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Article history: Phase equilibria in the Mg-rich region of the MgSnIn (at 415 C and 330 C), and MgSnZn (at 300 C)
Received 3 September 2013 ternary systems were determined by quenching experiments, electron probe micro-analyzer (EPMA), and
Received in revised form 17 October 2013 X-ray diffraction (XRD) techniques. The ternary isoplethal sections with constant 5 In and 10 Sn at.% of
Accepted 6 November 2013
MgInSn system, and 10 Sn at.% of MgInZn system were determined by differential scanning calorim-
Available online 14 November 2013
etry (DSC). No ternary compounds were found in the MgSnZn and MgSnIn isothermal sections. Crit-
ical evaluation and thermodynamic optimization of the MgSnInZn quaternary system were carried
Keywords:
out using CALPHAD (Calculation of Phase Diagrams) technique. The Modied Quasichemical Model in
Metals and alloys
Phase diagram
the Pair Approximation (MQMPA) was used for modeling the liquid solution, which exhibits a high
Thermodynamic modeling degree of short-range ordering behavior. The solid phases were modeled with the Compound Energy For-
Electron probe micro-analyzer malism (CEF). All available and reliable experimental data were reproduced within experimental error
SEM limits. A self-consistent thermodynamic database was constructed for the MgSnInZn quaternary sys-
tem, which can be used as a guide for Mg-based alloys development.
2013 Elsevier B.V. All rights reserved.
0925-8388/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.11.031
76 J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595
Table 1 Graham and Raynor [15] investigated several InMg binary alloys
Optimized phases and thermodynamic models used in the present work. by using XRD and metallography, and the peritectic reaction
Phase Pearson Strukturbericht Space Prototype Modela fcc + liquid M tet(In) was found to occur at 333.5 C. Ino et al. [16]
symbol designation group investigated the ordering phase transformation in the InMg sys-
Liquid MQMPA tem between 36.8 and 56.3 at.% In using XRD and thermal analysis.
fcc cF4 A1 Fm3m Cu CEF According to them, the b ? b0 (L12) and b ! b00 L10 transforma-
bct tI4 A5 I41/mmm Sn CEF tions go through two phase regions of b + b0 (L12) and b b00 L10 ,
bcc cI2 A2 Im3m W CEF
respectively. Phase equilibria in the InMg binary system was
hcp hP2 A3 P63/mmc Mg CEF
hcp (Zn) hP2 A3 P63/mmc Mg CEF
afterwards investigated up to 40 at.% Mg by Hiraga et al. [17] by
tet tI2 A6 F4/mmm In CEF using XRD, thermal analysis, and calorimetry. The solid solubility
b0 cP4 L12 F4/mmm AuCu3 CEF of magnesium in indium was found to reach about 5 at.%. The peri-
b1 hR16 R3m CEF tectic reaction fcc + liquid M tet(In) was reported to occur at 160 C
b2 hP9
P 62m Mg2Tl ST
by Hiraga et al. [17], which is quite different from the temperature
b3 oI28 D8g Ibam Mg5Ga2 ST
observed earlier by Graham and Raynor (333.5 C) [15]. In the In-
b00 tP4 L10 P4/mmm AuCu CEF
c0 cP4 L12 Pm3m AuCu3 CEF rich portion, a new ordered phase, c0 , with a Cu3Au-type structure,
Mg12Zn13 ST was reported by Hiraga et al. [17] based on thermal and X-ray anal-
Mg2Zn3 mC110 B2/m ST ysis. The In-rich region was reinvestigated by Pickwick et al. [18]
MgZn2 hP12 C14 P63/mmc MgZn2 ST
and Feschotte [19] by using differential thermal analysis (DTA),
Mg2Zn11 cP39 D8c Pm3 Mg2Zn11 ST
electrical resistivity measurements, and metallographic observa-
Mg51Zn20 oI142 D7b Immm Ta3B4 ST
Mg2Sn cF12 C1 Fm3m CaF2 ST tion methods. The temperatures of the peritectic reactions li-
b(InSn) tI2 A6 F4/mmm In CEF quid + hcp(Mg) M b and fcc + liquid M tet(In) were observed to
c(InSn) hP5 P6/mmm CEF occur at 305 0.5 C and 160 C, respectively, which is in good
a
MQMPA: Modied Quasichemical Model in the Pair Approximation; CEF:
agreement with the data of Hiraga et al. [17]. Pickwick et al. [18]
Compound Energy Formalism; ST: Stoichiometric Compound. also observed that the intermediate fcc solid solution is homoge-
neous over a wide range, from 23 to 86 at.% In. Watanabe [20]
re-examined the InMg system near the Mg3In composition and
2. Literature review the b3 phase, reported as Mg5In2 in Hanckes work [13], was
conrmed. According to Watanabe [20], the b3 phase is only stable
2.1. The InMg systems below 210 C and decomposes to b0 and b2 above this temperature.
The whole thermodynamic and phase equilibra data of the InMg
Phase equilibria in the Mg-rich portion (020 at.% In) of the binary system were compiled by Nayeb-Hashemi and Clark [21].
InMg binary system was rst studied by Hume-Rothery and Ray- Seven binary compounds were considered: b, b1, b2, b3, b0 , b00 and
nor [12] by means of thermal analysis and metallographic observa- c0 , where b0 and c0 are ordered phases with the fcc L12 structure
tion methods. The liquidus and solidus curves were determined (AuCu3), and b00 is another ordered fcc phase with the L10 structure
and a large solid solution eld located between 18.6 and 19.4 (AuCu).
at.% In in the Mg (hcp) phase was reported. The whole composition The thermodynamic properties of activities of In and Mg, en-
range of the InMg binary system was examined by Hancke [13] by thalpy and entropy mixing of the InMg liquid phase were studied
using XRD; four intermediate phases were reported: Mg5In2 (body- by calorimetric measurements [22,23], EMF measurements
centered rhombic), Mg2In (hexagonal), MgIn (body-centered [2327], and vapour pressure measurements [28]. Ehrlich [22]
tetragonal) and MgIn3. Later, the constitution of InMg alloys reported the experimental enthalpy of mixing of the InMg liquid
between 20 and 50 at.% In was studied by Raynor [14] by using phase at 650 C using direct calorimetric measurements. Moser
optical microscopy, electrolytic measurements, and XRD. The peri- and Castanet [23,27] studied the InMg liquid solution by an
tectic reaction liquid + Mg (hcp) M b was found to occur at 302 C at EMF technique based on the concentration cell: Mg(s)//
a liquid composition of 23.2 at.% In. Two intermediate phases, b1 (MgCl2LiClKCl)//MgIn(liq.). And the activities, enthalpy mixing
and b2, were found, and the solubility in b1 was found to lie and Gibbs energy of mixing at 577 C were derived in their work
between 23.5 and 25 at.% In. Raynor [14] also found that b1 and [23,27] based on the results from EMF measurements. Slaby and
b2 have very complex crystal structures, and noted that the crystal Terpilowski [24,25] investigated the MgIn liquid phase using
structure of b1 is different from that of Mg5In2 [13]). Moreover, EMF measurements with the type of cell: Mg(s)//(0.58LiCl + 0.42KCl
Raynor [14] pointed out that b2 may actually correspond to Mg2In, + 0.05MgBr2)//MgxIn1x. The enthalpy of mixing, entropy of mixing,
as reported earlier by Hancke [13]. Two ordering transformations, and the activity of In and Mg in the liquid phase at 650 C were
b ? b0 (L12), and b ! b00 L10 , are mentioned in Raynors work [14]. extrapolated by Slaby and Terpilowski [24,25] based on their
Table 2
Optimized binary model parameters of the MQMPA for the MgSnInZn liquid solution.
Note: T in K.
a
For all pure elements (Mg, Li, and Sn), Z iii 6.
J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595 77
(a) (b)
hcp(Mg)
Mg2Sn
Mg2Sn hcp(Mg)
fcc
(c) (d)
Mg2Sn
Mg2Sn
hcp(Zn)
Mg12Zn13
hcp(Mg)
Mg2Zn11
Fig. 1. Typical ternary BSE images obtained from (a) Mg78Sn10In12 (at.%) alloy annealed at 415 C for 20 days; (b) Mg80Sn10In10 (at.%) alloy annealed at 330 C for 35 days;
(c) Mg25Sn10Zn65 (at.%) alloy annealed at 300 C for 50 days; (d) Mg70Sn10Zn20 (at.%) alloy annealed at 300 C for 50 days.
Table 3
Equilibrium compositions in the MgSnX (X: In, Zn) ternary systems as measured in the present work.
System Temp. (C) Alloy nominal comp. (at.%) Phase equilibira Composition (at.%)
Phase 1/Phase 2/Phase 3 Phase 1 Phase 2 Phase 3
Mg Sn In Mg Sn In Mg Sn In
MgSnIn 415 Mg80Sn10In10 hcp(Mg)/Mg2Sn/ 84.77 0.39 14.84 67.81 31.91 0.28
Mg78Sn10In12 hcp(Mg)/Mg2Sn/fcc 80.55 0.34 19.11 67.82 31.79 0.39 77.73 0.15 22.12
Mg70Sn10In20 Mg2Sn/fcc/ 67.32 32.26 0.42 70.34 0.35 29.31
Mg65Sn10In25 Mg2Sn/fcc/ 67.30 32.50 0.20 64.07 0.15 35.78
330 Mg80Sn10In10 hcp(Mg)/Mg2Sn/ 84.73 0.15 15.12 67.76 31.93 0.31
Mg78Sn10In12 hcp(Mg)/Mg2Sn/b1 81.59 0.10 18.31 67.50 32.15 0.35 75.11 0.38 24.51
0
Mg70Sn10In20 Mg2Sn/b (L12)/ 67.83 31.87 0.30 70.92 0.13 28.95
Mg65Sn10In25 Mg2Sn/fcc/ 67.68 31.96 0.36 62.53 0.15 37.32
Mg Sn Zn Mg Sn Zn Mg Sn Zn
MgSnZn 300 Mg70Sn10Zn20 hcp (Mg)/Mg2Sn/Mg12Zn13 98.00 0.23 1.77 67.95 32.02 0.03 50.44 0.6 48.96
Mg50Sn10Zn40 Mg2Sn/Mg2Zn3/Mg12Zn13 67.42 32.46 0.12 42.73 0.02 57.25 50.80 0.04 49.16
Mg45Sn10Zn45 Mg2Sn/Mg2Zn3/ 67.87 32.09 0.04 38.99 3.17 57.84
Mg25Sn10Zn65 Mg2Sn/Mg2Zn11/hcp(Zn) 67.09 32.84 0.07 18.90 3.98 77.12 0.95 1. 5 97.55
60
20
)
T=473 o C T=495 o C 20
T=345 o C
Heat flow (exo
cooling T=597 o C
cooling T=521 o C
0 0
heating heating
T=352 o C
T=474 o C T=485 o C T=518 o C
-20 T=362 o C
-20 o
T=491 C
o
T=585 C
-40
-40
-60
-60
300 350 400 450 500 550 600 650 300 350 400 450 500 550 600
o
Temperature / C Temperature / oC
Fig. 2. The DSC curves of (a) Mg78Sn10In12 and (b) Mg25Sn10Zn65 alloys obtained in the present work.
78 J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595
Table 4
Thermal signals obtained from DSC measurements with the corresponding interpretation from the thermodynamic calculations for the MgSnIn ternary system.
800
Hume-Rothery and Raynor (1938): thermal and metallographic analysis
Raynor (1948): XRD, metallographic analysis and electrolytic measurements
but a little bit more positive than the data reported by Slaby and
700 Hiraga et al. (1968): XRD and thermal analysis
Pickwick et al. (1969): XRD, metallographic analysis and electrolytic measurements
Terpilowski [24,25] and a bit more negative than the data reported
Watanabe (1975): Thermal analysis and XRD
Feschotte (1976): XRD, metallographic analysis and electrolytic measurements by Nebell [26] and Moser and Castanet [23].
600
Thermodynamic optimization of the MgIn binary system was
not carried out previously. Consequently, the MgIn binary system
Temperature, oC
500 liquid
was optimized in the present work for the rst time.
400 fcc
hcp '(L12)
300
Table 5
The calculated results of invariant reactions in the InMg system compared with experimental data.
0
0
Calorimetric measurements:
Moser (1979): T=735 oC , T=675 oC
Ehrich (1965): T=650 oC
-2 EMF measurements: Enthalpy of formation, kJmol-atom -1 -2
Enthalpy of mixing , kJmol -1
o
Slaby (1965): T=650 C
Terpilowski (1967): T=650 o C
Nebell (1970): T=650 o C -4
Moser (1979): T=577 o C
-4
-6
-6 -8
-10
-8
-12
-14
In 20 40 60 80 Mg
Mg / at. % Mg 20 40 60 80 In
Mg / at.%
Fig. 4. Calculated enthalpy of mixing of the InMg liquid phase at 675 C in
comparison with the reported experimental data [2227]. Fig. 6. Calculated enthalpy of formation of solid phases of the InMg binary system
25 C.
0
Oelsen calorimetry. The enthalpy of mixing of the liquid phase
was determined with a calorimetric method by Wittig and Scheidt
[40], Kleppa [41], Yazawa et al. [42], Bros and Laftte [43], Rechch-
liquid standard states
-2 ach et al. [44] in the temperature range from 248 C to 500 C. Their
results are in a reasonable agreement with the experimental error
(Mg) (In) bar of 10 J/mol. The enthalpy of formation and activity of In in the
-4
solid phases for the temperature range from 75 C to 125 C were
determined by Cakir and Alpaut [35] using EMF measurements,
Vapor pressure measurements: and by Alpaut and Heumann [45] using quantitative thermal anal-
i ),
-6
Chirulli et al. (1983): T=627 oC
ysis, respectively.
ln (
EMF measurements:
Slaby and Terpilowski (1965): T= 650 o C
Nebell (1970): T= 650 oC
The InSn binary system was optimized by Lee et al. [36] with
-8 Moser and Castanet (1979): T= 577 oC Bragg-Williams ideal mixing modeling (BWM) for liquid phase in
1997, their optimization are in good agreement with the reported
experimental data at that time. In order to construct a self-consis-
In 20 40 60 80 Mg tent thermodynamic database of MgSnInZn quaternary system,
Mg / at. % the InSn system was re-optimized with the Modied Quasichem-
ical Model in the Pair Approximation (MQMPA) [46,47] for liquid
Fig. 5. Calculated activities of Mg and In in the liquid phase at 650 C in comparison phase, and with the recently reported experimental data in the
with the reported experimental data [24,2628].
present work.
Table 6
Optimized thermodynamic parameters for the quaternary MgSnInZn system.
15000:0; GZn:Mg 2 0
Ghcp
Zn 1 0
Ghcp
Mg 35359:6 8:84 T
250
Heumann and Alpaut (1964): DTA and XRD
Evans and Prince (1983): DTA and tensile testing
Wojtaszek and Kuzyk (1974): electrolytic resistance measurements
Kaplun (1983): thermal analysis method
200
Liquid
Temperature, oC
150
119 oC
100
(SnIn)
tet(In)
(SnIn)
50
bct(Sn)
In 20 40 60 80 Sn
Sn / at.%
Fig. 7. Calculated InSn phase diagram in comparison with the reported experi- Fig. 10. Calculated activity of In in solid InSn binary alloys at 100 C (reference
mental data [3032,34]. state tet(In)) in comparison with the reported experimental data [35].
0
4
EMF measurements:
-50 Cakir and Alpaut (1988)
DTA measurements:
Enthalpy of mixing, Jmol -1
-150
2
-200
Calorimetric measurements:
Wittig and Scheidt (1961), T=371 oC
Bros and Laffitte (1970), T=248 oC
-250 Yazawa et al. (1968), T=450 oC 1
Yazawa et al. (1968), T=300 oC
Kleppa (1956), T=450 oC
In 20 40 60 80 Sn
Sn / at.% In 20 40 60 80 Sn
Sn / at.%
Fig. 8. Calculated enthalpy of mixing of liquid InSn binary alloys at 450 C in
comparison with the reported experimental data [4043]. Fig. 11. Calculated enthalpy of formation of solid InSn binary alloys at 100 C in
comparison with the reported experimental data [35,45].
600
Valeniner (1943): thermal analysis
Rhines and Grobe (1944): thermal analysis
Sviirbely and Selis (1953), calorimetric measurements
500 Oelsen and Zuhlke (1956), calorimetric measurements liquid
Dutkiewicz and Moser (1983), metallographic investigation
Calculated metastable miscibility gap of liquid phase
400
Temperature, oC
liquid + hcp(Zn)
300
200
144 oC
100
tet(In) + hcp(Zn)
In 20 40 60 80 Zn
Zn / at. %
Fig. 9. Calculated activity of In and Sn in the liquid phase at 427 C in comparison Fig. 12. Calculated InZn phase diagram along with the reported experimental data
with the reported experimental data [3739]. [5053].
and Zakulski [48]. The phase diagram is constituted of a simple eu- determined by Svirbely and Selis [52], Oelsen and Zuhlke [53], Bohl
tectic, liquid + tet(In) M hcp(Zn), and was rst investigated by Wil- and Hildebrandt [54], and Moser [55] by performing EMF or calo-
son and Peretti [49] using the visual polythermal method and rimetric measurements. All the liquidus experimental data are in
optical microscopy. Soon after, Valentiner [50] and Rhines and a good agreement except for the early data collected by Wilson
Grobe [51] modied the phase diagram based on new data and Peretti [49]. The eutectic temperature was reported to lie in
obtained by thermal analysis. The phase relations were then the range of 141.5144 C. The temperature of 143.5 C reported
82 J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595
2.4. MgSnIn
(a) (b)
Fig. 15. Calculated isothermal sections of the MgSnIn ternary system at (a) 415 C and (b) 330 C along with the present experimental data obtained by EPMA
measurements.
J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595 83
800 800
(a) 10 at.% Sn Present work, DSC measurements
cooling heating
(b) 5 at. % In Present work, DSC measurements
Temperature,o C
Temperature,o C
500 500
liquid+Mg2Sn
Mg2Sn+fcc
400 hcp+Mg2Sn
400
hcp+Mg2Sn
300 liquid+Mg2Sn+fcc 300
fcc+Mg2Sn liquid+Mg2Sn+(InSn)
200 hcp+
200
+Mg2Sn
Mg2Sn
hcp+Mg2Sn+1
+1
100 100 Mg2Sn+(InSn)
tet(In)+Mg2Sn
bct(Sn)+(InSn)
Fig. 16. Calculated ternary isoplethal sections of (a) 10 Sn and (b) 5 In (at.%) in comparison with the present experimental data.
Fig. 17. Calculated activity of Mg (liquid reference states) with the (a) 0.25, (b) 1, (c) 3/1 in liquid MgInSn ternary alloys versus temperature along with the reported
experimental data (corrected for the Mg(s)/Mg(liq.) fusion below 650 C) [66].
equilibria measurements are needed. Consequently, the isothermal diagram for the MgZn system; the currently accepted phase dia-
sections at 415 and 330 C, and isoplethal sections at 10 Sn and 5 In gram, with ve intermediate compounds, was updated by Agarwal
(at.%) were studied in the present work rstly, and then a thermo- et al. [68]. Phase equilibria in the MgZn2Mg2SnZnSn region
dynamic optimization of MgSnIn ternary was carried out. were investigated by Godecke and Sommer [69] using thermal
analysis and metallographic methods. The liquidus projection
2.5. MgSnZn and six isoplethal sections were determined. According to Otani
[67] and Godecke and Sommer [69], no stable ternary compound
Phase equilibria in the MgSnZn ternary system was rst stud- exists in the MgSnZn system. The ternary solubility of Sn in
ied by Otani [67] using thermal analysis and optical microscopy. MgZn binary compounds and of Zn in Mg2Sn was studied by
Seven ternary isoplethal sections were reported. However, it Mingolo et al. [70] and Sirkin et al. [71] using Mossbauer spectros-
should be noted that Otani [67] employed an outdated phase copy and XRD. According to them, there is a limited solid solubility
84 J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595
Fig. 19. Calculated isothermal sections of the MgSnZn ternary system at (a) 300 C, (b) 340 C and (c) 500 C compared with present and reported experimental data [69].
J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595 85
Fig. 20. Calculated isoplethal sections of the MgSnZn ternary system (a) Mg2SnZn, (b) Mg2SnMgZn2, (c) Mg2Sn98Mg2Zn98, (d) Mg10Sn90Mg10Zn90, (e) Mg48Sn52
Mg48Zn52, (f) Mg97Zn3Sn97Zn3, (g) Mg30Zn70Mg30Sn70, (h) Mg10Zn90Sn10Zn90, (i) Mg98Sn2Zn98Sn2, (j) Mg90Sn10Zn90Sn10, (k) Mg60Sn40Zn60Sn40, and (l)
Mg15Sn85Zn15Sn85 along with the reported experimental data [67,69].
in the MgSnInZn quaternary system are listed in Table 1, along [46,47]. A detailed description of the MQMPA and its associated
with the model used to describe their thermodynamic properties. notation is given in Refs. [46,47]. The same notation is used in
The binary systems MgSn, MgZn and SnZn have been critical the present work, and a brief description of MQMPA is given as
evaluated and parameters of their thermodynamic models have follows:
been optimized by Jung et al. [85], Spencer [86] and Ghosh et al. For the binary (A + B) system, the quasichemical pair exchange
[73] using MQMPA for the liquid solution. Consequently, all the reaction can be considered:
thermodynamic parameters of MgSn, MgZn and SnZn binary
systems were taken from their work [73,85,86] without further
AApair BBpair 2ABpair ; Dg AB 1
modication for the present optimization of the MgSnInZn
where i j pair represents a rst-nearest-neighbor pair of atoms.
quaternary system.
The Gibbs energy change for the formation of one mole of (AB)
pairs according to Reaction (1) is Dg AB =2. Let nA and nB be the
3.1. Liquid phase number of moles of A and B, nAA, nBB, and nAB be the number of
moles of AA, BB and AB pairs. Z A and ZB are the coordination
The thermodynamic properties of the liquid phase were mod- numbers of A and B. Then the Gibbs energy of the solution is gi-
eled using the Modied MQMPA developed by Pelton et al. ven by:
86 J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595
Fig. 20 (continued)
G nA GoA nB GoB T DSconfig nAB =2Dg AB 2 where XAA, XAB and XBB are the mole fractions of the AA, BB and A
B pairs respectively; YA and YB are the coordination-equivalent
where GoA
and GoB
are the molar Gibbs energies of the pure fractions of A and B:
component A and B, and DSconfig is the congurational entropy of
nij
mixing given by randomly distributing the AA, BB and AB pairs X ij i; j A or B 4
in the one-dimensional Ising approximation. The expression for nAA nBB nAB
DSconfig is:
Z i ni
Yi i A or B 5
Z A nA Z B nB
config
DS RnA ln X A nB ln X B
! Moreover, the following elemental balance equations can be
X AA X BB X AB written:
R nAA ln 2 nBB ln 2 nAB ln 3
YA YB 2Y A Y B Z A nA 2nAA nAB 6
J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595 87
hcp(Mg)
Mg pair distribution is calculated by setting:
Mg51Zn20
Mg12Zn13
U5
@G
90
E2
U4 hcp(Mg) 0 9
70
@nAB nA ;nB
80
Mg2Sn
Co
0
T=750 oC
U3
60
.%
X 2AB Dg
/ at
T=700 oC 4 exp AB 10
Mg
50
MgZn2
X AA X BB RT
60
T=650 oC
0 5 Mg2Sn T=600 oC
40
e1
Moreover, the model permits ZA and ZB to vary with composi-
T=550 oC
T=500 oC tion as follows [47]:
30
MgZn2 T=450 oC
T=400 oC 1 1 2nAA 1 nAB
20
T=350 oC
T=300 oC
A A 11
U2
T=200 oC
Z A Z AA 2nAA nAB Z AB 2nAA nAB
10
U1
hcp(Zn)
Mg2Zn11 E1
bct(Sn)
1 1 2nBB 1 nAB
Zn 10 20 30 40 50 60 70 80 90 Sn B B 12
Z B Z BB 2nBB nAB Z AB 2nBB nAB
Sn / at.%
where Z AAA and Z AAB are the values of ZA when all nearest neighbors of
Fig. 22. Calculated liquidus projection of the MgSnZn ternary system.
an atom A are As, and when all nearest neighbors of an atom A are
Bs respectively. Z BBB and Z BAB are dened similarly. The composition of
maximum short-range ordering (SRO) is determined by the ratio of
Table 8 the coordination numbers Z AAB =Z BAB . The values of the coordination
Calculated invariant reactions in the liquidus projection of the MgSnZn ternary numbers chosen in the present study are listed in Table 2.
system.
The Gibbs energy of the liquid solution in a ternary system can
Label Temperature Reaction Composition of be interpolated from the Gibbs energies of the three sub-binary
(C) liquid (at.%) systems with different interpolation techniques based on the nat-
Mg Zn Sn ure of this ternary system, and small external model parameters
e1 566 L M MgZn2 + Mg2Sn 38.98 54.63 6.39 will be introduced into the models to get more self-consistent re-
E1 177 L M bct(Sn) + hcp Zn + Mg2Sn 8.07 15.12 76.81 sults with the experimental data if they are necessary. The Gibbs
U1 335 L + Mg2Zn11 M hcp Zn + Mg2Sn 13.30 40.32 16.38 energy of all ternary liquid phases are calculated using a symmet-
U2 357 L + MgZn2 M Mg2Zn11 + Mg2Sn 12.19 79.20 8.61
ric Kohler-like [88] type of ternary interpolation technique.
U3 414 L + MgZn2 M Mg2Zn3 + Mg2Sn 64.66 34.41 0.93
U4 349 L + Mg2Zn3 M Mg12Zn13 + Mg2Sn 70.03 28.56 4.18
U5 345 L + Mg51Zn20 M Mg12Zn13 + hcp 71.54 28.25 2.08 3.2. Solid solutions
E2 344.6 L M Mg12Zn13 + Mg2Sn + hcp 71.53 28.08 3.94
(a) (b)
(c)
Fig. 23. Calculated isoplethal sections of the InSnZn ternary system for Sn/Zn molar ratios of (a) 2:1, (b) 1:1 and (c) 1:2 in comparison with the reported experimental data
[76].
Fig. 24. Calculated isoplethal sections of the InSnZn ternary system for In/Sn molar ratios of (a) 5:95, (b) 15:85, (c) 1:2, (d) 52:48, (e) 2:1, and (f) 85:15 in comparison with
the reported experimental data [77].
J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595 89
(a) (b)
(c)
Fig. 25. Calculated isoplethal sections of the InSnZn system at constant (a) 10 In (at.%), (b) 9 Zn (wt.%), (c) 6 Zn (wt.%) in comparison with the reported experimental data
[76,92].
5 5
(a) Rechchach et al. (2001): T=500 oC
Anres et al. (2000): T=441 oC
(b) Rechchach et al. (2001): T=500 oC
Anres et al. (2000): T=483 oC
Fiorani et al. (1997): T=447 o C Fiorani et al. (1997): T=440 o C
calculated, T=500 oC
Enthalpy of mixing , kJmol -1
4 4 calculated, T=500 oC
Enthalpy of mixing , kJmol -1
calculated, T=483 oC
3 3
2 2
1 1
InSn 20 40 60 80 Zn In52Zn48 20 40 60 80 Sn
Zn / at.% Sn / at.%
Fig. 26. Calculated mixing enthalpies of ternary liquid InSnZn alloys (a) with the In/Sn molar ratio of 1:1, and (b) the In/Zn molar ratio of 52:48 and 1:1 at various
temperatures along with the reported experimental data [44,79,81].
Z T
3.3. Stoichiometric phases
SoT So298:15K Cp=TdT 15
T298:15K
The molar Gibbs energies of pure elements and stoichiometric
phases can be described by: where DHo298:15K is the molar enthalpy of formation of a given spe-
cies from pure elements (DHo298:15K of element stable at 298.15 K
GoT HoT TSoT 13 and 1 atm is assumed as 0 J mol1; reference state), So298:15K is the
absolute third law molar entropy at 298.15 K and Cp is the molar
Z T
heat capacity.
HoT DHo298:15K C p dT 14
T298:15K In the present study, the Gibbs energy of pure elements were
taken from the SGTE database [90]. As there are no experimental
90 J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595
16 Zn
Rechchach et al. (2010): T=500o C
Fiorani et al. (1997): T=483 o C
14 calculated: T=500 oC T=400 o C
90
Partial enthalpy of mixing, kJmol -1
calculated: T=483 oC
12
80
10
70
8
60
%
at.
6 T=350 o C
/
50
Zn
4 hcp(Zn)
40
2
30
T=300 o C
20
10 20 30 40 50 60 70 80 90 T=250 o C
InSn Zn
Zn / at. % T=200 o C
10
U2 bc
U1 t(S
Fig. 27. Calculated partial molar enthalpy of mixing of Zn in liquid InSnZn alloys T=150 o C (InSn) n)
tet(In) E1
at 500 C compared with the reported experimental data [44].
In 10 20 (InSn) 40 50 60 70 80 90 Sn
Sn / at. %
Table 9
-1
Calculated invariant reactions in the liquidus projection of the InSnZn ternary
system.
In/Sn=1/1
E1 107 L M b(InSn) + c(InSn) + hcp(Zn) 54.78 3.07 42.16
ln (
Calculated: T=427 oC
-3 In/Sn=3/1 U1 121 L + tet(In) M b(InSn) + hcp(Zn) 79.10 3.52 17.38
In/Sn=1/3
In/Sn=1/1 U2 186 L + bct(Sn) M c(InSn) + hcp(Zn) 8.88 11.68 79.44
4. Experimental procedures
), liquid standard state
-2.5
T=441 o C
T=484 oC MgSnIn and MgSnZn ternary alloys were prepared with pure Mg
T=532 oC (99.8 wt.%), Sn (99.9 wt.%), In (99.99 wt.%) and Zn (99.5 wt.%) from Alfa Aesar and
melted in a frequency induction furnace under argon atmosphere. In order to min-
-3.0 imize the interaction of sample with the crucibles, cubic-shaped crucibles with Ta
foil (99.5 wt.% purity, 0.15 mm thickness) were prepared. Each alloy was remelted
Moser (1974), 3 at. % Zn
T=441 o C
three times in the crucible in order to obtain a homogeneous alloy; the loss due to
Zn
T=484 oC evaporation was less than 5 wt.% for each sample. MgSnIn samples were sealed
ln (
-3.5 T=532 oC
into quartz capsules under argon atmosphere and equilibrated at 415 C for 20 days
and at 330 C for 35 days, respectively. The MgSnZn samples were sealed into
quartz capsules under argon atmosphere, and equilibrated at 330 C for 50 days.
These temperatures were chosen because they correspond to the temperatures at
which heat treatment is usually performed on Mg alloys. Quenching was carried
In97Zn3 10 20 30 40 50 60 70 80 90 Sn97Zn3
out in water without breaking the quartz tubes.
Sn / at. % Electron probe microanalysis (EPMA) of the quenched samples was performed
with the JEOL 8900 probe at McGill University using wavelength-dispersive spec-
Fig. 29. Calculated activity of Zn in the InSnZn liquid phase at constant 3 Zn
trometry (WDS). An accelerating voltage of 15 kV was used with a 20 nA beam cur-
(at.%) in comparison with the reported experimental data [78].
rent, a spot size of 2 lm and counting times of 20 s on peaks and 10 s on
backgrounds. Raw data were reduced with the PRZ correction using pure Mg, Sn, In
and Zn metal standards.
heat capacity data for AgIn, AgSn and AgMg intermetallics, The constituent phases of the quenched samples were identied by X-ray
their heat capacities were evaluated using the NeumannKopp rule diffraction (XRD). XRD patterns were obtained with the PANanalytical Xpert Pro
powder X-ray diffractometer at Concordia University using Cu Ka radiation at
[91]. The heat capacity of solid In and Sn from the SGTE database 45 kV and 40 mA. The spectra were acquired from 20 to 120 2h with a 0.02 step
show a maximum just above their melting points (that is in the li- size. The collected patterns were analyzed with the XPert HighScore Plus analysis
quid stable region). Consequently, the heat capacity of several software using the Pearsons crystal database.
J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595 91
Fig. 31. Calculated isothermal sections at (a) 300 C, and at (b) 350 C of the MgInZn ternary system.
Table 10
Calculated invariant reactions in the liquidus projection of the MgZnIn ternary system.
well repeated during heating and cooling occurring at 518 C and ent work, the optimization was mainly based on the experimental
521 C. The endothermic peak occurring at 485 C should be over- data [22,27] obtained by calorimetric methods. The calculated
lapped in the cooling spectrum because it is close to the rst exo- activities of Mg and In in the liquid phase at 650 C are shown in
thermic reaction occurring at 521 C. All the thermal signals Fig. 5 in comparison with experimental data [24,2628]. No exper-
obtained from the DSC measurements are presented in Table 4. imental thermodynamic data exist for intermetallic compounds.
All the phase equilibria compositions determined in the present Therefore, their heat capacities were obtained with the Neu-
work are listed in Table 3. As for the MgSnIn ternary system, mannKopp rule [91], with the Zero enthalpy of formation at
there is limited solubility of Zn in the Mg2Sn compound (less than 25 C, rstly. And then the enthalpy and entropy of formation were
0.2 at.%), and the solid solubility of Sn in the MgZn binary com- then adjusted by tting the phase diagram. The calculated enthal-
pounds is in the composition range from 0.0 to 4 2 at.%. pies of formation of compounds in the InMg system at 25 C are
shown in the Fig. 6. All the thermodynamic parameters optimized
5.2. Thermodynamic optimization in the present work are listed in Tables 2 and 6.
Fig. 33. Calculated isothermal sections of MgSnZn with 1 and 3 In (wt.%) at 300 C and 400 C.
J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595 93
the experimental data [35,45]. All the thermodynamic parameters 5.2.6. The InSnZn ternary system
optimized in the present work are listed in Tables 2 and 6. The calculated isoplethal sections of the InSnZn ternary sys-
tem for the Sn/Zn molar ratios of 2:1, 1:1 and 1:2 are shown in
Fig. 23ac along with the experimental data reported by Xie
5.2.3. The InZn system et al. [76]. Fig. 24af shows the calculated isoplethal sections of
The calculated InZn phase diagram along with the experimen- the InSnZn ternary system for the In/Sn molar ratios of 5:95,
tal data discussed above [5053,56] is shown in Fig. 12. The liquid 15:85, 1:2, 52:48, 2:1, and 85:15 along with the experimental data
phase has a tendency to form a metastable miscibility gap, which is of Sabbar et al. [77]. All the present calculated results are in good
depicted by a dotted line in Fig. 12. The consolute temperature of agreement with the experimental data [76,77], except isoplethal
the miscibility gap is very close to the stable liquidus line, which section of In/Sn = 15/85 (Fig. 24b). The singals observed in the isop-
was predicted by Oelsen and Zuhlke [53]. In the present work, lethal section of In/Sn = 15/85 around 115 C by Sabbar et al. [77]
the eutectic liquid tetIn $ hcpZn is calculated to lie at 144 C may due to the slow experimental heating/cooling rate. The calcu-
and 4.5 at.% Zn, which is in reasonable agreement with experimen- lated Scheil cooling simulations of alloys with the components of
tal data [51]. The calculated enthalpy mixing of the liquid phase at (In15Sn85)1xZnx (0 6 x 6 60 at.%) using the present thermody-
450 C is shown in Fig. 13 along with the experimental data [52 namic database show a reaction: liquid M c(InSn) + b(InSn) occur-
55,58,59]. Fig. 14 shows the calculated activity of Zn in the liquid ring at 118 C during the solidication process. This demonstrates
phase in the temperature range from 423 C to 857 C in compari- that the signal reported by [77] can be due to this nonequilibrium
son with the experimental data [5255,6062]. The calculated re- reaction. The calculated ternary isoplethal sections at 10 In (at.%), 9
sults have a good agreement with the experimental data. All the Zn (wt.%) and 6 Zn (wt.%) are shown in Fig. 25ac in comparison
thermodynamic parameters optimized in the present work are with the experimental data [76,92].
listed in Tables 2 and 6. The calculated mixing enthalpies of the ternary liquid phase for
the In/Sn molar ratio of 1:1 and In/Zn molar ratio of 52:48 and 1:1
at various temperatures are shown in Fig. 26a and b along with
5.2.4. The MgSnIn ternary system experimental data [44,79,81]. The calculated partial molar enthal-
According to our experimental results, there is a very limited py of mixing of Zn in liquid InSnZn alloys at 500 C in compari-
ternary solubility of Sn in MgIn binary compounds, and of In in son with the experimental data [44] is shown in Fig. 27. The
Mg2Sn. Consequently, we assumed that there is no ternary solubil- calculated activity of Zn in the liquid phase (liquid standard state)
ity in binary compounds in the present thermodynamic optimiza- for the In/Sn molar ratios of 1:3, 1:1 and 3:1 are shown in Fig. 28
tion. The calculated isothermal sections of the MgSnIn ternary along with experimental data from Nakamura et al. [80]. Fig. 29
system at 415 C and 330 C are shown in Fig. 15a and b along with shows the calculated activity of Zn in the liquid phase (liquid
the experimental data obtained in the present work. The calculated standard state) at 3 Zn (at.%) compared with the experimental data
ternary isoplethal sections at 10 Sn and 5 In (at.%) are shown in reported by Moser [78]. The calculated liquidus projection of the
Fig. 16a and b in comparison with our experimental data. The InSnZn ternary system is shown in Fig. 30. The calculated invari-
calculated phase boundaries and invariant reactions are listed in ant reactions in the liquidus projection of the InSnZn ternary
Table 3 together with our DSC experimental data. A good agree- system are listed in Table 9. All the optimized ternary thermody-
ment between the calculated results and experimental data can namic parameters of InSnZn ternary system in the present work
be seen. The calculated activity of Mg in the liquid phase with are listed in Tables 2 and 6.
the Sn/In molar ratios of 0.25, 1.00, and 0.75 versus temperature
are shown in Fig. 17ac. low Mg contents, our calculated results
5.2.7. The MgInZn and MgSnInZn systems
are in a good agreement with the experimental data of Zakulski
No experimental phase diagram and thermodynamic data exist
et al. [66]. The calculated liquidus projection of the MgSnIn ter-
for the MgInZn ternary system. According to the similar MgSn
nary system is shown in Fig. 18. There are a total of four ternary
In and MgSnZn systems, ones should expect some limited ter-
peritectic (U type) reactions and of one ternary eutectic (E type)
nary solubility for In in MgZn binary compounds and for Zn in
in the calculated MgSnIn system. The calculated invariant reac-
MgIn binary compounds. MgZn and MgIn liquids have quite
tions of the liquidus projection of the MgSnIn ternary system are
similar negative deviations from ideal mixing while InZn liquid
listed in Table 7. All the optimized ternary thermodynamic param-
has a nearly ideal mixing behavior. In the present work, the ther-
eters of MgSnIn ternary system in the present work are listed in
modynamic properties of the ternary liquid were extrapolated
Tables 2 and 6.
with the symmetric Kohler-like [88] technique within the MQMPA
model. Our calculated isothermal sections of the MgInZn ternary
system at 300 and 350 C are shown in Fig. 31. The calculated liq-
5.2.5. The MgSnZn ternary system
uidus projection of the MgInZn ternary system is shown in
As discussed above, there is a limited solid solubility of either
Fig. 32 and the calculated invariant reactions are listed in Table 10.
Zn in Mg2Sn or Sn in MgZn binary compounds. As a result, the ter-
No experimental data exist for the MgSnInZn quaternary
nary solubility for the terminal binary compounds in the present
system. Consequently, our thermodynamic optimization was per-
optimization did not considered. The present calculated ternary
formed by extrapolating the thermodynamic parameters employed
isothermal sections at 300, 340 and 500 C are shown in
for the bounding subsystems and no additional model parameter
Fig. 19ac. Other calculated isoplethal sections are depicted in
was used. The calculated isothermal sections of MgSnZn with
Fig. 20al along with their related experimental data [67,69]. The
1 and 3 wt.% In at 300 C and 400 C are shown in Fig. 33.
calculated ternary isoplethal section at constant 10 Sn (at.%) is
shown in Fig. 21 along with our DSC experimental data. The pres-
ent calculations are in good agreement with all the available exper- 6. Conclusions and discussions
imental data. The calculated liquidus projection of the MgSnZn
ternary system is shown in Fig. 22. The calculated invariant reac- Phase equilibria in the Mg-rich portion of the MgSnIn ternary
tions in the liquidus projection of the MgSnZn ternary system system at 415 C and 330 C, and the MgSnIn ternary isoplethal
are listed in Table 8. All the ternary thermodynamic parameters sections at 10 Sn and 5 In (at.%) were investigated in the present
optimized of MgSnZn ternary system are listed in Tables 2 and 6. work. No evidence of the existence of ternary compounds was
94 J. Wang et al. / Journal of Alloys and Compounds 588 (2014) 7595
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