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J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct
a r t i c l e
i n f o
Article history:
Received 8 November 2007
Received in revised form 5 March 2008
Accepted 5 March 2008
Available online 15 March 2008
Keywords:
Ternary phase diagram
Thermodynamic modelling
Modied quasichemical model
Mg alloys
a b s t r a c t
Thermodynamic modelling of the MgCuY system is carried out as a part of thermodynamic database
construction for Mg alloys. This system is being modelled for the rst time using the modied quasichemical model which considers the presence of short range ordering in the liquid. A self-consistent thermodynamic database for the MgCuY system was constructed by combining the thermodynamic
descriptions of the constituent binaries, MgCu, CuY, and MgY. All the three binaries have been reoptimized based on the experimental phase equilibrium and thermodynamic data available in the literature. The constructed database is used to calculate and predict thermodynamic properties, the binary
phase diagrams and liquidus projections of the ternary MgCuY system. The current calculation results
are in good agreement with the experimental data reported in the literature.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Magnesium alloys are getting considerable attention for automobile and aerospace applications because they are the lightest
among the commercially available structural alloys. They have
high specic properties but low corrosion resistance which limited
their use. While metallic glass, a new class of wonder material, is
attracting attention due to its high mechanical strength and good
corrosion resistance [1]. MgCuY alloy system is a promising candidate for metallic glass since it has the largest super cooled liquid
region among other Mg-alloy systems [25].
Despite its importance, this system has not yet been modelled
thermodynamically. Also, the available descriptions for the binaries are contradictory to each other and none of the assessment
was done considering the presence of short range ordering in the
liquid. Hence the main objective of this work is to construct a reliable thermodynamic database of the MgCuY system using sound
thermodynamic models. The three constituent binary systems
MgCu, CuY, and MgY were re-optimized using the modied
quasichemical model for the liquid phase. This model has the ability to take into consideration the presence of short range ordering
in the liquid.
* Corresponding author. Tel.: +1 514 848 2424x3146; fax: +1 514 848 3175.
E-mail address: mmedraj@encs.concordia.ca (M. Medraj).
URL: http://www.me.concordia.ca/~mmedraj (M. Medraj).
0021-9614/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2008.03.004
1065
Dg AB ,
Dg i
AB ,
jP1
Dg j
AB
where
and
are the parameters of the model and can
be expressed as functions of temperature Dg AB a bT=K. Also,
the atom to atom coordination numbers, ZA and ZB, can be expressed as a function of composition and can be represented by
the following equations:
1
1
2nAA
1
nAB
A
A
;
4
Z A Z AA 2nAA nAB
Z AB 2nAA nAB
1
1
2nBB
1
nAB
B
;
5
Z B Z BBB 2nBB nAB
Z BA 2nBB nAB
where nij is the number of moles of (ij) pairs, Z AAA and Z AAB are
the coordination numbers when all nearest neighbours of an A atom
are A or B atoms, respectively. The composition at maximum short
range ordering is determined by the ratio Z BBA =Z AAB . Values of Z AAB and
Z BBA are unique to the A B binary system and should be carefully
determined to t the thermodynamic experimental data (enthalpy
of mixing, activity, etc.). The value of Z AAA is common for all systems
Cu
containing A as a component. In this work, the value of Z Mg
MgMg , Z CuCu
and Z YYY was chosen to be 6 because it gave the best possible t
for many binary systems and is recommended by Dr. Peltons group
Mg
Y
Y
Y
Y
[810]. The values of Z Mg
MgCu , Z CuMg , Z MgY , Z YMg , Z CuY , and Z YCu are
chosen to permit the composition at maximum short range ordering in the binary system to be consistent with the composition that
corresponds to the minimum enthalpy of mixing. These values are
given in table 1. The tendency to maximum short range ordering
near the composition 40 atomic per cent (at.%) Mg in the MgCu
Y
system was obtained by setting Z Mg
MgCu 4 and Z CuMg 2. For the
CuY system, maximum short range ordering near 30 at.% Y was
TABLE 1
Atomatom coordination numbers of the liquid
A
Z AAB
Z BAB
Mg
Cu
Y
Mg
Cu
Mg
Mg
Cu
Y
Cu
Y
Y
6
6
6
4
3
2
6
6
6
2
6
4
yli ylj ym
k
6
7
8
c0
where i,j, . . . k represent components or vacancy, l, m and q represent sub-lattices, yli is the site fraction of component i on sub-lattice
l, fl is the fraction of sub-lattice l relative to the total lattice sites,
0
G(i:j:. . .k) represents a real or a hypothetical compound (end member) energy, and cL(i,j) represent the interaction parameters which
describe the interaction within the sub-lattice.
Modelling of the intermetallic solid solution phases requires
information regarding the crystal structure of the phases and their
homogeneity range. From the crystallographic data summarized in
table 2, the following model is applied to represent the MgCu2
phase:
Mg%; Cu8 : Cu%; Mg16 :
Here, the % denotes the major constituent of the sub-lattice. This
model covers the 0 6 XMg 6 1 composition range and, of course, includes the homogeneity range of 0.31 6 XMg 6 0.353 which was reported by Bagnoud and Feschotte [11].
The crystal structure data of the Cu6Y intermediate solid solution was obtained by Buschow and Goot [12] and are listed in
table 3.
According to Buschow and Goot [12] some of the Yttrium atomic sites are occupied by a pair of Cu atoms, which can be described
by the following model with two sub-lattices:
Y%; Cu2 Cu5
This is actually a WagnerSchottky type model [13]. The same model was used by Fries et al. [14] to represent Cu6Y in their assessment
of the CuY system. This type of model can be used only for intermediate phases with a narrow homogeneity range [15]. This model
covers 0.83 6 XCu 6 1 composition range. This range includes
homogeneity 0.84 6 XCu 6 0.87 which was reported by Fries et al.
[14]. The optimized model parameters are listed in table 4.
3. Experimental data evaluation
According to the CALPHAD method, the rst step of the thermodynamic optimization is to extract and categorize the available
TABLE 2
Crystal structure and lattice parameters of MgCu2 phase
Phase
MgCu2
a
b
Crystal data
Prototype
Pearson symbol
Space group
Space group No.
Lattice parameter/nm
Angles: a = 90, b = 90, c = 90
Atom
MgCu2
cF24
Fd3m
227
a = 0.7035
Cu
Mg
WPa
16d
8a
CNb
12
16
Atomic position
Reference
0.625
0
0.625
0
0.625
0
[68]
[11]
1066
TABLE 3
Crystal structure and lattice parameters of Cu6Y phase
Phase
Cu6Y
Crystal data
Atoms
Prototype
Pearson symbol
Space group
Space group No.
Lattice parameter/nm
TbCu7
hP8
P6/mmm
191
a = 0.4940
b = 0.4157
Y
Cu 1
Cu 2
Cu 3
WPa
1a
2e
2c
3g
CNb
20
8
12
16
Atomic position
References
0
0
0.333
0.5
0
0
0.667
0
0
0.306
0
0.5
[12]
TABLE 4
Optimized model parameters for the liquid, Mg-hcp, Cu-fcc, Mg2Cu and MgCu2phases
in the MgCu system
Phase
Terms
a/(J mol1)
Liquid
Dg AB
g i
AB
12975.95
6153.13
0
1.26
g j
AB
13528.50
Mg-hcp
0 Mg-hcp
8371.60
Cu-fcc
Mg2Cu
0 Cu-fcc
L
DGf
21923.39
28620.00
5.37
0.03
GCu:Cu2
MgCu
16743.20
GMg:Cu2
MgCu
37684.26
GCu:Mg2
MgCu
6278.7
13011.35
13011.35
6599.45
6599.45
MgCu
GMg:Mg2
0 MgCu2
LMg;Cu:Cu
0 MgCu2
LMg;Cu:Mg
0 MgCu2
LCu:Mg;Cu
0 MgCu2
LMg:Mg;Cu
0
1067
different measurement techniques, the reported values are mutually contradictory. Since vapour pressure measurements usually
do not provide highly reliable results, the values in [35,36] are considered more acceptable and hence were given higher weighing
factors during optimization.
The experimental results available for the CuY system are not
in good accord with each other. However after reviewing all the
available data for this system, it appears that the results of Guojun
et al. [41] and Fries et al. [14] are the most reliable and therefore
were given higher weighing factors during optimization.
1068
1500
1300
Liquid
T/K
1100
900
Cu (fcc)
Cu (fcc) + MgCu2
MgCu2 + CuMg2
700
Mg (hcp) + CuMg2
Mg (hcp)
500
300
0.00
0.20
0.40
0.60
Mole Fraction, Mg
0.80
FIGURE 1. Plot of temperature against mole fraction Mg to illustrate the calculated MgCu phase diagram:
1.00
1069
1.0
-2
0.8
-4
Activity Mg
-6
-8
-10
0.6
0.4
0.2
-12
0.0
0.20
0.40
0.60
0.8
1.0
0.0
0.0
0.20
Mole fraction Mg
0.40
0.60
0.80
1.00
Mole fraction Mg
Cu2Mg
CuMg2
-15
-30
-45
0.0
0.20
0.40
0.60
0.80
1.0
Mole fraction Mg
FIGURE 2. Plot of calculated thermodynamic properties against mole fraction Mg with the literature values: (a) enthalpy of mixing in kJ mol1 for the MgCu liquid at
T = 1100 K: O: [29] at 1100 K, : [31] at 1100 K, s: [33] at 1120 K and 1125 K, h: [34] at 1100 K. (b) Activity of Mg in the MgCu liquid at T = 1123 K: : [29] at 1100 K, M: [30]
at 1123 K, h: [31] at 1100 K, s: [32] at 1100 K. (c) Enthalpy of formation in kJ mol1 for the stoichiometric compounds: : [this work], e: [35], s: [36], h: [37].
1800
bcc-Y
T/K
1600
1400
)
(h
2Y
Cu
Cu6Y
Cu4Y
1200
Cu7Y2
CuY
Cu2Y(r)
1000
0.00
0.20
0.40
0.60
0.80
1.00
Mole fraction, Y
FIGURE 3. Plot of temperature against mole fraction Y to illustrate the calculated CuY phase diagram: s: [14],
1070
phase diagram are in fair agreement with the experimental data from
the literature.
4.1.2. Thermodynamic properties
The calculated enthalpy of mixing, shown in gure 2a, is in good
agreement with the experimental data. The calculated activity of
Mg in MgCu liquid at T = 1100 K is shown in gure 2b which
agrees well with the experimental results from the literature
[2932]. The experimental data for the activity of Cu could not
be found in the literature. Figure 2c shows good agreement beTABLE 5
Optimized model parameters for the liquid, CuY, Cu2Y(h), Cu2Y(r), Cu4Y, Cu7Y2, and
Cu6Y phases
Phase
Terms
a/(J mol1)
Liquid
Dg AB
g i
AB
g j
AB
28718.77
6278.70
6906.57
6.28
0.84
2.09
Cu6 Y
GCu:Cu
7Ghcp
Cu
hcp
Cu6 Y
GCu:Y
5Ghcp
Cu GY
65.8
0 Cu6 Y
LY;Cu2 :Cu
4794.8
22517.5
17416.2
21997.9
17,888
18775.5
0.45
3.311
1.63
2.44
1.65
1.73
CuY
Cu2Y (h)
Cu2Y (r)
Cu4Y
Cu7Y2
DGf
DGf
DGf
DGf
DGf
tween the calculated heats of formation of MgCu2 and Mg2Cu, obtained in this study and the experimental results reported by King
and Kleppa [35] and Eremenko et al. [36]. The measured values of
Smith and Christian [37] are less negative than those calculated
and also inconsistent with other experimental results. This is probably due to the inaccuracy involved in the vapour pressure measurement carried out by Smith and Christian [37].
4.2. The CuY binary system
4.2.1. Phase diagram
The CuY calculated phase diagram with the available experimental data from the literature is shown in gure 3. The solid solubilities of Y in Cu and Cu in Y are negligible and hence were not
included in this work. The optimized parameters are shown in table 5. Except few discrepancies with the results from Domagala
[38], the phase diagram shows reasonable agreement with all the
other experimental points. Composition of the eutectic point near
the Cu-rich side shows small deviation from the experimental data.
But the thermodynamic properties especially the enthalpy of mixing near the Cu-rich side shows strong agreement with the experimental data; hence this amount of error is acceptable. It is worth
noting that trying to be consistent with the experimental eutectic
composition resulted in deviation from the experimental thermodynamic properties of the CuY liquid. The solid phase transformation of Cu2Y(h) Cu2Y(r) was included in the current assessment
1.0
0.8
-9
Activity Cu
0
-3
-15
-21
0.6
0.4
0.2
-27
0.0
0.20
0.40
0.60
0.8
0.0
0.0
1.0
0.20
0.40
0.60
0.8
1.00
Mole fraction Y
CuY
-10
Cu2Y(r)
Cu4Y
Cu7Y2
Mole fraction Y
-20
0.0
0.20
0.40
0.60
0.80
1.0
Mole fraction Mg
FIGURE 4. Plot of calculated thermodynamic properties against mole fraction with literature values: (a) enthalpy of mixing in kJ mol1 for the CuY liquid at T = 1410 K: h:
[45] at 1373 K, s, $: [46] at 1410 K e: [47] at 1963 K. (b) Activity of Cu in the CuY liquid at T = 1623 K; s: [48] at 1623 K. (c) Enthalpy of formation in kJ mol1 for the
stoichiometric compounds: e: [this work], : [14], M: [42], s: [45].
1071
of this system and the temperature and composition of the two eutectic points around this compound remained within the limits of
the experimental errors.
TABLE 6
Optimized model parameters for liquid, hcp-Mg, b-Y, e, d, and c phases in MgY
system
Phase
Terms
A/(J mol1)
Liquid
Dg MgY
g i
MgY
g j
MgY
13059.70
6.45
13394.56
7.20
6529.85
1.26
0 Mg-hcp
L
1 Mg-hcp
L
2 Mg-hcp
L
0 Y-b
L
1 Y-b
L
12476.78
2724.56
8788.22
29760.18
2005.86
7.49
2.4
2
13.49
1.5
GeMg:Mg:Mg
GeMg:Y:Mg
0 e
GY:Y:Mg
0 e
GY:Mg:Mg
0 d
GMg:Mg:Mg
0 d
GMg:Y:Mg
0 d
GY:Y:Mg
0 d
GY:Mg:Mg
0 d
LMg;Y:Mg:Mg
0 d
LMg;Y:Y:Mg
0 d
LMg:Mg;Y:Mg
0 d
LY:Mg;Y:Mg
0 c
GMg:Y
0 c
GMg:Va
0 c
GY:Y
0 c
GY:Va
0 c
LMg;Y:Y
0 c
LMg;Y:Va
0 c
LMg:Y;Va
0 c
LY:Y;Va
1585
5891.23
6000
0
2148.82
8902.47
0
0
9006.45
641.82
3910.07
9006.45
10727.25
10464.50
13432.86
13483.55
15006.45
15006.45
5000
5000
0
0
0
0
0
0
0
0
88.50
11.86
3.46
88.50
1.26
0.0
0
0
16
15
7
7
hcp-Mg
b-Y
e (Mg%, Y)29 (Y%, Mg)10 (Mg)19
0
0
1800
1500
Liquid
cp
T/K
1200
Y+
h
L+
hcp
900
hcp
600
+ hcp
+ hcp
300
0.00
0.20
0.40
0.60
0.80
1.00
Mole fraction, Y
FIGURE 5. Plot of temperature against mole fraction yttrium to illustrate the calculated MgY phase diagram: s: [50], h: one phase region [50], j: two phase region [50],
M: [51], : [55], .: [56].
1.0
-2
0.8
Activity Mg
1072
-6
0.6
0.4
0.2
-10
0.0
0.0
0.20
0.40
0.60
0.8
0.0
1.0
0.20
0.40
0
-20
-40
-60
-80
-10 0
0.0
0.20
0.40
0.60
0.60
0.8
1.00
Mole fraction Y
Mole fraction Y
0.80
1.0
Mole fraction Y
-5
-15
-25
-35
0.0
0.20
0.40
0.60
0.80
1.0
Mole fraction Y
FIGURE 6. Plot of calculated thermodynamic properties against mole fraction yttrium with literature values: (a) enthalpy of mixing in kJ mol1 for the MgY liquid at
T = 984 K: h: at 1020 K, s: at 1057 K, M: at 984 K, e: at 975 K, : at 955 K. [60]. (b) Activity of Mg in the MgY liquid at T = 1173 K: j: [49] at 1173 K, .: [61] at 1173 K. (c)
Partial Gibbs free energy of mixing of Mg and Y at T = 1173 K: s: [49]. (d) Enthalpy of formation in kJ mol1 for the stoichiometric compounds: s: [this work], M: [55], h:
[62].
The univariant valleys are shown by the heavier lines and the
arrows on these lines indicate the directions of decreasing temperature. There are four ternary eutectic (E1 to E4) points, eight ternary
quasi-peritectic (U1 to U8) points and three maximum (m1 to m3)
points present in this system. A summary of the reactions at these
invariant points is given in table 7.
4.4.2. Thermodynamic properties
Ganesan et al. [49] measured the enthalpy of mixing of the ternary MgCuY liquid alloys by calorimetric method along ve different isopleths. Their results were compared with the present
calculated enthalpy of mixing for three different sections as shown
in gures 8a to c. The initial discrepancy with the experimental results in gure 8c reects the fact that the results of Ganesan et al.
[49] for the enthalpy of mixing of ternary alloys is not consistent
with the experimental binary enthalpy of mixing for the CuY
liquid.
The calculated activity of Mg in the ternary liquid alloy at
T = 1173 K is shown in gure 8d, with the experimental data of
Ganesan et al. [49]. The calculated values showed negative deviation from Raoults law unlike the measured activity that showed
positive deviation. The reason for this is not known. Nevertheless,
the present calculated activity of Mg showed similar trend as the
one calculated by Ganesan et al. [49] who, also, could not explain
this inconsistency.
1073
TABLE 7
Calculated equilibrium points and their reactions in the MgCuY system
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Reaction
Type
Y/at.%
Mg/at.%
Cu/at.%
709.8
662.6
956.3
910.1
680.9
672.89
761.22
849.4
957.4
961.4
794.23
1038
710.5
995.5
918.3
E1
E2
E3
E4
U1
U2
U3
U4
U5
U6
U7
U8
m1
m2
m3
7.7
17.8
5.1
54.6
14.7
17.4
8.8
9.8
10.6
5.8
27.3
54
8.8
8.0
49.6
79.2
59.6
15.9
22.4
67.9
58.3
51.4
40.6
25.2
15.9
52.2
32.1
77.4
19.9
26.1
13.1
22.6
79
23
17.3
24.3
39.8
49.6
64.2
78.3
20.5
13.9
13.8
72.1
24.3
mental data on melting temperatures and the enthalpies of formation of these compounds limited our thermodynamic model, but it
could be useful for the readers who are interested in the ternary
phase equilibrium below T = 600 K.
The liquidus surface in this model may have substantial deviations from reality because only indirect experimental data were
available to approximate the melting temperatures of ternary compounds. That forced us to make some assumptions based on the
available experiments on amorphous MgCuY alloys and binary
phase diagrams.
Inoue et al. [3] and Ma et al. [4] studied the MgCuY system to
nd suitable compositions for metallic glass. They used XRD and
DSC analyses to examine different amorphous samples. During
their experiments, proper equilibrium conditions did not prevail,
hence their experimental results cannot be used directly in this
work. But after reviewing their [3,4] works, some information
regarding the system can be obtained. The DSC analysis of Ma
1074
-5
-10
-15
0.0
0.20
0.60
0.8
Mole fraction Cu
1.0
-3
-6
-9
-12
0.0
0.20
Cu0.1Mg0.9
Cu
0.40
0.60
0.8
Mole fraction Y
1.0
Y
1.0
0.8
-7
Activity,Mg
Mg0.92Y0.8
0.40
-14
0.6
0.4
0.2
-21
0.0
0.20
Cu0.33Y0.67
0.40
0.60
Mole fraction Mg
0.8
1.0
Mg
0.0
0.0
0.20
Cu0.33Y0.67
0.40
0.60
Mole fraction Mg
0.80
1.00
Mg
FIGURE 8. Plot of thermodynamic properties against mole fraction for the MgCuY liquid: integral enthalpy of mixing in kJ mol1 for (a) (Mg0.92Y0.08)1xCux ternary liquid
at T = 1023 K: M: [49] at 1023 K. (b) (Cu0.1Mg0.9)1xYx ternary liquid at T = 1023 K: e: [49] at 1023 K. (c)(Cu0.33Y0.67)1xMgx ternary liquid at T = 1107 K: h: [49] at 1107 K. (d)
Activity of Mg at T = 1173 K, - - - ideal mixing: M, h, e, s: [49].
FIGURE 9. Liquidus projection of the MgCuY system with the ternary compounds (tentative).
1075
Reaction
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
T/K
Type
Y/at.%
Mg/at.%
Cu/at.%
709.8
682.0
760.8
956.3
1059.9
993.5
684.1
761.2
868.0
957.2
961.4
1038
900.2
710.54
766.1
995.5
1062.4
1136.3
1010.3
1013.4
E1
E2
E3
E4
E5
E6
U1
U2
U3
U4
U5
U6
U7
m1
m2
m3
m4
m5
m6
m7
7.7
14.6
9.0
5.1
37.1
60.8
14.8
8.8
9.7
10.6
6.0
54.8
26.6
8.7
9.6
8.0
35.5
46.6
58.9
45.1
79.2
68.1
51.6
15.9
5.5
11.1
68.1
51.7
39.3
25.4
15.7
32.1
60.7
77.5
55.5
19.9
6.4
6.8
17.1
38.2
13.1
17.3
39.4
79.0
57.4
28.1
17.1
39.5
51.0
64.1
78.3
13.1
12.7
13.8
34.9
72.1
58.1
46.6
24.0
16.7
a
1400
Liquid
1256K
Liquid + Y2Cu2Mg
Y2Cu2Mg
T/K
1200
Liquid + Y2Cu2Mg
1000
Y2Cu2Mg
+
CuY + Cu2Y
Liquid + Y2Cu2Mg +
+ + Y2Cu2Mg
800
0.10
0.16
0.22
0.28
0.34
0.40
Mole fraction Mg
b
1200
Liquid
Liquid + Cu7Y2
Liquid + Cu4Y
T/K
1000
MgCu2
+
Cu4Y
MgCu2
+
Cu4Y
852K
MgCu2
+
Cu6Y
800
YCu9Mg2
600
0.00
0.04
0.08
0.12
0.16
0.20
Mole fraction Mg
FIGURE 10. Plot of temperature against mole fraction Mg to show isopleths
(constant composition section) of the MgCuY system at (a) 40 at.% Y and at (b)75 at.% Cu, showing the tentative melting temperature of Y2Cu2Mg and YCu9Mg2
compound, respectively (tentative).
et al. [4] shows that near Mg65Cu25Y11 composition, a ternary eutectic point exists at a temperature around 730 K. Same composi-
tion for the eutectic was reported earlier by Inoue et al. [3].
Consequently, it can be assumed that the actual eutectic point
would be found near this composition at a similar temperature, if
proper equilibrium conditions are maintained. Depending on this
information, the heat and entropy of formation of the ternary compounds were varied until the eutectic composition and temperature are close to those reported by Inoue et al. [3] and the
melting temperatures for the ternary compounds were estimated
from the resulting liquidus surface.
Based on the abovementioned assumptions, the liquidus projection was recalculated as shown in gure 9. The eutectic point (E2)
is observed at a composition of Mg68Cu17.3Y14.6 and T = 682 K. The
composition deviates from that of Inoue et al. [3] and Ma et al. [4]
by about 8 at.% Cu and temperature around T = 50 K. A more accurate result can be obtained by introducing some ternary interaction
parameters, but since the experimental data were not for equilibrium conditions, it was decided to accept the current calculation
without using any interaction parameter. All the invariant points
calculated after incorporating the ternary compounds are listed
in table 8.
The melting temperature of the Y2Cu2Mg compound was adjusted to be 1256 K by a trial and error method, so that the eutectic
composition and temperature lies in the desired range. The compound melts congruently at this temperature as can be seen in gure 10a.
The melting temperature of YCu9Mg2 should be lower than that
of Y2Cu2Mg, since the overall Y content is less (8 versus 40 at.% Y).
The reported annealing temperature (673 K), which is lower than
that of Y2Cu2Mg, also supports this assumption. The XRD analysis
of Ma et al. [4] on the alloy composition Mg58.5Cu30.5Y11, shows
the existence of Mg2Cu, Mg24Y5 and one unidentied phase. It
may be assumed that this unidentied phase is in fact the Y2Cu2Mg
compound. To be consistent with this information, the melting
temperature of YCu9Mg2 was adjusted to be 852 K. A vertical section for 75 at.% Cu in gure 10b shows that this compound melts
incongruently. The presence of incongruently melting binary
(Cu6Y) compound near YCu9Mg2 also justies this.
The above discussion shows the legitimacy of the current work.
The analysis may not be totally accurate but at least it will give
closer approximation of the actual equilibrium in the MgCuY
system. Some key experiments on this system may resolve this
uncertainty. This should be attempted during further studies on
this system.
1076
5. Concluding remarks
A comprehensive thermodynamic assessment of the ternary
MgCuY system was conducted using available experimental
data. Based on the current assessment, the following conclusions
can be drawn:
The modied quasichemical model was used to describe the
liquid phase in the MgCuY system. The calculated phase diagrams of the binary systems as well as thermodynamic properties such as activity, enthalpy of mixing, and enthalpy of
formation of the compounds show good agreement with the
experimental data available in the literature.
A self-consistent database for the MgCuY system was constructed by combining the optimized parameters of the three
constituent binary systems. No ternary interaction parameters
were used for the extrapolation.
The presence of two ternary compounds was included in the
optimization considering the limited experimental information
available in the literature for these compounds.
More experimental investigation is required to obtain detailed
information regarding the two ternary compounds (Y2Cu2Mg
and YCu9Mg2). The melting temperatures of these two compounds should be determined experimentally which is very
important to establish a more accurate assessment of the
MgCuY system. Also, all the predicted invariant points in
the MgCuY ternary system are to be veried experimentally.
The present work can be used to design key experiments for further verication of this system.
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JCT 07-365