Journal of Alloys and Compounds 419 (2006) 81–83

The 1100 ◦C isothermal section of Nb–Mo–Zr ternary system

Changqing Xia ∗ , Xiaowei Gao, Yangyong Li
School of Materials Science and Engineering, Central South University, Changsha, Hunan Province 410083, PR China
Received 4 September 2005; received in revised form 29 September 2005; accepted 29 September 2005
Available online 15 November 2005

Abstract
The isothermal section of the Nb–Mo–Zr system at 1100 ◦ C has been successfully measured by means of electron probe microanalysis (EPMA)
and X-ray diffraction analysis on diffusion couple. This isothermal section consists of two single-phase regions, ␣(bcc) and (Mo,Nb)2 Zr, and one
two-phase region, ␣(bcc)+(Mo,Nb)2 Zr. The maximum solid solubility of Nb in (Mo,Nb)2 Zr phase is 30.40 at.% Nb.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Diffusion-couple; Isothermal section; Nb–Mo–Zr

1. Introduction The critical point of the monotectoid reaction occurs at 988 ◦ C

The refractory metals are some of those with good high-
temperature, creep and creep-rupture properties [1]. This makes
it necessary to study related phase diagrams. As the three impor-
tant elements of refractory metals, Nb, Mo and Zr have been
studied intensively for some years. The information on phase
diagrams for Nb–Mo, Nb–Zr and Mo–Zr binary system is avail-
able in the literature. The Nb–Mo phase diagram was reported
about 14 years ago by Okamoto [2] who calculated the liquidus
and solidus assuming ideal mixing for both liquid and solid
phases, where the heat of fusion data were adopted from litera-
ture [3]. Rudy [4] determined the solidus curve of the Nb–Mo
binary system based on isothermal and incipient melting temper-
atures of eight alloys. Kocherzinskii et al. [5,6] measured both
liquidus and solidus by differential thermal analysis (DTA) and
smoothed the data using fourth order polynomials, which are
thermodynamically unfounded. The liquidus and solidus cal-
culated by Okamoto agreed well with the experiment data of
Kocherzinskii et al.
The Nb–Zr system [7] is a simple isomorphous system
at higher temperatures with a liquidus/solidus minimum of
1740 ◦ C at 78.3 at.% Zr. The bcc solid solution ␤ between Nb
and ␤(Zr) undergoes a monotectoid reaction ␤1 → ␤2 + ␣(Zr) at
620 ◦ C, where ␣(Zr) is the terminal solid solution (␣(Zr,Nb)).
∗ Corresponding author. Tel.: +86 731 8830267; fax: +86 731 8876692.
E-mail address: xia-gro@mail.csu.edu.cn (C. Xia).
and 39.4 at.% Zr.
The Mo–Zr phase diagram has been constructed by Zinke-
vich et al. [8,9] by thermodynamic assessment. Invariant reac-
tion temperature of the L + ␣(Mo) → Mo2 Zr peritectic reac-
tion was 1915 ◦ C, and the ␣(Mo) and liquid compositions
were respectively given as 6.61 at.% Zr and 47.28 at.% Zr. The
L → Mo2 Zr + ␤(Zr) eutectic temperature was 1576 ◦ C, and the
Mo2 Zr and ␤(Zr) compositions were respectively 37.3 at.% Zr
and 81.9 at.% Zr. The ␤(Zr) → Mo2 Zr + ␣(Zr) eutectoid temper-
ature was 730 ◦ C, and the Mo2 Zr and ␤(Zr) compositions were
given as 33.9 at.% Zr and 93.1 at.% Zr.
For the Nb–Mo–Zr ternary system, an isothermal section of
the system at 1100 ◦ C was reported by Svechvikov and Spektor
[10], which shows that the ␣(bcc) phase is in equilibrium with the
Mo2 Zr phase at 1100 ◦ C. However, doubts still remain regarding
whether there is a solubility of Nb in Mo2 Zr phase at 1100 ◦ C
and if so whether the crystal structure of the phase has changed.
So a diffusion couple along with electron probe microanalysis
(EPMA) technique [11–15] was adopted in the present study to
establish a complete isothermal section of Nb–Mo–Zr system at
1100 ◦ C.
2. Experimental
The ternary diffusion couple used in this work was prepared from the ele-
mental components with the following purities, in as-ingot Nb (99.8 mass%),
Mo (99.7 mass%) and Zr (99.9 mass%). The technique of preparing the
specimens is given in Ref. [14]. The dimensions of niobium, molybdenum
and zirconium ingots are 5 mm × 5 mm × 10 mm, 5 mm × 5 mm × 10 mm and

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82 C. Xia et al. / Journal of Alloys and Compounds 419 (2006) 81–83

Fig. 1. Construction of a Mo–Nb–Zr diffusion couple.

5 mm × 10 mm × 10 mm, respectively. These components were ground, pol- Fig. 3. Chart of a Nb–Mo–Zr diffusion couple after heat-treatment. The areas
ished and assembled into a T-shaped diffusion couple (shown schematically indicated illustrate the photograph corresponding to Fig. 2.
in Fig. 1). The assembled couple was then sealed in a quartz tube containing
argon gas at a pressure of 0.13 Pa followed by annealing at 1100 ◦ C for 1660 h in
a GK-2B-type diffusion furnace. The local equilibriums of the diffusion triple
were formed and a diffusion layer between molybdenum and zirconium was
observed. The temperature of the diffusion furnace was controlled with a thyris-
tor regulator and was found to be within ±1 ◦ C as measured with a calibrated
Ni–Cr/Ni–Al thermocouple. After the heat treatments, this sample was water
quenched by breaking the tube.
The annealed sample was prepared by mechanical polishing using a cloth
with chromium oxide, and then etched with a mixture of 1 ml HF, 3 ml HNO3
(1.40), 1.5 ml HCl (1.19) and 94.5 ml distilled water. The microstructural inves-
tigation was carried out in an optical microscope (POLYVAR-MET), scanning
electron microscope (sirion-2000). X-ray diffraction analysis was done on a XD- Fig. 4. The EPMA data determined along the microprobe measure line marked
98 diffractometer with unfiltered copper radiation (λ = 1.5406 Å). The diffraction in Fig. 2.
graphs were calculated using the software of the Peking University X-ray diffrac-
tion analysis system. The composition of each phase in the annealed diffusion Table 1
couple was determined by electron probe microanalysis (JXA.8800R). Experimental tie lines determined by EPMA on the Nb–Mo–Zr diffusion triple
annealed at 1100 ◦ C for 1660 h ◦ C (at.%)
3. Results and discussion ␣ (Mo,Nb)2 Zr

Zr Mo Nb Zr Mo Nb
Fig. 2 shows the microstructure of the diffusion regions in
the couple of the Nb–Mo–Zr triple annealed at 1100 ◦ C for 3.09 96.91 0 32.19 67.81 0
3.17 95.62 1.21 31.98 67.02 1.00
1660 h. The schematic chart of the couple is presented in Fig. 3. 3.64 89.94 6.43 31.49 64.98 3.53
A layer of intermetallic compound with a thickness of approx- 3.87 76.82 19.31 32.55 61.20 6.26
imately 30 ␮m was observed and it was identified by EPMA 3.98 82.42 13.60 32.15 63.27 4.58
as (Mo,Nb)2 Zr. Fig. 4 shows the results of the electron probe 5.27 62.05 32.68 32.91 55.97 11.12
microanalysis, these data of EPMA measured were taken from 5.37 69.45 25.17 32.49 58.70 8.81
5.42 51.96 42.61 32.79 51.79 15.42
the couple along the measuring line marked in Fig. 2. Two tie- 5.81 33.57 60.63 32.48 42.52 25.00
lines were obtained by extrapolating the above EPMA data. 5.83 46.96 47.21 32.04 48.36 19.61
7.34 39.62 53.04 32.88 44.10 23.03
8.66 26.03 65.30 32.32 40.50 27.19
11.46 18.43 70.11 32.22 39.40 28.38
15.79 13.96 70.24 32.82 38.06 29.13
19.50 11.31 69.19 32.91 36.98 30.11
23.55 9.97 66.47 33.47 36.30 30.22
35.09 9.81 55.10 34.01 35.67 30.32
44.41 8.59 47.00 34.29 35.31 30.40
50.91 8.23 40.86 35.13 34.93 29.94
54.13 9.39 36.49 35.13 36.14 28.73
57.71 9.40 32.88 35.52 37.55 26.93
63.58 7.97 28.45 35.12 41.33 23.54
67.91 8.32 23.76 35.07 45.27 19.66
72.19 7.88 19.93 35.29 48.91 15.79
77.93 8.24 13.83 34.46 53.76 11.78
85.42 8.00 6.58 33.36 59.21 7.42
90.81 8.37 0.82 34.74 63.95 1.31
Fig. 2. Microstructure of the diffusion regions of the couple annealed at 1100 ◦ C 91.70 8.30 0 35.03 64.97 0
for 1660 h.
 C. Xia et al. / Journal of Alloys and Compounds 419 (2006) 81–83
Fig. 5. The isothermal section of Nb–Mo–Zr ternary system at 1100 ◦ C.
Many tie-lines were obtained in the same way. Table 1 lists the
tie-lines data obtained by extrapolating the microprobe mea-
surements. All the experiment data were taken from the couple
cross-section along the phase boundary by a JXA.8800R elec-
tron probe set with accelerating voltage of 15 kV and take off
angle 40◦ . According to the data in Table 1, the composition
of the intermetallic compound is determined as (Mo,Nb)2 Zr, in
which the maximum solubility of Nb is about 30.40 at.% Nb.
The composition range of zirconium in the (Mo,Nb)2 Zr phase
varied between 31.49 at.% Zr and 35.52 at.% Zr.
The X-ray diffraction spectra of the Nb–Mo–Zr diffusion
triple was observed, it shows the (Mo,Nb)2 Zr is an intermediate
phase based on the intermetallic compound Mo2 Zr, the crystal
structure of (Mo,Nb)2 Zr is as well as the crystal structure of
Mo2 Zr, they both have fcc (Cu2 Mg) crystal structure. The cal-
culated lattice constants of (Mo,Nb)2 Zr is a = 7.613 Å which is a
little larger than the standard lattice constants of Mo2 Zr. It may
because of the solid solution of Nb atoms in the Mo2 Zr crystal
cell by taking place of the smaller Mo atoms, which led to the
distortion of the crystal cell.
According to the EPMA data and X-ray diffraction analy-
sis, an isothermal section of the phase diagram for Nb–Mo–Zr
ternary system at 1100 ◦ C was established and presented in
Fig. 5. This isothermal section consists of a solid solution called
83
␣(bcc), an intermetallic compound phase (Mo,Nb)2 Zr and a two-
phase region ␣(bcc) + (Mo,Nb)2 Zr.
4. Conclusions
(1) The isothermal section of the phase diagram for the
Nb–Mo–Zr ternary system at 1100 ◦ C has been deter-
mined. This section consists of two single-phase regions,
␣(bcc) and (Mo,Nb)2 Zr and one two-phase region,
␣(bcc)+(Mo,Nb)2 Zr.
(2) The intermetallic compound (Mo,Nb)2 Zr has been observed
in the present study. The maximum solubility of Nb in
(Mo,Nb)2 Zr is approximately 30.40 at.% Nb.
Acknowledgement
This work was supported by the National Nature Science
Foundation of China (No. 50371105).
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