Rare Met.
(2018) 37(1):21–25
https://doi.org/10.1007/s12598-015-0466-9
Preparation of TiAl alloy powder by high-energy ball milling and
diffusion reaction at low temperature
Hui-Ping Shao*, Zhi Wang, Tao Lin,
Qing Ye, Zhi-Meng Guo
Received: 6 January 2014 / Revised: 3 March 2014 / Accepted: 28 February 2015 / Published online: 28 March 2015
Ó The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2015
Abstract In this paper, TiAl alloy powders were pre-
pared successfully by high-energy ball milling and diffu-
sion reaction in vacuum at low temperature. The titanium
powder, aluminum powder, and titanium hydride powder
were used as raw materials. The samples were character-
ized by scanning electron microscopy (SEM), X-ray
diffraction (XRD), field-emission scanning electron mi-
croscopy (FESEM), and differential thermal analysis
(DTA). The results show that the alloy powders with the
main intermetallic compounds of TiAl are obtained using
Ti–Al powders and TiH2–Al powders after heated for 2 h
at 500 °C, 3 h at 600 °C, and 3 h at 750 °C, respectively.
The average grain sizes of alloy powder are about 45 and
20 lm with irregular shape, respectively. The prepared
TiAl alloy powders are relatively pure, and the average
quality content of oxygen in the alloy powders is
0.33 wt%. The forming process of alloy powder contains
both the diffusion reaction of Ti and Al, which gives pri-
ority to the diffusion reaction of aluminum.
Keywords High-energy ball milling; Titanium hydride
powder; Titanium powder; TiAl alloy powder; Diffusion
reaction
1 Introduction
In recent years, c-TiAl-based alloys have attracted more
and more attention on high-temperature applications in
aerospace, automotive, and power generation industries.
H.-P. Shao*, Z. Wang, T. Lin, Q. Ye, Z.-M. Guo
Institute for Advanced Material and Technology, University of
Science and Technology Beijing, Beijing 100083, China
e-mail: shaohp@ustb.edu.cn
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Titanium aluminides based on c-TiAl have a great potential
to partly replace the heavy steels and nickel-based alloys in
certain applications due to their low density, high specific
strength, high specific stiffness, and good creep resistance
at elevated temperatures. Therefore, TiAl-based alloys are
known to be the most promising intermetallic compound
materials which have extensive application in areas of
aerospace, aviation, military industry and civilian, such as
the engine high-pressure compressor, low-pressure turbine
blade, convection bank, exhaust valve, nozzle in the
twenty-first century [1–5].
TiAl-based alloys prepared by powder metallurgy
method have such advantages as no porosity, no compo-
sition segregation, no shrinkage void, uniform, and fine
grain compared with the casting alloys, and their me-
chanical properties are close to the ideal design of the TiAl
alloy materials. Powder metallurgy (P/M) method was
widely used since it is an easy way to add alloy elements
with a high melting point and prepare composite materials.
Furthermore, P/M is also a near-net-shaping method for
parts with complex shape and can effectively solve the
difficulty in forming process of titanium–aluminum inter-
metallic compound [6]. TiAl-based alloy can be prepared
by P/M method with two kinds of raw materials: elemental
powders and pre-alloyed powders. The TiAl alloy prepared
by pre-alloyed powders has uniform composition, low
oxygen content, low impurity content, good formability,
and excellent mechanical properties [7].
Conventional preparation methods of TiAl alloy pow-
der, for example smelting and crushing method and me-
chanical alloying method, have many shortcomings, such
as hard preparing, time consuming, easily involving a va-
riety of impurities, or difficultly controlling. The main
methods for preparing high-quality pre-alloyed powder are
gas atomization (GA), centrifugal atomization (CA), and
123
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plasma rotating electrode pulverization (PREP). But the
initial investment of the equipment for these methods is
high and large amounts of inert gas are needed to ensure a
clean environment during the preparation stage, so the
preparation of TiAl alloy powders has high cost and dif-
ficulty in achieving mass production. In general, it is nec-
essary to explore the methods of preparation of TiAl alloy
powders [8–11].
In this process, TiAl alloy powders were prepared
through diffusion reaction under high vacuum with titani-
um hydride powder, titanium powder, and aluminum
powder as raw materials which were blended by high-en-
ergy ball milling with toluene as the process control agent.
According to XRD analysis, holding temperature and
holding time were adjusted to get the best preparation
process and the mechanism of the diffusion reaction was
researched at the same time. The high purity of TiAl alloy
powders produced by this method has a lower production
cost because this process is a simple preparation method.
2 Experimental
2.1 Material and equipment
Titanium powder with a average size of 30 lm, titanium
hydride powder with a average size of 46 lm, aluminum
powder with a average size of 6–8 lm, and toluene were
used.
A vibrating mill was used to mix the above powders. An
electric tube furnace with high vacuum pump was used to
treat the mixed powders. The alloyed powder was char-
acterized by scanning electron microscopy (SEM) and
field-emission scanning electron microscope (FESEM)
equipped with energy-dispersive spectroscopy (EDS). The
particle size of the powders was tested by a laser particle
size analyzer.
2.2 Ball milling
High-energy ball milling as a powder preparing technology
was applied in preparing the TiAl alloy powders, which can
shorten the diffusion distance between titanium and alu-
minum adequately and refine the grain size. This will in-
crease the speed of diffusion reaction. During ball milling,
powder was refined under the control of the fracture and
cold welding process. When these two processes achieved
a dynamic balance, the particle size of the powders did not
change significantly. During high-energy ball milling, it is
important to control the breaking process of powder and
efficiently obtain ultrafine powder. Most researchers pro-
mote the fracture process by adjusting the technological
parameters of high-energy ball milling, such as adding
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H.-P. Shao et al.
process treating agent or conducting ball milling at low
temperature.
Titanium–aluminum powders or titanium hydride–alu-
minum powders in a mole ratio of 1:1 were blended and
refined, respectively, by high-energy ball milling with
toluene as the process control agent. The ball milling tank
and balls were made from stainless steel. The vibration
frequency was 23.2 Hz, and the mass ratio of the balls to
powders was 5:1. The ball milling time cannot be too long
since the oxygen content increased and the process of ball
milling was hard to avoid involving impurities with the
extension of ball milling time. According to the previous
experience, the vibration time was generally set for 1 h.
The ball-milled powders were put into the vacuum drying
oven under 0.1 Pa at 40 °C.
Figure 1a, b shows the FESEM images of Ti–Al and
TiH2–Al mixed powders with high-energy ball milling for
1 h, respectively. The ‘‘white’’ area is titanium, the
‘‘black’’ area is aluminum powder as shown in Fig. 1a; the
‘‘white’’ area is titanium hydride, the ‘‘black’’ area is alu-
minum powder as shown in Fig. 1b. Both mixed powders
exist as independent particles of the two powders, not in
the form of composite particles of two powders.
2.3 Alloying
The mixed powders were heated by a vacuum tube furnace
with the vacuum degree of 4.0 9 10-3 Pa and the heating
rate of 5 °Cmin-1. The heat treating regime can be finally
determined through the results of the previous experiments.
The relatively pure TiAl alloy powders were prepared with
Ti and Al powders or TiH2 and Al powders by ball milling
at low temperature. The average content of oxygen in the
alloy powders is 0.33 wt%. The ball-milled powder of Ti
and Al was heated for 2 h at 500 °C and then 3 h at
600 °C. The ball-milled powder of TiH2 and Al was heated
for 3 h at 750 °C.
Figure 2 is XRD patterns of the above two kinds of
mixed powders after heat treatment in a vacuum environ-
ment. As shown in XRD patterns, TiAl and a small amount
Fig. 1 SEM images of high-energy ball-milled powders: a titanium
and aluminum powders and b titanium hydride and aluminum
powders
Rare Met. (2018) 37(1):21–25
Preparation of TiAl alloy powder 23

The particle size distribution of alloy powder prepared

by Ti–Al powders is wider, and the average particle size of
alloy powder is bigger, about 45 lm (Fig. 4a). The particle
size distribution of alloy powder prepared by TiH2–Al
powders is wider, and the average particle size of alloy
powder is smaller, about 20 lm (Fig. 4b). The reason is
that the titanium hydride powder has bigger brittleness than
titanium powder which is easy to be crushed to smaller size
of particles.

3 Results and discussion

3.1 Diffusion reaction of titanium powder and

Fig. 2 XRD patterns of alloyed powders with (1) Ti and Al powders;
aluminum powder
(2) TiH2 and Al powders

The intermetallic compound of Ti and Al elemental pow-

ders was synthesized by diffusion control, including the
generation of TiAl3, TiAl2, and Ti3Al intermediate phases.
When the temperature is lower than the melting point of
Al, Ti and Al particles occur diffusion reaction to form
TiAl3 phase on the Ti–Al particle interface, and gradually
form TiAl2, Ti3Al, and other various intermediate phases as
the reaction proceeds. TiAl2 and Ti3Al phases compete for
formation at the same time when TiAl3 persists. After
TiAl3 consumes up, the amount of Ti3Al and TiAl2 phases
Fig. 3 SEM images of a Ti–Al powders and b TiH2–Al powders
decreases and that of TiAl phase increases. The final re-
action product is the mixture of Ti3Al and TiAl phases, and
of Ti3Al alloy powders were prepared and the grain size of
the respective phase ratio is related to the composition of
the former is larger than that of the latter due to the fact that
the material and the specific process.
the width of the diffraction peak in the pattern (1) is wider
In short, the synthesis of Ti and Al is divided into three
than that in the pattern (2) in Fig. 2.
steps: the formation of TiAl3 phase, the formation of in-
Figure 3 shows that the alloy powder prepared by Ti–Al
termediate phases TiAl2 and Ti3Al and a small amount of
powders looks relatively ‘‘smooth’’ with irregular shape.
the TiAl phases, and the formation of TiAl phase, which
The alloy powders prepared with TiH2–Al powders have a
can be specifically described by the following three reac-
smaller size, and the surface is ‘‘soft spiny’’ with irregular
tions [12, 13]:
shape.

Fig. 4 Particle size distribution of alloyed powder with a Ti–Al powders and b TiH2–Al powders

Rare Met. (2018) 37(1):21–25 123

24
Fig. 5 FESEM images of alloyed powders by heating Ti–Al milled
powders at a 500 °C for 2 h and b 600 °C for 3 h
6Ti + 6Al ! 4Ti + 2TiAl3 ð1Þ
4Ti + 2TiAl3 ! Ti3 Al + TiAl + 2TiAl2 ð2Þ
Ti3 Al + 2TiAl2 + TiAl ! 6TiAl ð3Þ
Figure 5a shows the internal structure of alloy powders
prepared by titanium powder and aluminum powder heated
at 500 °C for 2 h and 600 °C for 1.5 h. As known from the
EDS results, the atom ratios of Ti to Al of Points 1–4 in
Fig. 5a are 42.88:57.12, 64.97:35.03, 65.09:34.91, and
99.29:0.71, respectively. It can be seen that the content of
Ti gradually reduces from the inside to the outside, and in
the middle part of the powder it is relatively pure Ti. A
variety of metaphases which may contain TiAl alloy phase
are observed in Points 2 and 3 in Fig. 5a, and the outermost
is a compound of Ti and Al which already exists. There is
no single aluminum and aluminum spreads to the titanium
to form alloy. In the middle of the powder, it still contains
some titanium phase due to the fact that the reaction is not
complete. It can be inferred that the spread of the diffusion
process mainly comes from aluminum atom migration.
Figure 5b shows the internal structure of alloyed pow-
ders prepared by titanium powder and aluminum powder
heated at 500 °C for 2 h and 600 °C for 3 h. As known
from the EDS results, the atom ratios of Ti to Al of Points
1–3 in Fig. 5b are 47.19:52.81, 48.21:51.89, and
47.84:52.16, respectively. It can be seen that a homoge-
neous alloy phase finally forms. The above analysis is in
accordance with the results of XRD.
3.2 Diffusion reaction of titanium hydride powder and
aluminum powder
Titanium hydride dehydrogenates at a certain temperature
and time, which vary with the factors of preparing raw
material: the particle size and heating rate. The dehydro-
genation reaction process is as follows [14, 15]:
TiH2 ! Ti + H2 ð4Þ
Figure 6 is the DTA curve of TiH2 powder (average
particle size of 46 lm) under a protective atmosphere of
argon at heating rate of 5 °Cmin-1. It is apparent that the
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H.-P. Shao et al.
Fig. 6 DTA curve of TiH2 powder with heating rate of 5 °Cmin-1
Fig. 7 FESEM images of alloyed powder by heating TiH2–Al milled
powders at a 500 °C for 2 h and b 750 °C for 3 h
dehydrogenation of TiH2 is an endothermic process which
has a small endothermic peak at 443 °C and a second larger
endothermic peak at 523 °C, as shown in Fig. 6. The
endothermic peak of the two separation description reveals
that thermal decomposition of the dehydrogenation
reaction of TiH2 powder is a multi-stage reaction. It can
be accounted for the dehydrogenation reaction of TiH2
powder at heating rate of 5 °Cmin-1 and temperature of
440–550 °C. The TiH2 and Al powders heated at 500 °C
for 2 h are the research object, because titanium hydride
can be almost dehydrogenated thoroughly and partially
alloyed at 500 °C for 2 h by the previous studies.
Figure 7a shows the internal structure of alloyed pow-
ders prepared by titanium hydride powder and aluminum
powder heated at 500 °C for 2 h. As known from the EDS
results, the atom ratios of Ti to Al of Points 1–4 in Fig. 7a
are 43.12:56.88, 62.26:37.74, 65.32:34.68, and 99.16:0.84,
respectively. It can be seen that the reaction of titanium
hydride and aluminum powder is similar to that of titanium
powder and aluminum powder, giving priority to the dif-
fusion of aluminum. Aluminum gradually spreads to tita-
nium that comes from dehydrogenation of titanium hydride
powder, forming mainly aluminum alloy phase at the sur-
face. And from outside to inside, aluminum content
gradually reduces, forming various sorts of metaphases. It
Rare Met. (2018) 37(1):21–25
Preparation of TiAl alloy powder
is still titanium in the center because the reaction does not
come to the end.
Figure 7b shows the internal structure of alloyed pow-
ders prepared by titanium hydride powder and aluminum
powder heated at 750 °C for 3 h. As known from the EDS
results, the atom ratios of Ti to Al of Points 1–3 in Fig. 7a
are 51.99:48.01, 52.60:47.40, and 50.65:49.35, respective-
ly. It can be seen that a homogeneous alloy phase finally
forms. The above analysis is in accordance with the results
of XRD.
The TiAl alloy powders were prepared by direct diffu-
sion reaction of Ti and Al using titanium powder and
aluminum powder as raw materials, and using titanium
hydride powder and aluminum powder as raw materials,
respectively. The amount of defects increases in the two
kinds of raw materials in the process of ball milling due to
mechanical forces, and the defects will gradually release
energy at the same time to promote alloying in the fol-
lowing alloying process. The alloy powders can be pre-
pared at a relative lower temperature due to direct diffusion
reaction of the titanium powder and aluminum powder. By
contrast, TiAl alloy powders cannot be got from titanium
hydride and aluminum powders at low temperature since
the system energy is low due to the low level of defects and
that dehydrogenation reaction is an energy absorbing pro-
cess. So the heating temperature should be raised to make
titanium hydride and aluminum powders change to a pure
TiAl alloy powder.
4 Conclusion
The relatively pure TiAl alloy powders were prepared
through diffusion reaction step at low temperature using
Ti–Al powders and TiH2–Al powders, respectively. The
prepared process of alloy powder by titanium powder and
titanium hydride powder were heated at 500 °C for 2 h and
then 600 °C for 3 h, and at 750 °C for 3 h, respectively, in
4.0 9 10-3 Pa vacuum conditions with heating rate of
5 °Cmin-1. The average content of oxygen in the alloy
powders is 0.33 wt%. The average grain sizes of prepared
alloyed powder are 45 and 20 lm with irregular shape,
respectively. The forming process of alloy powder contains
both the diffusion reaction of Ti and Al, which gives pri-
ority to the diffusion of Al.
Rare Met. (2018) 37(1):21–25
25
Acknowledgments This study was financially supported by the
National Natural Science Foundation of China (No. 51274039) and
the Guangdong Foundation of Research (No. 2011A090200091).
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