Journal of Alloys and Compounds 681 (2016) 606e612

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Journal of Alloys and Compounds

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Letter

Thermodynamic evaluation of the Cu-In-Zn system

a b s t r a c t

Keywords: Phase equilibria in the Cu-In-Zn system are calculated using a thermodynamic modeling approach. The
Cu-In-Zn ternary system thermodynamic model parameters for the constituent binaries Cu-In,Cu-Zn and In-Zn are taken from
Phase diagrams earlier assessments. Thermodynamic descriptions of the ternary liquid and copper-based solutions are
Thermodynamic modeling
obtained based on the experimental thermodynamic and phase equilibria data available in literature for
the Cu-In-Zn system. The liquidus surface projection, isothermal sections at 373 and 573 K, as well as
vertical sections xCu/xIn ¼ 1:2, 1:1, 2:1 and xIn ¼ 0.75, 0.5 are calculated.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction Liu et al. [8] (Cu-In), Liang et al. [9] (Cu-Zn) and Lee [10] (In-Zn).
In our work the thermodynamic models for the Cu-In-Zn liquid
Lead-zinc ores contain many valuable metals, including Cu, Ag, and copper-based solutions were developed using the thermody-
Au, Bi, Ge, In. To improve the processes of separation and purifica- namic descriptions of these phases in the binary subsystems
tion of these metals, the knowledge of phase diagrams of the [8e10] as well as the liquidus and activity of Zn data [6] for the
appropriate multicomponent systems is necessary. An effective xCu/xIn ¼ 1:2, 1:1, 2:1 cross sections. Thereafter, different phase di-
approach to solve this problem is thermodynamic modeling, that agram sections for the Cu-In-Zn system were calculated by mini-
is, the construction of the thermodynamic models of phases with mizing the Gibbs energy of the system. In doing so,
the determination of analytical expressions for their Gibbs energies thermodynamic models, developed in Refs. [8e10] for the solid
on the basis of all available experimental data (thermodynamic phases of the systems Cu-In, Cu-Zn, and In-Zn, were used.
properties of the phases and equilibria with their participation).
The obtained thermodynamic models of phases can then be used
for the calculation of phase equilibria in the system at arbitrary 2. Binary systems
external variable values by minimizing the Gibbs energy of the
system. According to [8e15], the set of phases existing in the systems
A strategic goal of our research is the study of thermodynamic Cu-In, Cu-Zn, In-Zn includes liquid, terminal solid solutions, inter-
properties and the liquid separation of the system Cu-In-Pb-Sn- mediate solid solutions b, g, h0 (Cu-In), b0 , b00 , g0 , d0 , ε (Cu-Zn), as
Zn (including their subsystems) by means of the EMF method well as compounds d (Cu0.7In0.3), h (Cu0.64In0.36), q (Cu11In9). Struc-
and thermodynamic modeling [1e3] and the extension of the in- tural information on the solid phases in the Cu-In-Zn system is pre-
dustrial thermodynamic data bank developed earlier by Hertz sented in Table 1.
et al. [4]. The molar Gibbs energies of liquid, terminal solid solutions and
The aim of this work is the calculation of phase equilibria in the intermediate solutions b, b0 , d0 , ε were described in Refs. [8e10] by
ternary system Cu-In-Zn, which is the subsystem of the quaternary the formula:
Cu-In-Pb-Zn system. The In-Pb-Zn and Cu-In-Pb subsystems of the
X
2 X
2 X
Cu-In-Pb-Zn system were modeled previously [2,5]. Gfm ¼ xk G+f
k
þ RT xk ln xk þ x1 x2 an;f n;f
12 þ b12 T
Experimental data for the system Cu-In-Zn are limited by the k¼1 k¼1 n0
work of Knott et al. [6], where the liquidus temperatures (measured 
with the DSC) and activities of zinc in the liquid alloys at 1023 K þ cn;f
12 T ln T ðx1  x2 Þ
n
(1)
(determined by the EMF method) were determined along cross-
+4
sections xCu/xIn ¼ 1:2, 1:1, 2:1. No ternary compounds were found where f denotes the physical state of solution, Gk are the Gibbs
in the system Cu-In-Zn [6] as well as in the system Ag-In-Zn [7]. In- energies of the pure components (these functions were taken from
formation about a thermodynamic modeling of the Cu-In-Zn sys- Refs. [8e10]); xk are the mole fractions of the components in so-
n;4
tem is absent in the literature. The optimizations of the binary lution; R is the gas constant; Т is the absolute temperature; a12 ,
n;4 n;4
subsystems of the ternary Cu-In-Zn system were performed by b12 , c12 are parameters of the excess Gibbs energy of the binary
solution f.

http://dx.doi.org/10.1016/j.jallcom.2016.04.082
0925-8388/© 2016 Elsevier B.V. All rights reserved.
 Letter / Journal of Alloys and Compounds 681 (2016) 606e612 607

Table 1
Structural information on solid phases in the Cu-In-Zn system.

Phase Composition Pearson symbol Space group Prototype

(Cu) Cu1-x-yInxZny cF4 Fm3 m Cu

0  x  0.10, 0  y  0.40
(In) In1-xZnx tI2 I4/mmm In
0  x  0.01
(Zn) Zn1-x-yInxCuy hP2 P63/mmc Mg
0  x  2  103, 0  y  0.03
b Cu1-xInx cI2 Im3 m W
0.19  x  0.23
b0 Cu1-xZnx cI2 Im3 m W
0.36  x  0.56
b00 Cu1-xZnx cP2 Pm3 m CsCl
0.42  x  0.51
g Cu1-xInx cP52 P4 3 m InMn3
0.28  x  0.32
g0 Cu1-xZnx cI52 I4 3 m Cu5Zn8
0.57  x  0.70
d Cu0.7In0.3 aP40 P1 Cu7In3
d0 Cu1-xZnx hP3 P6 CuZn3
0.71  x  0.77
ε Cu1-xZnx hP2 P63/mmc Mg
0.77  x  0.88
h Cu0.64In0.36 hP6 P63/mmc Ni2In
h0 Cu1-xInx hP4 P63/mmc NiAs
0.33  x  0.38
q Cu0.55In0.45 mC20 C2/m AlCu
(Cu11In9)

The three-sublattice models [8] were used for the thermody-

namic description of g and h0 solid solutions ((Cu)0.654(Cu,I- ð2Þ ð3Þ g0 ð2Þ ð3Þ g0
Df Gg0 ¼ yCu yCu Df GCu:Cu:Cu þ yCu yZn Df GCu:Cu:Zn
n)0.115(In)0.231 for the g phase and (Cu)0.545(Cu,In)0.122(In)0.333 for
the h0 phase). These models were chosen on the base of crystal ð2Þ ð3Þ g0 ð2Þ ð3Þ g0
þ yZn yCu Df GCu:Zn:Cu þ yZn yZn Df GCu:Zn:Zn
structures (InMn3-type for the g phase and NiAs-type for the h0  
ð2Þ ð2Þ ð2Þ ð2Þ
phase) and homogeneous ranges of the phases [8]. The molar Gibbs þ ð3=13ÞRT yCu In yCu þ yZn In yZn
energy of formation of these phases was described as follows:  
ð3Þ ð3Þ ð3Þ ð3Þ
þ ð8=13ÞRT yCu In yCu þ yZn In yZn (5)
Df Gf ¼ yfCu Df GfCu:Cu:In þ yfIn Df GfCu:Cu:In
n    o ðkÞ
where yi is a molar fraction of the element i in the sublattice k of
þ C f RT yfCu In yfCu þ yfIn In yfIn yfCu yfIn L0;f (2)
Cu;In the phase g0
The solid solution b00 (ordered modification of the b0 phase) was
where yfi is a molar fraction of the element i in the second sub- described in Ref. [9] by the two-sublattice model (Cu,Zn)0.5(-
lattice of the phase f, С f is a number of sites on sublattice 2 per Cu,Zn)0.5. The molar Gibbs energy of formation of this solution is
0
mole of formula unit of phase f (С g ¼ 0.115 and С h ¼ 0.122), L0;f
Cu;In is given as follows:
an interaction parameter.
ð1Þ ð2Þ ð1Þ ð2Þ
00 ð1Þ ð2Þ 00 00
The functions Df GfCu:Cu:In and Df GfCu:In:In were derived as fol-
00
Df Gb ¼ yCu yCu Df GbCu:Cu þ yCu yZn Df GbCu:Zn þ yZn yCu Df GbZn:Cu
lows: 2 
  ð1Þ ð2Þ 00 X ðkÞ ðkÞ
þ yZn yZn Df GbZn:Zn þ 0:5RT yCu In yCu
Df GfCu:Cu:In ¼ GfCu:Cu:In  1 xf;1
In Gfcc
Cu  xf;1 tetr
In GIn k¼1

¼ af;1 þ bf;1 T (3)  X

2
ðkÞ ðkÞ ð1Þ ð1Þ b
ð2Þ 00 ð2Þ ð2Þ
  þ yZn In yZn þ yCu yZn yi L0;
Cu;Zn:i
þ yCu yZn
Df GfCu:In:In ¼ GfCu:In:In  1  xf;2 fcc f;2 tetr
In GCu  xIn GIn ¼ a
f;2
þ bf;2 T k¼1
X
2
ð1Þ b 00
(4)  yi L0;
i¼Cu;Zn
i¼1
g;1 h0;1 g;2 h0;2
where xIn ¼ 0:231, xIn ¼ 0:333, xIn ¼ 0:346, xIn ¼ 0:455; Gfcc Cu , (6)
Gtetr
In are the molar Gibbs energies of fcc copper and tetragonal in-
dium, respectively; af,i, bf,i are the fitting parameters. 00
where Df GbCu:Zn , Df GbZn:Cu , L0;b00
, L0; b 00 00
are thermodynamic pa-
Cu;Zn:i i:Cu;Zn
The three-sublattice model (Cu)2/13(Cu,Zn)3/13(Cu,Zn)8/13 pro- rameters, which can be expressed as functions of the disordered
posed in Ref. [9] was used for the thermodynamic description of n;b0 00
phase parameters LCu;Zn and the ordering parameter DGb (see
the g0 solid solution, which has Cu5Zn8-type structure. This model equation (21) given in Ref. [16]).
was chosen on the base of neutron diffraction studies and it fits The equation (6) can be simplified by introducing the order
well with the model (Cu)2/13(Cu,Zn)3/13(Al,Cu,Zn)8/13 for the ternary ð2Þ ð1Þ ð1Þ ð2Þ
parameter h ¼ yZn  yZn ¼ yCu  yCu  0 (non-negativity of this
Al-Cu-Zn g0 phase [9]. The molar Gibbs energy of formation of the parameter is due to our way of designating the sublattices in the
Cu-Zn g0 phase was described as follows: model (Cu,Zn)0.5(Cu,Zn)0.5 ewe have assigned the numbers 1 and
2 to the Cu-rich and Zn-rich sublattices, accordingly) and using
608 Letter / Journal of Alloys and Compounds 681 (2016) 606e612

n;4 n;4 n;4

equations that follow from the material balance equations and from (k ¼ 1, 2, 3 correspond to Cu, In, Zn, respectively); aij , bij , cij are
the condition of the equality to one of the sum of the mole fractions the parameters of the excess Gibbs energy of the solution f in the
4 4
in sublattices: binary subsystems; aijk , bijk are fitting parameters describing excess
    Gibbs energy of the ternary solutions (functions (x1ex2)i (x1ex3)j
ð1Þ ð2Þ ð1Þ ð1Þ
xZu ¼ 0:5 yZn þ yZn ¼ 0:5 2yZn þ h ¼ yZn þ 0:5 h; xCu 4 4
(x2ex3)k were taken for the parameters aijk , bijk to extend on ternary
solutions the Redlich-Kister formalism (i.e. the use of functions
¼ 1  xZn
(xiexj)n for the description of excess Gibbs energy of binary solu-
ð1Þ ð1Þ ð2Þ ð2Þ tions [18])).
yCu ¼ 1  yZn ; yCu ¼ 1  yZn
Table 2
Set of parameters for the phases of the Cu-In-Zn system
4 4 4 4
ðLn;
ij
¼ an;
ij
þ bn;
ij
T þ cn;
ij
T ln T; L4ijk ¼ a4ijk þ b4ijk Tðf denotes phaseÞÞ.
From these equations it follows that:
Phase Parameter Value (J mol1) Reference
ð1 Þ ð2Þ ð1Þ ð2Þ
yZn ¼ xZu  0:5h; yZn ¼ xZu þ 0:5h; yCu ¼ xCu þ 0:5h; yCu L L0;L
Cu;In
41564.8 þ 238.616 T29.827 TlnT [8]
76057.8 þ 371.306 T44.994 TlnT
¼ xCu þ 0:5h L1;L
Cu;In

L2;L 42076.5 þ 192.395 T23.281 TlnT

(7) Cu;In

L0;L 40688.6 þ 12.8655 T [9]

Cu;Zn
Substituting the expressions (7) into (6) and using the Eq. (21) L1;L 2252.3e4.8069 T
Cu;Zn
[16], which connect thermodynamic parameters of the ordered L2;L 5405.9e2.9197 T
(b00 ) and disordered (b0 ) phases, we obtain:
Cu;Zn

L0;L 12401e4.4498 T [10]

In;Zn
2 
X  L1;L 3186 þ 1.756 T
00 ðkÞ ðkÞ ðkÞ ðkÞ In;Zn
Df Gb ¼ 0:5RT yCu ln yCu þ yZn ln yZn L2;L 679
In;Zn
k¼1
LL000 36435 this work
X
2
b0 00 LL002 21827
þ xCu xZn Ln; ðx
Cu;Zn Cu  xZn Þ þ DGb h2
n
(8) (Cu) 0;ðCuÞ
LCu;In 6475.9 þ 21.830 T [8]
n¼0 1;ðCuÞ
LCu;In 29935.2e5.672 T
00
where the h value is determined by minimizing DfGb with respect 47350.2e40.210 T
2;ðCuÞ
LCu;In
to h at the fixed values of T, xCu, xZn, according to the equation 0;ðCuÞ
LCu;Zn 40716 þ 8.3 T [9]
00
(vDfGb /vh) ¼ 0. This equation has two solutions, which correspond 1;ðCuÞ
LCu;Zn 4812.8e4 T
to the disordered and ordered phase states: h ¼ 0 and h > 0. The ðCuÞ
L000 15097 this work
00 00
solution for which (v2DfGb /vh2)>0 corresponds to the DfGb value (In) 0;ðInÞ
LIn;Zn 4430e4.4498 T [10]
00
minimized with respect to h. If the equation (v DfG /vh ) ¼ 0 is
2 b 2
1;ðInÞ 9717
LIn;Zn
valid at h ¼ 0, the corresponding T and xZn values determine a
(Zn) 0;ðZnÞ
LCu;Zn 15739e12.56 Ta [9]
second-order phase transition point [17].
0;ðZnÞ 23114 [10]
The coordinates of the ordering reactions b0 4b00 , g0 and b0 4b00 , LIn;Zn
20532.8 þ 12.724 T
(Cu) in the Cu-Zn system, calculated by using the h parameter and b [8]
b
L0;
Cu;In

Eq. (8) coincide with those calculated in Ref. [9] and presented in 1;b
LCu;In 13379.3e12.358 T
Table 5 of [9]. b0 L0; b0 48042 þ 9.97 T [9]
Cu;Zn
The molar Gibbs energies of formation of the stoichiometric 1;b0
LCu;Zn 6100e6 T
compounds d, h and q were described by the formula: L2; b0 1000
Cu;Zn
4 4 4 4 b00 L0; b00 48042 þ 9.97 T [9]
Df GCu;In ¼ GCu;In  xCu Gfcc
Cu  xIn Gtetr
In ¼a þb T
f f
(9) Cu;Zn
b00 6100e6 T
L1;
Cu;Zn
4
where xi is a molar fraction of the element i in f -phase. 2;b00
LCu;Zn 1000

The whole set of thermodynamic parameters, obtained in Refs. DGb

00
3075
[8e10] for the phases of the Cu-In-Zn system is given in Table 2. g DfGgCu:Cu:In 2204.8e3.443 T [8]
DfGgCu:In:In 7131.6 þ 0.112 T
The phase diagrams of the systems Cu-In, Cu-Zn and In-Zn, calcu- 0
g0 DfGgCu:Cu:Cu 100 [9]
lated by using these parameters are presented in Figs. 1e3. 0
DfGgCu:Cu:Zn 10950.2e2.282 T
0
DfGgCu:Zn:Cu 0
0
DfGgCu:Zn:Zn 2396.77e4.32643 T
3. Thermodynamic calculations of the Cu-In-Zn system d DfGdCu;In 7991.3 þ 1.170 T [8]
d0 L0;d0 54593.9 þ 12.8111 T [9]
Cu;Zn
The molar Gibbs energies of ternary solutions (liquid, (Cu) and d0 142 þ 6.0249 T
L1;
Cu;Zn
(Zn)) were described as follows: ε 36818.3 þ 6.5 T [9]
L0;ε
Cu;Zn

4
X
3
+4
X
3 X
2 X
3 X n;4 n;4 L1;ε
Cu;Zn
27160.5e10.8351 T
Gm ¼ xk Gk þ RT xk ln xk þ xi xj aij þ bij T h DfGhCu;In 8173.8 þ 1.380 T [8]
h0
k¼1 k¼1 i¼1 j¼iþ1 n0 h0 DfGCu:Cu:In 6301.5e0.940 T [8]
 n X  4 h0
156.7e7.030 T
n;4 DfGCu:In:In
þ cij T ln T xi  xj þ x1 x2 x3 aijk 0;h0
LCu;In 14526.5 þ 18.020 T
i;j;k0
 q DfGqCu;In 7525.6 þ 1.703 T [8]
4 i j k
þ bijk T ðx1  x2 Þ ðx1  x3 Þ ðx2  x3 Þ a
The authors of [9] gave two different functions for the value of paraneter LCu;Zn :
0;ðZnÞ

e15492.5e12.276 T (Table 4 of [9]) and e15739e12.56 T (Appendix A of [9]; this

(10) section contains parameters directly used in the calculation). The latter function
permits to reproduce correctly the calculated in Ref. [9] coordinates of the invariant
where xk are the mole fractions of the components in the solution reaction Lþε4(Zn) in the Cu-Zn system (Table 5 of [9]).
 Letter / Journal of Alloys and Compounds 681 (2016) 606e612 609

T,K

700
L

(Zn)
600

L+(Zn)
500

400 (In)+L
(In) (In)+(Zn)

In 20 40 60 80 Zn
at. % Zn
Fig. 1. Calculated phase diagram of the Cu-In system.
Fig. 3. Calculated phase diagram of the In-Zn system.

experimentally determined phase equilibrium temperatures and

the thermodynamic functions of the phases; Ti(P) and Zj(P) are
calculated values corresponding to Ti* and Zj*; ui and uj are the
weighting factors, taken as the inverse of the determination error of
Ti* and Zj*.
The Zj(P) values were found using the well-known thermody-
namic relations, and the Ti(P) values were found by solving (using
the Newton method) the system of equations following from the
phase equilibrium condition:

X
3
j
Gj  nk meq
k
¼0 (12)
k¼1
4
Gk ðx4 Þ  meq
k
¼ 0 ðk ¼ 1; 2; 3Þ (13)
X j
mj nk ¼ nok ¼ ð1  qÞ x1k þ q x2k ðk ¼ 1; 2; 3Þ (14)
j

Here, j and f are the stoichiometric phases and solutions,

respectively, participating in equilibrium; the index k denotes the
components of the Cu-In-Zn system; xf stands for the mole frac-
tions of the components of the f-phase; Gj is the Gibbs energy of
4
the j phase, Gk is the chemical potential of the k-th component of
the f-phase; meq k
is the auxiliary variable corresponding to the
j
chemical potential of the component k at equilibrium; nk are the
Fig. 2. Calculated phase diagram of the Cu-Zn system.
numbers of moles of component k in j-phase; mj is the amount of
j
the j-th phase at equilibrium; nk is the number of moles of
component k in one mole of the j-th phase; n+k is the total amount of
n;4 n;4 n;4 the k-th component in the system; x1k and x2k are the molar con-
The aij , bij , cij parameters were taken from the thermody-
namic descriptions of binary subsystems [8e10] (see Table 2.). tents of Cu, In and Zn at the endpoints of isopleth, and q is a co-
4 4 efficient (0  q  1).
The aijk , bijk parameters, referring to excess Gibbs energies of the
ternary liquid and copper-based solutions, were considered as The following experimental information was used to determine
fitting ones and were found by minimizing the objective function: thermodynamic parameters:
X  2 X  2
FðPÞ ¼ u2i Ti ðPÞ  Ti* þ u2j Zj ðPÞ  Zj* (11) 1. The values of the activity of zinc in liquid Cu-In-Zn alloys at 1023
i j K, determined in Ref. [6] from the EMF measurements along the
sections xCu/xIn ¼ 1:2, 1:1 and 2:1. The uncertainty for these
where P designates the sought set of parameters; Ti* and Zj* are the values was estimated to be 0.07.
610 Letter / Journal of Alloys and Compounds 681 (2016) 606e612

aZn

0.8 1023 K

0.6

0.4

0.2
1 Cu:In = 1:2
2 Cu:In = 1:1
Cu:In = 2:1
3

0.0
0 20 40 60 80 100
at. % Zn
Fig. 6. Calculated vertical section of the Cu-In-Zn system at xCu/xIn ¼ 1:1 in comparison
Fig. 4. Calculated activities of zinc in the liquid Cu-In-Zn alloys at constant ratios of with the experimental data [6].
xCu/xIn ¼ 1:2, 1:1 and 2:1 at 1023 K (lines 1e3), compared with the experimental
data [6].

ðCuÞ
aL000 ¼ 36435; aL002 ¼ 21827; a000 ¼ 15907 (15)
2. The liquidus temperatures for the vertical sections xCu/xIn ¼ 1:2,
1:1 and 2:1, determined by means of DSC [6]. The accuracy of This set of parameters was used for the calculations of phase
these data was estimated to be 20 K. equilibria in the Cu-In-Zn system. They were performed by mini-
mizing the Gibbs energy of the system. The procedure involved cal-
The function (11) was minimized by the Marquardt method [19], culations of T, xb, mj, and meq
k
using the Eqs. 12e14 for the set of
ðCuÞ ðCuÞ phases under consideration. Then, the position of the surface given
trying the different sets of fitting aLijk , bLijk , aijk , bijk parameters. As P P
a result of the optimization, we obtained the following set of pa- by the expression 3k¼1 xk meqk
ðxk  0; 3k¼1 xk ¼ 1Þ and formed by
rameters (in J mol1): the calculated mk values was determined relative to the Gibbs
eq

Fig. 5. Calculated vertical section of the Cu-In-Zn system at xCu/xIn ¼ 1:2 in comparison Fig. 7. Calculated vertical section of the Cu-In-Zn system at xCu/xIn ¼ 2:1 in comparison
with the experimental data [6]. with the experimental data [6].
 Letter / Journal of Alloys and Compounds 681 (2016) 606e612
Fig. 8. Calculated vertical section of the Cu-In-Zn system at xIn ¼ 0.75.
energies of all system phases, normalized to 1 mol of the compo-
nents. If none of the system phases had a Gibbs energy lying below
this surface, the calculated equilibrium was considered stable;
otherwise, it was treated as metastable.
The calculated activity of zinc in the liquid Cu-In-Zn alloys at
constant ratios of xCu/xIn ¼ 1:2, 1:1 and 2:1 at 1023 K is presented
in Fig. 4. The calculated results are in a good agreement with the
experimental data [6].
The calculated vertical sections of the Cu-In-Zn system at xCu/
xIn ¼ 1:2, 1:1 and 2:1 are presented in Figs. 5e7. The calculation re-
sults for the sections xCu/xIn ¼ 1:2 and 2:1 are in a good accordance
with the measurements [6]. As for the section xCu/xIn ¼ 1:1, there is
a large deviation between the experimental and calculated melting
temperatures for the three compositions (40, 50 and 60 at. % Zn).
Fig. 9. Calculated vertical section of the Cu-In-Zn system at xIn ¼ 0.5.
611
Fig. 10. Calculated isothermal section of the Cu-In-Zn system at 373 K. Numbers 1e16
denote the phase regions: (Cu)þd (1), (Cu)þb00 þd (2), (Cu)þb00 (3), b00 þd (4), b00 þdþh
(5), b00 þh (6), b00 þg0 þh (7), g0 þh (8), g0 þhþq (9), g0 þq (10), g0 þqþ(In) (11), g0 þ(In)
(12), g0 þεþ(In) (13), εþ(In) (14), εþ(In)þ(Zn) (15), (In)þ(Zn) (16).
The calculated vertical sections of the Cu-In-Zn–system at
xIn ¼ 0.75 and xIn ¼ 0.5 are presented in Figs. 8 and 9. They are char-
acterised by wide regions of the primary crystallization of (Cu), g0 ,
and ε phases. At lower temperatures the phase regions Lþh0 þ(Cu),
Lþqþg0 , and qþ(In)þg0 prevail on the phase diagrams.
The calculated isothermal sections of the Cu-In-Zn system at 373
K and 573 K are plotted in Figs. 10 and 11, respectively. At 373 K the
Fig. 11. Calculated isothermal section of the Cu-In-Zn system at 573 K. Numbers 1e20
denote the phase regions: (Cu)þd (1), (Cu)þdþh (2), (Cu)þh (3), (Cu)þb00 (4), (Cu)þ
g0 þh (5), (Cu)þg0 (6), (Cu)þb00 þg0 (7), g0 þh (8), g0 þhþh0 (9), g0 þh0 þq (10), g0 þh0
(11), g0 þq (12), g0 þqþL (13), qþL (14), g0 þL (15), g0 þεþL (16), εþL (17), εþ(Zn)þL
(18), (Zn)þL (19), εþ(Zn) (20).
612 Letter / Journal of Alloys and Compounds 681 (2016) 606e612

performed, based on the available thermodynamic assessments of

the binary systems Cu-In, Cu-Zn and In-Zn as well as experimental
data [6] for the ternary system. Five vertical sections and two
isothermal sections were calculated. The liquidus surface projec-
tion and coordinates of the invariant points were determined.

Acknowledgements

We would like to thank Prof. Lorie Wood from Brigham Young

University -Hawaii (USA) for the language help. This work was
financially supported by the Russian Foundation for Basic Research
(projects no. 14-08-00942 and 14-08-00963).

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The calculated liquidus surface projection of the system Cu-In-
Zn system is given in Fig. 12, where bold lines represent univariant V.P. Vassiliev*, V.A. Lysenko**
equilibria and the thin lines denote liquidus isotherms at Lomonosov Moscow State University, Chemistry Department, 119991,
773e1273 K. The points, located at the intersections of solid lines, Moscow, Russia
correspond to the invariant equilibria. The types and coordinates
*
of these equilibria are listed in Table 3. There are ten transition Corresponding author.
equilibria, one eutectic and one degenerated invariant equilibria
**
in this system. Most of the invariant points are located near the Corresponding author.
Cu-In side of the Gibbs triangle. E-mail addresses: valeryvassiliev@yahoo.fr (V.P. Vassiliev),
vallys2@yandex.ru (V.A. Lysenko).
4. Conclusion
20 February 2016
The first thermodynamic modeling of the Cu-In-Znsystem was Available online 14 April 2016