CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 133–138

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CALPHAD: Computer Coupling of Phase Diagrams and

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

Thermodynamic description of the system Ag–Sn–Zn

G. Vassilev a,n, V. Gandova b, N. Milcheva a, G. Wnuk c
a
University of Plovdiv, Faculty of Chemistry, 4000 Plovdiv, Bulgaria
b
University of Food Technologies, Inorganic and Physical Chemistry Department, Plovdiv 4000, Bulgaria
c
Rzeszów University of Technology, Rzeszów, Poland

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

Article history: Experimental data about phase equillibria (e.g. phase boundaries location, invariant equilibria tempera-
Received 4 January 2013 tures, etc.) and thermochemical quantities (i.e. thermodynamic activities, liquid phase enthalpies of
Received in revised form formation) of the system Ag–Sn–Zn have been considered simultaneously by using CALPHAD approach.
27 February 2013
Recently reassessed thermodynamic stability of the (fcc-Sn)-phase has been used. Optimized thermo-
Accepted 14 March 2013
dynamic parameters allowing the calculation of the respective ternary phase diagram have been derived.
Available online 14 May 2013
Unlike a previous optimization the solubilities of the third constituents in the respective binary phases
Keywords: have been taken into account (i.e. Zn-solubility in Ag–Sn based intermetallic compounds and
Thermodynamics Sn-solubility in Ag–Zn phases). Calculated isothermal sections and thermochemical values have been
Phase equilibrium
compared to corresponding experimental data in order to check up the agreement.
Computational modeling
& 2013 Elsevier Ltd. All rights reserved.
Silver alloys
Solders

1. Introduction new experimental information about this ternary system

Thermodynamic [1–6], structural and other specific properties
[7–10] of the system Ag–Sn–Zn have been a subject of intensive
studies. The reason for this interest is that these alloys are
prospective for development of lead-free solders [7].
The thermochemical properties of liquid and solid Ag–Sn–Zn
phases have been a subject to intensive studies [2–5,11]. Phase
equilibria and microstructure investigations have been done as
well [12–15]. Nevertheless, the invariant reactions and the tem-
peratures associated with them have not been experimentally
determined except a hypothetical ternary eutectic temperature at
217 1С, reported by McCormack [7]. Ohtani et al. [6] and Vassilev
et al. [13,14] have experimentally confirmed this suggestion. The
ternary eutectic point is nearer to that of the binary eutectic point
of the system Ag–Sn (XSn ¼ 0.965 and 221 1С (494 К)), than to that
one of the system Sn–Zn (XSn ¼ 0.912 and 198.5 1С).
Thermodynamic description of the ternary Ag–Sn–Zn system
has been presented by Ohtani et al. [6]. Nevertheless, the solubi-
lities of the third constituents in the respective binary interme-
tallic compounds (IMC), i.e. Sn in Ag–Zn IMC and Zn in Ag–Sn IMC
have not been taken into account in the latter description. More-
over, the thermodynamic stability of the (fcc-Sn)-phase has been
recently reassessed [18]. The appearance of a significant variety of
n
Corresponding author. Tel.: +359 32 261425; fax: +359 32 261403.
E-mail addresses: gpvassilev@gmail.com,
gpvassilev@uni-plovdiv.bg (G. Vassilev).
is another stimulus. Thus, the purpose of the present work is a
re-optimization of the Ag–Sn–Zn system using novel experimental
[12–16], unpublished [17] and assessed [18] data.
2. Phases, modeling and data
Phases and their models, as used in the present description, are
exhibited in Table 1. In general the phase names introduced by the
SOLDERS thermodynamic database [18] have been retained in this
work. The respective phases' names used by Ohtani et. al [6] are
shown too, for better comprehension.
One must be aware that two couple of phases – the binary solid
solutions of Sn and Zn in silver (FCC_A1 or (Ag)), as well as the IMC
Epsilon (or AgZn3) and HCP_A3 (or Ag4Sn) respectively, have
identical structures. Nevertheless, the latter pair exhibits rather
different solubility concerning the third constituent. Namely, the
experiments have shown that the Epsilon phase does not dissolve
Sn while HCP_A3 dissolves up to 15 at% Zn [12–14].
The latest thermodynamic optimization of the binary systems
(Ag–Sn, Ag–Zn, Sn–Zn) have been done in the frame of SOLDERS
thermodynamic database [18]. Thus, the corresponding binary
parameters were generally retained from SOLDERS thermody-
namic database [18].
The phase equilibria in the Ag–Sn system occur among one liquid
phase (L), two solid solutions (FCC_A1 and BCT_A5) and two
peritectically formed compounds—HCP_A3 and AgSb_Ortho (Fig. 1,
phases 3 and 4, respectively).

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134 G. Vassilev et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 133–138

Table 1
Phases and their modeling in the present Ag–Sn–Zn description. Column 1 – phase names according to SOLDERS database [18] and this work; Column 2 – phase models up to
this work; Column 3 - phase models up to [18]; Column 4 – phase names according to [6]; Column 5 – phase models up to [6].

1 2 3 4 5

Liquid, L (Ag,Sn,Zn) (Ag,Zn), (Ag,Sn) and (Sn,Zn) Liquid, L (Ag,Sn,Zn)

BCT_A5 (Ag,Sn,Zn) (Ag,Sn) and (Sn,Zn) (βSn) (Ag,Sn) and (Sn,Zn)
FCC_A1 (Ag,Sn,Zn)1(Va)0.5 (Ag,Zn)1(Va)1, (Ag,Sn)1(Va)1 (Ag) (Ag,Sn,Zn)1(Va)0.5
BCC_A2 (Ag,Sn,Zn,Va)0.5(Ag,Sn,Zn,Va)0.5 (Ag,Zn)1(Va)3 β(AgZn) (Ag,Zn)1(Va)3
AgZn_Zeta ¼ (Zn)0.333(Ag,Zn)0.667 (Zn)1(Ag,Zn)2 ζ(AgZn) (Ag,Zn)1(Va)0.5
n n n
AgZn_Brass γ(AgSnZn)
Epsilonnnn (Ag,Zn)1(Va)0.5 nn
Epsilonnnn (Ag,Zn)1(Va)0.5
HCP_Zn (Ag,Sn,Zn)1(Va)0.5 (Ag,Zn)1(Va)0.5, (Sn,Zn)1(Va)0.5 HCP_A3 (Ag,Zn)1(Va)0.5,(Sn,Zn)1(Va)0.5
AgSb_Ortho (Ag,Zn,Va)0.75(Ag,Sn)0.25 (Ag)0.75(Ag,Sn)0.25 Ag3Sn (Ag)0.75(Sn)0.25
nnnn nnnn
HCP_A3 (Ag,Zn,Va)0.8(Ag,Sn,Zn)0.2 (Sn,Zn)1(Va)0.5

n
—symbolises the phase (Ag,Sn,Zn)0.15385(Ag,Zn)0.15385(Ag)0.2308(Zn)0.4615.
nn
—no such phase in [18]. Epsilon and HCP_A3 have been modeled as a single phase.
nnn
—there is no solubility of Sn in Epsilon.
nnnn
—no phase named HCP_Zn [6]; this phase is noted as HCP_A3.

Fig. 1. Phase diagram of the system Ag–Sn, calculated in this work. The monophase
regions are represented by numbers as follows: 1 – liquid solutions (L); 2 – silver-
based solid solution (FCC_A1); 3 – HCP_A3; 4 – AgSb_Ortho; 5 and 6 – tin-based
phases (Diamond_A4) and (BCT_A5), respectively. The invariant equilibria P1, P2,
E1, ED occur at the following temperatures, in that order – 997, 760, 505 and 286 К.
In Figs. 1 and 2, the symbols Px stay for peritectic reactions, EDx
– for eutectoid reactions, Ex – for eutectic reactions and PDx – for
peritectoid reactions. The models of both Ag–Zn IMC (i.e. BCC_A2
and AgZn_Zeta) have been changed for the purpose of the present
assessment (Table 1). Thus, the phase AgSb_Ortho had previously
been treated [6,18] as stoichiometric, (Ag)0.75(Ag,Sn)0.25 while in
this work it has been modeled as nonstoichiometric, (Ag,Zn,
Va)0.75(Ag,Sn)0.25 (Table 1). The phase HCP_A3 (or Ag4Sn) has been
modeled as (Ag,Sn)1(Va)0.5 [6,18] while a two-sublattice model
(Ag,Zn,Va)0.8(Ag,Sn,Zn)0.2 has been applied here.
The binary phase diagram Ag–Zn calculated in this work is
represented in Fig. 2. A two-sublattice symmetrical model {(Ag,Sn,
Zn,Va)0.5(Ag,Sn,Zn,Va)0.5} has been introduced (see Table 1) for the
BCC_A2 phase (instead of a substitutional solid solution model used by
[6,18]).
AgZn_Brass phase (Ag–Sn–Zn system) exhibits very small Sn
solubility [13–15]. That is why tin solubility has been permitted in
one sublattice only (Table 1) while a four sublattice model was
retained from the SOLDERS thermodynamic database [18].
The phase equilibria of the system Sn–Zn are represented by a
relatively simple (eutectic) diagram. Thermodynamic optimizations of
the latter system have been done by [6,19,20]. The latter has been
retained in the SOLDERS thermodynamic database [18]. For the sake of
brevity this phase diagram is not represented in this work.
Detailed explications of the substitutional solution and sub-
lattice models and the respective parameters are available in the
literature (e.g. [6,22–26]). Thus, for the sake of brevity, shortened
descriptions of the phases and models are exhibited only (Table 1)
Fig. 2. Phase diagram of the system Ag–Zn calculated in this work. The monophase
regions are represented by numbers as follows: 1 – liquid solutions (L); 2 – silver-
based solid solution (FCC_A1); 3 – AgZn_Zeta; 4 – BCC_A2; 5 – AgZn_Brass,
6 – Epsilon, 7 – HCP_Zn. The invariant equilibria P1, P2, P3, P4, ED1, PD1 are
characterized by the following temperatures: 984, 928, 903, 704, 538 and 537 К,
respectively.
in the present assessment. The solution phases are described with
the substitutional solution model while the IMC are described
with sublattice models or they are treated as stoichiometric
phases. The modeling of the Epsilon-phase (Table 1) has been
kept as in the binary Ag–Zn system, because there is no solubility
of Sn in Epsilon [12,13].
The respective binary systems invariant temperatures and
special points chemical compositions calculated in this work are
represented in Table 2 in order to be compared to those of Ohtani
et al. [6], to SOLDERS thermodynamic database [18] and to
experimental values [21].
As mentioned, new experimental data were used for the
present optimization. Namely: two isothermal sections—at
380 1C [13,14] and at 260 1C [12]; enthalpy of mixing in liquid
alloys [5]; zinc activity coefficients (γZn) in liquid alloys [16,17];
EMF data about liquidus temperature in ternary Ag–Sn–Zn system
from [3]. All experimental data applied for the present assessment
have been included in Table 3. The enthalpy measurements of
Karlhuber et al. [3] have not been taken into account because they
contradict to newer experimental data of Knott et al. [5].
3. Results and discussion
The thermodynamic description of the Ag–Sn–Zn system obtained in this work
is presented in Table 4. The thermodynamic stabilities of the constituents' (i.e. Ag,
 G. Vassilev et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 133–138 135

Table 2
Invariant temperatures (T, K) and chemical compositions (Cϕi, mole fractions of the phase ϕi) calculated in this work compared to these of: Ohtani et al. [6], SOLDERS
thermodynamic database [18] and experimental values [21].

ϕ1 - ϕ2 - ϕ3 Ag–Sn T (K) Cϕ1 (xSn) Cϕ2 (xSn) Cϕ3 (xSn) Reference

FCC_A1¼ Liq+HCP_A3 997 0.115 0.206 0.128 This work

995 0.110 0.210 0.130 [6]
993 0.115 0.211 0.131 [18]
997.15 0.115 0.195 0.130 [21]

HCP_A3 ¼Liq+AgSb_Ortho 760 0.240 0.488 0.241 This work

750 0.227 0.479 0.250 [6]
755 0.239 0.484 0.250 [6]
753 0.228 0.496 0.250 [21]

L¼ AgSb_Ortho+BCT_A5 505 0.964 0.250 1.000 This work

494 0.960 0.250 1.000 [6]
504 0.961 0.250 1.000 [18]
494.15 0.962 0.250 0.9991 [21]

AgSb_Ortho ¼Diamond_A4+BCT_A5 286 0.250 1.000 1.000 This work

– – – – [6]
286 0.250 1.000 1.000 [18]
– – – – [21]

ϕ1 - ϕ2 - ϕ3 Ag–Zn (xZn) (xZn) (xZn)

FCC_A1¼ BCC_A2+Liq 984 0.318 0.369 0.371 This work

982 0.318 0.400 0.401 [6]
982 0.324 0.371 0.373 [18]
983 0.321 0.367 0.375 [21]

BCC_A2¼ AgZn_Brass+Liq 928 0.598 0.615 0.626 This work

934 0.596 0.610 0.621 [6]
933 0.583 0.612 0.624 [18]
933 0.586 0.610 0.618 [21]

BCC_A2¼ AgZn_Zeta+AgZn_Brass 537 0.510 0.483 0.600 This work

547 0.510 0.496 0.598 [6]
534 0.497 0.492 0.606 [18]
547 – 0.504 0.585 [21]

FCC_A1¼ BCC_A2+AgZn_Zeta 538 0.408 0.419 0.454 This work

523 0.400 0.413 0.434 [6]
543 0.404 0.420 0.450 [18]
531 0.402 – 0.456 [21]

Table 3
Experimental data applied in the optimization for the Ag–Sn–Zn system.

Experimental data Reference

2 isothermal sections, at 380 and 260 1C [12,13–15]

Enthalpy of mixing in liquid phase along 3 fixed Ag/Sn ratios, at 973 K and Zn mole fractions from ≈0 to ≈0.4 [5]
Activity coefficient, γZn, in liquid alloys, at 903 K [16]
Activity coefficient, γZn in liquid alloys, at 823, 903, 973 and 1073 K [17]
Activity coefficient, γZn in liquid alloys, at 900 K [3]
Ternary Ag–Sn–Zn system liquidus points interpolated by EMF data at Ag:Sn ratio 1:1 [3]
Ternary Ag–Sn–Zn system liquidus points interpolated by EMF at Ag:Sn ratio 1:3 [3]
Ternary Ag–Sn–Zn system liquidus points interpolated by EMF at Ag:Sn ratio 3:1 [3]

Sn and Zn) phases have been taken from [27]. As already mentioned the
thermodynamic stability of the (fcc-Sn) has been updated by [18] for the sake of
Ag–Sn system reoptimization. That is why the updated values are shown explicitly
in Table 4. Parameters marked with O were optimized in the present study.
As already mentioned, Figs. 1 and 2 show Ag–Sn and Ag–Zn phase diagrams
calculated in the present study. The agreement with the experimental data and
previous optimizations is very good (Table 2). The reasons to change the thermo-
dynamic descriptions of some binary phases have been discussed in the previous
section.
In the following, calculated results are compared with original experimental
data to verify and demonstrate the successfulness of the optimization. All calcula-
tions were carried out with the ThermoCalc software [28].
Isothermal sections calculated with the parameters optimized in this work are
shown in Figs. 3 and 4 (at 533 K and 653 K, respectively). They are compared with
experimental data of Jao et al. [12] and Vassilev et al. [13]. Very good agreements
are observed in both cases. Note that the solubilities of the third constituents in
the respective binary phases have been taken into account in this work
(i.e. Zn-solubility in Ag–Sn based intermetallics and Sn-solubility in Ag–Zn phases).
Such solubilities have not been modeled by Ohtani et al. [6] in their previous
optimization of this system.
New [16] and unpublished [17] experimental data of Wnuk about zinc-
activities in the ternary liquid phase, at 823, 903, 973 and 1023 K have been taken
into account for the first time in this work. The measurements have been done by a
modified isopiestic method, along approximately a section with Ag vs. Sn atomic
ratio of 1:9. Calculated Zn-activities values (this work) at 823 K and 1023 K have
been directly compared (point by point) to the respective experimental data of
Wnuk [17] in Figs. 5 and 6, in that order. Good agreement is observed. As one can
see feeble positive deviation from the ideal behavior are exhibited by the zinc-
activities.
Temperature and composition dependence of zinc activities at 823, 903, 973
and 1023 K along a section with Ag vs. Sn ratio 1:9 is shown in Fig. 7. It could be
concluded that the zinc activities diminish with the temperature rising.
Calculated and experimental liquid phase integral enthalpies of mixing at 973 K
along cross-sections with molar ratios Ag:Sn ¼ 1:3, 1:1, 3:1 are exhibited in Fig. 8.
136 G. Vassilev et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 133–138

Table 4 Table 4 (continued )

Thermodynamic description of the Ag–Sn–Zn system. Thermodynamic data of pure
components are given by [27] unless not shown in the table. Parameter values are Liquid (1 sublattice, sites: 1, constituents: Ag,Sn,Zn) Ref.
in J/mol.
AgSb_Ortho (2 sublattices, sites: 0.75:0.25, constituents: Ag,Va,Zn:Ag,Sn)
o AgSb_Ortho
Liquid (1 sublattice, sites: 1, constituents: Ag,Sn,Zn) Ref. GAg:Ag ¼ oGhser
Ag +(+2000) Oa
o AgSb_Ortho
GAg:Sn ¼ 2.98150E+02−11085.3+110.01471nT−23.18nTnLN(T)  Oa
LLAg,Sn ¼(−3177.49−10.16124nT+0.380505nTnLN(T))+ [18,19] 0.00359nTnn2+4389.5nTnn(−1)
(−16782.28+2.06521nT+0.437477nTnLN(T))(xAg−xSn)+ o AgSb_Ortho
GVa:Ag ¼ 0.25oGhser
Ag +(+35000) Oa
(+3190.34−107.09456nT+13.954838nTnLN(T)) (xAg−xSn)2 [18,20] o AgSb_Ortho
GVa:Sn ¼ 0.25oGhser
Sn +(+20000) Oa
LLAg,Zn ¼ (−27600+6.07nT)+(−5500)(xAg−xZn) LAgSb_Ortho
Va:Ag,Sn ¼ (+13000) Oa
LLSn,Zn ¼ (+19314.64−75.89949nT+8.751396nTnLN(T))+ [6,18] LAgSb_Ortho
Ag:Ag,Sn ¼(0) Oa
(−5696.28+4.20198nT)(xSn−xZn)+(+1037.22+0.98362nT)(xSn−xZn)2 LAgSb_Ortho
Ag,Va:Sn ¼(−3000) Oa
LLAg,Sn,Zn ¼ (30091+45nT)xAg+(37824−32nT)xSn+(112215−127nT)xZn Oa LAgSb_Ortho
Ag,Va:Ag ¼(−2000) Oa
o AgSb_Ortho
GZn:Sn ¼ 0.75oGhser o hser
Zn + 0.25 GSn +(+700) Oa
BCT_A5 (1 sublattice, sites: 1, constituents: Ag,Sn,Zn)
LBCT_A5
Ag,Sn ¼ (+18358.8) [18,19] HCP_A3 (2 sublattices, sites: 0.8:0.2, constituents: Ag,Va,Zn:Ag,Sn,Zn)
LBCT_A5
Ag,Zn ¼ (−10000) [18,20] o HCP_A3
GAg:Ag ¼ oGhcpAg +(+36439) Oa
n
LBCT_A5
Sn,Zn ¼ (+6514.76+25.70958 T) [6,18] o HCP_A3
GVa:Ag ¼ 0.2oGhcpAg Oa
o HCP_A3
FCC_A1 (2 sublattice, sites: 1:1, constituents:(Ag,Sn,Zn:Va)) GVa:Sn ¼ 0.2oGhcpSn +(+60) Oa
o FCC_A1
GSN (298.14 to 505.08 K)¼ −345.135+56.983315nT−15.961nTnLN(T) o HCP_A3
GAg:Sn ¼ 0.8oGhcp o hcp
Ag + 0.2 GSn +(+120400) Oa
−0.0188702nTnn2+3.121167E-06nTnn3−61960nTnn(−1); [18] LHCP_A3 n
Va:Ag,Sn ¼ (−209.66+2.232 T)+ (−7900) (xAg  xSn) Oa
o FCC_A1
GSN (505.08–800 K) ¼+8034.724−4.454731nT−8.2590486nTnLN LHCP_A3
Ag:Ag,Sn ¼(−209.66+2.232 T)
n
Oa
(T)  o HCP_A3
GZn:Ag ¼ 0.8oGhcp o hcp
Zn + 0.2 GAg +(−4000) Oa
0.016814429nTnn2+2.623131E-06nTnn3-1081244nTnn(−1)−1.2307E o HCP_A3
GVa:Zn ¼ 0.2oGhcpZn +(+3410) Oa
+25nTnn(−9);
o FCC_A1
GSN (800–3000 K)¼ −2746.959+130.53688nT−28.4512nTnLN(T) [18,19] Oa – optimized in this work value.
−1.2307E+25nTnn(−9); 3000 N !
n
LFCC_A1
Ag,Sn ¼(+745.45+11.498027 T)+(−36541.5)(xAg−xSn) [18,20]
n
LFCC_A1
Ag,Zn ¼(−24620+0.91 T) [6,18]
n
LFCC_A1
Sn,Zn ¼(+33433.94−11.14466 T) Oa
LFCC_A1
Ag,Sn,Zn ¼ (+38000)xAg+(0)xSn+(+20000)xZn

BCC_A2 (2 sublattices, sites: 0.5:0.5, constituents:

Ag,Zn,Va,Sn:Ag,Zn,Va,Sn)
o BCC_A2
GAg:Ag ¼ oGBCC
Ag +(25494) Oa
o BCC_A2 ¼ o BCC
GZn:Zn GZn +(+18000) Oa
o BCC_A2
GVa:Va ¼ (+16500) Oa
o n
GBCC_A2Ag:Zn ¼ oGbcc_A2 o bcc o bcc
Zn:Ag ¼ 0.5 GAg +0.5 GZn +(+18830.5−0.63 T) Oa
o BCC_A2
GVa:Ag ¼ 0.5oGBCCAg +(+5729.4) Oa
o BCC_A2
GVa:Ag ¼ 0.5oGBCCAg +(−160) Oa
o BCC_A2 o BCC
GZn:Va ¼ 0.5 GZn +(+216) Oa
o BCC_A2
GVa:Zn ¼ 0.5oGbccZn +(+216) Oa
¼ bcc_A2 n
LBCC_A2
Va:Ag,Zn LZn:Ag,Va ¼ (−15370+1.2 T) Oa
o BCC_A2Sn:Ag n
G ¼ GAg:Sn ¼ 0.5oGbcc
o BCC_A2 o bcc
Ag +0.5 GSn +(−6315+3.5 T) Oa
o BCC_A2 n
GZn:Sn ¼ oGBCC_A2 o bcc o bcc
Sn:Zn ¼ 0.5 GZn +0.5 GSn +(+10400−0.6 T) Oa
o BCC_A2
GVa:Sn ¼ oGBCC_A2 o bcc
Sn:Va ¼0.5 GSn +(+5000) Oa

AgZn_Zeta (2 sublattices, sites: 0.3333:0.6667, constituents: Zn:Ag,Zn) Fig. 3. Calculated isothermal section of the Ag–Sn–Zn system at 533 K, together
o AgZn_Zeta
GZn:Ag ¼0.6667oGbcc o bcc
Ag +0.3333 GZn +(−9066.66) [18,20] with experimental data points of Jao et al. [12]. The monophase regions are
o AgZn_Zeta ¼ o bcc
GZn:Zn GZn +(+233.33) [18,20] represented by numbers, while symbols show the chemical compositions [12] of
AgZn_Zeta
LZn:Ag,Zn ¼ (−10690) [18,20] the equilibrium phases, as follows: 1 – liquid solutions ( ); 2 – AgSb_Ortho (●),
AgZn_Brass (4 sublattices, sites: 0.15385:0.15385:0.2308:0.4615, constituents: 3 – HCP_A3 ( ), 4 – silver based solid solution (FCC_A1), (◯); 5 – BCC_A2 (■),
Ag,Zn,Sn:Ag,Zn:Ag:Zn) 6 – AgZn_Brass ( ), 7 – Epsilon, 8 – HCP_Zn.
o AgZn_Brass n n
GAg:Ag:Ag:Zn ¼0.5385oGHSER o HSER
Ag +0.4615 GZn +(−3781.1385−0.778 T LN [18,20]
(T))
o AgZn_Brass o HSER o HSER
GZn:Ag:Ag:Zn ¼0.38465 GAg +0.61535 GZn [18,20]
+(−6315.6615−0.6156nTnLN(T))
o AgZn_Brass o hser o HSER
GAg:Zn:Ag:Zn ¼0.38465 GAg +0.61535 GZn [18,20]
+(−965.9515−1.4435nTnLN(T))
o AgZn_Brass
GZn:Zn:Ag:Zn ¼ 0.2308oGhser o HSER
Ag +0.7692 GZn [18,20]
+(−4621.91−0.2934nTnLN(T))
LAgZn_Brass
Ag,Zn:Ag:Ag:Zn ¼ (0) [18,20]
LAgZn_Brass
Ag:Ag,Zn:Ag:Zn ¼ (0) [18,20]
AgZn_Brass
LZn:Ag,Zn:Ag:Zn ¼(0) [18,20]
AgZn_Brass
LAg,Zn:Zn:Ag:Zn ¼(0) [18,20]
o AgZn_Brass
GSn:Ag:Ag:Zn ¼ 0.38465oGhser o hser o hser
Ag +0.15385 GSn +0.4615 GZn Oa
+(−3011.9  0.78nTnLN(T))

Epsilon (2 sublattices, sites: 1:0.5, constituents: Ag,Zn:Va)

o Epsilon
GAg:Va ¼ oGhcp
Ag [6,18]
o Epsilon
GZn:Va ¼ oGhcp
Zn [6,18]
LAg,Zn:Va ¼(−21360−2.5nT)+(+37766.12−26.6016nT)
Epsilon
[6,18] Fig. 4. Calculated isothermal section of the Ag–Sn–Zn system at 653 K, together
HCP_Zn (2 sublattices, sites: 1:0.5, constituents: Ag,Sn,Zn:Va) with experimental data points of Vassilev et al. [13]. The monophase regions are
o HCP_Zn
GAg:Va ¼ oGhcpAg [18] representedal compositions [13] of the equilibrium phases, as follows: 1 – liquid
o HCP_Zn
GSn:Va ¼ oGhcpSn [18] solutions ( ); 2 – AgSb_Ortho (●), 3 – HCP_A3( ), 4 – silver-based solid solution
o HCP_Zn
GZn:Va ¼ GAgo hcp
[18] (FCC_A1), (◯); 5 – BCC_A2 (■), 6 – AgZn_Brass ( ), 7 – Epsilon ( ), 8 – HCP_Zn.
HCP_Zn
LAg,Sn:Va ¼ (+10000) [18]
n
LHCP_Zn
Ag,Zn:Va ¼(−18700+1.237 T) [18] Very good agreement between calculated and newer experimental of Knott et al.
n
LHCP_Zn
Sn,Zn:Va ¼ (+33433.94−11.14466 T) [18] [5] is obtained while the values calculated up to Ohtani et al. [6] deviate
considerably.
 G. Vassilev et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 133–138 137

Fig. 5. Calculated (this work) liquid phase Zn–activities values at 823 K, directly
compared to the respective experimental data [17]. The dashed line corresponds to
the Raoult's low. The reference state is liquid zinc.

Fig. 8. Liquid phase integral enthalpies of mixing at 973 K along cross-sections

with molar ratios Ag:Sn equal 1:3, 1:1 and 3:1. The continuous curves show
enthalpy values calculated in this work, the dashed curves – calculations by Ohtani
et al. [6]. The symbols (7) represent the experimental data of Knott et al. [5].
The reference states are the liquid phases of the pure constituents.

Fig. 6. Calculated (this work) liquid phase Zn–activities values at 1023 K, directly
compared to the respective experimental data of Wnuk [17]. The dashed line
corresponds to the Raoult's low. The reference state is liquid zinc.
Fig. 9. Calculated in this work isopleth at Ag:Sn ratio equal to 1:3. Interpolated
from EMF [3] ternary liquidus points data [(▼) are plotted]. The two-phase regions
are represented by numbers as follows: 1– Liquid; 2 – HCP_Zn; 3 – BCT_A5; 4 –
Epsilon; 5 – AgZn_Brass; 6 – HCP_A3; 7 – AgSb_Ortho; 8 – BCC_A2; 9 – AgZn_Zeta;
10 – FCC_A1.

Fig. 7. Calculated (this work) liquid phase Zn–activities values at 823, 903, 973 and
1023 K along a section with Ag vs. Sn ratio of 1:9. The reference state is liquid zinc. Fig. 10. Calculated in this work (solid curves) liquidus projection of the Sn–Ag–Zn
system. The dashed lines denote the liquidus projection obtained up to [6].

In Fig. 9 an isopleth at Ag:Sn ratio equal to 3:1 calculated in this work is shown.
Interpolated from EMF data ternary liquidus points are plotted as well. Relatively 4. Conclusions
good agreement between calculated and experimentally estimated liquidus tem-
peratures is observed. Thermodynamic description of the ternary Ag–Sn–Zn system
Calculated liquidus projections are exhibited in Figs. 10 and 11. The liquidus
projection calculated up to Ohtani et al. [6] is plotted in Fig. 10 as well. Generally,
applying new experimental phase equilibrium and thermochemi-
the agreement is good, but in the optimization of [6] the calculated AgZn_Brass and cal data was obtained. In this optimization, the unary and binary
FCC_A1 primary crystallization fields are larger. thermodynamic data of the systems and the phases' appellations
138 G. Vassilev et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 133–138
Fig. 11. Calculated Sn-rich portion of the liquidus surface (90–100 mass% Sn).
were taken, generally, from SOLDERS thermodynamic database.
Recently reassessed thermodynamic stability of the (fcc-Sn)-phase
has been used. The models of some phases (e.g. AgSb_Ortho,
HCP_A3, AgZn_Brass and BCC_A2) have been changed in order to
comply with the present assessment. Good correlation between
calculated and experimental topological and thermochemical data
was obtained.
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.2013.03.
003.
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