J. Phase Equilib. Diffus.

https://doi.org/10.1007/s11669-018-0668-6

Experimental Investigation of the Mo–Ti–Zr Ternary Phase

Diagrams
Huaqing Zhang1 • Cong Zhang2 • Peng Zhou3 • Yong Du1 • Yingbiao Peng4 •

Shuhong Liu1 • Jiong Wang1 • Kun Li1

Submitted: 24 March 2018 / in revised form: 25 July 2018

Ó ASM International 2018

Abstract In this work, the phase diagrams of the Mo–Ti–
Zr ternary system were determined by means of X-ray
diffraction, optical microscopy, and electron probe micro-
analysis. Two isothermal sections of the Mo–Ti–Zr ternary
system at 900 and 1100 °C were experimentally estab-
lished. There are three two-phase regions and one three-
phase region at both isothermal sections. The existence of
the three-phase region (b1 ? Laves ? b2) at 900 and
1100 °C indicates that the b phase (bcc solid solution)
separates into two phases, i.e. Mo, Ti rich solid solution b1
and Ti, Zr rich solid solution b2. No ternary compounds
were detected. The maximum solubilities of Ti in the Laves
phase were found to be 19.3 at.% at 900 °C and 18.3 at.%
at 1100 °C, respectively. The liquidus projection and
reaction scheme of the Mo–Ti–Zr system were also pre-
sented based on the present experimental work and litera-
ture information.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11669-018-0668-6) contains supple-
mentary material, which is available to authorized users.
& Yong Du
yong-du@csu.edu.cn
1
State Key Laboratory of Powder Metallurgy, Central South
University, Changsha 410083, Hunan, People’s Republic of
China
2
Collaborative Innovation Center of Steel Technology,
University of Science and Technology, Beijing 100083,
People’s Republic of China
3
College of Mechanical and Electrical Engineering, Hunan
University of Science and Technology, Xiangtan 411201,
People’s Republic of China
4 tance properties.[14–18] Hence, it is necessary to investigate
College of Metallurgy and Materials Engineering, Hunan
University of Technology, Zhuzhou 412008, Hunan, People’s
Republic of China
Keywords isothermal section  liquidus projection 
Mo–Ti–Zr ternary system  phase equilibria
1 Introduction
TZM (Titanium-Zirconium-Molybdenum) alloy consists of
Mo with a small amount of Ti, Zr and trace elements of C
(0.5-0.8 wt.% Ti, 0.08-0.1 wt.% Zr, 0.016-0.02 wt.% C).
The TZM alloy has attracted world-wide attention due to
the characteristics of high melting temperature, superior
creep and tensile strength at high temperatures, low coef-
ficient of thermal expansion and excellent corrosion resis-
tance properties in liquid metals.[1–5] TZM alloy has been
generally desired for elevated temperature applications in
the aerospace, power generation, military, nuclear indus-
tries and other fields,[6–8] including heat engines, heat
exchangers, nuclear reactors, radiation shields, extrusion
dies and boring bars.[9,10] Moreover, the Mo–Ti–Zr ternary
system is one important subsystem for the Ti(C, N)-based
cermets. It is of interest to establish a thermodynamic
database of Ti(C, N)-based cermets, when the experimental
data about some relevant systems[11–13] are available and
assessed thermodynamically. Ti(C, N)-based cermets are
well recognized for their wide industrial applications,
which are composed of high hardness phase and desirable
toughness binder phase. In order to get better physical and
mechanical properties and meet specific requirements of
various work conditions, secondary carbides such as Mo2C,
ZrC, WC, NbC, TaC and Cr3C2 are contained in the cer-
mets. The addition of Mo2C, Mo and ZrC into cermets can
improve the strength, toughness and thermal shock resis-
the phase equilibria in the Mo–Ti–Zr ternary system.

123

2 Literature Review
The binary sub-systems of the Mo–Ti–Zr system are
illustrated in the supplementary Fig. S1. The Mo–Ti system
was reviewed by Murray[19] and Shim et al.[20] and re-
assessed by Chung et al.[21] These investigations[19–21]
show that there are a monotectoid reaction and the misci-
bility gap of the bcc phase in the Mo–Ti system, as shown
in Fig. S1(a). The Mo–Zr phase diagram is taken from the
thermodynamic assessment.[22] It contains a stable Laves
phase Mo2Zr, which is formed through a peritectic reaction
(L ? (bMo) $ Mo2Zr) at 1921 °C.[22] The Ti–Zr binary
system was thermodynamically investigated by Kumer
et al.[23] Phase equilibria of the Ti–Zr system were rather
simple, and only complete liquid and two solid solution
phases exist in the system. Crystallographic data on the
stable solid phases in these binary are summarized by
Watson.[24]
The available literature data about experimental deter-
minations on the isothermal sections of the Mo–Ti–Zr
ternary system are reported by several groups of
authors.[25–31] These experimental data for the Mo–Ti–Zr
system were reviewed by Watson,[24] whereas the detailed
review about the phase boundaries of isothermal sections
were not presented. The experimental methods and results
in the literature[25–31] were summarized by Watson.[24]
According to the review,[24] the previous experimental data
are too meager for determining the exact phase relation-
ships of the Mo–Ti–Zr system. Therefore, Watson[24]
analysed the phase relationship of the binary systems and
preferred the results of literature.[25–27,31]
To facilitate the comparison of these experimental
results,[25–30] several isothermal sections are merged in one
diagram. The several isothermal sections at low tempera-
tures, where the a phase (hcp solid solution) appears, are
presented in the supplementary Fig. S2. Figure 1 is the
Fig. 1 The isothermal sections
at 900,[27] 1000,[28,30]
1200,[27,29] 1300[28] and
1500 °C[30] for the Mo–Ti–Zr
system
123
J. Phase Equilib. Diffus.
isothermal sections at higher temperatures, containing only
b (bcc solid solution) and Laves (Mo2Zr) phase. Appar-
ently, there are contradictions among the literature data: (1)
The experimental results given by Prokoshkin and
Zakharova[25–27] indicated that the b phase separates into
two phases: Mo, Ti rich solid solution (b1) and Ti, Zr rich
solid solution (b2), and Ti dissolves in the binary Laves
(Mo2Zr) phase as well. (2) According to experimental data
reported in Ref 28–30, there is no miscibility gap for b
solid solution and the solubility of Ti in Mo2Zr is ignored,
which are not consistent with the data from
references.[25–27]
As shown in Fig. S2, except for a single phase region (b)
and two two-phase regions (b1 ? Laves and b2 ? Laves),
the remaining phase regions for the isothermal section at
600 °C (green dash dot line) are larger than the phase
regions at 750 °C (purple dashed line) according to Pro-
koshkin and Zakharova.[25,26] The isothermal section at
800 °C (black bold line) is similar to that of the isothermal
section at 750 °C, whereas there is a three-phase region
(a ? b2 ? Laves) and larger two-phase region (a ? b) at
750 °C. The isothermal sections of the Zr-rich corner for
the Mo–Ti–Zr system were investigated by Kudryavtsev
and Tararaeva.[28] However, the results given by
Kudryavtsev and Tararaeva,[28] who did not find the phase
separation in the b phase, are inconsistent with the exper-
imental results.[25,26] There also exists a ? b ? Laves
three-phase region in the isothermal sections at 600 (yellow
dotted line) and 700 °C (red line) according to Kudryavt-
sev and Tararaeva,[28] but the three-phase region is larger
than that of Prokoshkin and Zakharova,[25,26] as shown in
Fig. S2(b).
As presented in Fig. 1, only three-phase region exists at
the isothermal sections of 900 (blue dotted line) and
1200 °C (red line) according to Prokoshkin and
Zakharova.[27] The three-phase region (b1 ? Laves ? b2)
J. Phase Equilib. Diffus.
at 1200 °C is smaller than the phase region at 900 °C, and
the phase boundaries (b1 ? Laves/b, b2 ? Laves/b and b1
?b2/b) at 1200 °C are closer to Mo–Zr edge compared
with the isothermal section at 900 °C according to Pro-
koshkin and Zakharova.[27] Therefore, there are two obvi-
ous features in the results of Prokoshkin and Zakharova.[27]
As the temperature increases, the phase boundaries
between the two-phase region and single-phase region are
closer to Mo–Zr edge, and the three-phase region is getting
smaller.
The isothermal section at 1200 °C (black thin line) was
also determined by Chuang et al.[29] However, the results
of Chuang et al.[29] contradict the isothermal section of the
Mo–Ti–Zr system at 1200 °C reported by Prokoshkin and
Zakharova.[27] Chuang et al.[29] presented a larger two-
phase region (b ? Laves), in comparison with the results
of Prokoshkin and Zakharova.[27] As shown in Fig. 1, the
isothermal sections at 1000 (purple dashed line) and
1500 °C (green bold line) reported by Zakharov and Sav-
itskii[30] have a similar characteristic with the results of
Prokoshkin and Zakharova.[27] The phase boundary
(b ? Laves/b) of isothermal section at 1500 °C is closer to
Mo–Zr edge than the phase boundary at 1000 °C. Except
for the results of Chuang et al.[29] and Kudryavtsev and
Tararaeva,[28] the sequence of these isothermal sections
from Ti corner to Mo–Zr edge is: 900 °C,[27] 1000 °C,[30]
1200 °C,[27] 1500 °C,[30] which suggests that the tendency
of phase boundaries (b ? Laves/b) for the isothermal
sections reported by Zakharov and Savitskii[30] agree with
the data reported by Ref 27. The characteristic also appears
in the results of Kudryavtsev and Tararaeva,[28] however,
the isothermal section at 1000 °C (black dash dot line)
disagreement with the experimental work done by Ref 30.
Zakharov and Savitskii[30] constructed a liquidus pro-
jection together with experimental data. The liquidus pro-
jection is similar to the one presented in Ref 26, which has
a critical point at 1750 °C. Since the phase separation of
the b phase was not observed by Zakharov and Savit-
skii,[30] they explained that the critical point from a
degenerate cone triangle, which is associated with the
transition from the peritectic reaction (L ? b1 $ Laves) to
eutectic reaction (L $ b2 ? Laves). Prokoshkin and
Zakharova[26] suggested that an invariant reaction (L ? b1
$ b2 ? Laves) at 1575 ± 10 °C exists in the Mo–Ti–Zr
system. The univariant equilibrium (L $ b1 ? b2) is a
critical point of the ternary miscibility gap on the liquidus
surface, and the temperature for this univariant equilibrium
is 1620 ± 25 °C.[26] The invariant reaction temperature
was determined by Zakharova and Prokoshkin[31] using
differential thermal analysis (DTA) method. The reliable
locations of the critical point and invariant point, as well as
primary phase region are not determined by Prokoshkin
and Zakharova,[26] who just estimated a liquidus projection
of the Mo–Ti–Zr system.
In order to elucidate whether there is a miscibility gap in
the b solid solution for the Mo–Ti–Zr system and provide
more new phase diagram data for future thermodynamic
optimization of the ternary system, the present work is
performed to measure the isothermal sections at 900 and
1100 °C as well as liquidus projection for the system. The
reaction scheme for the ternary system was also presented
in the present work.
3 Experimental Procedure
High-purity Mo (99.99 wt.%), Ti (99.99 wt.%) and Zr
(99.99 wt.%) were used as starting materials in the present
work. All samples with a weight of about 2-3 g were
prepared in an arc furnace under a high purity argon
atmosphere using a non-consumable tungsten electrode
(WKDHL-1, Opto-electronics Co, Ltd., Beijing, China).
Due to the large difference of the melting temperature
among Mo, Zr and Ti elements, the binary Mo–Zr alloys
were melted firstly and then the ingots melted with Ti to
obtain homogeneous specimens. In addition, the samples
were remelted at least four times to improve the homo-
geneity. The weight loss of each sample measured after
arc-melting was less than 1 wt.%, indicating that the
compositions of the alloys were considered to be close to
their nominal ones. In order to ensure the clean surface of
samples, they were polished with abrasive paper and rinsed
with alcohol. Then the samples were cut into two parts.
One part was used for microstructure characterization of
the as-cast state, and the other part was encapsulated in
quartz capsules under vacuum (B 1 Pa) and annealed at
900 °C for 40 days and 1100 °C for 20 days in a high-
precision heating furnace (L4514, Qingdao Institute &
Equipment Co. Ltd., China). After annealing, the tubes
with samples were quenched in cold water.
After metallographic preparation, all specimens were
divided into two parts. One part was powdered and ana-
lyzed by XRD technique (XRD, Bruker D8 Advance,
Germany) using a monochromatic Cu Ka (k = 1.54056 Å)
with a LYNXEYE_XE detector at 40 kV and 40 mA for
the sake of identifying the crystal structure of the con-
stituent phases. High purity Si (99.99 wt.%) powders were
used as internal standard in order to calculate the lattice
parameters of the observed phases in the annealed alloys
using the software Jade. 6.0.[32] The rest of samples were
metallographic polished and the microstructure was
observed by means of optical microscopy (OM, Leica
DMLP, Germany), and then using the electron probe
microanalysis (EPMA, JXA-8230, JEOL, Japan) to deter-
mine the composition of phases.
123
 J. Phase Equilib. Diffus.

4 Results and Discussion composition of the prepared samples. As shown in Fig. 3,

4.1 Isothermal Section of the Mo–Ti–Zr System
at 900 °C
Table 1 shows the nominal compositions of the samples
annealed at 900 °C for 40 days. The phases are identified
by means of XRD, while the compositions of phases were
determined through EPMA. The typical back-scattering
electron (BSE) images of several representative Mo–Ti–Zr
alloys are presented in Fig. 2 and the XRD patterns are
shown in the supplementary Fig. S3. According to the
present results, no ternary compounds have been found in
the Mo–Ti–Zr system. Only bcc solid solution and Laves
phases exist at this temperature. Figure 3 is the isothermal
section of the Mo–Ti–Zr system at 900 °C based on the
present experimental results, together with the nominal
samples 1# – 3# are located within the b1 ? Laves ? b2
three-phase region, samples 4# and 5# are located in the
b1 ? Laves two-phase region, samples 6# – 10# are all
located in the b2 ? Laves two-phase region. Sample 11# is
located within the b1 ? b2 two-phase region, and samples
12# and 13# are both located in b single phase area. It is
obvious that a three-phase equilibrium (b1 ? Laves ? b2)
is observed at 900 °C, which demonstrates the separation
of the b phase.
The microstructure of annealed alloy 1# (Mo-24.8 at.%
Zr-39.2 at.% Ti) shows three different kinds of contrasts in
Fig. 2(a). According to the EPMA results, the composi-
tions of the dark region, the gray region and the bright
region are Mo-8.32 at.% Zr-54.37 at.% Ti, Mo-33.29 at.%
Zr-47.95 at.% Ti and Mo-32.51 at.% Zr-19.32 at.% Ti,
which correspond to b1, b2, and Laves phases, respectively.

Table 1 Summary of the XRD and EPMA experimental results of the Mo–Ti–Zr alloys annealed at 900°C
No. Nominal composition (at.%) Phases Phase composition (at.%) Lattice parameter, a = b = c (nm)
Zr Ti Mo Zr Ti Mo

1# 24.8 39.2 36.0 Laves 32.51 19.32 48.17 0.76081

b1 8.32 54.37 37.31 0.32384
b2 33.29 47.95 18.76 0.33402
2# 24.1 48.6 27.3 Laves 33.39 19.29 47.32 0.76131
b1 13.07 55.72 31.21 0.32449
b2 31.74 48.52 19.74 0.33487
3# 27.8 48.2 24.0 Laves 32.70 19.35 47.95 0.76165
b1 12.10 55.73 32.17 0.3249
b2 30.94 49.35 19.71 0.3345
4# 16.8 28.1 55.1 Laves 32.48 17.34 50.18 0.75879
b1 5.38 36.57 58.05 0.31722
5# 18.1 48.2 33.7 Laves 33.68 19.17 47.15 0.76095
b1 10.17 55.61 34.22 0.32284
6# 32.8 25.1 42.1 Laves 32.70 18.23 49.07 0.76053
b2 38.87 45.28 15.85 0.33584
7# 33.7 41.2 25.1 Laves 32.62 18.85 48.53 0.76168
b2 32.89 48.15 18.96 0.3348
8# 44.4 23.7 31.9 Laves 32.62 18.09 49.29 0.76076
b2 56.51 31.86 11.63 0.34456
9# 40.8 8.8 50.4 Laves 33.93 5.66 60.41 0.75969
b2 76.72 15.04 8.24 0.35147
10# 56.5 6.3 37.2 Laves 35.45 4.50 60.05 0.75931
b2 85.25 6.72 8.03 0.3529
11# 21.6 52.4 26.0 b1 13.75 56.38 29.87 0.32375
b2 29.04 50.46 20.50 0.33736
12# 20.9 56.4 22.7 b 21.33 57.12 21.55 0.33037
13# 4.6 6.8 88.6 b1 3.24 4.37 92.39 0.31565

123
J. Phase Equilib. Diffus.
Fig. 2 BSE micrographs of the selected samples annealed at 900°C for 40 days: (a) Sample 1# (Mo-24.8 at.% Zr-39.2 at.% Ti); (b) Sample 4#
(Mo-16.8 at.% Zr-28.1 at.% Ti); (c) Sample 8# (Mo-44.4 at.% Zr-23.7 at.% Ti) and (d) Sample 11# (Mo-21.6 at.% Zr-52.4 at.% Ti)
Fig. 3 The experimental isothermal section of the Mo–Ti–Zr system
at 900 °C
Moreover, the maximum solubilities of Ti in Mo2Zr Laves
phase was found to be * 19.32 at.% Ti. Figure 2(b) is the
BSE image of sample 4# (Mo-16.8 at.% Zr-28.1 at.% Ti).
The gray region in the figure is the b1 phase, and the white
area is the Laves phase. Figure 2(c) shows the micrograph
of sample 8# (Mo-44.4 at.% Zr-23.7 at.% Ti). Two phases
are found in sample 8#, and phase compositions are listed
in Table 1. The BSE image of alloy 11# (Mo-21.6 at.% Zr-
52.4 at.% Ti) is presented in Fig. 2(d). In this figure, the
dark gray region is b1 phase, and the light gray is the b2
phase. It is observed in Fig. 2 that some holes existed in the
microstructure, which were very likely formed during the
water quench process after the annealing or during the
polishing because some small brittle particles flake off
from the bulk.
The results of the BSE microscopy are confirmed by the
XRD analysis. The XRD patterns of samples 1#, 4#, 8#,
11#, 12# and 13# are presented in the supplementary
Fig. S3. As can be seen, three phases were detected in alloy
1# and two phases were detected in alloys 4#, 8# and 11#.
These XRD measurements are consistent with the EPMA
results. As shown in Fig. S3(e) and (f), samples 12# and
13# are both in a single phase area, which are Ti–rich solid
solution and Mo-rich solid solution, respectively. The
calculated lattice parameters of these phases were listed in
Table 1. The lattice parameters of bcc solid solutions vary
123
 J. Phase Equilib. Diffus.

with the alloy compositions, while the lattice parameter of
the Laves phase also changes due to the dissolution of the
Ti.
4.2 Isothermal Section of the Mo–Ti–Zr System
at 1100 °C
To further characterize the Mo–Ti–Zr system, the isother-
mal section at 1100 °C was also experimentally determined
in the present work. The nominal compositions of the
prepared alloys are listed in Table 2, in which the identified
phases, phase compositions and calculated lattice parame-
ters are also presented. The BSE images of several chosen
Mo–Ti–Zr samples are shown in Fig. 4 and XRD patterns
are presented in the supplementary Fig. S4. According to
the present experimental work, the isothermal section of
the Mo–Ti–Zr system at 1100 °C is constructed in Fig. 5
together with the nominal compositions of the prepared
samples.
As shown in Fig. 3 and 5, the isothermal section at
1100 °C is similar to that of the isothermal section at
900 °C. The three-phase region (b1 ? Laves ? b2) is also
detected at 1100 °C. Figure 4(a) is the BSE image of
sample 2# (Mo-27.3 at.% Zr-37.5 at.% Ti), and three dif-
ferent phase contrasts can be observed in this figure. The
compositions of the dark gray region, the light gray region
and the white region are Mo-13.64 at.% Zr-48.19 at.% Ti,
Mo-33.94 at.% Zr-43.86 at.% Ti and Mo-32.66 at.% Zr-
18.33 at.% Ti according to EPMA results, which corre-
spond to b1, b2, and Laves phases, respectively. And the
solubility of Ti in Mo2Zr Laves is * 18.33 at.% Ti at
1100 °C. Compared with the isothermal section of 900 °C,
the three-phase region of the isothermal section at 1100 °C
is slightly smaller. Based on similar analysis procedure for
sample 2#, samples 1# and 3# are both located within the
b1 ? Laves ? b2 three-phase region. Figure 4(b) is the
BSE image of sample 4# (Mo-28.9 at.% Zr-15.4 at.% Ti),
and the gray region is the b1 phase and the white area is the
Laves phase. The similar results as those in sample 4# are
confirmed in samples 5# and 6#. Figure 4(c) shows the
micrograph of sample 8# (Mo-54.2 at.% Zr-15.2 at.% Ti),
and two phases are found and phase compositions are listed
in Table 2. Similar results as those to sample 8# are found
in samples 7# and 9#. The BSE image of alloy 10# (Mo-
26.4 at.% Zr-46.5 at.% Ti) is presented in Fig. 4(d). The

Table 2 Summary of the XRD and EPMA experimental results of the Mo–Ti–Zr alloys annealed at 1100°C
No. Nominal composition (at.%) Phases Phase composition (at.%) Lattice parameter, a = b = c (nm)
Zr Ti Mo Zr Ti Mo

1# 30.9 29.4 39.7 Laves 33.42 18.11 48.47 0.76017

b1 10.55 49.08 40.37 0.32279
b2 34.28 43.51 22.21 0.33687
2# 27.3 37.5 35.2 Laves 32.66 18.33 49.01 0.76107
b1 13.64 48.19 38.17 0.3223
b2 33.94 43.86 22.20 0.3366
3# 26.9 39.2 33.9 Laves 32.09 18.36 49.55 0.76155
b1 11.90 49.44 38.66 0.32258
b2 36.09 43.04 20.87 0.3362
4# 28.9 15.4 55.7 Laves 33.45 12.61 53.94 0.76019
b1 3.65 30.79 65.56 0.31741
5# 18.3 18.7 63.0 Laves 33.72 11.26 55.02 0.75966
b1 3.01 27.13 69.86 0.31785
6# 16.3 15.6 68.1 Laves 33.49 8.64 57.87 0.75901
b1 4.22 16.31 79.47 0.31656
7# 58.6 24.7 16.7 Laves 33.07 16.79 50.14 0.75931
b2 62.26 26.81 10.93 0.34553
8# 54.2 15.2 30.6 Laves 34.09 13.96 51.95 0.75956
b2 71.02 18.17 10.81 0.34935
9# 53.6 8.4 38.0 Laves 34.37 8.97 56.66 0.75850
b2 80.92 8.62 10.46 0.35149
10# 26.4 46.5 27.1 b1 13.83 50.84 35.33 0.32277
b2 31.26 46.08 22.66 0.33726

123
J. Phase Equilib. Diffus.
Fig. 4 BSE micrographs of the selected samples annealed at 1100°C for 20 days: (a) Sample 2# (Mo-27.3 at.% Zr-37.5 at.% Ti); (b) Sample 4#
(Mo-28.9 at.% Zr-15.4 at.% Ti); (c) Sample 8# (Mo-54.2 at.% Zr-15.2 at.% Ti) and (d) Sample 10# (Mo-26.4 at.% Zr-46.5 at.% Ti)
Fig. 5 The experimental isothermal section of the Mo–Ti–Zr system
at 1100°C
dark gray region is b1 phase and the light gray is the b2
phase in this figure.
The XRD patterns of samples 2#, 4#, 8# and 10# for the
isothermal section at 1100 °C are presented in the
supplementary Fig. S4, in which three phases were
observed in sample 2# and two phases were detected in
samples 4#, 8# and 10#. XRD results are consistent with
the EPMA results of the isothermal section at 1100 °C.
Among the literature data,[25–30] there are no experimental
data on the whole composition for the isothermal section at
1100 °C. The reliable phase equilibrium data at 1100 °C
were provided in the present work.
To compare the present experimental results with the
literature data, the present data (isothermal sections at 900
and 1100 °C) and the data reported by Prokoshkin and
Zakharova[27] (isothermal section at 900 and 1200 °C) are
merged into one diagram, as shown in Fig. 6. The presently
measured phase compositions at 900 °C (black dashed
line) are different from those reported by Prokoshkin and
Zakharova[27] at 900 °C (blue dotted line, Fig. 6). The
methods used by Prokoshkin and Zakharova[27] were XRD,
microstructural analysis, Vickers hardness and microhard-
ness, which have large errors for analyzing phase compo-
sitions compared to EPMA technique. For the Mo–Ni–Zr
system,[11] the annealing time at 900 °C is 40 days. How-
ever, the annealing time used by Prokoshkin and
Zakharova[27] at 900 °C is only 450 h for the Mo–Ti–Zr
123
 J. Phase Equilib. Diffus.

Fig. 6 The isothermal sections

of the Mo–Ti–Zr system
superimposed with the present
experimental results and the
literature data[27]

system, which is too short for alloys to reach equilibrium. Table 3 Nominal compositions and primary solidification phases of
In the present work, long annealing time of 40 days at Mo–Ti–Zr ternary system
900 °C and several experimental methods are employed, No. Nominal composition (at.%) Primary phase
leading to reliable experimental results.
Zr Ti Mo
As shown in Fig. 6, the three-phase region (b1-
? Laves ? b2) at 1100 °C (green bold line) is larger than 1# 24.5 3.8 71.7 b1
the phase region at 1200 °C[27] (red thin line), and the 2# 38.9 3.9 57.2 b1
phase boundaries (b1 ? Laves/b, b2 ? Laves/b and b1 3# 28.1 8.4 63.5 b1
?b2/b) at 1200 °C[27] are closer to Mo–Zr edge. In the 4# 36.5 8.6 54.9 b1
present results, the phase boundaries (b1 ? Laves/b, b2- 5# 16.3 15.4 68.3 b1
? Laves/b and b1 ?b2/b) at 1100 °C (green bold line) are 6# 28.9 15.4 55.7 b1
closer to Mo–Zr edge compared with the 900 °C (black 7# 41.7 15.2 43.1 b1
dashed line). 8# 31.3 26.1 42.6 b1
9# 33.7 41.3 25.0 b1
4.3 Liquidus Projection of the Mo–Ti–Zr System 10# 27.9 48.2 23.9 b1
11# 62.4 3.6 34.0 Laves
The nominal compositions and primary solidification pha-
12# 58.8 5.1 36.1 Laves
ses of the twenty-two as-cast alloys are summarized in
13# 56.5 6.3 37.2 Laves
Table 3. There are three primary crystallization fields, i.e.,
14# 57.2 7.5 35.3 Laves
b1, Laves and b2. Figure 7 shows the BSE images of
15# 53.2 11.2 35.6 Laves
several representative as-cast alloys in Mo–Ti–Zr system
16# 54.2 15.3 30.5 Laves
and the XRD patterns are presented in the supplementary
17# 64.7 7.4 27.9 b2
Fig. S5. The primary phase of the b1 is observed for
18# 67.4 9.8 22.8 b2
samples 1# – 10#. The BSE micrograph and XRD pattern
19# 75.1 10.3 14.6 b2
of sample 3# (Mo-28.1 at.% Zr-8.4 at.% Ti) are presented
20# 70.6 15.5 13.9 b2
in Fig. 7(a) and S5(a), respectively. Three different
21# 63.9 12.1 24.0 b2
microstructure regions can be observed in Fig. 7(a). The
22# 60.8 11.9 27.3 b2
gray dendrite microstructure is the primary phase b1 with a
composition of Mo-11.93 at.% Zr-10.16 at.% Ti, which is
bordered by Laves phase. The secondary solidification
phase Laves is formed by a peritectic reaction of L ? b1 $
Laves. The dark region is a eutectic structure b2 ? Laves consistent with the microstructure analysis. The primary
with a composition of Mo-68.15 at.% Zr-15.80 at.% Ti, phase of samples 11# * 16# is Laves phase. Fig-
which is related to the univariant eutectic reaction L $ ures 7(b) and S5(b) are the BSE image and XRD pattern of
b2 ? Laves. As shown in Fig. S5(a), the XRD results are sample 11# (Mo-62.4 at.% Zr-3.6 at.% Ti). The

123
J. Phase Equilib. Diffus.

Fig. 7 BSE micrographs of the as-cast alloys (a) Sample 3# (Mo-28.1 at.% Zr-8.4 at.% Ti); (b) Sample 11# (Mo-62.4 at.% Zr-3.6 at.% Ti);
(c) Sample 18# (Mo-67.4 at.% Zr-9.8 at.% Ti)

microstructure of sample 11# consists of a quadrilateral

primary phase Laves with a composition of Mo-35.43 at.%
Zr-4.03 at.% Ti, and the eutectic structure b2 ? Laves with a
composition of Mo-76.18 at.% Zr-3.72 at.% Ti. The solidi-
fication path of sample 11# could be in such a sequence:
L ? Laves ? b2 ? Laves. For samples 17# * 22#, the
primary phase is b2. As shown in Fig. 7(c) and S5(c), sample
18# (Mo-67.4 at.% Zr-9.8 at.% Ti) is single phase b2 formed
directly from the liquid phase.
These experimental results confirm an invariant reaction
(L ? b1 $ b2 ? Laves) in the Mo–Ti–Zr system. The
liquidus projection of the Mo–Ti–Zr system was con-
structed and presented in Fig. 8 together with the nominal
compositions of the as-cast samples in this work and the
experimental data from the literature.[30] The presently
obtained primary phase region of Laves is consistent with
the previous measurement.[30] The reaction scheme of the Fig. 8 Liquidus projection of the Mo–Ti–Zr system superimposed
with the present experimental samples and the literature data[30]
Mo–Ti–Zr system is illustrated in Fig. 9. The temperatures
of invariant reaction and critical point are from litera-
projection can provide new phase diagram data for future
ture.[26,31] In this work, the exact locations of the invariant
thermodynamic optimization of the Mo–Ti–Zr system.
point and critical point are not determined.
The presently obtained phase equilibria of the Mo–Ti–
Zr system at 900 and 1100 °C as well as the liquidus

123

Fig. 9 Reaction scheme of Mo–Ti–Zr system including the liquid
phase. b1: bcc (Mo, Ti) and b2: bcc (Ti, Zr)
5 Conclusions
In this work, the 900 and 1100 °C isothermal sections as
well as the liquidus projection of the Mo–Ti–Zr ternary
system were systematically determined using XRD analy-
sis and EPMA technique. No ternary compounds are found
at both 900 and 1100 °C in the Mo–Ti–Zr system. Phases
detected by EPMA measurement are confirmed by XRD
method. One three-phase region (b1 ? Laves ? b2) was
determined experimentally at 900 and 1100 °C, which
indicates that phase separation occurs for the b phase. In
addition, three two-phase regions (b1 ? Laves, b2-
? Laves and b1 ? b2) were also determined at 900 and
1100 °C. The presently measured phase compositions of
isothermal section at 900 °C are different from the litera-
ture data. The reliable phase equilibrium data at 1100 °C
were provided in the present work. For liquidus projection,
there are three primary crystallization regions, i.e., b1,
Laves, b2, and the primary phase region of Laves is in good
agreement with the previous measurement. An invariant
reaction (L ? b1 $ b2 ? Laves) is confirmed in the pre-
sent work. According to the present experimental results
and literature information, the reaction scheme is also
presented for the Mo–Ti–Zr ternary system.
Acknowledgment The financial support from the Science Challenge
Project of China (Grant No. TZ2016004) is acknowledged.
References
1. S. Majumdar, S. Raveendra, I. Samajdar, P. Bhargava, and I.G.
Sharma, Densification and Grain Growth During Isothermal
Sintering of Mo and Mechanically Alloyed Mo–TZM, Acta
Mater., 2009, 57, p 4158-4168
123
J. Phase Equilib. Diffus.
2. S. Majumdar, Formation of MoSi2 and Al Doped MoSi2 Coatings
on Molybdenum Base TZM (Mo–0.5Ti–0.1Zr–0.02C) Alloy,
Surf. Coat. Technol., 2012, 206(15), p 3393-3398
3. H.J. Shi, L.S. Niu, C. Korn, and G. Pluvinage, High Temperature
Fatigue Behaviour of TZM Molybdenum Alloy Under Mechan-
ical and Thermomechanical Cyclic Loads, J. Nucl. Mater., 2000,
278(2–3), p 328-333
4. G. Liu, G.J. Zhang, F. Jiang, X.D. Ding, Y.J. Sun, J. Sun, and E.
Ma, Nanostructured High-Strength Molybdenum Alloys with
Unprecedented Tensile Ductility, Nat. Mater., 2013, 12(4), p 344-
350
5. P. Zhang, X. Guo, C. Zhang, Q. Tao, and C. Shen, Deposition and
Oxidation Behavior of Mo(Si, Al)2/MoB Layered Coatings on
TZM Alloy, Int. J. Refract. Met. Hard Mater., 2017, 67, p 32-39
6. A.P. Alur, N. Chollacoop, and K.S. Kumar, High-Temperature
Compression Behavior of Mo–Si–B Alloys, Acta Mater., 2004,
52(19), p 5571-5587
7. G.R. Smolik, D.A. Petti, and S.T. Schuetz, Oxidation and
Volatilization of TZM Alloy in Air, J. Nucl. Mater., 2000,
283–287(Part 2), p 1458-1462
8. E. Ahmadi, M. Malekzadeh, and S.K. Sadrnezhaad, Preparation
of Nanostructured High-Temperature TZM Alloy by Mechanical
Alloying and Sintering, Int. J. Refract. Met. Hard Mater., 2011,
29(1), p 141-145
9. J.B. Lambert and J.J. Rausch, Properties and Selection: Nonfer-
rous Alloys and Special-Purpose Materials, ASM HandBook,
ASM Int., 1992, 2, p 1751-1752
10. C.B. Danisman, B. Yavas, O. Yucel, F. Sahin, and G. Goller,
Processing and Characterization of Spark Plasma Sintered TZM
Alloy, J. Alloys Compd., 2016, 685, p 860-868
11. S. Wang, C. Zhang, C. Lin, Y. Peng, and Y. Du, Measurement of
900 °C Isothermal Section in the Mo–Ni–Zr System, J. Phase
Equilib. Diffus., 2016, 37(6), p 672-679
12. S. Wang, C. Zhang, Y. Du, Y. Peng, Y. Pan, P. Zhou, and L.
Dreval, Experimental Investigation and Thermodynamic
Assessment of the Mo–Ni–Zr Ternary System, Calphad, 2017,
58, p 128-137
13. C. Lin, C. Zhang, S. Wang, P. Zhou, and Y. Du, Phase Equilibria
of the Co-Mo-Zr Ternary System at 1100 & °C, J. Phase Equilib.
Diffus., 2017, 38(4), p 552-560
14. Y. Li, N. Liu, X. Zhang, and C. Rong, Effect of Mo Addition on
the Microstructure and Mechanical Properties of Ultra-Fine
Grade TiC–TiN–WC–Mo2C–Co Cermets, Int. J. Refract. Met.
Hard Mater., 2008, 26(3), p 190-196
15. X. Zhang and N. Liu, Effects of ZrC on Microstructure,
Mechanical Properties and Thermal Shock Resistance of TiC–
ZrC–Co–Ni Cermets, Mater. Sci. Eng., A, 2013, 561, p 270-276
16. X. Zhang, N. Liu, C. Rong, and J. Zhou, Microstructure and
Mechanical Properties of TiC–TiN–Zr–WC–Ni–Co Cermets,
Ceram. Int., 2009, 35(3), p 1187-1193
17. S. Zhang, Titanium Carbonitride-Based Cermets: Processes and
Properties, Mater. Sci. Eng., A, 1993, 163(1), p 141-148
18. P. Ettmayer, H. Kolaska, W. Lengauer, and K. Dreyer, Ti(C, N)
Cermets—Metallurgy and Properties, Int. J. Refract. Met. Hard
Mater., 1995, 13(6), p 343-351
19. J.L. Murray, The Mo–Ti (Molybdenum-Titanium) System, Phase
Diagram of Binary Titanium Alloys, Metals Park, OH, ASM Intl.,
1987, p 169-175
20. J.H. Shim, C.S. Oh, and D.N. Lee, A Thermodynamic Evaluation
of the Ti-Mo-C System, Metall. Mater. Trans. B, 1996, 27, p 955-
966
21. H.J. Chung, J.H. Shim, and D.N. Lee, Thermodynamic Evalua-
tion and Calculation of Phase Equilibria of the Ti–Mo–C–N
Quaternary System, J. Alloys Compd., 1999, 282, p 142-148
22. R.J. Pérez and B. Sundman, Thermodynamic Assessment of the
Mo–Zr Binary Phase Diagram, Calphad, 2003, 27, p 253-262
J. Phase Equilib. Diffus.
23. K.C.H. Kumar, P. Wollants, and L. Delacy, Thermodynamic
Assessment of the Ti–Zr System and Calculation of the Nb–Ti–Zr
Phase Diagram, J. Alloys Compd., 1994, 206, p 121-127
24. A. Watson and MSIT, Mo–Ti–Zr Ternary Phase Diagram Evalu-
ation, Phase Diagrams, Crystallographic and Thermodynamic
Data: Datasheet From MSI Eureka in SpringerMaterials, MSI
Materials Science International Services GmbH (http://materials.
springer.com/msi/docs/sm_msi_r_10_018033_01).
25. D.A. Prokoshkin and M.I. Zakharova, Isothermal Sections at 600
and 750 °C in the Phase diagram of the Mo–Ti–Zr system, Inorg
Mat., 1967, 3, p 70–75, translated from Izv. Akad. Nauk SSSR,
Neorg. Mater., 1967, 3, p 87-93
26. D.A. Prokoshkin and M.I. Zakharova, On the Phase Equilibria in
the System Mo-Ti-Zr, Dokl. Akad. Nauk SSSR, 1967, 172(6),
p 1382-1384 (in Russian)
27. D.A. Prokoshkin and M.I. Zakharova, Isothermal Section of the
Mo-Ti-Zr Phase Diagram at 1200, 900, and 800°C, Struktura i
Svoistva Zharoprochn Metallich Materialov, Nauka, Moscow,
1967, p 48–53 (in Russian).
28. D.L. Kudryavtsev and E.M. Tararaeva, The Zirconium Corner of
the Zirconium-Molybdenum-Titanium Phase Diagram, Fiz.
Khim. Splavov Tsirkoniya, Nauka, Moscow, 1968, p 227–231 (in
Russian)
29. Y.C. Chuang, C.H. Tang, and H.L. Chuang, The Isothermal
Sections at 1200 °C of the Equilibrium Diagrams of the Systems
Mo–Ti–Zr and Mo–Nb–Zr, Acta Metall. Sin., 1966, 9(1), p 63-70
(in Chinese)
30. A.M. Zakharov and E.M. Savitskii, Phase Diagram of the Ternary
Mo-Zr-Ti System, Inorg. Mater. (Engl. Trans.), 1967, 3(4),
p 586–587, translated from Izv. Akad. Nauk SSSR, Neorg.
Mater., 1967, 3.
31. M.I. Zakharova and D.A. Prokoshkin, Polythermal Sections of
Phase Diagram of the Mo-Ti-Zr system, Izv. Akad. Nauk SSSR,
Met., 1968, 2(219), p 199-223 (in Russian)
32. JADE 6.0, Users Guide for XRD Pattern Processing., USA: In:
Materials Data I, (Ed.). CA, USA,; 2005.
123