Intermetallics 9 (2001) 5±8

www.elsevier.com/locate/intermet

Cluster/site approximation calculation of the ordering phase

diagram for Cd±Mg alloys
J. Zhang a, W.A. Oates b, F. Zhang c, S-L. Chen c, K-C. Chou d,
Y.A. Chang e,*
a
Baotou University of Iron and Steel Technology, PR China
b
Science Research Institute University of Salford, Salford M5 4WT, UK
c
CompuTherm LLC, 437 S. Yellowstone Drive, Madison, WI 53719, USA
d
University of Science and Technology Beijing, Beijing, PR China
e
Department of Material Science and Engineering, University of Wisconsin, Madison, WI 53706, USA

Received 4 February 2000; accepted 23 March 2000

Abstract
We have used the modi®ed cluster/site approximation in a phenomenological calculation of the phase diagram and single phase
thermodynamic properties for cadmium±magnesium alloys in the order/disorder region. Values for the three cluster energies di€er
little from those obtained by LMTO-ASA calculations on unrelaxed alloys of ideal c/a ratio. Only two other parameters contained
in contributions to the Gibbs energy are required. One comes from a con®guration independent term and the other is an entropy
factor coming from the cluster/site approximation. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: B. Phase diagram; Thermodynamic and thermochemical properties; Order/disorder transformations

1. Introduction four contributions considered, making 32 energy terms

The Cd±Mg system is a prototype ordering system for
hcp alloys in the same way that the Au±Cu system ful®ls
this role for fcc alloys. The experimental ordering phase
diagram is shown in Fig. 1(a) [1]. The diagram has been
calculated using the so-called `®rst principles' method
[2±4]. In this calculation, cluster expansions were carried
out for the con®gurational energy, the cell elastic
relaxation energy (local atomic relaxations were neglec-
ted), the vibrational energy and the electronic energy in
order to obtain e€ective cluster interactions (ECIs) for
the cluster and sub-clusters of a 7 point cluster. The
ECIs were then used in a cluster variation method
(CVM) calculation of the con®gurational entropy [5] in
the tetrahedron±octahedron approximation. The cell
relaxation cluster expansion was based on experimental
results for disordered alloys but all the other ECIs were
obtained from total energy calculations on ordered
phases. Eight distinct ECIs were used for each of the
* Corresponding author.Tel.: +1-608-262-3732; fax: +1-608-262-
0389.
E-mail address: chang@engr.wisc.edu (Y. A. Chang).
0966-9795/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0966-9795(00)00072-8
in all. The ®nal calculated phase diagram is shown in
Fig. 1(b). Its topology is correct but it does not have the
quantitative accuracy which can be obtained from a
phenomenological calculation and which is necessary
for technological applications. It is clear that an
approach is needed which will provide a quantitative
description of the Cd±Mg and similar systems.
In the present paper we present results obtained from
applying the modi®ed cluster/site approximation (CSA)
[6,7] for the calculation of the con®gurational free
energy. We use the model phenomenologically in order
to try to describe the experimental phase diagram and
the single phase thermodynamic properties quantita-
tively.
2. The cluster/site approximation
The CSA is an adaptation of the generalised quasi-
chemical method, introduced many years ago by Fowler
for treating equilibria in molecular gaseous assemblies
[8] and subsequently used for clusters in solid solutions
by Yang and Li [9±12]. Unlike the clusters in a cluster
6 J. Zhang et al. / Intermetallics 9 (2001) 5±8

Gn ÿ …n
ÿ 1†
G1 ‡ GECI …x; T† …1†
Is a geometrical factor, the number of clusters per
, the
Fig. 1. Ordering phase diagrams for Cd±Mg alloys: (a) Experimental
(redrawn from the assessment of Chueh et al. [1]). The experimental
points are from [17]. (b) Calculated from `®rst principles' (redrawn
from Asta et al. [2]).
variation method (CVM) calculation [5], the CSA clus-
ters are non-interfering Ð they are permitted to share
only corners. It follows that the only energy parameters
required are the cluster energies themselves Ð since
as an adjustable parameter, more ¯ex-
there is no cluster overlap, the energies of sub-clusters
do not enter into the energy equation.
Cluster non-interference always results in a two-term
expression for the con®gurational free energy. Addition
of a con®guration independent term (one which
depends on molar composition, x, only and not on the
details of sublattice occupation) is used to take into
account excess elastic energies due to atomic size mis-
match or changing cell relaxations and also any excess
excitational contributions. The modi®ed CSA equation
for the Gibbs energy of mixing, for a binary A±B alloy
when a cluster containing n atoms is used, is:

GM ˆ
where
G1 is the point approximation contribution and
the cluster contribution is given by:
X
n

Gn ˆ yiA iA ‡ fn …2†
iˆ1
Here the yiA are the sublattice fractional occupations by
A atoms on sublattice i, iA are Lagrangian multipliers,
closely related to species chemical potentials [13] and fn
is the (lattice gas) cluster Helmholtz energy, which can
be calculated from the various cluster energies and the
iA .
site, when there is complete non-interference. GECI …x; T†
is the con®guration independent excess free energy and
is expressed as a Redlich±Kister polynomial in x,T with
coecients l [14]:
X X
GECI …x; T† ˆ x…1 ÿ x† …1 ÿ 2x†n l…n†  T

…3†
nˆ0 ˆ0

GM in Eq. (1) is thus seen to be a functional of
l's in Eq. (3) and the yiA occurring in both Eq. (2) and

G1, and has to be minimised with respect to these
independent variables. Note that the iA in Eq. (2) are
uniquely related to the yiA so that either can be used in
the minimisation.
The modi®ed CSA [7] has three important advantages
over the CVM in phenomenological calculations of
phase diagrams:
1. By using non-interfering clusters, the number of
independent variables in the energy functional is chan-
ged from being the cluster probabilities in the CVM to
being the point probabilities in the CSA, e.g. from 104
to 104 for a 10 component system with a tetrahedron
cluster. This large reduction in the number of variables
makes the CSA attractive for application to multi-
component alloys [6].
2. Non-interfering clusters means fewer energy para-
meters since there are no sub-clusters to consider.
3. By using
ibility is obtained in describing Gibbs energy-composi-
tion curves. This point was illustrated in the earlier
calculation of the Au±Cu ordering phase diagram [7].
The tetrahedron approximation was used in the pre-
sent calculations. When the c/a ratio in hcp alloys is not
equal to the ideal, two irregular tetrahedra should be
considered [15]. Since Cd has a c/a ratio which is a long
way from the ideal ratio we initially used both types but
 J. Zhang et al. / Intermetallics 9 (2001) 5±8 7

subsequently found that an equally good description stable phase structures. These zero kelvin con®gura-
could be obtained by using a single, regular tetrahedron. tional formation energies were calculated using LMTO-
The results given in the following section refer to those ASA for alloys with the ideal c/a ratio and in the unre-
obtained from the regular tetrahedron. laxed geometry. These energies proved to be excellent
From Eq. (1), the parameters are the three cluster for our purpose, with our ®nal values di€ering only
energies (for Cd3Mg, Cd2Mg2 and CdMg3), the para- slightly from them (the values of Asta et al. [2] are given
meters in the Redlich±Kister polynomial and . When in brackets):
has the value corresponding to strictly non-interfering Cluster energies/kJ (mol.atoms)ÿ1:
clusters ( =1 in this case), then the phase diagram cal-
culated by Li for fcc alloys [11] is obtained in which the
Cd3 Mg ˆ ÿ9:3 …ÿ10:3†
three ordered phases have their own critical regions but
the disordered phase is stable down to zero kelvin over
wide composition ranges between the ordered phases.
The critical compositions are also found at the stoichi-
metric values, as is the case in a CVM calculation. When,
however, is increased (a relatively large change in
produces only small but important changes in the relative
free energies of ordered and disordered phases), then, at
®rst, it is found that the critical compostions for the
Cd3Mg and CdMg3 phases move towards the mid-com-
postion and then, at 1.8 the congruent maximum is
lost completely, just as is observed in the Cd±Mg system.
From our previous experience with the calculation of
the Au±Cu phase diagram [7], we expected that, whilst it
might be possible to calculate an acceptable phase dia-
gram without the GECI …x; T† term, this term would be
essential in order to simultaneously obtain agreement
with the single phase thermodynamic properties.

3. Results

As a starting point for our calculations we used the

cluster energies calculated by Asta et al. [2] for the

Fig. 3. CSA calculated thermodynamic properties. The experimental

points are from Hultgren [16]: (a) enthalpy of mixing for both ordered
Fig. 2. CSA calculated ordering phase diagram for Cd±Mg alloys. (at 298 K) and disordered (at 543 K) alloys. (b) chemical potentials of
The experimental points are from [17]. Cd and Mg in disordered Cd±Mg alloys at 543 K.
8 J. Zhang et al. / Intermetallics 9 (2001) 5±8
Cd2 Mg2 ˆ ÿ13:7 …ÿ13:5†
CdMg3 ˆ ÿ9:95 …ÿ9:5†
Other than the values for the cluster energies, it was
only necessary to vary the Redlich±Kister con®guration
independent term and the entropy factor,
. Our ®nal phases using only ®ve model parameters in total.
values are as follows:
Redlich±Kister parameter: l0=21.62 kJ (mol.
atoms)ÿ1
ˆ 1:8
The calculated ordering phase diagram is shown in
Fig. 2 together with the experimental points from Fig.
1(a). Calculated and experimental results for the
enthalpies of mixing for ordered and disordered phases
are shown in Fig. 3(a) and the component element che-
mical potentials in the disordered phase in Fig. 3(b).
The assessed values recommended by Hultgren [16] were
used as the `experimental results'. It can be seen that the
agreement between calculated and experimental results
is extremely good in all three ®gures. Better agreement
could undoubtedly be obtained by introducing tem-
perature and/or composition dependent parameters but
there seems to be little else to be gained by this proce-
dure. The main point is that a satisfactory thermo-
dynamic description of the ordering phase diagram and
single phase properties can be obtained by using the
procedures outlined.
4. Conclusions
In order to obtain an accurate description of experi-
mental phase diagrams and the thermodynamic proper-
ties of ordered and disordered phases in an alloy system,
it is necessary to use parameterised solution phase
models. Models based on the point approximation are
capable of giving satisfactory thermodynamic descrip-
tions only when the compositional range of existence of
a phase is narrow and the phase is not involved in any
order/disorder transition. When these conditions break
down, as is the case for the Cd±Mg system, then point
approximation models run into diculties. Consider-
able improvement in the modelling, whilst still retaining
simplicity, can be obtained by using the modi®ed CSA.
Although not as soundly based as the CVM, it has
de®nite advantages for use in phenomenological calcula-
tions. In the case of the Cd±Mg system, we have found
it possible to obtain an excellent description for the
ordering phase diagram and the single phase thermo-
dynamic properties for both ordered and disordered
Acknowledgements
To the National Science Foundation and the USAF
Wright Labs. for partial ®nancial support (Grant No.
NSF-DMR-94-21780 and SBIR Contract No. F33615-
97-C-5276); to Dr. Bruce MacDonald of the Metal
Program of the Materials and Processing Center of NSF
and Dr. Dennis Dimiduk of the Wright Labs. for their
interest in this work.
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