Journal of Alloys and Compounds 366 (2004) L9–L12

Letter
Effect of Al content on the self-propagating high-temperature synthesis
reaction of Al–Ti–C system in molten magnesium
H.Y. Wang a , Q.C. Jiang a,∗ , X.L. Li b , F. Zhao a
a Department of Materials Science and Engineering, Jilin University, Nanling Campus, No. 142 Renmin Street, Changchun 130025, PR China
b The Key Laboratory of Automobile Materials, Jilin University, Ministry of Education, No. 142 Renmin Street, Changchun 130025, PR China

Received 8 May 2003; received in revised form 15 July 2003; accepted 15 July 2003

Abstract

The effect of Al content on the self-propagating high-temperature synthesis (SHS) reaction of the Al–Ti–C preform in molten magnesium
was investigated. As the Al content in the preforms was increased over the range of 20–40 wt.%, the TiC particulate sizes decreased from ∼5.0
to ∼1.0 ␮m. Microstructural characterization of the TiC/Mg (AZ91D) composite showed relatively uniform distribution of TiC particulates
in the matrix material and the presence of minimal micro-porosity.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Magnesium; Composites; In situ; Self-propagating high-temperature synthesis (SHS) reaction; Aluminum content

1. Introduction fortunately, research efforts on the processing of in situ TiC

During the past decade, considerable research efforts have
been directed towards the development of in situ metal ma-
trix composites (MMCs), in which the reinforcements are
formed in situ by exothermal reactions among elements or
between an element and a compound [1,2]. Because of the
formation of clean, ultrafine and stable ceramic reinforce-
ments, the in situ MMCs exhibit excellent mechanical prop-
erties. In the field of the self-propagating high-temperature
synthesis (SHS), the Al–Ti–C system has been extensively
studied by a number of researchers, and it has been com-
monly considered to be a typical system widely used for
fabricating in situ MMCs [3–10].
The effect of aluminum addition on the SHS reaction be-
tween titanium and carbon to form TiC under an argon pro-
tective atmosphere has been extensively studied by Lee and
Chung [5] and Choi and Thee [6]; while less work has been
carried out on the reaction in molten magnesium. TiC par-
ticulate reinforced magnesium MMCs are very interesting
because TiC is thermodynamically stable and enhances the
hardness and wear resistance of the composites [10,11]. Un-
∗ Corresponding author. Tel.: +86-431-5705592;
fax: +86-431-5705592.
E-mail address: jiangqc@mail.jlu.edu.cn (Q.C. Jiang).
particulate reinforced magnesium MMCs are rather limited
[11,12].
In the present study, the effect of Al content on the SHS
reaction of the Al–Ti–C preform in molten magnesium was
investigated. The purpose of this study is to provide an opti-
mal process parameter for in situ formed TiC/Mg composite
production. It is expected that the preliminary results can be
significant in promoting the development of in situ synthesis
of TiC/Mg composites.
2. Experimental
The preforms in this study were made from commercial
powders of aluminum (98.0% purity), titanium (99.5% pu-
rity), and graphite (99.9% purity), all with an average parti-
cle size less than 44 ␮m. Titanium and carbon powders with
an atomic ration of 1:1 mixed with 10–50 wt.% aluminum
powder were used for the powder blends. After being suffi-
ciently mixed, the blends were pressed into cylindrical pre-
forms (20 mm diameter and 15 mm length) by using a stain-
less steel die with two plungers. The green preforms were
pressed uniaxially at pressures ranging from 70 to 75 MPa
to obtain densities of 75 ± 2% theoretical density. The pre-
forms were dried in a vacuum oven at 450 ◦ C for 3 h to
remove any trace of moisture. About 1 kg of commercial

0925-8388/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0925-8388(03)00737-0
L10 H.Y. Wang et al. / Journal of Alloys and Compounds 366 (2004) L9–L12

AZ91D magnesium alloy melts were prepared in a graphite

crucible in an electric resistance furnace at 760 ◦ C under a
SF6 /CO2 protective atmosphere. One hundred and twenty
grams of prepared preforms with a 10 wt.% Al content were
added into 1 kg sample of molten magnesium. After about
2 min, one of the preforms was removed from the melt and
water-quenched immediately. After about 10 min, the molten
magnesium was stirred with a graphite stirrer for 20 min to
assist the dispersion of the generated TiC particulates into
the molten magnesium. The preforms with various amounts
of aluminum (20–50 wt.%) were also carried out using steps
similar to those employed for the preforms of 10 wt.% Al. Fig. 2. XRD patterns of the water-quenched preforms fabricated by a
It should be noted that the preforms of 50 wt.% Al cannot SHS reaction in molten magnesium from the green preforms with a Ti/C
(molar ratio) = 1.0 mixed with (a) 10 wt.%, (b) 20 wt.%, (c) 30 wt.%,
be removed from the melt because the preforms had dis-
and (d) 40 wt.% Al.
persed into the molten magnesium in 2 min. The composite
melts were cast into a copper mold to produce ingots of Φ
55 mm × 100 mm. action in the melts was not observed. It was found that the
Microstructures and phases of the water-quenched pre- preforms of 50 wt.% Al had dispersed into the molten mag-
forms and composites were investigated by using scanning nesium in 2 min, and there was a substantial amount of un-
electron microscopy (SEM) (Model JSM-5310, Japan), reacted carbon that floated on the surface of the melts during
energy-dispersive spectral (EDS) (Model Link-Isis, Britain), stirring. Furthermore, a large amount of residual Ti (identi-
and X-ray diffraction (XRD) (Model D/Max 2500PC fied by XRD result) was found in the bottom of the melts
Rigaku, Japan). after stirring.
According to [12], the exothermic reaction that occurs in
molten magnesium is a SHS reaction with a simultaneous
3. Results and discussion combustion mode, since the exothermic reaction is initiated
throughout the entire preform by the heat of molten magne-
When the Al content was 20–40 wt.% in preforms, an sium.
exothermic reaction in the melts was observed immediately Figs. 1 and 2 show the SEM microstructures and XRD
after the preforms were added into the molten magnesium; patterns of the water-quenched preforms fabricated by a SHS
however, when the Al content was 10 or 50 wt.%, the re- reaction in molten magnesium from the green preforms with

Fig. 1. Typical SEM microstructures of the water-quenched preforms fabricated by a SHS reaction in molten magnesium from the green preforms with
a Ti/C (molar ratio) = 1.0 mixed with (a) 10 wt.%, (b) 20 wt.%, (c) 30 wt.%, and (d) 40 wt.% Al.
 H.Y. Wang et al. / Journal of Alloys and Compounds 366 (2004) L9–L12
a Ti/C (molar ratio) = 1.0 mixed with 10–40 wt.% Al, re-
spectively. According to the XRD patterns, the quenched
preform of 10 wt.% Al consists of Mg, TiAl, TiC, and resid-
ual Ti and C, as shown in Fig. 2(a). However, the preforms
of 20–40 wt.% Al consist of Mg, TiC and Al, as shown in
Fig. 2(b)–(d). Based on the results, it is believed that the TiC
formation reaction in the quenched preform did occur. The
presence of Mg phase in the quenched Al–Ti–C preforms
is attributed to the infiltration and diffusion of the molten
magnesium into the preforms.
According to [11,12], the addition of aluminum provides
an easier route for the TiC formation in the Al–Ti–C pre-
form. During the SHS process, the reactions between Al and
Ti to form TiAlx (TiAl, TiAl3 ) compounds occur initially,
which further react with C to form a more thermodynami-
cally stable TiC. In the present study, SEM and EDS results
indicate that the surface of Ti in the quenched preform of
10 wt.% Al is coated with a thin TiAl layer; in this case,
a slight reaction between TiAl and C to form TiC occurs
(identified by XRD result, shown in Fig. 2(a)). However, a
slight heat release by the reaction cannot further initiate the
SHS reaction and then dissipates into the molten magne-
sium. As the Al content is increased to 20–40 wt.%, the heat
release of reaction between Ti and Al per unit volume of the
preform is increased. When the rate of heat release exceeds
the rate of heat dissipation, further reaction can occur, and
then the heat liberated by the reaction can further raise the
temperature, facilitating a faster and faster reaction. As the
Al content is further increased to 50 wt.%, the preform has
dispersed into the molten magnesium before the exothermic
reaction is initiated owing to the aluminum melting. XRD
analysis shows that no TiAlx or TiC is found in the magne-
sium alloy, which confirms that the reaction did not occur.
Table 1 shows the effect of Al content in the Al–Ti–C
system on the TiC particulate sizes in the water-quenched
preforms fabricated by SHS in molten magnesium. The TiC
particulate sizes are decreased from ∼5.0 to ∼1.0 ␮m when
Al content in the preforms ranges from 20 to 40 wt.%. This
is attributed to the decrease of the combustion temperature
Fig. 3. Typical SEM microstructure of TiC/Mg (AZ91D) composite synthesized by a SHS reaction in molten magnesium for preforms with a Ti/C (molar
ratio) = 1.0 mixed with 30 wt.% Al.
L11
Table 1
Effect of Al content in the Al–Ti–C system on the TiC particulate sizes
in the water-quenched preforms fabricated by SHS in molten magnesium
Al content in the Al–Ti–C system (wt.%) TiC particulate size (␮m)
20 ∼5.0
30 ∼2.5
40 ∼1.0
because grain growth of TiC is an exponential function of the
combustion temperature [6]. In addition, Al phase serves as
a diluent and might prevent the diffusion of carbon between
TiC grains. It is reported that the grain growth of TiC in the
combustion reaction between Ti and C is controlled by the
C diffusion through TiC [5,6,13].
Although TiC is formed in the preforms of 20–40 wt.%
Al, it should be noted that it is difficult for TiC synthesized
in the preform of 20 wt.% Al to disperse into the molten
magnesium. The combustion temperature in the preform of
20 wt.% Al is higher than that in the preform of 30–40 wt.%
Al [5,6]; therefore, the TiC particulates formed in this case
are more densified and even sintered together. When 5 wt.%
Mg powder is added into the green preform with a Ti/C (mo-
lar ratio) = 1.0 mixed with 20 wt.% Al, the generated TiC
particulates can easily disperse into the molten magnesium
alloy [11]. Because 5 wt.% Mg also serves as a diluent and
assists the dispersion of the generated TiC particulates into
the molten magnesium.
Fig. 3(a) and (b) shows the SEM microstructure and XRD
pattern of the TiC (5 wt.%)/Mg (AZ91D) composite fabri-
cated by the SHS reaction of the preforms with a Ti/C (molar
ratio) = 1.0 mixed with 30 wt.% Al, respectively. The as-cast
microstructure of the in situ processed composite reveals
a relatively uniform distribution of TiC particulates with
a spherical size of ∼2.5 ␮m. Furthermore, microstructural
characterization also shows the absence of macro-pores and
blowholes; however, the presence of minimal micro-porosity
could be detected in the composite. It has been reported
that the composite was successfully synthesized in molten
L12 H.Y. Wang et al. / Journal of Alloys and Compounds 366 (2004) L9–L12
Table 2
Hardness and wear rates of the as-cast unreinforced AZ91D alloy and
TiC (5 wt.%)/AZ91D composite
Material Hardness (HB) Wear rates
(10−3 g/m)
AZ91D alloy 60 1.2088
TiC (5 wt.%)/AZ91D composite 80 0.8207
magnesium by the reaction of the preforms with a Ti/C (mo-
lar ratio) = 1.0 mixed with 40 wt.% Al [12].
Hardness and wear rates of the as-cast unreinforced
AZ91D alloy and TiC (5 wt.%)/AZ91D composite are listed
in Table 2. The sliding abrasive wear rates were tested
under loads of 5N using a pin-on-disc apparatus. Both the
unreinforced AZ91D alloy and the TiC (5 wt.%)/AZ91D
composite were used as pin materials with 6 mm diameter
and 12 mm height, and 1000 mesh SiC abrasive papers were
used as the counterface. It is clear that the hardness and the
wear resistance of the TiC (5 wt.%)/AZ91D composite are
higher than those of the unreinforced AZ91D alloy as ex-
pected. Improvement of the hardness and wear resistance of
the composite must from the presence of TiC particulates.
4. Conclusions
The effect of Al content on the self-propagating
high-temperature synthesis reaction of the Al–Ti–C pre-
forms in molten magnesium was investigated. The TiC par-
ticulate sizes were decreased from ∼5.0 to ∼1.0 ␮m when
Al content in the preforms ranged from 20 to 40 wt.%. In
situ formed TiC/Mg composite utilizing the SHS reaction of
molten magnesium and Al–Ti–C preforms with a 30 wt.%
Al content was synthesized successfully. Microstructural
characterization showed relatively uniform distribution of
TiC particulates in the matrix material and the presence of
minimal micro-porosity. The hardness and wear resistance
of the TiC (5 wt.%)/AZ91D composite were higher than
those of the unreinforced AZ91D alloy.
Acknowledgements
This work is supported by the National Natural Science
Foundation of China (No. 50171029) and the Nanoscience
Foundation of Jilin University (No. 2001NM004).
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