CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 45 (2014) 49–54

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CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Thermodynamic assessment of the Sr–In and Sr–Bi systems

supported by first-principles calculations
Yao Wang a, Jinghua Xin a, Chong Chen a, Shuhong Liu a,b,n, Biao Hu a, Yong Du a,b
a
State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083, PR China
b
Sino-German Cooperation Group “Microstructure in Al alloys”, Central South University, Changsha, Hunan 410083, PR China

art ic l e i nf o a b s t r a c t

Article history: Based on the available experimental phase equilibria and thermodynamic data, the Sr–In and Sr–Bi
Received 25 March 2013 systems have been assessed by means of the CALPHAD technique. The solution phases (Liquid, (αSr),
Received in revised form (βSr), (In) and (Bi)) were modeled with the Redlich–Kister polynomial. All the intermetallic compounds
29 November 2013
(SrIn5, SrIn3, Sr2In5, SrIn2, Sr2In3, SrIn, Sr5In3, Sr3In, SrBi3, Sr11Bi10, αSr5Bi3, βSr5Bi3 and Sr2Bi) were treated
Accepted 1 December 2013
as stoichiometric compounds. The enthalpies of formation at 0 K for SrIn5, SrIn3, SrIn2, SrIn, Sr5In3, Sr3In,
Available online 12 December 2013
SrBi3, αSr5Bi3, βSr5Bi3 and Sr2Bi were computed by first-principles calculations in order to assist the
Keywords: thermodynamic modeling. A set of self-consistent thermodynamic parameters for each of the two
Sr–In systems has been obtained, and the present calculations can satisfactorily reproduce the available
Sr–Bi
experimental data.
Phase diagram
& 2013 Elsevier Ltd. All rights reserved.
First-principles calculations
Thermodynamic modeling

1. Introduction 2. Literature review

Al alloys are widely used for commercial applications mainly
due to the low density and good mechanical properties. Sr, In and
Bi are important additional elements that can affect mechanical
properties of Al alloys. Sr is widely utilized in Al-Si casting alloys to
modify the morphology of the eutectic silicon phase into a fine
fibrous or lamellar structure, which can provide abundant stress
risers and thus limits the attainment of maximum strength and
ductility [1,2]. With the addition of In, the electromigration
resistance of Al alloys can be greatly improved [3]. The small
addition of Bi in Al alloys can solve the embrittlement by Na
contamination, which is difficult to avoid in the normal manufac-
turing process [4].
The thermodynamic descriptions for the Sr–In and Sr–Bi binary
systems are part of our efforts to establish a thermodynamic
database for multi-component Al alloys [5–9]. However, thermo-
dynamic descriptions for the two systems are not available in the
literature. The purpose of the present work is to develop a set of
self-consistent thermodynamic parameters for both the Sr–In and
Sr–Bi systems by means of the CALPHAD method supplemented
with first-principles calculations.
n
Corresponding author: Tel.: þ 86 731 88877300; fax: þ86 731 88710855.
E-mail address: shhliu@csu.edu.cn (S. Liu).
2.1. The Sr–In system
The only experimental phase diagram on the Sr–In system was
investigated by Bruzzone [10] using thermal analysis (TA), metal-
lographic methods and X-ray diffraction (XRD). The mutual solu-
bilities between (Sr) and (In) are negligible. Eight intermetallic
phases SrIn5, SrIn3, Sr2In5, SrIn2, Sr2In3, SrIn, Sr3In2, and Sr3In were
reported. The SrIn2 and Sr3In phases melt congruently at 1203 and
831 K, respectively. The other compounds SrIn5, SrIn3, Sr2In5,
Sr2In3, SrIn and Sr3In2 were formed via the peritectic reactions.
Three eutectic reactions, i.e. Liquid2(In) þSrIn5, Liquid2Sr5In3
þSr3In and Liquid2Sr3Inþ(αSr), and six peritectic reactions,
i.e. Liquid þSrIn32SrIn5, Liquid þSr2In52SrIn3, Liquid þSrIn22
Sr2In5, Liquid þSrIn22Sr2In3, Liquid þSr2In32SrIn, Liquid þSrIn
2Sr3In2, were determined to be at 429, 818, 790, 693, 813, 893,
1081, 990 and 845 K, respectively. The temperature of (αSr)2
(βSr) transition was observed to be 883 K, which was 63 K higher
than the generally accepted one [11]. Thus the experimental data
on this transition was not used. Later Bruzzone et al. [12] reported
a Sr5In3 phase instead of Sr3In2 and determined the crystal
structure of Sr5In3 to be Cr5B3 type crystal by single crystal and
powder techniques. In the present work, the Sr5In3 phase was
considered instead of Sr3In2, which was in consistent with the
assessment of Okamoto [13].
There were no thermodynamic data available in the literature.
The crystal structures of the solid phases in the Sr–In system are

0364-5916/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.calphad.2013.12.001
50 Y. Wang et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 45 (2014) 49–54

Table 1 method. A eutectic reaction Liquid2(Bi)þSrBi3 occurs at about

Crystallographic data of the solid phases in the Sr–In and Sr–Bi systems. 0.47 at% Sr. Schweitzer and Weeks [16] measured the liquidus in
the composition range from 0 to 10 at% Sr. Zhuravlev and Smirnova
System Phase Pearson Lattice References
symbol/ parameters [17] measured the Sr–Bi phase diagram in the composition range
space [nm] from 0 to 45 at% Sr based on TA and metallographic methods.
group/ A eutectic reaction Liquid2(Bi)þSrBi3, two peritectic reactions,
prototype LiquidþSrBi2SrBi3, and Liquidþ αSr3Bi22SrBi, and a polymorphic
Sr–In (In) tI2 a¼ 0.3251 c ¼ 0.4947 [27]
transformation αSr3Bi22βSr3Bi2 were reported to be at 533, 833,
I4mmm 983 and 973 K, respectively.
In a¼ 0.3279 c ¼ 0.5033 This work According to Okamoto and Massalski [18], if the liquidus is very
(αSr) cF4 a¼ 0.6076 [28] asymmetric with respect to the congruent melting point of a line
Fm3m compound, the situation merits a closer examination. The liquidus
Cu a¼ 0.6023 This work
(βSr) cI2 a¼ 0.4870 [29]
of the SrBi3 and Sr2Bi phases reported by Shukarev et al. [14] are
Im3m
not symmetric at the congruent melting points. Hence, the types
W of the two invariant reactions Liquid2SrBi3 þSrBi and Liquid2
SrIn5 hP6 a¼ 0.5937 c ¼ 0.4827 [10] Sr2Biþ Sr3Bi2 reported by Shukarev et al. [14] are suspectable but
P6=mmm only the temperatures were adopted. In view of the noticeable
CaCu5 a¼ 0.6301 c ¼ 0.5270 This work
difference for the melt point of Sr between the one from Shukarev
SrIn3 hP8 a¼ 0.6769 c ¼ 0.5481 [10]
P63 =mmc et al. [14] and the generally accepted one [11], the element Sr used
Mg3 Cd a¼ 0.7141 c ¼ 0.5249 This work by Shukarev et al. [14] might be impure. Therefore, the experi-
SrIn2 hP6 c ¼ 0.8021 [31] mental results [17] were considered more reliable within the
P63 =mmc composition range from 0 to 45 at% Sr. The two invariant reactions
CaIn2 a¼ 0.5080 c ¼ 0.8116 This work
Liquid þ SrBi2SrBi3 and Liquid þSr3Bi22Sr2Bi were considered in
SrIn oF64 a¼ 1.0230 b ¼2.6140 c ¼ 0.8400 [32]
Fdd2 the present work. Since there were no experimental data available
SrIn a¼ 1.0222 b ¼2.6040 c ¼ 0.8365 This work in the literature over the composition range from 45 to 100 at% Sr,
Sr5In3 tI32 a¼ 0.8744 c ¼ 1.6429 [33] the experimental data [14] were utilized in the present modeling
I4mcm but assigned a relatively low weight factor.
Cr5 B3 a¼ 0.8788 c ¼ 1.6496 This work
Sr3In cF16 a¼ 0.8360 [10]
The crystal structures and lattice parameters for the SrBi3 and
Fm3m Sr2Bi phases were first determined by Zhuravlev and Melik-Adamy
BiF3 a¼ 0.8639 This work [19], Eisnmann and Deller [20], respectively. Similarly to the Sr5In3 in
Sr–Bi (Bi) hR2 a¼ 0.4546 [30]
the Sr–In binary system, Bruzzone et al. [12] observed a phase Sr5Bi3
R3m
in the Sr–Bi system and determined the crystal structure of Sr5Bi3 to
As a¼ 0.4558 This work be Yb5Sb3 structure by means of single crystal and powder technique.
SrBi3 cP4 a¼ 0.5042 [19] Later, Eisnmann and Deller [20] reported a Sr5Bi3 phase with the
Pm3m crystal structure of Mn5Si3-type. Considering the impure Sr in the
AuCu3 a¼ 0.5060 This work work of Shukarev et al. [14] and the reported polymorphic transfor-
Sr11Bi10 tI84 a¼ 1.2765 c ¼ 1.8407 [21]
I4=mmm
mation [17] as well as the work by Shukarev et al. [12] and Eisnmann
Ho11 Ge10 a¼ 1.3021 c ¼ 1.8196 This work and Deller [20], the Sr5Bi3 phase instead of Sr3Bi2 was taken account
αSr5Bi3 hR16 a¼ 0.9630 c ¼ 0.7630 [20] of in the present assessment. No crystal structure data for Sr3Bi2 and
P63 =mcm SrBi phases were available in the literatures. Derrien et al. [21]
Mn5 Si3 a¼ 0.9754 c ¼ 0.7542 This work
investigated the crystal structures of Sr11Bi10 and Ba11Bi10 compounds
βSr5Bi3 oP32 a¼ 1.3370 b ¼1.0233 c ¼ 0.8890 [12]
Pnma based on the single-crystal X-ray data and refined by full-matrix
Yb5 Sb3 a¼ 1.3681 b ¼1.0302 c ¼ 0.8917 This work least-squares. According to X-ray diffraction from single crystal data,
Sr2Bi tI12 a¼ 0.5010 c ¼ 1.7680 [20] Deller and Esienmann [22] showed the existence of Ca11Bi10 in Ca–Bi
I4=mmm system instead of “CaBi” reported in previous research by Smirnov
La2 Sb c ¼ 1.8091 This work
and Rudnichenko [23]. Ca11Sb10 were also investigated to be con-
gruent melted at 985 1C in the Ca–Sb system by Niyazova et al. [24]
using differential thermal analysis and microscopic analysis. The
crystal structure of Ca11Sb10 was also determined by Deller and
summarized in Table 1. These crystal structure data are the basis Esienmann [22]. The structure of the phase Sr11Sb10 was determined
for the subsequent first-principles calculations. in [25]. The five phases Sr11Bi10, Ba11Bi10, Ca11Bi10, Ca11Sb10 and
Sr11Sb10 are isostructural. Considering the similarity of systems with
2.2. The Sr–Bi system elements in the same main group and no crystal structure for SrBi
determined, the phase SrBi was substituted for Sr11Bi10 in the
The phase equilibria in the Sr–Bi system have been investigated present work.
by Shukarev et al. [14], Pleasance [15], Schweitzer and Weeks [16] The activities of Sr in the liquid phases with Bi at 900 K were
and Zhuravlev and Smirnova [17], respectively. Shukarev et al. [14] determined by Klebanov et al. [26] using the emf (electron motive
constructed the entire phase diagram based on the results of TA and force) method in the composition range from 0 to 16.8 at% Sr. As
microscopic observation. Four intermetallic compounds, SrBi3, SrBi, the reported activity coefficients are rather scattered, these
Sr3Bi2 and SrBi2, were reported. Four eutectic reactions, Liquid2 experimental data [26] were not utilized in the present modeling.
(Bi)þ SrBi3, Liquid2SrBi3 þ SrBi, Liquid2Sr2BiþSr3Bi2 and Liquid2 By means of the calorimetric method, the enthalpies of formation
Sr2Biþ(βSr) and one peritectic reaction LiquidþSr3Bi22SrBi, were (ΔH f ) for the compounds SrBi, Sr3Bi2 and Sr2Bi were measured to be
determined to be at 535, 855, 1086, 931 and 993 K, respectively.  89.8775.64,  10672.17, and  10471.67 kJ/(mol–atom), resp-
SrBi3, Sr3Bi2 and Sr2Bi melt congruently at 905, 1218 and 1131 K, ectively [14]. Considering the impure of the element Sr in the
respectively. Pleasance [15] investigated the phase equilibria in the samples prepared by Shukarev et al. [14], these results were believed
composition range from 0 to 25.4 at% Sr by TA and the flotation unreliability and not considered in the present optimization.
 Y. Wang et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 45 (2014) 49–54 51

The crystal structures of the solid phases in the Sr-Bi system 4. Thermodynamic model
were also summarized in Table 1.
4.1. Unary phase

3. Enthalpies of formation calculated via first-principles The descriptions of the Gibbs energy of the pure element i
calculations (i¼Sr, In, Bi) in the phase φ are adopted from the SGTE database
compiled by Dinsdale [11], and the function is expressed by the
In order to assist the thermodynamic modeling, first-principles following equation:
calculations were employed to obtain the enthalpies of formation φ 1
Gi ðTÞ  H ser 2
i ¼ a þ b  T þ c  T  ln T þ d  T þ e  T
(ΔH f ) for the compounds SrIn5, SrIn3, SrIn2, SrIn, Sr5In3, Sr3In,
SrBi3, Sr11Bi10, αSr5Bi3, βSr5Bi3 and Sr2Bi. The total energies of the þf  T3 þg  T7 þh  T 9 ð2Þ
SrIn5, SrIn3, SrIn2, SrIn, Sr5In3, Sr3In, SrBi3, Sr11Bi10, αSr5Bi3, βSr5Bi3, where H ser
is the mole enthalpy of the element i at 298.15 K and
i
Sr2Bi, Tetragonal_A6_In, Fcc_A1_Sr and Rhombohedral_A7_Bi were 1 bar in its standard element reference (SER) state, and T is the
calculated by using density functional theory (DFT) [34] within a absolute temperature.
generalized gradient approximation (GGA) [35] and with projector
augmented-wave (PAW) pseudo-potentials [36], as implemented
in the Vienna ab initio simulation package (VASP) [37,38]. The GGA 4.2. Solution phase
proposed by Perdew, Burke and Ernzerh of (PBE) [39] was utilized
in the calculation. A plane-wave cutoff energy of 320 eV and an The liquid, (αSr), (βSr), (In), (Bi) phases are treated as com-
energy convergence criterion of 10  6 eV for electronic structure pletely disordered solutions. The Gibbs energy is described by
self-consistency were used in the calculation. The k-points meshes Redlich–Kister polynomial [42]:
φ φ
for Brillouin zone (BZ) sampling were constructed using Mon- Gφ
m H
ser
¼ xsr  0 GSr þ xi  0 Gi þ R  T  ðxSr  ln xSr þ xi  ln xi Þ
khorst–Pack scheme and at least 10,000 per reciprocal atom were
n
employed. The structure was fully relaxed using the Methfessel– þ xSr  xi  ∑ Lj;φ ðxSr  xi Þj ð3Þ
Paxton smearing method [40] and a final self-consistent static j¼0
calculation via the tetrahedron smearing method with Blochl
where H ser is the abbreviation of xSr  H SER SER
Sr þ xi  H i , xSr and xi
corrections [41] was performed.
are the mole fractions of Sr and component i (i ¼In, Bi), respec-
The enthalpy of formation of a compound can be defined as the φ φ
tively, and R is the gas constant. xsr  0 GSr þ xi  0 Gi denotes the
difference in total energy of the compound and the energies of its j;φ
mechanical mixing to the Gibbs energy. L is the jth interaction
constituent elements in their stable states. The enthalpy of
formation of the SrpXq (X¼In, Bi) compound is defined as follows:
Table 3
p q Calculated invariant equilibria in the Sr–In and Sr–Bi systems along with the
Δf EðSrp X q Þ ¼ EðSrp X q Þ  EðSrÞ  EðXÞ ð1Þ
pþq pþq experimental data.

where EðSrp Inq Þ, EðSrÞ and EðXÞ are static energies (per atom) at 0 K System Reaction Composition (at% Sr) T(K) Reference
for compound SrpXq. The calculated results are listed in Table 2. The
Sr–In Liquid ¼(In) þIn5Sr 0 0 16.7 429 [10]
ab initio method is not employed to calculate the enthalpy of
0.9 0 16.7 423.3 This work
formation for the compounds Sr2In3 and Sr2In5, because the crystal Liquid þSrIn3 ¼ SrIn5 8 25 16.7 693 [10]
structures of these compounds are not experimentally determined. 8.1 25 16.7 692.7 This work
Liquid þSr2In5 ¼SrIn3 13.7 28.6 25 813 [10]
Table 2 12 28.6 25 813.7 This work
Enthalpies of formation for the intermetallic compounds in the Sr–In and Sr–Bi Liquid þSrIn2 ¼ Sr2In5 16.4 33.3 28.6 893 [10]
systems. 14.7 33.3 28.6 892.4 This work
Liquid ¼SrIn2 – – – 1203 [10]
System Phase ΔH f (kJ/mol-atom) Source 33.3 33.3 – 1202.8 This work
Liquid þSrIn2 ¼ Sr2In3 46.8 33.3 40 1081 [10]
46.6 33.3 40 1081 This work
Sr–In Sr3In  13.54 First-principles calculations
Liquid þSr2In3 ¼SrIn 53 40 50 990 [10]
 22.00 CALPHAD
53.9 40 50 990 This work
Sr5In3  33.86 First-principles calculations
Liquid þSrIn ¼ Sr5In3 69.4 50 62.5 845 [10]
 34.00 CALPHAD
68.3 50 62.5 844.4 This work
SrIn  42.62 First-principles calculations
Liquid ¼Sr5In3 þSr3In 73 62.5 75 818 [10]
 42.84 CALPHAD
71.6 62.5 75 822 This work
SrIn2  45.45 First-principles calculations
Liquid ¼Sr3In 75 75 – 831 [10]
 45.00 CALPHAD
75 75 – 829 This work
SrIn3  32.58 First-principles calculations
Liquid ¼Sr3Inþ (αSr) 85 75 100 790 [10]
 37.70 CALPHAD
84 75 100 789.7 This work
SrIn5  14.97 First-principles calculations
Sr–Bi Liquid ¼(Bi) þ SrBi3 0.3 0 25 533 [17]
 26.00 CALPHAD
0.3 0 25 531 This work
Sr–Bi SrBi3  89.87 7 5.64 Experimental data[14] Liquid þSr11Bi10 ¼ SrBi3 24 52.4 25 833 [17]
 43.22 First-principles calculations 23.6 52.4 25 834 This work
 42.56 CALPHAD Liquid þαSr5Bi3 ¼ Sr11Bi10 30 62.5 52.4 883 [17]
Sr11Bi10  76.19 First-principles calculations 28.7 62.5 52.4 883 This work
 74.06 CALPHAD αSr5Bi3 ¼ βSr5Bi3 62.5 62.5 – 973 [17]
αSr5Bi3  84.51 First-principles calculations 62.5 62.5 – 973 This work
 82.00 CALPHAD Liquid ¼βSr5Bi3
βSr5Bi3  82.84 First-principles calculations 62.5 62.5 – 1218 This work
 80.00 CALPHAD Liquid þβSr5Bi3 ¼ Sr2Bi
Sr2Bi  104 7 1.67 Experimental data[14] 75 62.5 66.7 1131 This work
 73.23 First-principles calculations Liquid ¼(αSr) þSr2Bi 88 0 66.7 931 [14]
 76.47 CALPHAD 91.3 0 66.7 931 This work
52 Y. Wang et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 45 (2014) 49–54

parameter of phase φ, and it is equal to Lj;φ ¼ aj þ bj  T. The liquidus. The optimization procedure for the Sr–Bi binary system is
parameters aj and bj are to be optimized in the present work. analogous with that for the Sr–In system.
Comparison of the calculated invariant equilibria temperatures
4.3. Compounds and compositions along with the experimental ones are listed in
Table 3. It can be seen that the present calculations agree well with
All the compounds are treated as stoichiometric compounds. the experimental data [10,14,17]. The deviation between the
The Gibbs energy of SrIn, for example, is expressed by the calculated and measured invariant reaction temperature is less
following equation: than 6 K, The thermodynamic parameters obtained in the present
SrIn work are listed in Table 4.
GSrIn SER SER
m  H In  H Sr ¼ a
SrIn
þb  T þ 0:5  0 GFcc_A1 þ 0:5  0 GTet_A6
Sr In Fig. 1 shows the calculated Sr–In phase diagram along with the
ð4Þ experimental data [10]. It can be seen that most of experimental data
where a SrIn
and b
SrIn
are the parameters to be evaluated in the can be well reproduced by the present calculation. The calculated
present optimization. melting points of the SrIn2 and SrIn3 at 1202.8 and 829 K, respectively,
are consistent with the experimental results [10].
The calculated enthalpies of formation at 298.15 K along with
5. Results and discussion the results of first-principles calculations are presented in Fig. 2
and listed in Table 2. The SrIn2 phase has the most negative
The optimization of the thermodynamic parameters was car- enthalpy of formation since its melting point is the highest among
ried out by means of the PARROT module of the Thermo-Calc the existing compounds. The differences between the calculated
software [43], which works by minimizing the squared sum of enthalpies of formation and first-principles calculation for SrIn5
differences between experimental values and computed ones. and Sr3In are a little large. There may be some deviations within
The step by step optimization procedure carefully described by error bar occurring during our first-principles calculations. How-
Du et al. [44] was utilized in the present work. ever, we have checked the calculations overall, no improvement
Taking the Sr–In system as an example, the optimization began
with SrIn5. The enthalpy of formation of SrIn5 calculated by first-
principles calculations was used as the initial value of coefficient
aSrIn5 in Eq. (4). Then, the parameters a0 and b0 in Eq. (3) for the
liquid phase were adjusted to reproduce experimental liquidus data
SrIn
associated with the SrIn5 phase. The value of b 5 was also assessed
by using phase equilibrium data associated with the liquid and SrIn5.
Subsequently, SrIn3, Sr2In5, SrIn2, Sr3In5, SrIn, Sr5In3 and Sr3In were
introduced in the modeling one by one. To account for liquidus data
associated with SrIn3, Sr2In5, SrIn2, Sr2In3, SrIn, Sr5In3 and Sr3In, the
parameters aSrIn3 , aSr 2 In5 , aSrIn2 , aSr 2 In3 , aSrIn , aSr 5 In3 and aSr 3 In were
SrIn Sr In SrIn Sr In
evaluated. In the next step, the parameters b 3 , b 2 5 , b 2 , b 2 3 ,
SrIn Sr In Sr In
b , b 5 3 and b 3 for the compounds SrIn3, Sr2In5, SrIn2, Sr2In3,
SrIn, Sr5In3 and Sr3In were evaluated to describe the nine invariant
reactions and the phase relations associated with them. Finally, the
thermodynamic parameters for all phases were adjusted simulta-
neously by taking into account all the phase equilibrium and
thermodynamic data. It was found that a1 and a2 for liquid phase
in Eq. (3) could yield a significant improvement for the description of Fig. 1. Calculated Sr–In phase diagram with the experimental data [10].

Table 4
Summary of the thermodynamic parameters in the Sr–Bi and Sr–In systems asa.

Systems Phases Model Evaluated parameters

Sr–In Liquid (Sr, In)1 0 Liquid

LSr;In ¼  109580:9 þ 11:2333  T;
1 Liquid
LSr;In ¼  31; 000;
2 Liquid
LSr;In ¼ 4000
SrIn5 (Sr)0.167(In)0.833 0 SrIn5
GSr;In ¼ 0:167  GSr Fcc_A1
þ 0:833  GIn Tet_A6
 26; 000 þ 5:61  T
SrIn3 (Sr)0.25(In)0.75 0 SrIn3
GSr;In ¼ 0:25  GFcc_A1 þ 0:75  GTet_A6  37; 700 þ 9:15  T
Sr In
Sr2In5 (Sr)0.286(In)0.714 0 Sr2 In5
GSr;In ¼ 0:286  GFcc_A1 þ 0:714  GTet_A6 41416:1 þ9:495  T
Sr In
SrIn2 (Sr)0.333(In)0.667 0 SrIn2
GSr;In ¼ 0:333  GFcc_A1 þ 0:667  GTet_A6
 45; 000 þ 8:9  T
Sr In
Sr2In3 (Sr)0.4(In)0.6 0 Sr2 In3
GSr;In ¼ 0:4  GFcc_A1 þ 0:6  GTet_A6  44266:3 þ 8:95  T
Sr In
SrIn (Sr)0.5(In)0.5 0 SrIn
GSr;In ¼ 0:5  GFcc_A1 þ0:5  GTet_A6  42839:8 þ 10:45  T
Sr In
Sr5In3 (Sr)0.625(In)0.375 0 ISr5 In3
GSr;Bi ¼ 0:625  GFcc_A1
Sr þ 0:375  GTet_A6
In  34; 000 þ 8:373  T
Sr3In (Sr)0.75(In)0.25 0
GSr 3 In Fcc_A1
þ 0:25  GTet_A6
Sr;In ¼ 0:75  GSr In  22; 000 þ 3:2  T

Sr–Bi Liquid (Sr, Bi)1 0 Liquid

LSr;Bi ¼  146500 þ 1:5571  T;
1 Liquid
LSr;Bi ¼ 18755:1 þ20:5  T;
2 Liquid
LSr;Bi ¼ 14828:9;
3 Liquid
LSr;Bi ¼  42268:8
SrBi3 (Sr)0.25(Bi)0.75 0 SrBi3
GSr;Bi ¼ 0:25  GSrFcc_A1 Rho_A7
þ 0:75  GBi  42557:7 þ 12:37  T
Sr11Bi10 (Sr)0.524(Bi)0.476 0 SrBi
GSr;Bi ¼ 0:524  GFcc_A1 þ 0:476  GRho_A7 74; 060 þ 26  T
Sr Bi
αSr5Bi3 (Sr)0.625(Bi)0.375 0 αSr5 Bi3 0
GSr;Bi ¼ 0:625  GFcc_A1 þ 0:375  GRho_A7  82; 000 þ 27:55  T
Sr Bi
βSr5Bi3 (Sr)0.625(Bi)0.375 0
GβSr 5 Bi3
¼ 0:625  GFcc_A1 þ 0:375  GRho_A7  80; 000 þ 27:5  T
Sr;Bi Sr Bi
Sr2Bi (Sr)0.667(Bi)0.333 0
GSr 2 Bi Fcc_A1
þ 0:333  GRho_A7
Sr;Bi ¼ 0:667  GSr Bi  76469:8 þ 26:2  T

a
Gibbs energy in J/mol, temperature (T) in Kelvin and pressure (P) in Pa. The Gibbs energies for the pure elements are from the SGTE compilation [11].
 Y. Wang et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 45 (2014) 49–54
Fig. 2. Calculated enthalpies of formation of the Sr–In system at 298 K compared
with the first-principles calculations.
Fig. 3. Calculated Sr–Bi phase diagram with the experimental data [14–17].
can be obtained. The enthalpies of formation at 0 K for the
compounds were computed by first-principles calculations just
in order to assist the thermodynamic modeling. Since the calcu-
lated phase diagram can match the experimental data well, the
results could be accepted in this work.
A comparison of the calculated Sr–Bi phase diagram along with
the experimental data [14,17] is presented in Fig. 3. It can be seen
that these experimental data are well reproduced by the present
thermodynamic description. It is indicated that the melting
temperature of the βSr5Bi3 phase is calculated to be 1218 K.
According to the present calculation, the computed peritectic
reaction Liquid þ βSr5Bi32SrBi2 is located at 1131 K. The com-
pound SrBi3 is formed via a peritectic reaction Liquid þ Sr11-
Bi102SrBi3, which is consistent with the experimental result [17].
The calculated enthalpies of formation compared with the
results of first-principles calculations and experimental data [14]
are presented in Fig. 4 and listed in Table 3. The present calculation
results yield a good agreement with the results of the first-
principles calculations. The calculated enthalpies of formation for
the αSr5Bi3 and βSr5Bi3 phases at 298.15 K from CALPHAD model-
ing are  82 and  80 kJ/mol-atom, respectively, which agree well
with the results of the first-principles calculations. The enthalpies
of formation of Sr–Bi are very negative. Some clues can be
obtained in Miedema model to explain the trend of enthalpy of
53
Fig. 4. Calculated enthalpies of formation for the Sr–Bi system at 298 K compared
with the first-principles calculations and the experimental data [14].
formation corresponding to change of element in intermetallic
phases. According to the Miedema model, the enthalpy of forma-
tion will be more negative with the smaller atomic radius
difference and larger electronegativity difference between the
elements A and B. In the cases of Sr–In and Sr–Bi systems, the
elements Sr and Bi have smaller atomic radius difference and
greater electronegativity difference. Thus, the intermetallic com-
pounds in the Sr–Bi system will have more negative enthalpies of
formations.
The thermodynamic parameters from the present work have
been successfully merged into thermodynamic database for multi-
component Al alloys [45–49].
6. Conclusions
 The experimental phase diagram data and thermodynamic data
available for the Sr–In and Sr–Bi systems were critically
evaluated. The enthalpies of formation for the compounds
SrIn5, SrIn3, SrIn2, SrIn, Sr5In3, Sr3In, SrBi3, Sr11Bi10, αSr5Bi3,
βSr5Bi3 and Sr2Bi were obtained via first-principles calcula-
tions, which were used to assist the thermodynamic modeling
of the two systems.
 A set of self-consistent parameters for the Sr–In and Sr–Bi
systems has been obtained by the CALPHAD approach. A
comprehensive comparison shows that the calculated phase
diagram and thermodynamic properties are in good agreement
with experimental data and first-principles calculations.
Acknowledgments
The financial support from the National Basic Research Program
of China (Grant no. 2011CB610401) and the National Natural
Science Foundation of China (Grant nos. 51101172 and 51021063)
are greatly acknowledged.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.calphad.2013.12.001.
54 Y. Wang et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 45 (2014) 49–54
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