Journal of Alloys and Compounds 379 (2004) L4L7

Letter
In situ synthesis of TiB
2
/Mg composite by self-propagating
high-temperature synthesis reaction of the AlTiB
system in molten magnesium
H.Y. Wang
a
, Q.C. Jiang
a,
, Y.G. Zhao
a
, F. Zhao
b
a
Department of Materials Science and Engineering, Jilin University at Nanling Campus,
No.142 Renmin Street, Changchun 130025, PR China
b
The Key Laboratory of Automobile Materials, Ministry of Education, Jilin University,
No.142 Renmin Street, Changchun 130025, PR China
Received 28 January 2004; received in revised form 17 February 2004; accepted 17 February 2004
Abstract
The synthesis of in situ formed TiB
2
/Mg composite utilizing the self-propagating high-temperature synthesis (SHS) reaction that occurred
between the molten magnesium and green preforms consisting of Al, Ti and B powders was investigated. The result shows that it is feasible
that the smelting temperature of the magnesium matrix alloy is selected at 860

C, which is slightly higher than the exothermic reaction

temperature of 852

C on the DTA curve, prepared for the SHS reaction in the AlTiB system. An as-cast microstructure of the composite
reveals a relatively uniform distribution of TiB
2
particulates with hexagonal or rectangular size of 2.0 m. Furthermore, an analysis of the
powders extracted from the TiB
2
/Mg composite conrms that a small amount of blocky TiAl
3
phase is also present in the composite.
2004 Elsevier B.V. All rights reserved.
Keywords: Magnesium; Composites; In situ; Self-propagating high-temperature synthesis (SHS) reaction; Particulate
1. Introduction
Particulate reinforced aluminum and magnesium metal
matrix composites (MMCs) have a great potential to be
applied in automobile and aerospace industries because of
their high specic tensile strength and modulus, as well
as their high wear resistance [13]. Traditionally, MMCs
have been produced by various processing techniques such
as powder metallurgy, preform inltration, spray deposi-
tion, casting technologies, i.e. squeeze casting, rheocast-
ing and compocasting [19]. In all the above techniques
the reinforcing second-phase particulates (including car-
bides, borides, oxides, nitrides, etc.) are combined with
the matrix material (either in molten or powder form) by
ex situ methods. In this case, the scale of the reinforc-
ing phase is limited by the starting powder size, which is
typically of the order of micrometers to tens of microme-
ters and rarely below 5 m [10]. Other main drawbacks

Corresponding author. Tel.: +86-431-5705592;

fax: +86-431-5705592.
E-mail address: jiangqc@mail.jlu.edu.cn (Q.C. Jiang).
that have to be overcome are the interfacial reaction and
poor wettability between the reinforcements and the ma-
trices due to surface contamination of the reinforcements
[1012].
To overcome the inherent problems that are associated
with conventionally processed MMCs, new in situ process-
ing techniques have been developed, in which the reinforce-
ments are in situ synthesized in a metallic melt by chemical
reactions among elements or between an element and a
compound during the composite fabrication [11,12]. Some
of these technologies include directed melt/metal oxidation
(DIMOX), exothermic dispersion (XD), self-propagating
high-temperature synthesis (SHS), ux-assisted synthesis
(FAS), vaporliquidsolid (VLS) reaction and mechanical
alloying (MA) [1318]. Compared with the conventional
MMCs produced by ex situ methods, the in situ MMCs
exhibit the following advantages: (a) the in situ formed
reinforcements are thermodynamically stable at the matrix,
leading to less degradation in elevated-temperature service;
(b) the reinforcement-matrix interfaces are clean, resulting
in a strong interfacial bonding; and (c) the in situ formed re-
inforcing particulates are ner in size and their distribution
0925-8388/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2004.02.036
H.Y. Wang et al. / Journal of Alloys and Compounds 379 (2004) L4L7 L5
in the matrix is more uniform, yielding better mechanical
properties [1113].
Titanium diboride (TiB
2
) ceramic particulate possesses
many desirable properties, such as high hardness, low den-
sity, high melting temperature, high modulus and high cor-
rosion resistance [4]. These outstanding features portray it
to be a good potential reinforcing candidate in aluminum
and magnesium matrixes. In the past decade, however, many
of the studies have been focused on in situ TiB
2
particulate
reinforced Al MMCs due to the availability and relatively
low fabrication cost [4,15,1930], while less work has been
carried out on Mg MMCs [16,17].
More recently, AlTiB as a typical system in the
eld of SHS reaction to synthesize TiB
2
particulate has
been extensively studied by a number of researchers
[11,15,18,22,26,3032]; however, existing studies agree that
there is a lack of understanding of the reaction mechanisms
[11]. In our previous study [32], a TiB
2
/Mg composite has
been successfully fabricated by a master alloy route, a high
volume fraction TiB
2
Al master alloy being synthesized via
SHS reaction in AlTiB system and subsequently added
to a Mg alloy melt. Unfortunately, research effort on the
processing of in situ formed TiB
2
/Mg composite by a SHS
reaction in molten magnesium is rather limited.
In the present study, the feasibility of in situ synthesis of
TiB
2
/Mg composite utilizing the SHS reaction of the green
preforms consisting of Al, Ti and B powders in molten mag-
nesium alloy was investigated. The purpose of this study is
to develop a simplied casting process route to produce a
ne TiB
2
particulate reinforced magnesium alloy composite.
2. Experimental
The starting materials were made from commercial pow-
ders of 50 wt.% Al (98.0% purity, 29 m), 34.5 wt.% Ti
(99.5% purity, 15 m) and 15.5 wt.% B (98.0%, 3 m).
Titanium and boron powders were at a ratio corresponding
to that of stoichiometric TiB
2
. Powder blends were prepared
by ball milling for 8 h, and then were cold-isostatically
pressed into cylindrical preforms (20 mm diameter and
15 mm length) at pressures ranging from 7075 MPa to ob-
tain densities of 70 2% theoretical density. The preforms
were dried in a vacuum oven at 100

C for 3 h to remove
any trace of moisture. Processing of the in situ TiB
2
/Mg
composites consists of adding the prepared preforms to
molten magnesium, slurry stirring and casting.
Based on the chemical compositions of AZ91 alloy
(Mg9% Al1% Zn), commercial pure Mg, Al and Zn were
selected to prepare the matrix. About 1 kg of pure magne-
sium melt was prepared at predetermined temperature in
a steel crucible in an electric resistance furnace of 5 kW
under an argon protective atmosphere. The desired amounts
of alloying elements and 100 g of prepared green preforms
were added into the 1 kg of molten magnesium. After about
10 min, the molten magnesium alloy was stirred at 600 rpm
for 20 min using a graphite impeller to facilitate the incor-
poration and uniform distribution of the generated TiB
2
particulates in the metallic matrix. The composite melt was
cast into a copper mold to produce ingots of 55100 mm.
The SHS reaction temperatures and products were studied
by differential thermal analysis (DTA) (Model Rigaku-8150,
Japan) and X-ray diffraction (XRD) (Model D8 DIS-
COVER, Germany). Microstructure and phase analyses of
the composite were investigated by using scanning electron
microscopy (SEM) (Model JSM-5310, Japan) equipped
with energy-dispersive spectrum (EDS) (Model Link-Isis,
Britain) and XRD (Model D/Max 2500PC Rigaku, Japan).
3. Results and discussion
To study the SHS reaction temperatures of the AlTiB
system, 35 mg reactant mixtures with a molar ratio of Ti/B =
1:2 mixed with 50 wt.% Al are heated at 20

C/min to about
1100

C under an argon atmosphere in the DTA apparatus,

and the result is shown in Fig. 1. The DTA curve indicates
only one endothermic peak with the minimum at 660

C,
which corresponds to the melting of aluminum. Furthermore,
there are three exothermic peaks with maximums at 636, 852
and 1008

C, respectively. It is interesting to note that the

exotherm of 636

C is a solid state reaction, which may cor-

respond to a reaction between solid Al and solid B to form
solid AlB
2
. This result is in agreement with [29]. To develop
an understanding of the exothermic reaction of 852

C, the
AlTiB mixtures were heated to 852

C and quenched im-

mediately in the DTA apparatus, and the XRD pattern of the
products is shown in Fig. 2. According to XRD result, the
DTA products consist of TiB
2
, TiAl
3
, AlB
2
and Al, indicat-
ing the TiB
2
has been formed during the exothermic reaction
of 852

C. However, XRD analysis also reveals that the -

nal products (1100

C) of DTA consist of the similar phases

compared with that of exotherm of 852

C. As a result, it is
difcult to deduce a reaction that occurred in the exotherm
of 1008

C. Further work is continuing in this area.

Based on DTA result, the smelting temperature of matrix
alloy is selected at 860

C, slightly higher than the exotherm

Fig. 1. DTA curve of the AlTiB system with a molar ratio of Ti:B = 1:2
mixed with 50 wt.% Al.
L6 H.Y. Wang et al. / Journal of Alloys and Compounds 379 (2004) L4L7
Fig. 2. XRD pattern of the DTA products of the AlTiB system with a
molar ratio of Ti:B = 1:2 mixed with 50 wt.% Al.
temperature of 852

C. When the green preform was added

into the molten magnesium, an exothermic reaction in the
melts was immediately observed as expected. According to
[13,33], the exothermic reaction that occurs between pre-
from and molten magnesium is a SHS reaction.
Fig. 3(ad) show the SEM microstructures, XRD pattern,
and EDS analysis of TiB
2
/Mg composite fabricated by the
SHS reaction of AlTiB system in molten magnesium, re-
spectively. As-cast microstructures (Fig. 3(a and c)) of the
in situ processed composite reveal a relatively uniform dis-
tribution of TiB
2
particulates with hexagonal or rectangular
size of 2.0 m. Furthermore, microstructural characteriza-
tion also shows the absence of macro- and micro-pores in the
composite, while they are always detected in the composite
Fig. 3. (a) SEM microstructure of TiB
2
/Mg composite fabricated by the SHS reaction of the AlTiB system (with a molar ratio of Ti:B = 1:2 mixed
with 50 wt.% Al) in molten magnesium, (b) XRD pattern of the composite, (c) magnication of TiB
2
particulates, and (d) EDS analysis of TiB
2
.
fabricated by the ex situ method. In addition to the major Mg
phase and TiB
2
particulate, the Mg
17
Al
12
() eutectic phase
is also detected in the composite by the XRD; however, the
presence of TiAl
3
phase cannot be identied by the XRD
(Fig. 3(b)) due to its low intensity. It is worth noting that a
small amount of TiAl
3
akes should be present in the com-
posite, since it is difcult to avoid it in the AlTiB system
synthesized by the SHS reaction [15,22,26,31,32], as de-
tected in the DTA products (Fig. 2). It will be discussed later.
Furthermore, the magnication and EDS analysis of TiB
2
particulates reveal that no oxygen is detected on the particu-
late surfaces, as shown in Fig. 3(c and d), indicating the in-
terface between the in situ formed TiB
2
and matrix is clean.
In order to conrm the presence of the TiAl
3
phase, the
TiB
2
particulate and TiAl
3
phase were extracted by dissolv-
ing the Mg matrix by using a 3638% hydrochloric acid
solution. The SEM microstructure and EDS analysis of the
TiB
2
and TiAl
3
powders extracted from the TiB
2
/Mg com-
posite are shown in Fig. 4(a and b), respectively. As ex-
pected, the results reveal the blocky TiAl
3
phase to be present
in the composite. This may have a harmful effect on the
property of the composite due to its brittleness [4,20].
Based on the above experimental results, the overall reac-
tion that occurred during the SHS reaction in the AlTiB
system in molten magnesium might take place as follows:
(x +3)Al +2Ti +2B TiB
2
+TiAl
3
+xAl (1)
H.Y. Wang et al. / Journal of Alloys and Compounds 379 (2004) L4L7 L7
Fig. 4. (a) SEM microstructure and (b) EDS analysis of the TiB
2
and TiAl
3
powders extracted from TiB
2
/Mg composite by using a 3638% hydrochloric
acid solution.
It has been reported that the TiAl
3
phase can be effectively
suppressed by the incorporation of an appropriate amount
of C or an excess of B into the AlTi (TiO
2
)B system
[4,20,28,31]. Further work is continuing in order to com-
pletely eliminate the brittle TiAl
3
phase in the in situ formed
TiB
2
/Mg composite.
4. Conclusion
DTA result of the AlTiB system with a molar ratio of
Ti:B = 1:2 mixed with 50 wt.% Al reveals that TiB
2
has
been formed during the exothermic reaction of 852

C; based
on DTA, therefore, it is feasible that the smelting temperature
of the magnesium matrix alloy is selected at 860

C for the
SHS reaction in the AlTiB system.
An in situ formed TiB
2
/Mg composite was successfully
fabricated by utilizing the SHS reaction that occurred be-
tween the molten magnesium and green preforms consisting
of Al, Ti and B powders. An as-cast microstructure of the
composite reveals a relatively uniform distribution of TiB
2
particulates with hexagonal or rectangular size of 2.0 m.
Furthermore, an analysis of the powders extracted from the
TiB
2
/Mg composite conrms that a small amount of blocky
TiAl
3
phase is also present in the composite.
Acknowledgements
This work is supported by the National Natural Sci-
ence Foundation of China (No. 50171029 and 50371030)
and the Nanoscience Foundation of Jilin University (No.
2001NM004).
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