Vol. 5
Abstract
A statistically mechanical-based equation of state has been employed to calculate the liquid density of refractory
metals over a wide range of temperatures and pressures. There are three temperature-dependent quantities that are
required to use the EOS: the second virial coefficients B2, an effective van der Waals co-volume, b and a correction
factor, . The second virial coefficients are calculated from a two-parameter corresponding states correlation, which is
constructed with two constants as scaling parameters, i.e., melting temperature Tm and molar density in melting point
m. Our calculations on the liquid density of tantalum, rhenium, molybdenum, titanium, zirconium, hafnium, and niobium
from undercooled temperatures up to several hundred degrees above the boiling point (1650 K-7400 K) and pressures
ranging from 0 up to 200 MPa reproduces very accurately the experimental PVT data. In order to evaluate the
proposed correlation equation for the second virial coefficient, we have compared our results for these systems with
those obtained earlier. Our results are in favor of the preference of the TM EOS over two other equation of state.
Keywords: Refractory Metals, Density, Equation of state, Tao- Mason EOS.
Introduction
fluids is a very useful quantity, especially if it has a firm
Refractory metals are extraordinarily resistant to heat basis in statistical-mechanical theory.
and wear. The expression is mostly used in the context of
Previously we have successfully extended a
materials science, metallurgy and engineering. The statistically mechanical-based equation of state to
definition of which elements belong to this group differs. calculate PVT properties of refrigerant fluid mixtures,
The most common definition includes five elements: two LNG, CNG and Ionic liquids (Yousefi et al., 2009; Karimi
of the fifth period (niobium and molybdenum) and three of et al., 2011a; Karimi et al., 2011b; Yousefi & Karimi,
the sixth period (tantalum, tungsten, and rhenium). They 2011). It is the purpose of this work to employ the
all share some properties, including a melting point above previous equation of state to predict the liquid density of
2000 C and high hardness at room temperature. They refractory metals.
are chemically inert and have a relatively high density. Tao-Mason equation of state
Their high melting points make powder metallurgy the
Song and Mason proposed an analytical equation of
method of choice for fabricating components from these state (SM EOS) in 1989 which was based on statisticalmetals. Some of their applications include tools to work mechanical perturbation theory for hard spheres (Song &
metals at high temperatures, wire filaments, casting Mason, 1989). To derive a density-explicit EOS, they
molds, and chemical reaction vessels in corrosive considered Weeks-Chandler-Andersen decomposition of
environments. Partly due to the high melting point, the potential energy (Weeks et al., 1971) as well as the
refractory metals are stable against creep deformation to Carnahan-Starling formula for the pair distribution
very high temperatures.
function at contact (Carnahan & Starling, 1969). They
The experimental measurements are very difficult developed the SM analytical equation of state to real
due to handling with high temperatures. Static molecular fluids (Song & Mason, 1990a; Song & Mason,
measurements are difficult to perform on most metals 1990b) by introducing the average contact pair
because of the typically high values of critical distribution function and tested the resulting EOS against
temperature and pressure, problems with sample- PVT experimental data (Song & Mason, 1990c). The
container contamination, and physical strength limits of general form of the SM EOS reads as:
high- pressure vessels. Therefore, these measurements
=1+
+ [ ( ) 1]
(1)
are typically carried out using dynamic techniques due to
the problems inherent in performing the measurements
Where P is the pressure, is the number density, kT
statically. Because of difficulties in experimental has the usual meaning; B2 is the second virial coefficient,
measurements, accurate predictions using theoretical is a scaling factor, G() is the effective contact pair
methods are of special importance.
distribution function, and is the packing fraction.
The description of properties of fluids using accurate
Ihm et al. (1992) presented and applied a strong
equation of state is considered as an efficient tool for the principle of corresponding states for non-polar fluids (Ihm
calculation of thermodynamic properties (Chapmann et et al., 1991; Ihm et al., 1992; Song & Mason, 1992) to the
al., 1988; Boublik et al., 1999). In fact, equations of state SM EOS. This modification reduced the order of SM EOS
attempt to describe the relationship between temperature, from five to three. Although the resulting cubic EOS
pressure, and volume for a given substance or mixture of (hereafter we refer it as ISM EOS) was not accurate in the
substances. An accurate analytical equation of state for non-analytical critical and two phase regions, they
Research article
Indian Society for Education and Environment (iSee)
Refractory metals
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2365
Vol. 5
) +
Where
= 0.143
= 1.64 + 2.65[
1 b
1 + 1.8(
)
)
(3)
1]
(4)
T
)
Tm
-c1 (
=a1 e
b =a1 1-c1
T 1/4
)
Tm
-c2 /(
+a2 [1-e
T
Tm
-c1
T
Tm
c2
+a2 1- 1+
T
4
Tm
(7)
e
1
4
c2
T 4
Tm
(8)
Where the constant a1, a2, c1, c2 are -0.0860, 2.3988,
0.5624, 1.4267, respectively. Knowing the temperaturedependent parameters, the equation of state can be
Metal
Ta
Re
Mo
Ti
Nb
Zr
Hf
9.
16.
23.
30.
37.
44.
51.
2. a
73.06
-70.96
5.17
22836.90
-42.98
1.85
282.58
10.
17.
24.
31.
38.
45.
52.
3. b
-1245.10
1576.41
-7.41
-352352.21
1069.46
7.30
-6000.23
Research article
Indian Society for Education and Environment (iSee)
11.
18.
25.
32.
39.
46.
53.
4. c
8461.60
-13563.10
6.24
2174137.70
-10183.32
-153.34
51363.35
12.
19.
26.
33.
40.
47.
54.
Refractory metals
http://www.indjst.org
5. d
-27852.55
57825.52
-2.51
-6704879.10
48227.74
1086.00
-220330.84
13.
20.
27.
34.
41.
48.
55.
6. e
43978.82
-122371.09
0.49
10333677.00
-113640.84
-3502.78
473962.54
14.
21.
28.
35.
42.
49.
56.
7. f
-26701.19
102573.72
-0.04
-6367083.50
106098.04
3727.74
-409882.57
F.Yousefi & M.Kaveh
Indian J.Sci.Technol.
2366
Vol. 5
Metal
Ta
Re
Mo
Ti
Nb
Zr
Hf
m.p [g/cm3]
15.00
18.90
9.33
4.11
8.57
5.80
12.00
Tc[K]
16500
18900
1450
5850
12500
15030
10400
(9)
Table 3. The calculated results for the saturated liquid density of Ta, Re and Mo at high pressure compared with the
experimental data (Jager et al., 1992; Hixon & Winkler, 1992; Thevenin et al., 1993) and other models.
T [K]
P [bar]
tantalum
3270
200
3350
200
3475
200
3675
200
3875
200
4075
200
4275
200
4525
200
4700
200
4900
200
5100
200
5250
200
5450
200
5600
200
5800
200
6000
200
6200
200
6400
200
6600
200
6800
200
7000
200
7200
200
7400
200
Total
rhenium
3453
120
3500
120
3600
120
3700
120
3800
120
3900
120
4000
120
4100
120
4200
120
4300
120
4400
120
4500
120
3453
200
3535
200
3699
200
3840
200
4042
200
4216
200
4386
200
4605
200
4800
200
4977
200
5180
200
5350
200
5569
200
5725
200
Total
molybdenum
2896
200
3143
200
3353
95.08
200
3563
200
3773
200
3983
200
4193
200
4403
200
4613
200
4823
200
5033
200
Total
cal [mol/Lit]
Exp [mol/Lit]
Dev% [TM]
Dev% [Mousazadeh]
82.78
81.25
79.62
78.56
78.76
78.64
76.27
76.85
76.60
76.09
75.39
74.81
73.99
73.38
72.56
71.77
71.00
70.25
69.50
68.73
67.94
67.12
66.30
82.16
81.43
80.72
80.02
79.33
78.65
77.98
77.33
76.68
76.05
75.43
74.81
74.21
73.03
72.46
71.89
71.33
70.24
69.71
68.67
68.16
67.17
66.20
0.76
0.22
1.37
1.83
0.72
0.01
2.19
0.62
0.11
0.06
0.05
0.00
0.29
0.47
0.14
0.17
0.46
0.01
0.30
0.09
0.32
0.08
0.15
0.45
0.67
1.06
1.17
0.84
0.53
0.26
0.00
0.50
0.59
0.79
0.98
0.91
1.08
0.22
0.39
0.55
0.71
0.11
0.27
0.32
0.15
0.72
1.27
0.61
1.10
1.52
1.67
1.39
1.12
0.86
0.61
0.09
0.00
0.24
0.47
0.43
0.67
0.16
0.09
0.33
0.57
0.05
0.31
0.17
0.10
0.34
0.78
0.57
7.53
7.46
97.09
6.53
95.86
95.21
94.52
93.90
93.34
92.88
92.50
92.21
97.53
97.37
96.56
5.59
94.22
93.25
2.55
92.08
1.75
90.37
0.54
0.17
9.26
8.21
95.96
95.87
95.30
94.98
94.50
94.10
93.63
93.24
92.70
92.17
91.64
91.04
100.35
99.65
98.95
97.83
96.74
95.27
93.77
92.62
91.79
90.97
90.39
89.96
89.32
88.20
.63
1.66
1.88
1.63
1.44
1.18
0.95
0.71
0.69
0.78
0.94
1.28
2.81
2.29
.41
2.29
2.61
.12
1.30
0.59
0.04
0.66
0.17
.23
.06
.01
1.24
2.84
2.64
2.64
2.39
2.31
2.16
2.10
1.96
1.99
2.03
2.07
2.19
1.59
1.38
1.64
1.32
1.34
0.77
0.09
0.00
0.10
0.10
0.46
0.81
1.14
0.62
1.49
3.50
3.29
3.26
2.96
2.85
2.65
2.54
2.35
2.33
2.30
2.28
2.34
1.01
0.83
1.14
0.88
0.98
0.91
0.07
0.00
0.24
0.37
0.91
1.41
1.95
1.59
1.73
7.28
6.18
97.28
96.14
95.19
93.76
92.70
91.42
90.18
88.98
87.87
86.66
85.13
.00
.04
.12
.15
.07
.03
.00
.05
.01
.03
.01
0.05
1.10
0.48
0.00
0.09
0.16
0.11
0.06
0.00
0.02
0.14
0.69
0.26
0.99
0.46
0.03
0.12
0.09
0.05
0.03
0.02
0.08
0.00
0.48
0.21
3.90
2.63
1.39
0.18
9.03
7.88
6.63
5.13
Refractory metals
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100
2367
Vol. 5
88.48
88.18
88.12
87.76
87.39
87.70
87.39
86.57
87.02
88.46
88.23
88.01
87.78
87.55
87.33
87.55
86.87
86.65
0.02
0.06
0.13
0.03
0.18
0.43
0.18
0.35
0.43
0.20
1.40
1.03
0.67
0.33
0.00
0.32
0.00
0.94
1.23
0.66
0.76
0.56
0.36
0.18
0.00
0.18
0.41
0.51
0.68
0.40
84.94
84.62
84.40
84.19
83.98
83.77
83.57
83.36
83.15
82.93
82.72
82.50
82.28
84.95
84.62
84.40
84.19
83.98
83.77
83.56
83.35
83.14
82.92
82.71
82.50
82.29
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.01
0.01
0.02
0.00
0.01
0.01
0.99
0.72
0.57
0.42
0.27
0.13
0.00
0.13
0.25
0.37
0.49
0.60
0.71
0.43
0.78
0.57
0.46
0.34
0.22
0.11
0.00
0.11
0.21
0.30
0.39
0.49
0.58
0.35
68.88
68.75
68.59
68.44
68.29
68.15
68.00
67.85
67.70
67.55
67.40
67.25
67.11
66.97
66.81
66.66
66.52
66.39
66.21
68.88
68.74
68.59
68.44
68.29
68.14
68.00
67.85
67.70
67.55
67.40
67.26
67.11
66.96
66.81
66.67
66.52
66.37
66.22
0.00
0.01
0.00
0.01
0.00
0.01
0.01
0.00
0.1
0.00
0.00
0.02
0.01
0.01
0.01
0.01
0.00
0.02
0.01
0.01
2.45
2.11
1.78
1.46
1.16
0.85
0.56
0.28
0.00
0.27
0.53
0.79
1.04
1.28
1.52
1.76
1.98
2.21
2.42
1.29
2.29
2.03
1.78
1.54
1.31
1.08
0.85
0.63
0.41
0.20
0.00
0.22
0.41
0.61
0.80
1.00
1.18
1.37
1.54
1.01
66.82
66.65
66.50
66.34
66.12
66.07
65.89
65.74
66.82
66.66
66.51
66.35
66.20
66.04
65.88
65.73
0.00
0.02
0.02
0.01
0.12
0.04
0.02
0.01
0.03
Research article
Indian Society for Education and Environment (iSee)
0.61
0.40
0.20
0.00
0.19
0.38
0.56
0.74
0.39
0.75
0.55
0.35
0.16
0.04
0.22
0.40
0.59
0.38
Refractory metals
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Refractory metals
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