Journal of Alloys and Compounds 285 (1999) 150–155 L

Assessment of the Re–Ta binary system

Yuwen Cui*, Zhanpeng Jin
Department of Materials Science and Engineering, Central South University of Technology, Changsha, Hunan 410083, China
Received 2 October 1998

Abstract

Using the CALPHAD method, the thermodynamic properties of each phase of the Re–Ta system were optimized using the
experimental information on the phase diagram and the thermochemical quantities. A consistent set of parameters is presented. The
calculated phase diagram is compared with experimental data, and the agreement is satisfactory in most cases.  1999 Elsevier Science
S.A. All rights reserved.

Keywords: Thermodynamic assessment; Phase diagram; Rhenium; Tantalum

1. Introduction which was remarkably different from that of Brophy et al.

Tantalum plays an important role in some Ni base
superalloys, which increases the stability of the g9 phase,
and thus leads to improved rupture properties and room
temperature tensile properties. Rhenium is a solid solution
strengthening element in the Ni base superalloys, and the
incorporation of Re into the superalloys can improve both
their creep and fatigue behavior. Recently, as a promising
material in microelectronics, the properties of amorphous
alloys of the Re–Ta system have received attention [1,2],
since they have a greater thermal stability than convention-
al amorphous alloys of iron and cobalt. The Re–Ta system
is therefore essential to the processing and design of these
new materials.
Several investigators have contributed to the study of the
Re–Ta system [3–7]. Greenfield and Beck [3] reported the
solubility of Re in Ta and the composition ranges of the
intermediate phases, along with their crystal structures.
Knapton [4] indicated results similar to those of Greenfield
and Beck [3]. Moreover, he also confirmed that the s
phase is only stable at high temperature. By means of
melting point measurements, X-ray diffraction and fluores-
cence, and metallography, Brophy et al. [5] determined the
phase relationships in this system which were considered
to be most elaborate up to now. In the same year, Tylkina
et al. [6] also studied the Re–Ta system in terms of
metallography, X-ray diffraction, melting point and hard-
ness measurements. They published a phase diagram
*Corresponding author.
[5], especially in the high temperature portion. Later, using
metallography, X-ray diffraction, as well as the measure-
ments of properties of hardness, strength, specific electric
resistance and plastics, Savitski et al. [7] measured the
solubilities of Re in Ta in more detail. Unfortunately, most
of the above experimental data are not always consistent
with each other and might be even in contradiction. In
addition, due to the considerable difficulties experienced in
physico-chemical research at elevated temperatures, no
experimental information on the liquidus are available.
Accordingly, the aim of this paper is to assess the Re–Ta
binary system thermodynamically using the CALPHAD
method. This work is a part of a series of studies devoted
to the assessment of Ni base superalloys.
2. Selection of experimental data
2.1. Phase equilibrium data
Since the data from Greenfield and Beck [3] and
Knapton [4] were tentative, they were not utilized in the
assessment. Employing the X-ray lattice parameters meth-
od, Brophy et al. [5] gave precise results for the phase
boundaries of the x phase and the tantalum solid solution.
Their data were thus accepted. Considering the experimen-
tal method, the data of Savitski et al. [7] were chosen to
establish the solubilities of Ta in Re.
The data of Brophy et al. [5] were preferred for
determining the invariant reactions Liq↔Hcp(Re)1x,

0925-8388 / 99 / $ – see front matter  1999 Elsevier Science S.A. All rights reserved.
PII: S0925-8388( 98 )01005-6
 Y. Cui, Z. Jin / Journal of Alloys and Compounds 285 (1999) 150 – 155
Liq↔x and s↔Bcc(Ta)1x. These data were generally
adopted in the literature [1,2,8–10]. It should be noted that
Brophy et al. [5] reported a s liquidus with a fairly abrupt
change of slope. As already pointed out by Okamoto and
Massalski [11,12], however, such a situation was unlikely
in a phase diagram, because an abrupt change of slope in
the liquidus is caused by an abrupt change in the thermo-
dynamic properties of either liquid phase or solid phase in
equilibrium with liquid. Unfortunately, the data from
Tylkina et al. [6] involved a more rapid change of slope of
the s liquidus without any clear reasons. Furthermore,
there are also considerable discrepancies between the
compositions and temperatures of reactions Liq↔s1
Bcc(Ta) and Liq1x↔s from Brophy et al. [5] and Tylkina
et al. [6]. As a result, to ensure a favorable thermodynamic
reliability of the Re–Ta system, the data of the invariant
reaction Liq1x↔s were taken from Tylkina et al. [6]
while a compromise was made between these two sets of
data to locate the reaction Liq↔s1Bcc(Ta). In the latter
circumstance, since the uncertainty of temperature of
reaction Liq↔s1Bcc(Ta) was not given by Tylkina et al.
[6], unlike the other reactions, it was thus considered just
as an indicative value and finally given a low weight in the
optimization.
2.2. Thermodynamic data
Based on the Re–Ta–C ternary phase diagram and the
enthalpies of formation of the TaC x carbide, i.e.
DH 0f (TaC x ), together with the activity of C for the TaC x
phase, Brewer and Wengert [13] yielded the limits to
enthalpies of formation of s and x phases. They fixed DH 0f
for s and x(Re 3 Ta 2 ) between 233 and 213 kJ / mol at
2730 K, for x(Re 3.7 Ta 2 ) between 229 and 215 kJ / mol at
2700 K, and for x(Re 3.6 Ta 2 ) between 223 and 215
kJ / mol at 2700 K, respectively. Later, De Boer et al. [14]
predicted the enthalpies of formation of s and x phases,
and the partial enthalpies of solution. Since Brewer and
Wengert [13] considered more experimental information,
their data rather than from De Boer et al. [14], were
employed in the assessment.
3. Thermodynamic models
3.1. Pure elements
According to the Scientific Group Thermodata Europe
(SGTE), the temperature dependence of the molar Gibbs
energy of pure Re and Ta, referred to the stable element
reference (SER), is given by the following expression:
5 A 1 BT 1 CT ln T 1 DT 2 1 ET 21
0
Gi (T ) 2 H Ser
i
1 FT 3 1 IT 7 1 JT 29 (1)
151
The coefficients in this expression were taken from the
SGTE database [15].
3.2. The solution phases
Liquid, Hcp(Re) and Bcc(Ta) phases were described by
a substitutional solution model, and their molar Gibbs
energies were expressed as follows:
w w
Gm 5 XRe 0 G Re 1 XTa 0 G Ta 1 RT(XRe ln XRe 1 XTa ln XTa )
1 E Gm (2)
where 0 G wRe and 0 G wTa denote the Gibbs energies for pure
Re and Ta, respectively. The excess Gibbs energy E Gm was
expressed using a Redlich–Kister polynomial [16]:
OL
n
E i
Gm 5 XRe XTa Re,Ta (XRe 2 XTa )i (3)
i 50
where L is the interaction parameter.
3.3. The intermediates phases
s phase is isotypic with FeCr phase, and contains five
independent sites (sublattices) with 2, 4, 8, 8 and 8 atoms
per site, respectively. Savitski and Tylkina [17] reported
the s phase at a composition Re 3 Ta 2 . Greenfield and Beck
[3] located the s phase at 41 at.% Ta. Brophy et al. [5]
reported the existence of the s phase at the composition
range from 41 to 41.7 at.% Ta. In this paper, since it has
only negligible homogeneity range, the s phase was
treated as a stoichiometric phase with formula Re 3 Ta 2 in
spite of its cell complexity. The Gibbs energy was
described by the following expression:
Ser 0 Hcp 0 Bcc
G(s) 2 H 5 3* G Re 1 2* G Ta 1 A 1 B*T (4)
where A and B are the adjustable parameters.
x phase is isomorphous with aMn [3,18]. It has 58
atoms per unit cell [19], and these atoms are distributed
over four sublattices in the ratio 2:8:24:24 with CN16-,
16-, 13-, and 12-fold coordination polyhedral, respectively.
Considering the crystallographic, the phase stability in-
formation and the proposal by Ansara et al. [19] at the
Rinberg Workshop on solution phases, a sublattice model,
(Re,Ta) 24 (Ta) 10 (Re) 24 , was adopted to describe the x
phase. The sublattice model yields the following expres-
sion for the Gibbs energy per mole of formula units:
x x
Gm 5 1 y Re 0 G Re:Ta:Re 1 1 y Ta 0 G Ta:Ta:Re
1 24RT( 1 y Re ln 1 y Re 1 1 y Ta ln 1 y Ta )
x
1 1 y Re
1
y Ta L Re,Ta:Ta:Re (5)
where j y i is the site fraction of the component i in the j
sublattice. The 0 G parameter represents the Gibbs energy
of the compound in the virtual state of the x phase, and is
152 Y. Cui, Z. Jin / Journal of Alloys and Compounds 285 (1999) 150 – 155

given relative to the selected reference state for the Table 1

The summary of parameters in the Re–Ta system a
elements. L is the interaction parameter and also expressed
as a Redlich–Kister polynomial as in Eq. (3). 0 G and L are Liquid phase
0 Liq
to be assessed from the available experimental data. L Re,Ta 5 256 168.511.539T
1 Liq
L Re,Ta 518 926.1215.753T

Hcp(Re)
4. Optimization and results 0 Hcp( Re)
L Re,Ta 523 892.0122.427T
1 Hcp( Re)
L Re,Ta 5 245 765.2220.926T
The optimization of parameters was carried out using
Bcc(Ta)
the Parrot module in the Thermo-Calc program developed 0 Bcc( Ta)
L Re,Ta 5 2151 443135.226T
by Sundman et al. [20]. 1 Bcc( Ta)
L Re,Ta 540 255.8219.400T
During the optimization, the parameters of liquid, 2 Bcc( Ta)
L Re,Ta 5870.4
Hcp(Re) and Bcc(Ta) were optimized together at first. The
intermediate phases were then added one by one to adjust s phase
0 s
L Re,Ta 55(215 051.723.020T )13 0 G Re
Hcp
12 0 G Ta
Bcc

their parameters. Finally, all the parameters were opti-

mized together to give a better description. x phase
The assessed parameters of each phase in the Re–Ta 0
G xRe:Ta:Re 558(29969.821.433T )148 0 G Hcp 0
Re 110 G Ta
Bcc

system are listed in Table 1. Fig. 1 presents the calculated 0

G xTa:Ta:Re 558(224 402.713.875T )124 0 G Hcp
Re 134 0
G Bcc
Ta
0 x
phase diagram of the Re–Ta system. The comparison L Re:Ta:Ta:Re 5 2679 899.2
1 x
L Re:Ta:Ta:Re 5 2209 855.6
between the calculated phase diagram and various ex-
a
perimental data is given in Fig. 2. The agreement between Values for liquid, Hcp(Re) and Bcc(Ta) are given in J / mol of atoms,
and in J / mol formula units for the intermediate phases.
the calculated phase diagram and experimental data is

Fig. 1. The calculated Re–Ta system according to present assessment.

 Y. Cui, Z. Jin / Journal of Alloys and Compounds 285 (1999) 150 – 155 153

Fig. 2. The calculated Re–Ta phase diagram in comparison with the experimental data.

satisfactory with respect to the somewhat scattered ex-
perimental data. Table 2 summarizes the compositions and
temperatures of the calculated invariant equilibria and the
experimental data.
As shown in Fig. 2, the homogeneity range of the x
phase and the solubility ranges of Hcp(Re) and Bcc(Ta)
were reasonably well reproduced by the present calcula-
tion. Moreover, it should be pointed out that, due to the
substantial difficulties encountered in the research of
refractory metal and the effects of contamination of the
Ta-rich alloys at elevated temperatures, the Bcc(Ta)
solidus data may possess large uncertainty and thus are
considered not reliable enough. Further details prove
necessary concerning this region.
Fig. 3 shows the detailed Re–Ta system in the com-
position range from 30 to 60 at.% Ta and the temperature
from 2200 to 3200 K, together with the experimental data.
It can be seen from Fig. 3, the calculated x / x1s phase
boundary lies at lower tantalum contents than indicated by
Brophy et al. [5]. An attempt to achieve a better fit was not
made because (a) it would require more parameters for the
x phase; (b) the boundary defined by Brophy et al. [5]
refers to a thermodynamic unusual curvature, it is therefore
considered unreliable; (c) the present treatment allows a
better fit to the invariant reactions.
Fig. 4 presents the calculated enthalpies of formation of
x and s phases compared with the evaluated values [13].
The calculated enthalpy of formation of the x phase is in

Table 2
Comparison between the calculated and the experimental invariant points in the Re–Ta system
Reaction Reaction type Compositions, at.% Ta Temperature (K) Reference
Liq↔(Re)1x Eutectic 16.4 5.2 20.5 3033 Brophy et al. [5]
Peritectic – 5.2 19.5 3103625 Tylkina et al. [6]
Eutectic 16.4 2.1 20.6 3040 Present work
Liq↔x Congruent 21.5 21.5 3068 Brophy et al. [5]
Congruent 23.9 23.9 3070 Present work
Liq1x↔s Peritectic – 37.6 41.0 3018 Brophy et al. [5]
Peritectic – 36.0 47.0 2953625 Tylkina et al. [6]
Peritectic 42.8 34.2 40.0 2958 Present work
Liq↔s1(Ta) Eutectic 49.7 41.7 54.6 2968 Brophy et al. [5]
Eutectic – 48.0 58.0 |2673 Tylkina et al. [6]
Eutectic 48.5 40.0 54.7 2920 Present work
s↔(Ta)1x Eutectoid 40.0 52.5 39.8 2737 Brophy et al. [5]
Eutectoid 40.0 53.6 36.7 2735 Present work
154 Y. Cui, Z. Jin / Journal of Alloys and Compounds 285 (1999) 150 – 155

Fig. 3. A part of calculated Re–Ta system compared with the experimental data.

Fig. 4. The calculated enthalpies of formation of the intermediate phases compared with the predicted values.
 Y. Cui, Z. Jin / Journal of Alloys and Compounds 285 (1999) 150 – 155
reasonable agreement with the evaluations of Brewer and
Wengert [13]. The agreement for the s phase is also
acceptable, and better fit was unnecessary since it would
make the s phase stable even at low temperature or lead to
a large positive excess entropy contribution.
5. Conclusions
Using the CALPHAD method, a set of parameters
describing the phase equilibria of the Re–Ta system was
assessed from experimental data. A comparison between
calculated and experimental data is made, and the agree-
ment is satisfactory.
Acknowledgements
This work has been financially supported by GE Com-
pany, USA, under Research Contract Number 9622031.
The authors are grateful to Dr. J.C. Zhao (R&D, GE
Company) for his valuable advice in this work.
References
[1] V.V. Vavilova, L.N. Galkin, M.V. Glazov, Dokl. Akad. Nauk SSSR
300 (5) (1988) 1157.
155
[2] Yu.V. Barmin, V.V. Vavilova, I.V. Zolotukhin, Dokl. Akad. Nauk SSSR
307 (2) (1989) 371.
[3] P. Greenfield, P.A. Beck, J. Metals 8 (1956) 265.
[4] A.G. Knapton, J. Inst. Metals 26 (1958) 28.
[5] J.H. Brophy, P. Schwarzkopf, J. Wulff, Trans. AIME 218 (1960)
910.
[6] M.A. Tylkina, I.A. Tsyganova, E.M. Savitski, Zhur. Neog. Khimii 5
(8) (1960) 1905.
[7] E.M. Savitski, M.A. Tylkina, O.Kh. Khamidov, Dokl. Akad. Nauk
SSSR (1969) 200.
[8] S. Tournier, B. Vinet, Mater. Sci. Forum 235–238 (1997) 349.
[9] Metals Handbook, 8th, 1973, pp. 322, 374.
[10] T.B. Massalski, J.L. Murry, L.H. Bennett, H. Baker, Binary Alloy
Phase Diagrams, A.S.M.,, Metals Park, OH, 1986.
[11] H. Okamoto, T.B. Massalski, J. Phase Equilibria 12 (1991) 148.
[12] H. Okamoto, T.B. Massalski, J. Phase Equilibria 14 (1993) 316.
[13] L. Brewer, P.R. Wengert, Metall. Trans. 4 (1973) 83.
[14] F.R. De Boer, R. Boom, W.C.M. Mattens, A.R. Miedema, A.K.
Niessen, Cohesion in Metal: Transition Metal Alloys, North-Hol-
land, Amsterdam, 1988.
[15] A.T. Dinsdale, CALPHAD 15 (1991) 317.
[16] O. Redlich, A. Kister, Ind. Eng. Chem. 40 (1948) 345.
[17] E.M. Savitski, M.A. Tylkina, Zhur. Neog. Khimii 3 (1958) 815.
[18] P. Villars, L.D. Calvert, Pearson’s Handbook of Crystallographic
Data For Intermetallic Phases, 2nd, ASM International, Materials
Park, OH, 1991.
[19] I. Ansara, T.G. Chart, A.F. Guillermet, F.H. Hayes, U.R. Kattner,
D.G. Pettifor, N. Saunder, K. Zeng, CALPHAD 21 (1997) 171.
[20] B. Sundman, B. Jansson, J.O. Andersson, CALPHAD 9 (1985) 153.