Powder Metallurgy

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Characterisation of in situ Al–TiB2 nanocomposite

powder synthesised by mechanical alloying

Z. Sadeghian, M. H. Enayati & P. Beiss

To cite this article: Z. Sadeghian, M. H. Enayati & P. Beiss (2011) Characterisation of in situ
Al–TiB2 nanocomposite powder synthesised by mechanical alloying, Powder Metallurgy, 54:1,
46-49

To link to this article: http://dx.doi.org/10.1179/174329009X409615

Published online: 12 Nov 2013.

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 Characterisation of in situ Al–TiB2
nanocomposite powder synthesised by
mechanical alloying
Z. Sadeghian*1,2, M. H. Enayati1 and P. Beiss2
Production of in situ Al–TiB2 nanocomposite powder was studied using mechanical alloying (MA).
Two approaches were used to obtain Al–20TiB2 (wt-%) nanocomposite powder. In the first
approach the synthesis of Al–20TiB2 (wt-%) was investigated by ball milling an elemental Al–Ti–B
powder mixture. The second approach involved a double step milling procedure to achieve an
Al–20TiB2 (wt-%) composite powder. The microstructure of as milled powder particles was
investigated by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The thermal
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behaviour of MA powders was studied by differential scanning calorimetry (DSC). From these
studies it was possible to conclude that TiB2 can be formed in situ using the second approach
without the production of undesirable phases; however, the first approach tends to form an
undesirable Al3Ti intermetallic phase in addition to the TiB2 ceramic reinforcement.
Keywords: Nanocomposite powder, Al–TiB2, Mechanical alloying, Thermal stability

Introduction collisions to cold draw and fracture particles repeat-

TiB2 as a refractory compound is an attractive
reinforcement for a range of applications including high
temperature components as it possesses a high modulus,
excellent refractory properties and chemical inertness.1
TiB2 is particularly suitable as a reinforcing phase for Al
based composites because of its thermodynamic stabi-
lity. It also presents high resistance to plastic deforma-
tion even at high temperatures.2–5
During the last decade, in situ metal matrix compo-
sites (MMCs) have been developed,6 in which the
reinforcements are synthesised in the metal matrix
during fabrication by chemical reactions of the consti-
tuents. In comparison to traditionally fabricated materi-
als, in situ MMCs undergo less degradation at high
temperatures. This is because of their superior thermo-
dynamic stability, stronger interface bonding resulting
from the clean reinforcement/matrix interfaces and finer
and more uniform distribution.7 Because of the wide
range of potential applications of these materials, the
structure and properties of the in situ ceramic phase
needs to be optimised over a variety of processing
techniques.6,7 These techniques include exothermic
dispersion (XDTM), reactive gas injection, reactive
sintering, reactive milling and mechanical alloying
(MA). Mechanical alloying is a solid state powder
processing method which uses high energy ball sample
1
Department of Materials Engineering, Isfahan University of Technology,
Isfahan, 84156-83111, Iran
2
Institute for Materials Applications in Mechanical Engineering, RWTH
Aachen University, 52062 Aachen, Germany
*Corresponding author, email z.sadeghian@iwm.rwth-aachen.de
edly.8 In recent years, the MA technique has been
considered for fabricating in situ MMCs. In situ
fabrication of TiB2 reinforced MMCs by the MA
process has been investigated in a few studies.9,10
It has been reported that an Al3Ti compound has
formed during the in situ production of Al– TiB2
composites as an undesirable byproduct. This was
detected in several different techniques including casting
and reactive pressing.11,12 The MA of the elemental Al,
Ti and B powders also led to the formation of Al3Ti
after subsequent annealing. Al3Ti intermetallic is a
brittle phase and is known to reduce the fatigue life of
composites considerably. This is owing to the generation
of microscopic cracks during cyclic deformation.13
Because of its undesirable characteristics the production
of this Al3Ti phase during the fabrication process needed
to be eliminated.
This study investigates the synthesis of TiB2 rein-
forced Al matrix composites by mechanical alloying via
an in-situ method. Additionally, the effect of the initial
aluminium content on the final microstructure and
elimination of unwanted phases is discussed.
Experimental procedure
Materials and methods
Elemental powders of Al (99?8%, 63 mm), Ti (99?9%, 40–
60 mm) and B (.99%, 2 mm) were used as starting
materials. A Fritsch planetary ball mill with a rotating
speed of 360 rpm was used for ball milling. The ball/
powder weight ratio was 10 and the diameter of the
chromium steel balls was 15 mm. The chromium steel
ball mill vessel was evacuated and filled with argon to

ß 2011 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 4 November 2008; accepted 13 January 2009
46 DOI 10.1179/174329009X409615 Powder Metallurgy 2011 VOL 54 NO 1
 Sadeghian et al. Characterisation of in situ Al–TiB 2 nanocomposite powder

a as received; b as milled for 40 h

1 Patterns (XRD) of Al–13?8Ti–6?2B (wt-%) powder mixture

prevent oxidation during the mechanical alloying

process. To avoid severe adhesion of aluminium powder
to the balls and the vessel, 1 wt-% zinc stearate was
added to the mixture as a process control agent.
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Two different approaches were used to produce Al–

20TiB2 (wt-%) nanocomposites. These are summarised
in Table 1. The first approach aimed to synthesise the
Al–TiB2 composite powder by mechanical alloying of a
Al–13?8Ti–6?2B (wt-%) powder mixture. In the second
approach a double step process was used to obtain Al–
TiB2 metal matrix powder. In the first step Ti and B
powders were milled with a small amount of aluminium
powder. The composition of the powder was Al–62Ti–
28B (wt-%). The product of this first stage was then
subjected to further milling with additional aluminium
powder to achieve the Al–20TiB2 (wt-%) composition.
Characterisation
A SEIFERT 30033 PTS diffractometer employing
monochromatic Cu Ka1 radiation (l50?15406 nm) was
used to measure structural changes during mechanical
alloying. XRD scans were performed with a step size of 2 a cross-sectional SEM micrograph of Al–13?8Ti–6?2B
0?05u in 2h and a dwell time per step of 20 s. The cross- (wt-%) powder particle milled for 40 h using route 1, b
sectional microstructure of the powder particles was and c show EDS analysis of dark and bright areas
studied using a LEO 1450 VP scanning electron respectively
microscope (SEM). The thermal behaviour of as milled
powder was measured using differential scanning
of lattice strains during mechanical alloying.8 Neither
calorimetry (DSC) on Netzsch 402 equipment under
the titanium nor the aluminium peak shifted during ball
flowing Ar gas.
milling. This suggested that no Ti in Al solid solution
was formed. While the equilibrium solubility of Ti in Al
Results and discussion at room temperature is negligible, the solubility of Ti in
Figure 1 shows the XRD patterns of the Al–13?8Ti– the Al lattice can be increased up to y3 wt-% using
6?2B (wt-%) powder mixture obtained from the first MA.14
route. The XRD patterns of the as mixed powder show A typical powder particle microstructural cross-
peaks of elemental Al and Ti. The absence of boron section obtained from the first route is shown in
XRD peaks is due to its amorphous structure. After Fig. 2a. This was after 40 h of ball milling. The EDS
40 h of milling the width of Ti and Al peaks increased analysis revealed that the small dark areas in the Al
and their intensities reduced. This is due to the matrix were boron rich phases, while the white layers
refinement of the crystalline size and the enhancement were titanium rich remnants (Fig. 2b and c).
Table 1 Milling routes used for producing Al–20TiB2 (wt-%)

First step Second step

Composition Milling time Composition Milling time

First route Al–13.8Ti–6.2B (wt-%) 40 h – –

Second route Al–62Ti–28B (wt-%) 20 h Al–22.2premilled powder (wt-%) 20 h

Powder Metallurgy 2011 VOL 54 NO 1 47

 Sadeghian et al. Characterisation of in situ Al–TiB 2 nanocomposite powder
3 Trace (DSC) of Al–13?8Ti–6?2B (wt-%) powder obtained
from first route
In order to evaluate the thermal behaviour of Al–
13?8Ti–6?2B (wt-%) powder particles obtained by the
first route, powders were heated up to 550uC in DSC.
The DSC trace exhibited two exothermic peaks at 350
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and 450uC and a weak peak at 190uC. These are shown
in Fig. 3. In comparison with the as milled powder the
XRD pattern of powder after being heated to 210uC
suggested no structural changes had taken place
(Fig. 4b). Therefore, the weak peak at 190uC was
probably caused by elimination of crystal defects. The
XRD pattern of the powder taken after being heated
up to 400uC (Fig. 4c) revealed a new phase which could
not be attributed to any known phase in the Al–Ti–B
system. This could be a metastable phase. Heating up
to 550uC resulted in the development of Al3Ti
(Fig. 4d). Lu et al. also observed the Al3Ti phase after
annealing ball milled Al–Ti–B powder at 450uC.15 The
formation enthalpies of TiB2 and Al3Ti at room
temperature are 2323?6 and 275?31 kJ/mol respec-
tively, suggesting that the Ti–B reaction is thermo-
dynamically more favourable than the Al–Ti reaction.
However, the presence of the large fraction of Al in the
initial powder mixture seems to have limited the
interdiffusion of Ti/B and therefore the formation of
the TiB2.
Figure 5 shows the XRD patterns of Al–62Ti–28B
and Al–20TiB2 (wt-%) powders obtained by the second
route. After 10 h of milling, peaks of TiB2 appeared on
the XRD pattern (Fig. 5b). No peak shift was observed
a as milled for 40 h; b after annealing in DSC up to
210uC; c up to 400uC; d up to 550uC
4 Patterns (XRD) of Al–13?8Ti–6?2B (wt-%) powder mixture
48 Powder Metallurgy 2011 VOL 54 NO 1
a as received; b as milled for 10 h; c as milled for 20 h;
d Al–90TiB2 (wt-%) powder obtained by first step plus
20 h ball milling with addition of elemental Al powder
5 Patterns (XRD) of Al–62Ti–28B (wt-%) powder mixture
for titanium and aluminium, which indicates that no
solid solution formed during ball milling.
Figure 5c shows that the XRD peaks of elemental Ti
and Al disappeared after 20 h of milling. It should be
noted that no traces of the undesirable Al3Ti inter-
metallic phase were observed on the XRD pattern. The
disappearance of the aluminium peaks can be explained
by the high lattice strain induced in the Al lattice and by
the relatively small volume fraction of aluminium
(y13 vol.-%) in the powder. Comparison of these
results with the XRD data obtained from the first route
suggests that the lower Al content in the initial powder
mixture promoted the formation of TiB2 in the matrix.
Lü et al. also reported that TiB2 could not be detected
during the ball milling of Al–Ti–B mixtures even after a
milling time of 40 h.15
After 20 h ball milling, elemental aluminium powder
was added to the premilled Al– 62Ti–B (wt-%) powder.
Ball milling continued for another 20 h to achieve Al–
20TiB2 (wt-%) composition. As can be seen in Fig. 5d no
structural change occurred in the powder except some
broadening of XRD peaks. This was attributed to the
refinement of crystal size and enhancement of lattice strain.
Figure 6a shows a typical cross-section of a final Al–
20TiB2 (wt-%) powder particle after a total milling time
of 40 h. The EDS analysis showed that these particles
were TiB2 phase (Fig. 6b). A fine and uniform distribu-
tion of TiB2 particles within the aluminium matrix was
achieved. Higher SEM magnification of the powder
(Fig. 7) revealed that most of the TiB2 particles have a
size ranging from several nanometres to 100 nm. Only a
few particles are in the range of 500 nm to 1 mm.
The DSC trace of powder particles after a total
milling time of 40 h (Fig. 8) showed no exothermic peak
up to 550uC. Furthermore, XRD patterns taken after
the DSC run remained unchanged when compared with
that of the as milled powder (Fig. 9b). No traces of
undesirable phases such as Al3Ti were observed from
XRD patterns after heating in DSC.
These results show that by adding the aluminium in
two stages it is possible to prevent the formation of
undesirable compounds even when exposed to high
temperatures. The resulting Al–TiB2 nanocomposite
powder is expected to have good thermal stability
during subsequent consolidation processes.
 Sadeghian et al. Characterisation of in situ Al–TiB 2 nanocomposite powder

8 DSC trace of final Al–20TiB2 (wt-%) powder obtained by

second route after total milling time of 40 h
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6 a typical cross-sectional SEM micrograph of final Al–

20TiB2 (wt-%) powder particle obtained by second route
after total milling time of 40 h; b EDS analysis of bright
particles

Conclusions
Al–TiB2 nanocomposite material was obtained by
mechanical alloying of elemental powders. By reducing
the fraction of Al in the starting powder mixture and
using a two step milling method it was possible to
produce Al–TiB2 nanocomposite while avoiding the
production of an undesirable Al3Ti intermetallic com-
pound. The resultant Al–TiB2 nanocomposite powder
exhibited good thermal stability which made it suitable
for subsequent consolidation.
7 High magnification SEM micrograph of final Al–20TiB2
(wt-%) powder particle obtained by second route after
total milling time of 40 h
a as received; b final Al–20TiB2 (wt-%) powder obtained
by second route following annealing in DSC up to 550uC
9 Patterns (XRD) of Al–62Ti–28B (wt-%) powder mixture
Acknowledgements
Sadeghian’ sincere thanks go to the Deutscher
Akademischer Austauschdienst (DAAD) for supporting
the project.
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