Thermodynamic Assessment of The Phase Diagrams of The Cu-Sb and SB-ZN Systems

Section I: Basic and Applied Research
Thermodynamic Assessment of the Phase Diagrams of

the Cu-Sb and Sb-Zn Systems
X.J. Liu, C.P. Wang, I. Ohnuma, R. Kainuma, and K. Ishida
(Submitted 12 May 2000; in revised form 15 August 2000)

Thermodynamic assessments have been made for the Cu-Sb and Sb-Zn binary systems by means
of the CALPHAD technique. The Gibbs energies of the liquid, bcc, and fcc phases are described
by a substitution solution model and a Redlich-Kister formalism. All of the compounds were
treated as stoichiometric compounds. Moreover, the liquidus temperatures of the Zn-rich portion
in the Sb-Zn system were measured to check the unusual shape reported by previous work. It was
confirmed that the liquidus line is not peculiar but smooth. A consistent set of the thermodynamic
parameters was optimized to obtain a better fit between calculated results and experimental data
including phase diagram and thermodynamic quantities.
1.2 The Sb-Zn System
1. Introduction
In view of environmental and health concerns, substantial
effort is being made to develop Pb-free solder alloys as
replacements for the most commonly used Pb-Sn solder
[1993Jin, 1993McC]. The elements Sb, Zn, and Cu are
important in microsoldering alloys. Therefore, a knowledge
of the phase equilibria in the Sb-Cu and Sb-Zn binary systems
is desirable for the design of Pb-free solder alloys. A large
number of experimental investigations have been directed
toward establishing the phase diagrams of both systems. The
investigations carried out on each binary phase diagram have
been summarized by [1990Mas, 1994Sub], respectively, as
shown in Fig. 1 and 2. Some information on the solid phases
in both systems is listed in Table 1.
Although thermodynamic calculations have already been
carried out for the Cu-Sb system [1991Nit, 1991Tep] and
for the Sb-Zn system [1993Zab], some unresolved problems
remain as follows.
[1993Zab] carried out a thermodynamic assessment paying particular attention to the unusual shape of the liquidus
line in the Zn-rich portion [1927Tak], where the Gibbs energy
of liquid phase was described by both associated and regular
solution models. Although the calculated results show good
agreement with the experimental data in both models, the
thermodynamic parameters for the liquid phase assessed by
[1993Zab] have many terms, which often makes it impossible
to obtain a better fit in the assessment of higher-order systems.
Furthermore, some intermetallic phases were not considered
in the calculation.
The purpose of the present paper is to reassess the phase
diagrams and the thermodynamic parameters of the Cu-Sb
and Sb-Zn systems.
2. Thermodynamic Models
2.1 Solution Phases
1.1 The Cu-Sb System

Two assessments reported by [1991Nit] and [1991Tep]
are in good agreement with both experimental phase equilibria data and the measured thermodynamic properties. However, the problem with both assessments is that the phase
was treated as an fcc phase, and the lattice stabilities of Cu
and Sb in the fcc phase were used for the phase in their
calculations. However, it had been reported earlier that the
phase has a D03 structure [1940Age, 1941Hof], which is
an ordered phase of the disordered bcc (A2) structure. Thus,
the phase should be treated as a bcc phase, rather than an
fcc phase, to allow the calculations to be applied to higherorder systems in which the phase with the A2, B2, or D03
structure appears.
The Gibbs energies of liquid, bcc, fcc, (Sb), and (Zn)

phases are described by a substitutional solution model with
Redlich-Kister polynomials [1948Red], as follows:
Gm 0Gixi 0Gjxj RT(xi ln xi xi ln xi)
xixjLi,j
Li,j
m
Li,j
(xi xj)m
(i, j Cu,Sb or Sb,Zn,
m0
respectively)
is temperature dependent and is estimated on the

where mLi,j
basis of the available thermodynamic and phase diagram data.
2.2 Intermetallic Compound Phases

X.J. Liu, C.P. Wang, I. Ohnuma, R. Kainuma, and K. Ishida, Department of Materials Science, Graduate School of Engineering, Tohoku
University, Sendai 980-8579, Japan. Contact e-mail: ishida@
material.tohoku.ac.jp.
432
The single-phase stability ranges of the compound phases

in both systems are very narrow and cannot be clearly determined for some compounds. In the present assessment, all
Journal of Phase Equilibria Vol. 21 No. 5 2000
Basic and Applied Research: Section I
Fig. 1 Phase diagram of the Cu-Sb binary system [1994Sub]
Fig. 2 Phase diagram of the Sb-Zn binary system [1990Mas]
compound phases are treated as stoichiometric line compounds, for which the Gibbs energies of formation of the
compounds can be written as
G
CupSbq
G
p
q
for the Cu-Sb system
0
CupSbq
Gfcc
Cu
GA7
Sb
0 hcp
GSbmZnn 0GSbmZnq m0GA7
Sb n GZn
for the Sb-Zn system
where 0GCupSnq and 0GSbmZnn express the Gibbs energies of

the compound phases CupSbq and SbmZnn in the Cu-Sb and
Sb-Zn systems, respectively.
433

Table 1 Solid phases in the Cu-Sb and Sb-Zn systems
System
Phase
Cu-Sb
(Cu)
(Sb)
(Sb)
(Zn)
Sb-Zn
Composition
(at.% Sb)
Strukturbericht
designation
05.8
19.430.8
15.516.0
18.520.0
22.825.3
21.321.6
32.033.3
100
100
4750
4446
4243
41.543
3940
0
A1
D03
A3
D0a
C38
A7
A7
Be
A3
Prototype
Cu
BiF3
Mg
Cu3Ti
Cu10Sb3
Cu2Sb
As
As
CdSb
Mg
Modeling phase
Fcc, (Cu,Sb)
Bcc, (Cu,Sb)
Cu17Sb3, (Cu)0.85(Sb)0.15
Cu4Sb, (Cu)0.8(Sb)0.2
Cu3Sb, (Cu)0.75(Sb)0.25
Cu10Sb3, (Cu)0.77(Sb)0.23
Cu2Sb, (Cu)0.67(Sb)0.33
A7, (Sb)
A7, (Sb, Zn)
SbZn, (Sb)0.5(Sb)0.5
Sb9Zn11, (Sb)0.45(Sb)0.55
Sb17Zn23, (Sb)0.425(Sb)0.575
Sb17Zn23, (Sb)0.425(Sb)0.575
Sb4Zn6, (Sb)0.4(Sb)0.6
A3, (Sb,Zn)
Table 2 Comparison of enthalpies of formation for intermetallic phases assessed in the present calculation with
the experimental data (kJ/mol)
System
Phase
This work(a)
Previous work
Reference
Cu-Sb
(Cu17Sb3)
(Cu4Sb)
(Cu3Sb)
(Cu10Sb3)
(Cu2Sb)
2.68
5.142
4.718
4.936
4.351
Sb-Zn
(SbZn)
0.27 at 502 C
4.23 at 450 C
4.205 at 502 C
1.35 at 500 C
11.89 at 450 C
9.517 0.627 at 427 C
4.35(b)
5.28(b)
5.78(b)
[1973Hul]
[1956Kle]
[1973Hul]
[1982Bro]
[1981Zab]
[1973Hul]
[1981Zab]
[1981Zab]
[1981Zab]
11.541
(Sb9Zn11)
(Sb17Zn23)
(Sb17Zn23)
(Sb4Zn6)
8.749
7.348
7.731
4.918
(a) Not temperature dependent

(b) Experimental data are taken as the average values
The unary data for the pure elements were taken from
[1991Din] and are listed in Tables 3 and 4.
3. Computerized Optimization
The evaluation of thermodynamic parameters has been
done with PARROT computer software developed by
[1985Sun].
3.1 The Cu-Sb System
The liquid-phase parameters assessed by [1991Tep] are
found to be acceptable for an adequate description of the
434
liquid phase and have been used in the present assessment

with no alterations. The parameters for the phase were
optimized by combining the lattice stabilities of the bcc
phases for the pure elements, experimental data for the phase
equilibria, and thermodynamic properties.
The calculated phase diagram for the Cu-Sb system with
the temperatures of invariant reactions is shown in Fig. 3(a)
and is also shown in Fig. 3(b) with a comparison between
calculated and experimental results [1904Bai, 1906Hio,
1920Rei, 1931Arc, 1934Hum, 1936Mur, 1937Mer, 1938Shi,
1939Osa, 1959Vec, 1983Heh]. It is seen that good agreement
is obtained between the calculated and experimental results
for both temperatures of invariant reactions and the various
phase boundaries. Figure 4 gives the calculated activities of

Table 3 Thermodynamic parameters used in the
calculation of the Cu-Sb binary phase diagram
(J/mol)
Table 4 Thermodynamic parameters used in the

calculation of the Sb-Zn binary phase diagram
(J/mol)
Liquid phase, format (Cu,Sb)
Liquid phase, format (Sb,Zn)
For 298.151358.02 K:
0 L
GCu 12,964.84 9.510243 T 5.83932 1021 T 7 GHSERCU
For 1358.023200 K:
0 L
GCu 13495.4 9.920463 T 3.64643 1029 T 9 GHSERCU
For 298.15903.9 K:
0 L
GSb 19,822.595 21.920597 T 1.73785 1020 T 7 GHSERSB
For 903.92000 K:
0 L
GSb 19,913.982 22.026755 T 1.610442 1027 T 9
GHSERSB
0 L
LCu,Sb 16,154.82 23.99549 T 4.0284 T ln (T )
1 L
LCu,Sb 35,130.8 50.3301 T 5.2316 T ln (T )
2 L
LCu,Sb 29,263.28 15.3192 T
3 L
LCu,Sb 2300.89
4 L
LCu,Sb 8873.94
phase (bcc), format (Cu,Sb)

For 298.153200 K:
GCu 4017 1.255 T GHSERCU
For 298.153000 K:
0
GSb 19,874 15.1 T GHSERSB
0
LCu,Sb 50,092.341 41.561183 T
1
LCu,Sb 331,192.835 110.62385 T
2
LCu,Sb 301,571.206 15 T
3
LCu,Sb 984.45639 77.2521 T
4
LCu,Sb 90 T
0
For 298.15903.9 K:
0 L
GSb 19,822.595 21.920597 T 1.73785 1020 T 7 GHSERSB
For 903.92000 K:
0 L
GSb 19913.982 22.026755 T 1.610442 1027 T 9
GHSERSB
For 298.15692.73 K:
0 L
GZn 7157.27 10.292343 T 3.58652 1019 T 7 GHSERZN
For 692.733000 K:
0 L
GZn 7450.123 10.736234 T 4.70657 1026 T 9 GHSERZN
0 L
LSb,Zn 11,740.942 0.1283 T
1 L
LSb,Zn 427.582 0.809855 T
2 L
LSb,Zn 34,440.943 33.59286 T
(Zn) phase, format (Sb,Zn)
For 298.155000 K:
0 (Zn)
GSb 19,874 13 T GHSERSB
For 298.153000 K:
0 (Zn)
GZn GHSERZN
0 (Zn)
LSb,Zn 50,000
(Sb) phase, format (Sb,Zn)
phase (CU10SB3), format (Cu)0.77(Sb)0.23

G 4936.6 0.94 T 0.77 GHSERCU 0.23 GHSERSB
For 298.156000 K:
0 (Sb)
GSb GHSERSB
For 298.153000 K:
0 (Sb)
GZn 2300 11.5 T GHSERZN
phase (CU17SB3), format (Cu)0.85(Sb)0.15

0
G 2680 1.8 T 0.85 GHSERCU 0.15 GHSERSB
phase (CU2SB), format (Cu)0.67(Sb)0.33
0
G 4350.772 3.888 T 0.67 GHSERCU 0.33 GHSERSB
0
G 4718 1.69 T 0.75 GHSERCU 0.25 GHSERSB

G 5142 0.8 GHSERCU 0.2 GHSERSB
phase (SB19ZN31), format (Sb)0.38(Zn)0.62

0
G 5042.71 2.743826 T 0.38 GHSERSB 0.62
GHSERZN
G 4918.01 3.37557 T 0.4 GHSERSB 0.6 GHSERZN

G 8748.7632 1.3365 T 0.45 GHSERSB 0.55
GHSERZN
0
GSb 19874 13.7 T GHSERSB
0
LCu,Sb
phase (SB17ZN23L), format (Sb)0.425(Zn)0.575

0
G 7730.454 0.425 GHSERSB 0.575 GHSERZN
phase (fcc), format (Cu,Sb)

0
GCu GHSERCU
0
phase (SB17ZN23H), format (Sb)0.425(Zn)0.575

G 7348 0.5 T 0.425 GHSERSB 0.575 GHSERZN
8534 10.44293 T
phase (SBZN), format (Sb)0.5(Zn)0.5

0
G 11,542.68 5 T 0.5 GHSERSB 0.5 GHSERZN
(Sb) phase, format (Sb)

0 (Sb)
GSb GHSERSB
Symbols:
Symbols:
GHSERCU 7770.458 130.485403 T 24.112392 T ln (T )

0.00265684 T 2 1.29223 107 T 3 52478
T1
(298.15 K T 1358.02 K)
GHSERCU 13,542.33 183.804197 T 31.38 T ln (T )
3.64643 1029 T9
(1358.02 K T 3200 K)
GHSERSB 9242.858 156.154689 T 30.5130752 T ln (T )
0.007748768 T 2 3.003415 106 T 3 100,625
T1
(298.15 K T 903.9 K)
GHSERSB 11,738.671 169.485713 T 31.38 T ln (T )
1.610442 1027 T9
(903.9 K T 2000 K)
GHSERSB 9242.858 156.154689 T 30.5130752 T

ln (T ) 0.007748768 T 2 3.003415 106T 3 100,625
T1
(298.15 K T 903.9 K)
GHSERSB 11,738.671 169.485713 T 31.38 T ln (T )
1.610442 1027 T9
(903.9 K T 2000 K)
GHSERZN 7285.787 118.469269 T 23.701314 T ln (T )
0.001712034 T 2 1.264963 106 T 3
(298.15 K T 692.73 K)
GHSERZN 11,070.597 172.344911 T 31.38 T ln (T )
4.70657 1026T9
(692.73 K T 3000 K)
435
(a)
Fig. 3 (a) Calculated phase diagram of the Cu-Sb system by the present assessment (Continued on next page)
Cu and Sb at 502 C and shows good agreement with experimental data [1973Hul, 1982Bro]. A comparison on the
enthalpy of mixing at 502 C for calculated results and experimental data [1973Hul,1982Bro] is shown in Fig. 5. It should
be noted that the enthalpy of mixing curve with a U-shape in
the region of the bcc phase, as determined experimentally
by [1982Bro], is well described by the present assessment.
However, it can be seen that for the Cu2Sb compound, the
enthalpy of formation at 500 C [1982Bro] is very different
from those measured at 502 C [1973Hul] and 450 C
[1956Kle]. This might be because it is difficult to determine
the enthalpy of formation of this compound exactly due to the
very narrow and undetermined phase region, as shown in Fig.
1. The present calculated result is in good agreement with
the data of [1973Hul, 1956Kel]. The calculated enthalpies of
formation for intermetallic phases together with some experimental data are listed in Table 2. These indicate that the two
are in reasonable agreement with each other.
3.2 The Sb-Zn System
The thermodynamic parameters for the liquid and compound phases were evaluated on the basis of experimental
436
data for phase equilibria and thermodynamic properties. Figure 6(a) is the calculated phase diagram where the temperatures of invariant reactions are labeled, and a comparison
between the calculated phase diagram and experimental data
is shown in Fig. 6(b). Good agreement with the phase diagram
exists between calculation and experiment [1927Tak], except
for the liquidus curve in the concentration region at 64 to 76
at.% Zn, where [1927Tak] determined that the liquidus had
an unusual shape without explanation. It is necessary to
increase the temperature- and composition-dependent terms
to reproduce the experimental data in this part of the curve.
This discrepancy was previously discussed in the report of
[1993Zab]. In order to test the results of [1927Tak], differential scanning calorimetry measurements were made with heating and cooling rates of 1 C/min with sintered Al2O3 as the
reference specimen. The new experimental results are listed
in Table 5 and shown in Fig. 6. These newer results indicate
that the liquidus curve in the relevant composition range
should have a smooth shape, and not the unusual shape
reported by [1927Tak].
In addition, the calculated results for the phase equilibria
at high temperature in the composition range of 57 to 62
at.% Zn are different from the phase diagram reviewed by
(b)
Fig. 3 Continued. (b) Comparison between the calculated phase diagram and experimental data
Fig. 4 Activities of Cu and Sb in the solid phases of the Cu-Sb system
437
Fig. 5 Enthalpies of formation of the solid phases of the Cu-Sb system
(a)
Fig. 6 (a) Calculated phase diagram of the Sb-Zn system by the present assessment (Continued on next page)
438
(b)
Fig. 6 Continued. (b) Comparison between the calculated phase diagram and experimental data
Table 5 Transformation temperatures determined by DSC

Composition of alloys and transformation temperature (C)
Reaction
Liquidus line
L}
L } (Zn)
Sb-72.4 at.%
Zn
Sb-76.4 at.%
Zn
Sb-77.6 at.%
Zn
Sb-81.3 at.%
Zn
Sb-83.4 at.%
Zn
541
455
409
528
455
409
516
455
409
508
455
410
503
455
409
[1990Mas] (Fig. 2). [1990Mas] accepted the results of

[1966Vui], in which a eutectic reaction (L } ) was
reported at high temperature. However, in the present assessment, a peritectic reaction (L } ) is obtained; this
seems to be reasonable and is supported by previous work
[1927Tak, 1958Han].
The experimental data for the thermodynamic properties
were also considered during the optimization. Figure 7 to 10
show, respectively, the calculated activity, enthalpy of mixing, Gibbs energy of mixing, and chemical potential in comparison with experimental data, and it can be seen that there
is generally good agreement between calculated results and
experimental data [1973Hul, 1974Rub, 1961Sch, 1986Ger].

The enthalpies of formation for the compounds are also compared with the same experimental data, in Table 2. As can
be seen, the calculated values are in fair agreement with the
experimental data.
4. Summary
Thermodynamic reassessments of the phase diagrams and
thermodynamic properties of the Cu-Sb and Sb-Zn systems
439
Fig. 7 Activities of Sb and Zn in the liquid phase of the Sb-Zn system
Fig. 8 Enthalpy of mixing in the liquid phase of the Sb-Zn system
have been carried out. Good agreement between the calculated results and experimental data, including phase equilibria
and thermodynamic properties, has been obtained for both
systems.
References
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Fig. 9 Gibbs energy of mixing in the liquid phase of the Sb-Zn system
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Section I: Basic and Applied Research