Journal of ELECTRONIC MATERIALS, Vol. 37, No.

7, 2008 Regular Issue Paper

DOI: 10.1007/s11664-008-0464-x
 2008 TMS

Phase Equilibria of the Sn-Sb Binary System

SINN-WEN CHEN,1,3 CHIH-CHI CHEN,1 WOJCIEH GIERLOTKA,1,2

AN-REN ZI,1 PO-YIN CHEN,1 and HSIN-JAY WU1

1.—Department of Chemical Engineering, National Tsing Hua University, #101, Sec. 2, Kuang-Fu
Road, Hsin-Chu 300, Taiwan. 2.—Non-Ferrous Metals Department, AGH University of Science
and Technology, Mickiewicza 30, 30-059 Krakow, Poland. 3.—e-mail: swchen@mx.nthu.edu.tw

Sn-Sb alloys are important high-temperature solders. However, inconsisten-

cies are found in the available phase diagrams, and some phase boundaries in
the Sn-Sb system have not been determined. Sn-Sb alloys were prepared,
equilibrated at 160
C to 300
C, and the equilibrium phases and their com-
positions were determined. The b-SnSb phase has a very wide compositional
homogeneity range, and its composition varies from Sn-47.0at.%Sb to
Sn-62.8at.%Sb. There is no order–disorder transformation of the b-SnSb
phase. There are three peritectic reactions in the Sn-Sb system, L + Sb = b-SnSb,
L + b-SnSb = Sn3Sb2, and L + Sn3Sb2 = Sn, and their temperatures are 424
C,
323
C, and 243
C, respectively. Thermodynamic models of the Sn-Sb binary
system were developed using the CALPHAD approach based on the experi-
mental results of this study and the data in the literature. The calculated
phase diagram and thermodynamic properties are in good agreement with the
experimental determinations.

Key words: Sn, Sb, DTA, CALPHAD, thermodynamics

INTRODUCTION tem has been investigated by various groups.8–16

However, the phase boundaries at temperatures
Soldering is the most important joining technol-
lower than 250
C have not been determined and the
ogy in the electronics industry.1–6 Step soldering
available phase diagrams8–10 are not consistent.
refers to the circumstance that soldering processes
One compound, b-SnSb, with large compositional
occur at various steps because more than one
homogeneity range and an order–disorder trans-
soldering process is needed for some electronic
formation was proposed by Hansen and Anderko.8
products.1–3 To avoid remelting of the earlier solder
In addition to the b phase, Predel and Schwermann9
joints in the later soldering processes, solders with
proposed another compound, Sn3Sb2, which was
different melting points are used. The melting
stable only within a small temperature range.
points of Sn-Sb alloys are higher than that of con-
Vassiliev et al.10 suggested four compounds, b, b¢,
ventional eutectic Sn-Pb solder and they have been
b¢¢, and b¢¢¢, in the Sn-Sb binary system.
used as high-temperature solders in step soldering
In the recent phase equilibrium study of ternary
processes.4–6 In addition, various Sn-Sb-based
Sn-Sb-Cu and Sn-Sb-Ag systems,17,18 the phase
alloys have been developed as high-temperature
boundaries along the Sn-Sb binary side were found
solders in compliance with recent Pb-free require-
to be inconsistent with all of the available binary
ments7 for electronic products.
phase diagrams.8–10 This study experimentally
Knowledge of Sn-Sb phase equilibria is essential
determined the phase diagram of the binary Sn-Sb
for the understanding and development of Sn-Sb-
system focusing on resolving the differences in the
based alloys. The phase diagram of the Sn-Sb sys-
available phase diagrams, and also establishing the
phase boundaries which have not been determined
previously. The phase equilibrium results deter-
(Received December 17, 2007; accepted March 31, 2008; mined in this study and the thermodynamic and
published online May 1, 2008)

992
Phase Equilibria of the Sn-Sb Binary System
phase equilibrium data in the literature8–30 are
then used together for thermodynamic modeling
using the CALPHAD approach.31
PHASE EQUILIBRIA
Experimental Procedures
Sn-Sb alloys were prepared with pure Sn shots
(99.9%, SHOWA, Japan) and Sb shots (99.999%,
Sigma-Aldrich, USA). Proper amounts of pure ele-
ments were weighed and encapsulated in a quartz
tube. The sample capsule was placed in a furnace at
1000
C for 3 days to ensure that Sn shots and Sb
shots were molten and completely mixed, and then
quenched in water. The quenched sample was
equilibrated at a predetermined temperature for
8–12 weeks. The equilibrated alloys were cut into
several pieces for metallographic analysis, X-ray
diffraction (XRD) analysis, and differential thermal
analysis (DTA).
A scanning electron microscope (SEM) (JSM-5600,
JEOL, Japan) equipped with backscattered elec-
tron imaging (BEI) and optical microscopy were
used for microstructural observations. The compo-
sitions of equilibrated phases were determined by
electron probe microanalysis (EPMA) (JEOL, JXA-
8200, Japan) with wavelength dispersive spectros-
copy (WDS). Powder XRD (BRUKE D8A, Germany,
with Cu Ka1 radiation) was used for structural
Fig. 1. (a) Optical micrograph of alloy #01 annealed at 280
C for 8 weeks. (b) Optical micrograph of alloy #09 annealed at 210
C for 12 weeks
(c) Optical micrograph of alloy #11 annealed at 300
C for 12 weeks. (d) SEI micrograph of alloy #12 annealed at 300
C for 12 weeks.
993
analysis. The phase transformation temperatures
were determined from the DTA heating curves
(Perkin Elmer, DTA-7, USA) at a scanning rate of
8
C/min.
Results and Discussion
Figure 1a shows an optical micrograph of alloy
#01 (Sn-30at.%Sb) annealed at 280
C for 8 weeks;
two phases are observed. The composition of the
matrix region is Sn-12.8at.%Sb, and that of the
bright phase is Sn-43.3at.%Sb. Based on the phase
diagram by Predel and Schwermann,9 alloy #01 is in
the L + Sn3Sb2 two-phase region at 280
C. The
bright phase is the Sn3Sb2 phase and the matrix
region was the liquid phase prior to quenching.
According to the phase diagrams by Hansen and
Anderko8 and Vassiliev et al.,10 alloy #01 is also in a
L + solid two-phase field. However, their phase
diagrams8,10 do not have the Sn3Sb2 phase, and the
bright phase is the b-SnSb phase. The compositions
of the solid phase at 280
C predicted by the three
phase diagrams8–10 are 42 at.%, 45 at.%, and
50 at.%, respectively. Only the result based on the
phase diagram of Vassiliev et al.10 is very differ-
ent from the experimental determination. Similar
results are found for alloy #02 (Sn-15.0at.%Sb)
equilibrated at 280
C; it is in a L + solid two-phase
region. The equilibrium phases of Sn-Sb alloys are
summarized in Table I.
994 Chen, Chen, Gierlotka, Zi, Chen, and Wu

Table I. Experimental Results of Sn-Sb Phase Equilibria Determined in This Study

Composition

Alloy # Nominal Composition Equilibrium Phase Sn (at.%) Sb (at.%) Temperature (°C)

01 Sn-30.0at.%Sb Liquid 87.2 12.8 280

Sn3Sb2 56.7 43.3
02 Sn-15.0at.%Sb Liquid 88.2 11.8 280
Sn3Sb2 56.7 43.3
03 Sn-41.5at.%Sb Liquid 89.6 10.4 250
Sn3Sb2 57.0 43.0
04 Sn-42.0 at.%Sb Liquid 89.5 10.5 250
Sn3Sb2 56.7 43.3
05 Sn-44.0at.%Sb b-SnSb 55.9 44.1 250
06 Sn-46.0at.%Sb b-SnSb 54.6 45.4 250
07 Sn-48.0at.%Sb b-SnSb 52.1 47.9 250
08 Sn-50.0at.%Sb b-SnSb 49.7 50.3 250
09 Sn-30.0at.%Sb Sn 91.2 8.8 210
Sn3Sb2 57.0 43.0
10 Sn-15.0at.%Sb Sn 91.8 8.2 210
Sn3Sb2 56.8 43.2
11 Sn-45.0at.%Sb Sn3Sb2 56.7 43.3 300
b-SnSb 53.5 46.5
12 Sn-70.0at.%Sb b-SnSb 38.9 61.1 300
Sb 10.6 89.4
13 Sn-70.0at.%Sb b-SnSb 42.4 57.6 210
Sb 7.4 92.6
14 Sn-70.0at.%Sb b-SnSb 45.2 54.8 160
Sb 7.0 93.0
15 Sn-80.0at.%Sb b-SnSb 38.8 61.2 300
Sb 10.5 89.5
16 Sn-80.0at.%Sb b-SnSb 42.0 58.0 210
Sb 7.2 92.8
17 Sn-80.0at.%Sb b-SnSb 44.8 55.2 160
Sb 6.8 93.2

No phase boundaries can be discerned in either
the optical or BEI micrographs of alloy #05
(Sn-44.0at.%Sb) annealed at 250
C for 8 weeks. The
composition is uniform within experimental uncer-
tainties through the entire sample, and it is in a
single-phase region. Similar results are found for
alloys #06 (Sn-46.0at.%Sb), #07 (Sn-48.0at.%Sb),
and #08 (Sn-50.0at.%Sb), and they are all in a sin-
gle-phase region. The compositions of the equili-
brated phases are listed in Table I; they are all
identical to the nominal compositions within
experimental uncertainties. The results agree with
the phase diagrams by Hansen and Anderko8 and
Predel and Schwermann,9 and again are not con-
sistent with that by Vassiliev et al.,10 who proposed
the formation of four stoichiometric compounds
based on their electromotive force, differential
thermal analysis, and X-ray diffraction studies.
However, all the evidences are secondary and not
very significant.10 The validity of their phase dia-
gram is doubtful and will not be further discussed.
The DTA heating and cooling curves of the
Sn-20.0wt.%Sb (Sn-19.6at.%Sb) alloy are shown in
Fig. 2a. The scanning rate was 8
C/min. Two reac-
tions are observed, at temperatures of 314.4
C and
243.1
C, respectively. Since superheating is less
significant than undercooling, the reaction temper-
atures were determined from the heating curve.
According to both phase diagrams,8,9 314.4
C is the
liquidus temperature. According to the phase dia-
gram of Hansen and Anderko,8 243.1
C is the tem-
perature of the peritectic reaction, L + b-SnSb =
Sn. According to the phase diagram of Predel and
Schwermann,9 243.1
C is the temperature of the
eutectoid reaction, Sn3Sb2 = Sn + b-SnSb, and the
L + Sn3Sb2 = Sn peritectic reaction should occur at
a higher temperature of 250
C. However, as shown
in Fig. 2a, only one reaction peak is found in that
temperature range. Similar results were found by
Allen and Perepezko,16 and no second reaction peak
could be discerned around 240
C to 250
C.
It should be mentioned that the temperatures in
the DTA figures such as Fig. 2a are raw experi-
mental data without calibration. The reaction tem-
peratures reported in this study are the calibrated
results. Calibration was conducted based on the
calibration curves determined from pure Sn, Sb, Pb,
and eutectic Sn-Pb alloy. The reaction temperature
of the peritectic reaction, which is an invariant
reaction, is determined from the onset of the reac-
tion peak. The temperatures of the other non-
invariant type of reactions, such as the liquidus
Phase Equilibria of the Sn-Sb Binary System
Fig. 2. (a) DTA heating and cooling curves of the Sn-20.0wt.%Sb alloy. (b) DTA heating and cooling curves of the Sn-30.0wt.%Sb alloy. (c) DTA
heating and cooling curves of the Sn-40.0wt.%Sb alloy. (d) DTA heating and cooling curves of the Sn-75.0wt.%Sb alloy.
temperature, were determined from the peak tem-
perature that corresponds to the completion of the
melting process. More detailed discussion of the
DTA and differential scanning calorimetry (DSC)
curves can be found in the literature.32–35
Figure 2b shows the DTA heating and cooling
curves of the Sn-30.0wt.%Sb (Sn-29.5at.%Sb) alloy.
Three reaction peaks are observed, at temperatures
of 357.2
C, 322.6
C, and 243.1
C, respectively. The
reaction temperature of 357.2
C is the liquidus tem-
perature. According to the phase diagram of Hansen
and Anderko,8 322.6
C is the temperature of the
peritectic reaction, L + b-SnSb = b¢-SnSb, resulting
from the order–disorder reaction. According to the
phase diagram of Predel and Schwermann,9 322.6
C
is the temperature of the peritectic reaction, L + b-
SnSb = Sn3Sb2. Different from the prediction of the
phase diagram of Predel and Schwermann,9 only one
reaction peak is found around 240
C to 250
C. The
reaction temperature at 243.1
C is the peritectic
reaction temperature according to the phase diagram
of Hansen and Anderko.8 Similar DTA results of the
Sn-40.0wt.%Sb (Sn-39.4at.%Sb) alloy are found, as
995
shown in Fig. 2c. The reaction temperatures are
243
C, 323
C, and 391
C, respectively.
Based on the above DTA experimental results, the
phase diagram of Hansen and Anderko8 is likely a
more realistic one. Figure 2d shows the DTA heating
and cooling curves of the Sn-75.0wt.%Sb alloy. Two
reaction peaks are observed, at reaction tempera-
tures of 424
C and 549
C. The liquidus temperature
is 549
C, and 424
C is the temperature of the
L + Sb = b-SnSb peritectic reaction. If the phase
diagram proposed by Hansen and Anderko8 were
correct, there should be a eutectoid reaction peak
caused by the order–disorder transformation reac-
tion of the b-SnSb phase. No reaction peak is observed
at temperatures lower than 424
C, which indicates
that the order–disorder transformation reaction of
the b-SnSb phase does not exist. Careful experimen-
tal structural determinations of the b-SnSb phase by
Allen and Perepezko16 do not support the existence of
the order–disorder transformation reaction either.
Based on the phase equilibrium experiments and
DTA results, a new Sn-Sb binary phase diagram is
proposed, as shown in Fig. 3a. The Sn3Sb2 phase
996
Fig. 3. (a) The Sn-Sb binary phase diagram superimposed with the experimental determinations of this study. (b) The calculated Sn-Sb binary
phase diagram superimposed with the experimental determinations. (c) The calculated Sn-Sb binary phase diagram.
exists and is stable all the way to below room
temperature, there is no phase transformation in
the b-SnSb phase, and there are three peritectic
reactions: L + Sb = b-SnSb, L + b-SnSb = Sn3Sb2,
and L + Sn3Sb2 = Sn. The DTA results are well
illustrated with the proposed phase diagram. The
conclusion that the composition of the Sn3Sb2 phase
is Sn-43at.%Sb is based on the compositional
determinations of alloys #01 and #02 and the phase
equilibrium results of alloys #03 (Sn-41.5at.%Sb)
and #04 (Sn-42at.%Sb). Similar to the results for
alloys #01 and #02, an L + solid two-phase micro-
structure was observed for both alloys #03 and #04
equilibrated at 250
C. If the composition of the
Sn3Sb2 phase were Sn-40at.%Sb as proposed previ-
ously,9 alloys #03 and #04 should be in the Sn3Sb2 +
b-SnSb two-phase region, which is different from
experimental observations.
Figure 1b shows an optical micrograph of alloy
#09 (Sn-30at.%Sb) annealed at 210
C for 12 weeks;
two phases are observed. The composition of the
darker area is Sn-8.8at.%Sb and that of the brighter
area is Sn-43at.%Sb. Based on the Sn-Sb binary
phase diagram as shown in Fig. 3a, the darker area
is the Sn phase and the brighter phase is the Sn3Sb2
phase. Similar results are found for alloy #10
(Sn-15.0at.%Sb) annealed at 210
C for 12 weeks, and
the equilibrated alloy #10 is in the Sn + Sn3Sb2 two-
Chen, Chen, Gierlotka, Zi, Chen, and Wu
phase region. Figure 1c shows an optical micro-
graph of alloy #11 (Sn-45at.%Sb) annealed at 300
C
for 12 weeks. A Sn3Sb2 + b-SnSb two-phase struc-
ture is observed. As summarized in Table I, their
compositions are Sn-43.3at.%Sb and Sn-46.5at.%Sb,
respectively. It should be mentioned that it is
extremely difficult to differentiate the Sn3Sb2 phase
and the b-SnSb phase metallographically. This is
likely why there are inconsistencies and uncer-
tainties in the previous phase diagram determina-
tions. Figure 1c is a strong piece of evidence that
both the Sn3Sb2 phase and the b-SnSb phase exist.
Sn-70at.%Sb (#12 to #14) and Sn-80at.%Sb (#15 to
#17) alloys were prepared and annealed at 300
C,
210
C, and 160
C to determine the phase bound-
aries of the b-SnSb and Sb phases in the b-SnSb +
Sb two-phase region, since there were no experi-
mental data previously. Figure 1d shows a second-
ary electron image (SEI) micrograph of alloy #12
annealed at 300
C for 12 weeks. Two phases are
observed. The composition of the bright phase is
Sn-61.1at.%Sb; it is the b-SnSb phase. The composi-
tion of the dark phase is Sn-89.4at.%Sb; it is the Sb
phase. Similar results were found for alloys #12 to
#17, and they are all in the b-SnSb + Sb two-phase
region. The Sb-rich end boundary of the b-SnSb
phase and the equilibrium Sn solubility in the Sb
phase are determined and summarized in Table I.
Phase Equilibria of the Sn-Sb Binary System
Fig. 4. (a) XRD pattern of alloy #01. (b) XRD pattern of alloy #09. (c)
XRD pattern of alloy #12.
These data are included in the proposed Sn-Sb
binary phase diagram as shown in Fig. 3a.
Another factor also contributing to the difficulty
of discerning the Sn3Sb2 phase and the b-SnSb
phases is their structural similarities. Figure 4a
shows the X-ray diffraction pattern of alloy #01.
Diffraction peaks of both Sn and Sn3Sb2 phases are
present in Fig. 4a. The major distinction between
the Sn3Sb2 and b-SnSb phases is the characteristic
997
peaks near 2h = 51 deg.16 For the b-SnSb phase,
near 2h = 51 deg, there are two peaks at 51.1 deg
and 51.7 deg, which represent the (003) and (021)
planes, respectively. However, for Sn3Sb2 phase,
near 2h = 51 deg, there is only one peak at 51.7 deg.
Figure 4b shows the X-ray diffraction pattern of
alloy #09. As in Fig. 4a, near 2h = 51 deg, only one
peak at 51.7 deg is found in Fig. 4b. X-ray diffrac-
tion patterns suggest that the Sn3Sb2 phase at
210
C is the same as that at 280
C. The phase
equilibrium result of alloy #09 demonstrates the
existence of the Sn3Sb2 phase at temperatures lower
than 243
C, which is in agreement with our pro-
posed Sn-Sb phase diagram as shown in Fig. 3a.
Figure 4c shows the X-ray diffraction pattern of
alloy #12. As mentioned previously, there are two
peaks at 2h = 51.1 deg and 51.7 deg, corresponding
to the b-SnSb phase. The XRD diffractogram shown
in Fig. 4c confirms that the equilibrium phases of
alloy #12 are the Sb and b-SnSb phases.
THERMODYNAMIC MODELING
Modeling Procedure
The CALPHAD approach31 was used in this study
for thermodynamic modeling and calculation of
phase diagrams. The modeling procedures followed
the guidelines prepared by Schmid-Fetzer et al.36
Phase equilibrium data and thermodynamic prop-
erties of each phase were evaluated. Proper ther-
modynamic descriptions of each phase were
established. The thermodynamic parameters for all
phases in the system were optimized by using the
ThermoCalc software37 and the phase diagram was
calculated with the Panda software.38
Thermodynamic Properties
Heat of mixing of molten Sn-Sb alloys of various
compositions was measured by Kawakami,19
Witting and Gehring,20 Yasawa et al.,21 Sommer
et al.22, and Azzaoui et al.23 at temperatures vary-
ing from 510
C to 835
C. Kleppa24 examined the
dissolution enthalpy of solid antimony in liquid tin
at 450
C. Chemical potentials of the liquid phase
were measured by the electromotive force (EMF)
technique. Frantic and McDonald,25 Vassiliev
et al.,26 Yanko et al.,27 Hao et al.,28 Itho et al.,29
and Vassiliev et al.30 made experimental measure-
ments of various molten Sn-Sb alloys at tempera-
tures varying from 333
C to 1097
C.
Thermodynamic Description of the Phases
Jonsson and Argen thermodynamically modeled the
binary Sn-Sb system.39 Although the phase equilib-
rium results are different, they made good evaluations
of the thermodynamic properties and their thermody-
namic models are adopted in this system. The following
phases are taken into consideration in this study: Sn
(BCT_A5), Sn3Sb2, b-SbSn, Sb (Rhombohedral_A7),
and liquid. Detailed information on the structures of
these phases is given in Table II40 and below.
998 Chen, Chen, Gierlotka, Zi, Chen, and Wu

Table II. Structures of the Binary Sn-Sb Phases

Phase PearsonÕs Symbol Space Group Prototype

Sn (BCT_A5) tI4 I41/amd b-Sn

Sb (Rhombohedral_A7) hR2 R3m NaCl
Sn3Sb2 – – –
SnSb cF8 Fm3m aAs

Table III. Gibbs Free Energies of Pure Components in the Binary Sn-Sb System
Comp. Phase T (K) Function (J/mol)

Sb Liquid 298.15–903.78 Gliquid

Sb ¼ 10579:47 þ 134:231525
T  30:5130752
T
lnðTÞ
þ0:007748768
T 2  3:003415E  06
T 3 þ 100625
T 1
1:74847E  20
T 7
903.78–2000 liquid
GSb ¼ 8175:359 þ 147:455986
T  31:38
T
lnðTÞ

Sn Liquid 100–250 Gliquid

Sn ¼ 855:425 þ 108:677684
T  25:858
T
lnðTÞ
þ5:1185E  04
T 2  3:192767E  06
T 3 þ 18440
T 1
þ1:47031E  18
T 7
250–505.08 liquid
GSn ¼ 1247:957 þ 51:355548
T  15:961
T
lnðTÞ
0:0188702
T 2 þ 3:121167E  06
T 3  61960
T 1
þ1:47031E  18
T 7
505.08–800 liquid
GSn ¼ 9496:31  9:809114
T  8:2590486
T
lnðTÞ
0:016814429
T 2 þ 2:623131E  06
T 3
1081244
T 1
800–3000 Gliquid
Sn ¼ 1285:372 þ 125:182498
T  28:4512
T
lnðTÞ

Sb Rhombohedral_A7 298.15–903.78 Rhombohedral A7

GSb ¼ 9242:858 þ 156:154689
T
30:5130752
T
lnðTÞ þ :007748768
T 2
3:003415E  06
T 3 þ 100625
T 1
903.78–2000 Rhombohedral A7
GSb ¼ 11738:83 þ 169:485872
T  31:38
T
lnðTÞ
þ1:616849E þ 27
T 9
Sn Rhombohedral_A7 100–250 Rhombohedral A7
GSn ¼ 5923:517 þ 122:765451
T  25:858
T
lnðTÞ
þ5:1185E  04
T 2  3:192767E  06
T 3
þ18440
T 1
250–505.08 GnRhombohedral A7
¼ 3820:135 þ 65:443315
T  15:961
T
lnðTÞ
0:0188702
T 2 þ3:121167E06
T 3 61960
T 1
505.08–800 Rhombohedral A7
GSn ¼ 4559:724 þ 4:005269
T  8:2590486
T
lnðTÞ
0:016814429
T 2 þ 2:623131E  06
T 3
1081244
T 1  1:2307E þ 25
T 9
800–3000 Rhombohedral A7
GSn ¼ 6221:959 þ 138:99688
T  28:4512
T
lnðTÞ
1:2307E þ 25
T 9
Sb BCT_A5 298.15–903.78 BCT A5
GSb ¼ 3757:142 þ 148:154689
T  30:5130752
T
lnðTÞ
þ0:007748768
T 2 3:003415E  06
T 3 þ 100625
T 1
903.78–2000 BCT A5
GSb ¼ 1261:17 þ 161:485872
T  31:38
T
lnðTÞ
þ1:616849E þ 27
T 9

Sn BCT_A5 100–250 GBCT

Sn
A5
¼ 7958:517 þ 122:765451
T  25:858
T
lnðTÞ
þ5:1185E04
T 2 3:192767E  06
T 3 þ 18440
T 1
250–505.08 BCT A5
GSn ¼ 5855:135 þ 65:443315
T  15:961
T
lnðTÞ
0:0188702
T 2 þ 3:121167E  06
T 3  61960
T 1
505.08–800 BCT A5
GSn ¼ 2524:724 þ 4:005269
T  8:2590486
T
lnðTÞ
0:016814429
T 2 þ 2:623131E  06
T 3 1081244
T 1
1:2307E þ 25
T 9
800–3000 GBCT
Sn
A5
¼ 8256:959 þ 138:99688
T  28:4512
T
lnðTÞ
1:2307E þ 25
T 9
Phase Equilibria of the Sn-Sb Binary System 999

Substitutional Solution—Sn (BCT_A5), same distance d = 0.307 nm. The same is true for
Sb (Rhombohedral_A7), Liquid each Sb atom with six Sn first neighbors. The struc-
ture contains one sublattice of Sb atoms and another
Sn (BCT_A5), Sb (Rhombohedral_A7), and liquid
sublattice of Sn atoms. Since the compositions vary
phases are described by the solution model:41
X X within a rather wide range, some Sn atoms should be
Gm ðTÞ ¼ x0i Gi ðTÞ þ RT xi lnðxi Þ able to occupy the Sb sublattice and vice versa.
i i ! Jonsson and Argen39 proposed the Bragg–Williams–
XX X Gorsky model44 for the description of the b-SnSb
v v
þ xi xj Lij ðxi  xj Þ : ð1Þ phase. Similarly, a two-sublattice model is used in
i j1 v this work. However, this model does not assume

 symmetric Gibbs free energies for G(Sb:Sn) and
PP Pv v
The xi xj Lij ðxi  xj Þ part is the G(Sn:Sb) because experimental information shows
i j1 v that the Sn3Sb2 phase is stable at low temperatures
Redlich–Kister polynomial for the excess Gibbs free and thus asymmetric parameters are needed.
energy. The Gibbs energy of the pure element The Gibbs free energy of the b-SnSb phase can be
0
Gi(T) = Gi(T)-HSER
i is referred to the constant described as:
enthalpy value of the standard element reference
HSER
i at 298.15 K and 1 bar as recommended by the GSbSn
m
I
¼ YSb II  SbSn
YSb I
GSb:Sn þ YSn II  SbSn
YSb GSn:Sb
Scientific Group Thermodata Europe (SGTE),42 I
þYSn YSnII  SbSn
GSn:Sn
and is represented by Eq. 2:
0 0 0 0 00 00
þ 12 RTðYSb lnYSb þ YSn lnYSn þ YSb lnYSb
0 2 1 3
Gi ðTÞ ¼ a þ bT þ cTlnðTÞ þ dT þ eT þ fT 00 00
þYSn lnYSn Þ þ xs GSbSn ; ð3Þ
4 7 9
þ gT þ mT þ nT : ð2Þ xs
where the term GSbSn represents the excess Gibbs
The reference states are Sn (BCT_A5) and Sb free energy.
(Rhombohedral_A7). The 0Gi(T) expression may be
given for several temperature ranges, where the Stoichiometric Compound Sn3Sb2
coefficients a, b, c, d, e, f, g, m, and n have different Binary stoichiometric compound Sn3Sb2 is des-
values. The thermodynamic functions of pure ele- cribed as a line compound using the following:
ments 0Gi(T) are taken from the SGTE unary (pure X
elements) TDB v.4,42 and are listed in Table III. Gm ðTÞ ¼ a þ bT þ xi GHSER
i : (4)
i

b-SnSb Phase
The b-SnSb phase is a quasicubic NaCl (B1) face-
centered cubic (FCC) type and was first described as
an FCC cell.43 In the NaCl structure, each Sn atom is
surrounded by six first-neighbor Sb situated at the
Results and Discussion
Through the optimization procedures as men-
tioned, the interaction parameters were determined
as summarized in Table IV. The enthalpy of mixing

Table IV. Interaction Parameters of the Binary Sn-Sb System

Phase Function (J/mol)

Liquid 0
Lliquid
SbSn ¼ 5536:588 þ 1:5399
T
1
Lliquid
SbSn ¼ 177.931
2 liquid
LSbSn ¼ 883.186
Sn (BCT_A5) 0 BCT A5
LSbSn ¼ 14643:226 þ 6:6374
T
1 BCT A5
LSbSn ¼ 37586:892 þ 62:2440
T
Sb (Rhombohedral_A7) 0 Rhombohedral A7
LSbSn ¼ 2682:850 þ 8:0154
T
1 Rhombohedral A7
LSbSn ¼ 758.851
0
b-SnSb GSbSn
Sb:Sb ¼ 3243.791 þ GHSERSB
0
GSbSn
Sb:Sn ¼ 2951:157  0:5260
T þ 0:5
GHSERSB
þ 0:5
GHSERSN
0 SbSn
GSn:Sn ¼ 4000  0:0431
T þ GHSERSN
0 SbSn
LSn:Sb;Sn ¼ 0 LSbSn
Sb;Sn:Sn ¼ 573:048

Sn3Sb2 0
GSn3 Sb2
Sb:Sn ¼ 3295:845  0:1739
T þ 0:43
GHSERSB
þ 0:57
GHSERSN
1000
of the liquid phase was described without temper-
ature dependency. The two terms in the interaction
parameter of the liquid phase have different signs,
which indicates that the enthalpy and excess
entropy of mixing have the same sign.41,43 As shown
in Fig. 5, the calculated enthalpies of mixing are in
good agreement with the experimental determina-
tions.20,22,23 Since the enthalpy of mixing is consid-
ered temperature independent in this study, the
calculated results are the same for all the reaction
Fig. 5. Comparison between the calculated enthalpy of mixing and
experimental determinations.20,22,23
Fig. 6. Comparison between the calculated heat of dissolution of
solid antimony in liquid tin and experimental determinations at
450
C.24
Chen, Chen, Gierlotka, Zi, Chen, and Wu
temperatures. Only the results of Azzaoui et al.23 at
the Sn-rich part show slightly lower values than the
calculated values; however, a 200 J/mol difference
can be considered as still within the experimental
uncertainties of heat effect measurements. Addi-
tionally, Fig. 6 shows the calculated heat of disso-
lution of solid antimony in liquid tin at 450
C
together with the experimental determinations by
Kleppa,24 and the results are in very good agree-
ment.
Fig. 7. Comparison between the calculated chemical potentials of
Sn and experimental data26,30 at 627
C and 497
C.
Fig. 8. Comparison between the calculated activity of Sn and
experimental data25 at 905
C.
Phase Equilibria of the Sn-Sb Binary System
Table V. Invariant Reactions in the Binary Sn-Sb System
Experimental
Reactions T (°C) T (°C)
L + Sb = b-SnSb 424 424.1
L + b-SnSb = Sn3Sb2 323 322.5
L + Sn3Sb2 = Sn 243 242.9
Figure 7 shows the calculated chemical potentials
of Sn at 627
C and 497
C together with Vassiliev
et al.Õs determinations.26,30 As can be seen from
Fig. 7, the calculation fits well to their experimental
results, which show small temperature dependency.
The calculated activities of Sn at 905
C are shown
in Fig. 8 together with the experimental determi-
nations by Frantic and McDonald.25 Except between
0.5 and 0.6 mole fraction of Sn, where experimental
results show larger negative deviation from RaoultÕs
law, the calculated results from the thermodynamic
models are generally in good agreement with the
experimental values.
Figure 3b and c shows the calculated phase dia-
grams of the Sn-Sb system with/without the experi-
mental data. The stoichiometric ratio of the Sn3Sb2
phase is 43 at.%Sb and is stable all the way to below
room temperature. The calculated peritectic tem-
peratures of the ternary invariant reactions, L + Sb =
b-SnSb, L + b-SnSb = Sn3Sb2, and L + Sn3Sb2 = Sn
are 424.1
C, 322.5
C, and 242.9
C, respectively. The
calculated compositions and temperatures of the
three peritectic reactions are listed in Table V and
are in good agreement with the experimental results
determined in this study and those in the litera-
ture.9,23
The liquidus line is in very good agreement with
the results by Iwase et al.,11 and is in good agree-
ment with the DTA experimental results by Predel
and Scherman9 at the Sn-rich corner. The calcu-
lated phase boundary of the b-SnSb in L + b-SnSb is
also in very good agreement with the data of Iwase
et al.11 There are few data in the phase boundaries
of the b-SnSb phase and Sb phase in the b-SnSb + Sb
two-phase field, and there were no previous exper-
imental determinations for temperature lower than
250
C. As shown in Fig. 3c, the calculated phase
boundaries of the b-SnSb and Sb phases in the
b-SnSb + Sb region coincide with the experimental
determinations.
CONCLUSIONS
The Sn-Sb binary phase diagram has been revised
based on both experimental determinations and
thermodynamic modeling. Thermodynamic model-
ing of the Sn-Sb system shows good agreement with
the experimental determinations. The composition of
the Sn3Sb2 phase is Sn-43at.%Sb and remains stable
to below room temperature. The b-SnSb phase does
not have an order–disorder transformation, and it
1001
Calculated Results
Compositions of Phases (xSb)
L: 0.495 Sb: 0.879 b: 0.628
L: 0.185 b: 0.470 Sn3Sb2: 0.43
L: 0.062 Sn3Sb2: 0.43 Sn: 0.100
has a wide compositional homogeneity range. The
temperatures of the three peritectic reactions, L +
Sb = b-SnSb, L + b-SnSb = Sn3Sb2, and L + Sn3Sb2 =
Sn, are 424
C, 323
C, and 243
C, and the compositions
of the b-SnSb phase at the peritectic reactions at
424
C and 323
C are 62.8 at.%Sb and 47.0 at.%Sb,
respectively.
ACKNOWLEDGEMENTS
The authors acknowledge the financial support of
the National Science Council of Taiwan ROC (Grant
#NSC95-2218-E007-028).
REFERENCES
1. R.J. Klein Wassink, Soldering in Electronics, 2nd ed. (Isle of
Man, British Isles: Electrochemical, 1989).
2. J.H. Kim, S.W. Jeong, and H.M. Lee, J. Electron. Mater. 31,
557 (2002). doi:10.1007/s11664-002-0125-4.
3. S.-W. Chen, P.-Y. Chen, and C.-H. Wang, J. Electron. Mater.
35, 1982 (2006). doi:10.1007/s11664-006-0303-x.
4. H. Ohtani and K. Ishida, J. Electron. Mater. 23, 747 (1994).
doi:10.1007/BF02651369.
5. J.W. Jang, P.G. Kim, K.N. Tu, and M. Lee, J. Mater. Res. 14,
3895 (1999). doi:10.1557/JMR.1999.0527.
6. S.F. Corbin, J. Electron. Mater. 34, 1016 (2005). doi:10.1007/
s11664-005-0089-2.
7. Official Journal of the European Union (2003) L 37/19-L 37/
23, 13.2.2003.
8. M. Hansen and K. Anderko, Constitution of Binary Alloys
(New York: McGraw Hill, 1958), p. 1175.
9. B. Predel and W. Schwermann, J. Inst. Met. 99, 169 (1971).
10. V. Vassiliev, M. Lelaurain, and J. Hertz, J. Alloy Compd.
247, 223 (1997).
11. K. Iwase, N. Aoki, and A. Osava, Sci. Rep. Res. Inst. Tohoku
Univ. 20, 353 (1931).
12. R. Blondel and P. Laffite, Comp. Rend. Acad. Sci. Paris 200,
1472 (1935).
13. D. Hanson and W.T. Pell-Wallpole, J. Inst. Met. 58, 299–310
(1936).
14. B.L. Eyre, J. Inst. Met. 88, 223 (1959).
15. A. Stegherr, Doktor-Ingenieurs Genehmigete Disseration,
Technischen Hochshule Aachen, 1969.
16. W.P. Alen and J.H. Perepezko, Scripta Metall. Mater. 24,
2215 (1990). doi:10.1016/0956-716X(90)90513-G.
17. C. Lee, C.Y. Lin, and Y.W. Yen, Intermetallics 15, 1027
(2007). doi:10.1016/j.intermet.2006.12.002.
18. P.-Y. Chen, C.-N. Chiu, C.-H. Wang, and S.-W. Chen,
unpublished work (2007).
19. M. Kawakami, Sci. Rep. Res. Inst. Tohoku Univ. 19, 521
(1930).
20. F.E. Witting and E. Gehring, Ber. Bunsenges Phys. Chem.
71, 372 (1971).
21. A. Yasawa, T. Kawashima, and K. Itagaki, J. Jpn. Inst. Met.
32, 1288 (1968).
22. F. Sommer, R. Luck, N. Rupf-Bolz, and B. Predel, Mater.
Res. Bull. 18, 621 (1983). doi:10.1016/0025-5408(83)90221-0.
23. M. Azzaoui, M. Notin, and J. Hertz, Z. Metallkd 84, 545
(1993).
1002
24. O.J. Kleppa, J. Phys. Chem. 60, 842 (1956). doi:10.1021/
j150541a003.
25. R.O. Frantic and H.J. McDonald, Trans. Electrochem. Soc.
88, 243 (1946).
26. V. Vassiliev, M. Azzaoui, and J. Hertz, Z. Metallkd 86, 545
(1995).
27. J.A. Yanko, A.E. Drake, and F. Hovorka, Trans. Electro-
chem. Soc. 89, 357 (1946).
28. I.S. Hao, T. Kang, and P.C. Park, Kor. Metall. Trans. 15, 361
(1977).
29. K. Itho, K. Koiko, and Y. Narita, Nippon Kogo Kaishi 96,
97–101 (1980).
30. V. Vassiliev, Y. Feutelais, M. Sghaier, and B. Legendre,
J. Alloy Compd. 314, 198 (2001).
31. L. Kaufman and H. Bernstein, Computer Calculation of
Phase Diagrams (New York: Academic, 1970).
32. S.-W. Chen, C.-C. Huang, and J.-C. Lin, Chem. Eng. Sci. 50,
417 (1995). doi:10.1016/0009-2509(94)00244-L.
33. S.-W. Chen, C.-C. Lin, and C.-M. Chen, Metall. Mater.
Trans. A 29A, 1965 (1998). doi:10.1007/s11661-998-0022-4.
34. W.J. Boetinger, U.R. Kattner, K.-W. Moon, and J.H. Pere-
pezko, DTA and Heat Flux DSC Measurements of Alloy
Melting and Freezing (Washington: NIST, 2006).
Chen, Chen, Gierlotka, Zi, Chen, and Wu
35. M. Sorai, Comprehensive Handbook of Calorimetry and
Thermal Analysis (Wiley, Ltd, 1998), p. 221.
36. R. Schmid-Fetzer, D. Andersson, P.Y. Chevalier, L. Eleno,
O. Fabrichnaya, U.R. Kattner, B. Sundman, C. Wang, A.
Watson, L. Zabdyr, and M. Zinkevich, Calphad 31, 38
(2007). doi:10.1016/j.calphad.2006.02.007.
37. ThermoCalc Classic v.R., Foundation Computational Ther-
modynamic (Sweden: Stockholm, 2006).
38. Pandat, CompuTherm LLC, 437 S. Yellowstone Dr. Suite
217 Madison, WI 53719, USA.
39. B. Jonsson and J. Argen, Mater. Sci. Tech. 2, 913 (1986).
40. T.B. Massalski, J.L. Murray, L.H. Bennet, and H. Baker,
Binary Alloy Phase Diagrams, ed. T.B. Massalski (American
Society for Metals, Metals Park, OH, 1986), pp. 3304–3306.
41. N. Saunders and P. Miodownik. Calphad, Calculation of
Phase Diagrams a Comprehensive Guide (Elsevier Science,
1998).
42. PURE 4.4 SGTE Pure Elements (Unary) Database, Scien-
tific Group Thermodata Europe, 1991–2006.
43. E.G. Bowen and W. Morris-Jones, Philos. Mag. 20, 913
(1935).
44. R. Fowler and E.A. Guggenheim, Statistical Thermody-
namics (Cambridge University Press, 1951), p. 571.