1 0.500 −34974 −35905 −3.123 0.000
Li2 Sn5 0.714 −21424 −21834 −1.375 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mg – Tm 1
Mg – Tm (Magnesium – Thulium)
2000
liquid
1800
1600
1400
T / K
1200
bcc
1000 hcp
MgTm
800
Mg 24 Tm 5
Mg 2 Tm
hcp
600
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mg x Tm Tm
The rare earth elements have attracted some attention as additives to light metal alloys in the aerospace and
automotive industry due to the improvement of mechanical properties of Al- and Mg-alloys at high temper-
atures. A review on the literature of the Mg-Tm system has been given by [1988Nay]. Du et al. [2004Du]
prepared a thermodynamic optimisation of the Mg-Tm system, which is mostly based on an experimental
investigation of the phase equilibria at elevated temperatures throughout the composition range from 0 to
70 at.% Tm [1995Sac]. The Mg-rich part of the phase diagram and the solubility of thulium in crystalline
magnesium has been measured by [1977Rok]. No experimental reports have been available for the solu-
bility of Mg in solid Tm and for the thermodynamic mixing properties of the melt. The thermodynamic
properties of the intermetallic compounds are also not investigated experimentally except for the standard
enthalpy of formation of MgTm which has been determined by [1967Ogr].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Mg – Tm
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mg – Tm 3
15 1.0
10 T∆Sm 0.8
Energies / (kJ/mol)
5
0.6 a Mg a Tm
Activities
0 ∆Hm
0.4
−5
0.2
−10
∆Gm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Mg x Tm Tm Mg x Tm Tm
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1900 K.
T =1900 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xTm ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Mg24 Tm5 0.172 −4529 −5013 −1.623 0.000
Mg2 Tm1 0.333 −8197 −9442 −4.176 0.000
MgTm 0.500 −8744 −9774 −3.454 0.343
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Mg – Tm
References
[1967Ogr] J.R. Ogren, N.J. Magnani, J.F. Smith: Trans. AIME 239 (1967) 766–771.
[1977Rok] L.L. Rokhlin: Izv. Akad. Nauk SSSR, Met. (1977) 181–183; transl.: Russ. Metall. (1977)
152–154.
[1988Nay] A.A. Nayeb-Hashemi, J.B. Clark in: “Phase Diagrams of Binary Magnesium Alloys”, A.A.
Nayeb-Hashemi, J.B. Clark (eds.), ASM Intl., Metals Park, OH, 1988, pp. 333–336.
[1995Sac] A. Saccone, D. Macció, S. Delfino, R. Ferro: J. Alloys Comp. 220 (1995) 161–166.
[2004Du] Z. Du, H. Liu, G. Ling: J. Alloys Comp. 373 (2004) 151–155.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mg – Yb 1
Mg – Yb (Magnesium – Ytterbium)
1200
liquid
1100
1000
900 bcc
800
T / K
C14
700
600
400
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mg x Yb Yb
This system was assessed by Guo and Du [2006Guo], from the available experimental information on the
phase diagram and thermodynamics. The interest of magnesium alloys is the potential weight saving in
comparison with aluminium, and rare earth elements improve casting characteristics and enhance high tem-
perature properties in these alloys. The phase diagram has been established by McMasters and Gschneid-
ner [1965McM] using differential thermal analysis, metallographic methods and X-ray diffractography. It
presents four solution phases, the liquid with a complete miscibility range, the magnesium rich hexagonal
(hcp), and ytterbium rich bcc and fcc terminal solid solutions. There is only one non-stoichiometric in-
termetallic compound, Mg2 Yb, with a C14 structure, isotypic with MgZn2 , having a homogeneity range
of 63.8-70.7 at.% Mg. The enthalpy of mixing of liquid alloys has been determined by Agarwal et al.
[1995Aga] at 1013 K, 1016 K and 1018 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Mg – Yb
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mg – Yb 3
12 1.0
8 T∆Sm
0.8
Energies / (kJ/mol)
0.6 a Mg a Yb
Activities
0
∆Hm
−4
0.4
−8
0.2
−12 ∆Gm
−16 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Mg x Yb Yb Mg x Yb Yb
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1100 K.
T =1100 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xYb ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
C14 0.333 −12533 −12533 0.000 0.000
References
[1965McM] O.D. McMasters, K.A. Gschneidner Jr.: J. Less-Common Met. 8 (1965) 289–298.
[1995Aga] R. Agarwal, H. Feufel, F. Sommer: J. Alloys Comp. 217 (1995) 59–64.
[2006Guo] C. Guo, Z. Du: J. Alloys Comp. 422 (2006) 102–108.
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Mn – Sc 1
Mn – Sc (Manganese – Scandium)
2000
liquid
1800 bcc
1600
bcc
1400
fcc
T / K
1200
cub
1000
Mn 23 Sc 6
800 hcp
Mn 2 Sc
cbcc
MnSc4
600
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mn x Sc Sc
Manganese and scandium can both be encountered in light metal alloys where Sc improves the mechan-
ical properties at higher temperatures and Mn is added for grain refining. The Mn-Sc system has been
investigated by DTA and SEM/EDX across the whole composition range and an optimised thermodynamic
dataset has been reported in [1998Pis]. Prior to this study the phase diagram of Mn-Sc has been largely
unknown. In addition to the Laves phase Mn2 Sc [1961Dwi] two more intermetallic compounds have been
found, Mn23 Sc6 and MnSc4 [1998Pis]. The available thermodynamic data have been limited to only 2
values. The enthalpy of mixing in the liquid has been measured by [1985Esi] at a composition of 15 at.%
Sc and 1873 K and the enthalpy of formation of Mn2 Sc has been reported by [1983Shi]. Both values are
reproduced quite well by the calculations [1998Pis]. The investigation of the phase diagram has been com-
plicated by the sluggish formation of MnSc4 and reactions of the Sc-rich alloys with the crucible in the
DTA experiments [1998Pis]. Although the solubility of Sc in solid Mn has been found to be 1 at.% Sc at
the eutectic temperature [1998Pis] the calculated value from the optimised dataset is much lower.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Mn – Sc
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mn – Sc 3
10 1.0
T∆Sm
5
0.8
Energies / (kJ/mol)
0
0.6 a Mn a Sc
Activities
−5
∆Hm 0.4
−10
0.2
−15
∆Gm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Mn x Sc Sc Mn x Sc Sc
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2000 K.
T =2000 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSc ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Mn23 Sc6 0.207 −10172 −10172 0.001 0.000
Mn2 Sc1 0.333 −15500 −15500 0.001 0.000
Mn1 Sc4 0.800 −7344 −7344 0.000 0.000
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Mo – V 1
Mo – V (Molybdenum – Vanadium)
3000
2900
liquid
2800
2700
2600
T / K
2500
2400
2300
bcc
2200
2100
2000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mo xV V
Molybdenum and vanadium are important alloying elements for steel and they are added both together in
concentrations of some percent to certain hot work tool steels. The phase diagram of the Mo-V system is
quite simple consisting of only the liquid and the solid bcc phases each with complete miscibility of the
components. The literature on the Mo-V system has been reviewed by [1989Smi, 1999Zhe] and optimised
thermodynamic datasets have been reported in [1999Zhe, 2002Bra]. Both reviews conclude that the most
reliable data on the phase diagram have been reported by Rudy [1969Rud]. It has also been concluded that
no reliable thermodynamic data of mixing have been available which are consistent with the phase diagram
data. In order to estimate the thermodynamic excess quantities in the bcc solid solution, [1999Zhe] took
account of theoretical considerations given in [1980Bre]. However, under these conditions the calculated
two-phase region is clearly more narrow than measured by [1969Rud] although the mixing properties have
been described by 4 coefficients for each phase [1999Zhe]. In view of these results [2002Bra] decided to
re-assess the system using only reliable experimental data, essentially those of [1969Rud]. In the resulting
optimisation these data are well reproduced using a strictly regular solution model for both phases with only
one coefficient for each phase. The optimisation of [2002Bra] is recommended here because it provides a
better fit to the accepted data with much less parameters. Below 1160 K a miscibility gap in the bcc phase
is predicted, however, no experimental evidence is available.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Mo – V
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mo – V 3
20 1.0
15 T∆Sm
0.8
Energies / (kJ/mol)
10
0.6
Activities
5
∆Hm
0 aV a Mo
0.4
−5
0.2
−10 ∆Gm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Mo xV V Mo xV V
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2900 K.
T =2900 K.
Table IIIa. Integral quantities for the stable phases at 2000 K.
Phase xV ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
bcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −3674 1732 2.703 1732 0.000 0.000
0.200 −5242 3079 4.161 3079 0.000 0.000
0.300 −6117 4041 5.079 4041 0.000 0.000
0.400 −6573 4619 5.596 4619 0.000 0.000
0.500 −6715 4811 5.763 4811 0.000 0.000
0.600 −6573 4619 5.596 4619 0.000 0.000
0.700 −6117 4041 5.079 4041 0.000 0.000
0.800 −5242 3079 4.161 3079 0.000 0.000
0.900 −3674 1732 2.703 1732 0.000 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Mo – V
12 1.0
T∆Sm
8 0.8
Energies / (kJ/mol)
4 0.6
Activities
∆Hm
0 0.4 aV a Mo
−4 0.2
∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Mo xV V Mo xV V
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =2000 K.
T =2000 K.
References
[1969Rud] E. Rudy: “Compendium of Phase Diagram Data”, AFML, Wright-Patterson AFB, Ohio,
Rep. No. AFML-TR-65-2, Part 5, 1969, pp. 118–120.
[1980Bre] L. Brewer, R.H. Lamoreaux in: “Molybdenum: Physico-Chemical Properties of its Com-
pounds and Alloys”, L. Brewer (ed.), Atomic Energy Rev. Spec. Issue 7, IAEA, Vienna,
1980.
[1989Smi] J.F. Smith in: “Phase Diagrams of Binary Vanadium Alloys”, J.F. Smith (ed.), ASM Intl.,
Metals Park, OH, 1989, pp. 144–147.
[1999Zhe] F. Zheng, B.B. Argent, J.F. Smith: J. Phase Equilibria 20 (1999) 370–372.
[2002Bra] J. Bratberg, K. Frisk: Calphad 26 (2002) 459–476.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mo – Zr 1
Mo – Zr (Molybdenum – Zirconium)
3000
2800 liquid
2600
2400
2200 bcc
2000
T / K
1800
bcc
1600 C15
1400
1200
1000
hcp
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mo x Zr Zr
Mo is added in certain amounts to zirconium based alloys for the nuclear power industry in order to enhance
their mechanical properties. Similarly, zirconium belongs to the group of alloying elements for Mo-based
metals in order to further increase their strength and creep resistance at high temperatures. The literature
on the Mo-Zr system has been reviewed in [1976Kub, 2002Zin, 2003Jer] and thermodynamic assessments
have been reported in [2002Zin, 2003Jer]. The phase equilibria in the Mo-Zr system have been studied in
several investigations but no measurements of thermodynamic data have been reported. The assessment of
[2003Jer] is preferred here because in the dataset of [2002Zin] the liquid and the bcc phases are modelled
with quite high excess entropies which seem to be unrealistic. This causes the slopes of the boundaries
for the single-phase bcc regions to be too steep and in the liquid an artificial inverse miscibility gap opens
above 4660 K. Although this is in some distance above the liquidus it indicates a certain weakness in the
optimisation.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Mo – Zr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Mo – Zr 3
12 1.0
T∆Sm
8
0.8
4
Energies / (kJ/mol)
0 0.6
Activities
−4 ∆Hm
0.4 a Zr a Mo
−8
−12
0.2
∆Gm
−16
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Mo x Zr Zr Mo x Zr Zr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2900 K.
T =2900 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZr ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
C15 0.333 −7231 −7245 −0.048 0.000
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: N – Si 1
N – Si (Nitrogen – Silicon)
4000
gas
3500
3000
2500
T / K
2000 liquid
1500
Si 3 N 4
1000 A4
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
N x Si Si
Silicon nitride, Si3 N4 is a lightweight, strong and tough ceramic material which is of broad technical inter-
est, e.g.. for structural and wear-resistant applications up to high temperatures. A survey of the literature
and a thermodynamic optimisation of the binary Si-N system has been given by [2003Ma]. The phase di-
agram of the Si-N system consists of a few phases only: solid Si (A4), the liquid, silicon nitride (Si 3 N4 ),
and the gas phase. In the assessment [2003Ma] the solid phases have been treated as pure Si and Si 3 N4 ,
respectively. The very small solubility of nitrogen in solid Si which is known experimentally [1959Kai,
1973Yat] has been omitted from the assessment. The liquid has been modelled as a substitutional solution
with the species Si and N and the gas phase has been modelled with the species N, N2 , N3 , SiN, Si2 N, Si,
Si2 , and Si3 which have been taken from the SGTE substance database. The description for Si 3 N4 has been
optimised based on the heat capacity values of [1976Guz] and on enthalpies of formation and entropies of
formation mainly from [1959Peh]. Data for the eutectic have been selected from [1973Yat] and data for the
decomposition of Si3 N4 into liquid and gas are from [1981Dör]. Calculated partial pressures of nitrogen in
the equilibrium of Si3 N4 with Si-rich melt are in good agreement with the experimental data of [1930Hin].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: N – Si
−5
Si 3 N 4
−10
gas
log 10 a N2
−15 liquid
−20
A4
−25 Fig. 2. Calculated temperature-
activity phase diagram. Reference
−30 state: 12 N2 (gas, 0.1 MPa).
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
1000 K / T
Table III. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Si3 N4 0.429 −91714 −105603 −46.583 −3.146
References
[1930Hin] W.B. Hincke, L.R. Brantley: J. Am. Chem. Soc. 52 (1930) 48–52.
[1959Peh] R.D. Pehlke, J.F. Elliott: Trans. Metall. Soc. AIME 215 (1959) 781–785.
[1959Kai] W. Kaiser, C.K. Thurmond: J. Appl. Phys. 30 (1959) 427–431.
[1973Yat] Y. Yatsurugi, N. Akiyama, Y. Endo: J. Electrochem. Soc. 120 (1973) 975–979.
[1976Guz] I. Ya. Guzman, A.F. Demidenko, V.I. Koshchenko, M.S. Fraifel’d, Yu.V. Egner: Izv. Aked.
Nauk SSSR, Neorg. Mater. 12 (1976) 1879–1881; transl.: Inorg. Mater. 12 (1976) 1546–
1548.
[1981Dör] P. Dörner, L.J. Gauckler, H. Krieg, H.L. Lukas, G. Petzow, J. Weiss: J. Mater. Sci. 16 (1981)
935–943.
[2003Ma] X. Ma, C. Li, F. Wang, W. Zhang: Calphad 27 (2003) 383–388.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Nb – Ta 1
Nb – Ta (Niobium – Tantalum)
3400
3300 liquid
3200
3100
T / K
3000
2900
2800
2700 bcc
2600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Nb x Ta Ta
The phase diagram of the Nb-Ta system is very simple consisting only of the liquid and the bcc phases with
complete miscibility for both components. The literature on the Nb-Ta has been reviewed in [1996Kris,
2004Xio] and a thermodynamic dataset has been optimised by [2004Xio] using the element data recom-
mended by SGTE. From the few available investigations on the phase diagram only the data of [1969Rud]
are considered to be reliable [1996Kris, 2004Xio] since they are compatible with the currently accepted
melting temperatures of the elements. No data for the thermodynamics of Nb-Ta mixtures have been re-
ported in the literature. Based on these limited information the system has been described as an ideal
solution in the liquid and as a regular solution in the bcc phase [2004Xio].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Nb – Ta
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Nb – Ta 3
20 1.0
T∆Sm
15
0.8
10
Energies / (kJ/mol)
5 0.6
Activities
∆Hm
0
0.4 a Ta a Nb
−5
−10
0.2
−15
∆Gm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Nb x Ta Ta Nb x Ta Ta
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3300 K.
T =3300 K.
Table IIIa. Integral quantities for the stable phases at 2600 K.
Phase xTa ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
bcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −6911 117 2.703 117 0.000 0.000
0.200 −10610 208 4.161 208 0.000 0.000
0.300 −12933 273 5.079 273 0.000 0.000
0.400 −14238 312 5.596 312 0.000 0.000
0.500 −14660 325 5.763 325 0.000 0.000
0.600 −14238 312 5.596 312 0.000 0.000
0.700 −12933 273 5.079 273 0.000 0.000
0.800 −10610 208 4.161 208 0.000 0.000
0.900 −6911 117 2.703 117 0.000 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Nb – Ta
15 1.0
T∆Sm
10
0.8
Energies / (kJ/mol)
5
0.6
Activities
∆Hm
0
0.4 a Ta a Nb
−5
0.2
−10
∆Gm
−15 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Nb x Ta Ta Nb x Ta Ta
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =2600 K.
T =2600 K.
References
[1969Rud] E. Rudy: “Compendium of Phase Diagram Data”, AFML, Wright-Patterson AFB, Ohio,
Rep. No. AFML-TR-65-2, Part 5, 1969.
[1996Kris] R. Krishnan, S.P. Garg, N. Krishnamurthy, E. Paul in: “Phase Diagrams of Binary Tantalum
Alloys”, S.P. Garg, M. Venkatraman, N. Krishnamurthy, R. Krishnan (eds.), The Indian
Institute of Metals, Calcutta, 1996, pp. 118–120.
[2004Xio] W. Xiong, Y. Du, Y. Li, B.Y. Huang, H.H. Xu, H.L. Chen, Z. Pan: Calphad 28 (2004)
133–140.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ni – Pb 1
Ni – Pb (Nickel – Lead)
2000
liquid
1800
1600
1400
T / K
1200
1000 fcc′
800
600
fcc″
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ni x Pb Pb
Alloys based on Ni-Pb or Cu-Ni-Pb are used as bearings in heavy-duty diesel engines. The literature on the
Ni-Pb system has been reviewed in [1991Nas, 1999Gho, 2000Wan] and optimised thermodynamic datasets
have been reported in [1999Gho, 2000Wan]. The Ni-Pb system has been been investigated repeatedly with
various techniques. The liquidus has been determined by thermal analysis [1907Por, 1908Vos], chemi-
cal analysis [1955Pel, 1958Ald, 1959Fle, 1961Dav], and EMF measurements [1964Cav, 1981Tas]. The
temperatures given in [1908Vos] had to be corrected due to a deviation in the melting point of pure Ni
[1991Nas]. The activities of Ni in Pb-rich melts have been determined in EMF experiments [1964Cav] and
activities of Pb in Ni-rich melts have been obtained by an isopiestic technique [1986Pom]. The location of
the consolute point on the miscibility gap in the liquid has been estimated by [1960Mil] by extrapolating
data from the Fe-Ni-Pb system. Both assessments [1999Gho, 2000Wan] provide good descriptions of the
experimental data and they may be considered to be equivalent. The present tables and diagrams have been
calculated with the data of [2000Wan] but that does not mean that those of [1999Gho] have been rejected.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ni – Pb
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ni – Pb 3
14 1.0
12
T∆Sm
10 0.8
Energies / (kJ/mol)
8
∆Hm
6 0.6
Activities
a Pb a Ni
4
2 0.4
0
−2 0.2
∆Gm
−4
−6 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ni x Pb Pb Ni x Pb Pb
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1900 K.
T =1900 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Ni – Ru 1
Ni – Ru (Nickel – Ruthenium)
2800
2600
liquid
2400
2200
2000
T / K
1800
hcp
1600
fcc
1400
1200
1000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ni x Ru Ru
The Ni-Ru binary system contains two components interesting in the nuclear field, nickel being a major
component of stainless steel structures of the vessel, and ruthenium being selected as representative of a
family of non-volatile fission products. Experimental information on the phase diagram has been reported
in the compilations of Hansen and Anderko [1958Han], Elliott [1965Ell] and Shunk [1969Shu]. It is based
on the investigations of Raub and Menzel [1961Rau], and Kornilov and Myasnikova [1964Kor]. There is
complete solubility of the components in the liquid state and a limited mutual solubility of Ni and Ru in
the solid state, being maximal at the peritectic temperature. No thermodynamic data are available for the
binary system. The system was assessed by Chevalier and Fischer [2001Che], and by Hallstr öm [2004Hal].
The excess Gibbs energy of the liquid, fcc and hcp solution phases was optimised from the selected phase
diagram information. A regular substitution model was used for the first two phases, and a sub-regular
description for the hcp phase. The agreement with the experimental information [1961Rau, 1964Kor] is
quite satisfactory.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ni – Ru
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ni – Ru 3
16 1.0
T∆Sm
12
0.8
8
Energies / (kJ/mol)
4 0.6
Activities
0 ∆Hm
0.4 a Ru a Ni
−4
−8
0.2
−12 ∆Gm
−16 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ni x Ru Ru Ni x Ru Ru
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2700 K.
T =2700 K.
Table IVa. Integral quantities for the stable phases at 1700 K.
Phase xRu ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −2763 3743 3.827 1832 1.124 −0.008
0.200 −3629 6932 6.212 3444 2.052 −0.011
0.298 −3801 9510 7.830 4806 2.767 −0.012
hcp 0.593 −3584 10118 8.060 5969 2.440 −0.009
0.600 −3578 9930 7.946 5935 2.350 −0.008
0.700 −3409 7141 6.206 5226 1.127 −0.006
0.800 −3036 4272 4.299 4037 0.139 −0.004
0.900 −2282 1750 2.372 2313 −0.331 −0.002
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ni – Ru
14 1.0
12 T∆Sm
10 0.8
∆Hm
Energies / (kJ/mol)
8
0.6
Activities
6
a Ru a Ni
4
0.4
2
0 0.2
−2
∆Gm
−4 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ni x Ru Ru Ni x Ru Ru
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1700 K.
T =1700 K.
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ni – Zn 1
Ni – Zn (Nickel – Zinc)
1900
1700 liquid
1500
1300 b.p. Zn
T / K
fcc B2
1100
900
700 γNiZn
NiZn 8
NiZn
500 TC hex
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ni x Zn Zn
The Ni-Zn system is of interest for galvanising of high silicon steels where Ni is added to the bath in order
to reduce coating thickness and to improve the coating adhesion and its appearance. The Ni-Zn system
has been reviewed in [1991Nas] as well as by [2000Vas, 2002Su, 2003Mie] who also reported optimised
thermodynamic datasets. Over the years, numerous studies of the Ni-Zn have been published and the
optimisations [2000Vas, 2002Su, 2003Mie] are based essentially on the same experimental data but they
differ in the thermodynamic modelling, especially the description of the non-stoichiometric intermetallic
phases.
Data on the phase equilibria have been measured over the complete composition range and temperatures
from the liquidus down into the subsolidus regions. Furthermore there are numerous studies of the zinc
activity in the liquid as well as in the solid solution phases and enthalpies of formation have been determined
at several temperatures.
In [2000Vas] the deviation from stoichiometry on the Zn-deficient side of the B2 and NiZn phases and
on the Ni-poor side of γNiZn has been modelled by introducing vacancies into one of the sublattices. In
[2002Su] it has been criticised that these phases contain unphysically high vacancy concentrations even at
low temperatures and alternative modelling of these phases has been presented. However, the overall fit of
the phase diagram and the thermodynamic data is still best in the assessment of [2000Vas] and therefore,
this dataset is presented here.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ni – Zn
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ni – Zn 3
8 1.0
T∆Sm
4
0.8
Energies / (kJ/mol)
0.6 a Ni a Zn
Activities
−4
−8
0.4
−12 ∆Hm
0.2
−16
∆Gm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ni x Zn Zn Ni x Zn Zn
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =1800 K.
T =1800 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ni – Zn
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZn ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
NiZn8 0.889 −10220 −10215 0.015 −0.085
References
[1991Nas] P. Nash, Y.Y. Pan in: “Phase Diagrams of Binary Nickel Alloys”, P. Nash (ed.), ASM Intl.,
Materials Park, OH, 1991, pp. 382–390.
[2000Vas] G.P. Vassiliev, T. Gomez-Acebo, J.-C. Tedenac: J. Phase Equilibria 21 (2000) 287–301.
[2002Su] X. Su, N.-Y. Tang, J.M. Toguri: J. Phase Equilibria 23 (2002) 140–148.
[2003Mie] J. Miettinen: Calphad 27 (2003) 263–274.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Os – Si 1
Os – Si (Osmium – Silicon)
3400
3200 liquid
3000
2800
2600
2400
T / K
2200
2000
1800
1600
Os 2 Si 3
OsSi 2
1400
OsSi
1200
hcp A4
1000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Os x Si Si
A survey on the literature of the Os-Si system and a thermodynamic assessment has been reported in
[2001Liu]. The complete phase diagram of the system has been investigated by [1988Sch]. In addition
to these data [2001Liu] have selected results from [1962Fin, 1983Mas]. Except for the enthalpy of forma-
tion of Os2 Si3 [1998Mes] no other thermodynamic data have been determined experimentally.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Os – Si
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Os – Si 3
5 1.0
0
T∆Sm 0.8
−5
Energies / (kJ/mol)
−10 0.6 a Os a Si
Activities
−15
−20 0.4
∆Gm
−25
0.2
−30 ∆Hm
−35 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Os x Si Si Os x Si Si
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3400 K.
T =3400 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Os1 Si1 0.500 −25045 −25415 −1.242 0.000
Os2 Si3 0.600 −29912 −30450 −1.805 0.000
Os1 Si2 0.667 −28148 −28745 −2.001 0.000
References
Landolt-Börnstein SGTE
New Series IV/19B
2 Binary Systems: Pd – Rh 1
Pd – Rh (Palladium – Rhodium)
2400
liquid
2200
2000
1800
T / K
1600 fcc
1400
1200
1000
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Pd x Rh Rh
The system Pd-Rh is characterised by two solution phases, liquid and fcc with continuous miscibility at
higher temperatures and a broad miscibility gap opening in the fcc phase at lower temperatures [1959Rau2,
1987Shi]. The melting range is experimentally ill defined [1994Oka]. The thermodynamic assessment
of the Pd-Rh system was carried out by Korb [2004Kor]. The calculated miscibility gap agrees well with
[1959Rau2] and [1959Rau1] in the Pd-rich region and with [1987Shi] near the critical point. The calculated
liquidus and solidus must be seen as a result of the thermodynamic calculations, see [1994Oka].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Pd – Rh
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Pd – Rh 3
15 1.0
T∆Sm
10 0.8
Energies / (kJ/mol)
5 0.6
Activities
∆Hm
0 0.4 a Rh a Pd
−5 0.2
∆Gm
−10 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Pd x Rh Rh Pd x Rh Rh
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2250 K.
T =2250 K.
Table IVa. Integral quantities for the stable phases at 1575 K.
Phase xRh ∆Gm ∆Hm ∆Sm GEm Sm
E
∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
fcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −2547 1710 2.703 1710 0.000 0.000
0.200 −3494 3059 4.161 3059 0.000 0.000
0.300 −3959 4041 5.079 4041 0.000 0.000
0.400 −4166 4647 5.596 4647 0.000 0.000
0.500 −4206 4871 5.763 4871 0.000 0.000
0.600 −4108 4705 5.596 4705 0.000 0.000
0.700 −3857 4142 5.079 4142 0.000 0.000
0.800 −3377 3176 4.161 3176 0.000 0.000
0.900 −2460 1797 2.703 1797 0.000 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Pd – Rh
10 1.0
8 T∆Sm
0.8
6
Energies / (kJ/mol)
4 ∆Hm 0.6
Activities
2
0.4 a Rh a Pd
0
−2
∆Gm 0.2
−4
−6 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Pd x Rh Rh Pd x Rh Rh
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =1575 K.
T =1575 K.
References
[1931Tam] G. Tammann, H.J. Rocha in: “Festschrift zum 50-jährigen Bestehen der Platinschmelze G.
Siebert GmbH”, Hanau, (1931) pp. 317–320.
[1959Rau1] E. Raub: J. Less-Common Met. 1 (1959) 3–18.
[1959Rau2] E. Raub, H. Beeskow, D. Menzel: Z. Metallkd. 50 (1959) 428–431.
[1987Shi] J.E. Shield, R.K. Williams: Scr. Metall. 21 (1987) 1475–1479.
[1994Oka] H. Okamoto: J. Phase Equilibria 15 (1994) 208–212 and 369.
[2004Kor] J. Korb, unpublished assessment, GTT-Technologies, 2004.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Pd – Sm 1
Pd – Sm (Palladium – Samarium)
2000
liquid
1800
1600
βPdSm
1400
bcc
T / K
1200 fcc
Pd 7 Sm
hcp
1000
800
Pd 21 Sm 10
Pd 4 Sm 3
Pd 2 Sm 3
Pd 3 Sm 7
Pd 5 Sm
Pd 3 Sm
αPdSm
600 C19
400
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Pd x Sm Sm
Intermetallic compounds of palladium with rare earth metals are of interest due to their potential use in
hydrogen diffusion membranes for purification and isotope enrichment. A review on the Pd-Sm system and
a thermodynamic assessment has been given by [2000Du]. The optimisation is based on the phase diagram
data which have been reported in [1973Loe] across the whole composition range with additional investi-
gations in Pd-rich alloys by [1989Sak]. Enthalpies of formation have been reported for PdSm [1975Pal,
1998Guo] and for Pd3 Sm and Pd4 Sm3 [1998Guo]. Data for the other intermetallic compounds have been
estimated. For the liquid no thermodynamic data have been available. From the dataset [2000Du] a rather
unusual transformation behaviour is calculated for the Sm-phases having dissolved small amounts of Pd, as
shown in the enlarged part of the phase diagram, Fig. 2. However, it should be noted that the only inves-
tigation in this region of the system [1973Loe] does not provide any quantitative data for the solubility of
Pd in either of the phases of Sm. It has only been stated that the solubility of Pd in Sm is certainly below
1 at.% and that dissolution of Pd in Sm results in a peritectic reaction at 1228 K.
References
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Pd – Sm
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Pd – Sm 3
1400
liquid
1300
bcc
1200
T / K
1100
1000 C19
Fig. 2. Partial phase diagram for
Pd 3 Sm 7 + C19 the system Pd-Sm.
900
0.985 0.990 0.995 1.000
x Sm Sm
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Pd – Sm
10 1.0
0
−10 T∆Sm 0.8
Energies / (kJ/mol)
−20
−30 0.6 a Pd a Sm
Activities
−40
−50 0.4
−60
∆Gm
−70 0.2
−80 ∆Hm
−90 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Pd x Sm Sm Pd x Sm Sm
Fig. 3. Integral quantities of the liquid phase at Fig. 4. Activities in the liquid phase at T =1900 K.
T =1900 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSm ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Pd7 Sm1 0.125 −50065 −54184 −13.816 0.000
Pd5 Sm1 0.167 −61735 −65216 −11.673 0.000
Pd3 Sm 0.250 −76326 −78630 −7.730 0.000
Pd21 Sm10 0.323 −79495 −81600 −7.059 0.000
Pd4 Sm3 0.429 −83754 −85887 −7.153 0.000
αPdSm 0.500 −85011 −87873 −9.596 0.000
βPdSm 0.500 −84633 −87373 −9.191 0.000
Pd2 Sm3 0.600 −83287 −90298 −23.516 0.000
Pd3 Sm7 0.700 −73285 −82372 −30.477 0.000
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Pd – Tb 1
Pd – Tb (Palladium – Terbium)
2100
liquid
βPd 3 Tb 2
1900
1700
bcc
1500
βPdTb
T / K
1300
fcc
αPd 3 Tb 2
1100
900
hcp
Pd 21 Tb 10
Pd 4 Tb 3
Pd 2 Tb 3
Pd 2 Tb 5
Pd 3 Tb
αPdTb
700
Pd 7 Tb
500
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Pd x Tb Tb
Intermetallic compounds of palladium with rare earth metals are of interest due to their potential use in
hydrogen diffusion membranes for purification and isotope enrichment. Only few and insufficient experi-
mental data are known of the Pd-Tb system. After comparing the phase diagrams of palladium with some of
the heavier rare earth metals (Gd, Dy, Ho,Er) a phase diagram of Pd-Tb has been proposed by [1990Bor].
The melting temperatures of the intermetallic Pd-Tb compounds have been interpolated from series of
known values for Pd-compounds with adjacent rare earth elements. The melting point of PdTb which
has been measured by [1975Pal] is in agreement with the interpolation. The region of the phase diagram
around the compound Pd7 Tb has been experimentally investigated by [1993Tak]. Enthalpies of formation
have been determined for PdTb [1974Pal, 1995Guo] and Pd2 Tb5 [1974Pal]. Based on these investigations
a thermodynamic assessment has been prepared by [2000Du]. However, in view of the scarce available
data it is much desired to verify the phase diagram and further thermodynamic properties by selected key
experiments.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Pd – Tb
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Pd – Tb 3
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Pd – Tb
10 1.0
0
−10 T∆Sm 0.8
Energies / (kJ/mol)
−20
−30 0.6 a Pd a Tb
Activities
−40
−50 0.4
−60
∆Gm
−70 0.2
−80 ∆Hm
−90 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Pd x Tb Tb Pd x Tb Tb
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2000 K.
T =2000 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xTb ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Pd7 Tb1 0.125 −47937 −52022 −13.703 0.000
Pd3 Tb 0.250 −79090 −82053 −9.937 0.000
Pd21 Tb10 0.323 −80159 −82457 −7.710 0.000
αPd3 Tb2 0.400 −81089 −82910 −6.105 0.000
βPd3 Tb2 0.400 −80966 −82753 −5.993 0.000
Pd4 Tb3 0.429 −81420 −83082 −5.575 0.000
αPdTb 0.500 −81709 −83719 −6.742 0.000
βPdTb 0.500 −81597 −83566 −6.606 0.000
Pd2 Tb3 0.600 −79334 −84434 −17.105 0.000
Pd2 Tb5 0.714 −57901 −61113 −10.771 0.000
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ru – Si 1
Ru – Si (Ruthenium – Silicon)
2800
2600 liquid
2400
2200
T / K
2000
1800
Ru 2 Si
1600
Ru 4 Si 3
1400 Ru 2 Si 3
RuSi
hcp A4
1200
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ru x Si Si
Ruthenium silicides are of interest for manufacturing high-density integrated circuit devices since they have
a very good lattice match with silicon and relatively low electrical resistance. Other potential applications
are in light emitting diodes and thermoelectrical devices.
Assessed thermodynamic datasets for the Ru-Si system have been reported by [2001Du, 2001Liu] which
are based on essentially the same experimental data from the literature. Here, the assessment of [2001Du]
has been selected for presentation. The phase diagram data have been selected mainly from [1999Per] with
additional information from [1965Obr]. The system contains seven stable phases: the liquid with a con-
tinuous miscibility range, the Ru-based hcp phase with limited solubility of Si, the terminal Si-phase with
practically no solubility for Ru and 4 ruthenium silicides with narrow homogeneity ranges. The compound
Ru5 Si3 which has been reported in [1970Eng, 1988Wei] has not been confirmed in the redetermination of
the phase diagram by [1999Per]. For the thermodynamic modelling of RuSi and Ru 2 Si3 heat capacity mea-
surements have been available [1997Kun, 1998Per]. The specific heat of the remaining two compounds has
been approximated according to the Neumann-Kopp rule. Enthalpies of formation have been determined
experimentally for Ru4 Si3 [1997Per], RuSi [1988Top, 1997Per, 1998Cic] and Ru2 Si3 [1997Per, 1998Cic,
1998Mes]. Since the transformation temperatures of the polymorphic forms of both RuSi and Ru 2 Si3 are
not known in both cases only a single compound is used in the modelling. No thermodynamic data have
been reported for the liquid. More recently, a new compound, RuSi 2 , has been observed by DTA to form
peritectoidally at 1235 K [2002Iva].
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ru – Si
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ru – Si 3
20 1.0
T∆Sm
10
0.8
Energies / (kJ/mol)
0.6 a Ru a Si
Activities
−10
−30
0.2
−40 ∆Gm
−50 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ru x Si Si Ru x Si Si
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2700 K.
T =2700 K.
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ru – Si
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xSi ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ru2 Si1 0.333 −34167 −35195 −3.446 0.000
Ru4 Si3 0.429 −45949 −47788 −6.169 0.000
Ru1 Si1 0.500 −51627 −52988 −4.562 −0.315
Ru2 Si3 0.600 −47019 −47723 −2.360 −0.149
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ru – Zr 1
Ru – Zr (Ruthenium – Zirconium)
2800
2600 liquid
2400
2200
2000
Ru 2 Zr
1800
T / K
1600
bcc
1400
hcp
1200
1000
RuZr
800 hcp
600
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ru x Zr Zr
The Ru-Zr binary system contains two components interesting for the nuclear field, ruthenium being se-
lected as representative of a family of non-volatile fission products, and zirconium being a major component
of the zircalloy cladding. Experimental information on the phase diagram has been reported in the compi-
lations of Hansen and Anderko [1958Han], Elliott [1965Ell] and Shunk [1969Shu], and more recently by
Okamoto [1993Oka]. The phase diagram is based on the investigations of Raub and Röschel [1963Rau],
and Eremenko et al. [1980Ere, 1988Ere]. There is complete solubility in the liquid, and a limited one in
the solid state: 2 at.% Zr in hcp-Ru at 1983 K, 1 at.% Ru in hcp-Zr at 940 K, 11.4 at.% Ru in bcc-Zr at
1494 K. Two intermetallic compounds were identified, Ru2 Zr and RuZr, with a limited non-stoichiometry
range. The enthalpy of formation of RuZr has been measured calorimetrically [1988Top]. The system was
assessed by Chevalier and Fischer [1995Che]. The excess Gibbs energy of the liquid, hcp and bcc solution
phases was optimised from the selected experimental information. A sub-regular substitution model was
used for the first two phases, and a regular one for the third one. The heat capacity of the compounds which
have been considered to be stoichiometric, Ru2 Zr and RuZr, was estimated from the pure components by
the Neumann-Kopp rule. The enthalpy of formation and entropy at room temperature were estimated in
consistency with the available experimental information. The agreement with the experimental information
[1963Rau, 1988Ere, 1988Kle] is quite satisfactory.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Ru – Zr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Ru – Zr 3
20 1.0
10 T∆Sm
0.8
0
Energies / (kJ/mol)
−10 0.6 a Ru a Zr
Activities
−20
−30 0.4
∆Hm
−40
0.2
−50 ∆Gm
−60 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Ru x Zr Zr Ru x Zr Zr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2700 K.
T =2700 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZr ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Ru2 Zr1 0.333 −37235 −36957 0.932 0.000
Ru1 Zr1 0.500 −66529 −68650 −7.113 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Ru – Zr
References
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Sn – V 1
Sn – V (Tin – Vanadium)
2300
2100 liquid
1900
1700
1500
bcc
T / K
1300
1100
900
Sn 3 V 2
SnV 3
700
500
bct
300
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Sn xV V
The literature on the Sn-V system has been reviewed in [1989Smi, 2002Stu] and a thermodynamic dataset
has been optimised by [2002Stu] using the element data recommended by SGTE. In the assessment the
selected data for the phase diagram have been taken from the literature [1969Dar, 1973Mar, 1979Gon] as
well as from new experiments done by the assessors [2002Stu]. The heat capacity of SnV 3 has been adjusted
to the experimental data of [1975Kna]. The partial enthalphy of solution of V in the melt at 1783 K from
0-67 at.% V has been determined by Esin et al. [1977Esi] and it has been used in the optimisation of the
liquid. However, in a more recent calorimetric investigation of liquid Sn-V alloys [2000Bou] a much higher
value of the partial enthalpy of V in the limit of pure Sn has been reported than by [1977Esi]. The dataset
should not be used at too high temperatures because an artificial inverse miscibility gap opens in the liquid
above 3300 K.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: Sn – V
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: Sn – V 3
6 1.0
4
0.8
T∆Sm
Energies / (kJ/mol)
0.6
Activities
0
aV a Sn
−2 ∆Hm
0.4
−4
0.2
−6 ∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Sn xV V Sn xV V
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =2200 K.
T =2200 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xV ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
Sn3 V2 0.400 −21588 −26353 −15.984 0.000
SnV3 0.795 −15538 −16710 −3.932 −0.504
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: Sn – V
References
[1969Dar] J.B. Darby, Jr,. D.B. Jugle: Trans. Metall. Soc. AIME 245 (1969) 2515–2518.
[1973Mar] L.V. Marchukova, N.M. Matveeva, I.I. Kornilov: Russ. Metall. 2 (1973) 157–159.
[1975Kna] G.S. Knapp, S.D. Bader, H.V. Culbert, F.Y. Fradin, T.E. Klippert: Phys. Rev. B 11B (1975)
4331–4338.
[1977Esi] Yu.O. Esin, M.G. Valishev, P.V. Gel’d: Russ. J. Phys. Chem. 51 (1977) 273. Fradin, T.E.
Klippert: Phys. Rev. B 11B (1975) 4331–4338.
[1979Gon] L.V. Goncharuk, V.N. Eremenko, G.M. Lukashenko, V.R. Sidorko: Dokl. Akad. Nauk
SSSR 245 (1979) 865–867.
[1989Smi] J.F. Smith in: “Phase Diagrams of Binary Vanadium Alloys”, J.F. Smith (ed.), ASM Intl.,
Metals Park, OH, 1989, pp. 270–274.
[2000Bou] A. Bouhajib, A. Nadiri, Y. Yacoubi, R. Castanet: Phys. Chem. Liq. 38 (2000) 261–268.
[2002Stu] T. Studnitzky, B. Onderka, R. Schmid-Fetzer: Z. Metallkd. 93 (2002) 48–57.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: V – W 1
V – W (Vanadium – Tungsten)
3800
3600 liquid
3400
3200
3000
T / K
2800
2600
2400
bcc
2200
2000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
V xW W
The literature on the V-W system has been reviewed in [1991Nag] and thermodynamic datasets have been
optimised by [2005Bra, 2005Hua]. The phase diagram consists only of the liquid and the bcc phases with
continuous solubility for the components. The phase diagram has been investigated several times with some
conflicting results especially in the V-rich part where older investigations found a minimum in the solidus
line. Later investigations [1969Rud, 1975Kol] found that the solidus increases monotonically when W is
added to vanadium alloys. Therefore, the previous minimum was attributed to higher levels of impurity
in the samples of the older investigations. No data on the thermodynamics of mixing have been available.
For the optimisation of the thermodynamic dataset [2005Bra] have selected the solidus data of [1969Rud]
and the liquidus data of [1960Bar] for samples with more than 30 at.% W. The evaluation of [2005Bra] is
preferred here over that of [2005Hua] because the latter authors propose excess entropies for the liquid and
bcc phases which are quite high. The dataset of [2005Bra] predicts a miscibility gap in the bcc phase below
1070 K, however, no experimental evidence is available.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: V – W
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: V – W 3
25 1.0
20 T∆Sm
15 0.8
Energies / (kJ/mol)
10
5 0.6
Activities
∆Hm
0
−5 0.4 aW aV
−10
−15 0.2
∆Gm
−20
−25 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
V xW W V xW W
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3700 K.
T =3700 K.
Table IIIa. Integral quantities for the stable phases at 2000 K.
Phase xW ∆Gm ∆Hm ∆Sm GEm
E
Sm ∆CP
[J/mol] [J/mol] [J/(mol·K)] [J/mol] [J/(mol·K)] [J/(mol·K)]
bcc 0.000 0 0 0.000 0 0.000 0.000
0.100 −3801 1605 2.703 1605 0.000 0.000
0.200 −5469 2852 4.161 2852 0.000 0.000
0.300 −6414 3744 5.079 3744 0.000 0.000
0.400 −6913 4279 5.596 4279 0.000 0.000
0.500 −7069 4457 5.763 4457 0.000 0.000
0.600 −6913 4279 5.596 4279 0.000 0.000
0.700 −6414 3744 5.079 3744 0.000 0.000
0.800 −5469 2852 4.161 2852 0.000 0.000
0.900 −3801 1605 2.703 1605 0.000 0.000
1.000 0 0 0.000 0 0.000 0.000
Landolt-Börnstein SGTE
New Series IV/19B
4 2 Binary Systems: V – W
12 1.0
10 T∆Sm
8 0.8
Energies / (kJ/mol)
6
4 0.6
Activities
∆Hm
2
0 0.4 aW aV
−2
−4 0.2
−6 ∆Gm
−8 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
V xW W V xW W
Fig. 4. Integral quantities of the stable phases at Fig. 5. Activities in the stable phases at T =2000 K.
T =2000 K.
References
[1960Bar] V.V. Baron, Yu.V. Efimov, E.M. Savitskii: Izv. Akad. Nauk SSSR, Otd. Tekh. Nauk, Metall.
Top. 1 (1960) 70–74; transl.: Russ. Met. Fuels 1 (1960) 45–49.
[1969Rud] E. Rudy: Compendium of Phase Diagram Data, AFML, Wright-Patterson AFB, Ohio, Rep.
No. AFML-TR-65-2, Part 5, 1969.
[1975Kol] V.M. Koltygin, M.V. Pikunov, A.S. Petukhova: Izv. Vyssh. Uchebn. Zaved. Tsvetn. Metall.
6 (1975) 126–129.
[1991Nag] S.V. Nagender Naidu, A.M. Sriramamurthy, M. Vijayakumar, P. Rama Rao in: “Phase Di-
agrams of Binary Tungsten Alloys”, S.V. Nagender Naidu, P. Rama Rao, Eds., The Indian
Institute of Metals, Calcutta, 1991, pp. 295–300.
[2005Bra] J. Bratberg: Z. Metallkd. 96 (2005) 335–344.
[2005Hua] S. Huang, J. Vleugels, L. Li, O. Van der Biest: J. Alloys Comp. 395 (2005) 68–74.
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: W – Zr 1
W – Zr (Tungsten – Zirconium)
3800
3600
liquid
3400
3200
3000
2800
2600
T / K
2400
2200
2000 bcc
1800
W 2 Zr
1600 bcc
1400
1200
1000 hcp
800
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
W x Zr Zr
The W-Zr binary system contains two components, tungsten and zirconium, interesting for many appli-
cation fields. The selected phase diagram, originates from the assessment of Nagender Naidu and Rama
Rao [1987Nag]. It is based on metallographic analysis, incipient-melting data, X-ray diffraction [1953Dom,
1953Gea], dilatometry, liquidus measurements [1953Gea], and on invariant temperatures reported by Savit-
skii and Zakharov [1962Sav]. The intermetallic phase W2 Zr was identified with a narrow non-stoichiometry
range (33 - 35 at%.Zr) and decomposes peritectically. The mutual solid solubility of Zr in bcc-W and W
in bcc-Zr is limited. The solubility of W in hcp-Zr is negligible, and equal to 0.25 at.% [1953Dom] at
the eutectoid temperature. A solubility of Zr in (W) equal to 1.5 at.% at 1922 K was reported by Elliott
[1965Ell]. There is a complete miscibility in the liquid state. There are no experimental data available for
the solution thermodynamics of the W-Zr system. This system was assessed by Chevalier [2005Che]. A
sub-regular substitution model was used for the liquid and a regular one for the bcc solid solution. The heat
capacity of W2 Zr was estimated from the pure elements by using the Neumann-Kopp rule. The enthalpy
and entropy of formation of W2 Zr were optimised in consistency with the temperatures of the invariant
reactions. The calculated phase diagram and the invariant reactions are in very satisfactory agreement with
the experimental data. However, there is a need for further experimental determinations of thermodynamic
properties of W2 Zr and liquid.
Landolt-Börnstein SGTE
New Series IV/19B
2 2 Binary Systems: W – Zr
SGTE Landolt-Börnstein
New Series IV/19B
2 Binary Systems: W – Zr 3
25 1.0
20
T∆Sm
15 0.8
Energies / (kJ/mol)
10
0.6
Activities
5
0 ∆Hm a Zr aW
0.4
−5
−10 0.2
−15 ∆Gm
−20 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
W x Zr Zr W x Zr Zr
Fig. 2. Integral quantities of the liquid phase at Fig. 3. Activities in the liquid phase at T =3700 K.
T =3700 K.
Table IV. Standard reaction quantities at 298.15 K for the compounds per mole of atoms.
Compound xZr ∆f G◦ / (J/mol) ∆f H ◦ / (J/mol) ∆f S ◦ / (J/(mol·K)) ∆f CP◦ / (J/(mol·K))
W2 Zr1 0.333 −3033 −2892 0.471 −0.028
References
[1953Dom] R.F. Domagala, D.J. McPherson, M. Hansen: Trans. AIME 197 (1953) 73–79.
[1953Gea] G.A. Geach, G.F. Slattery: Trans. AIME 197 (1953) 747–748.
[1962Sav] E.M. Savitskii, A.M. Zakharov: Russ. J. Inorg. Chem. 7 (1962) 1337–1340.
[1965Ell] R.P. Elliott, “Constitution of Binary Alloys”, First supplement, McGraw-Hill Book Com-
pany, New-York, Saint Louis, San Francisco, Toronto, London, Sydney, 1965.
[1987Nag] S.V. Nagender Naidu, P. Rama Rao: J. Alloy Phase Diagrams 3 (1987) 47–56.
[2005Che] P.-Y. Chevalier, Unpublished work, July 2005.
Landolt-Börnstein SGTE
New Series IV/19B