Advanced Powder Technology 25 (2014) 16931698

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

Synthesis and characterization of Al (Al2O3TiB2/Fe) nanocomposite

by means of mechanical alloying and hot extrusion processes
Sh. Rizaneh, G.H. Borhani, M. Tavoosi
Department of Material Science, Malek-Ashtar University of Technology, Shahin-Shahr, Isfahan, Iran

a r t i c l e

i n f o

Article history:
Received 21 April 2014
Received in revised form 2 June 2014
Accepted 19 June 2014
Available online 12 July 2014
Keywords:
Al-base nanocomposite
Complex reinforcement
Mechanical alloying
Hot extrusion

a b s t r a c t
Synthesis and characterization of Al(Al2O3TiB2/Fe) nanocomposite by means of mechanical alloying
and hot extrusion processes was the goal of this study. For this regards, mechanical alloying was done
in two steps; formation of Al2O3TiB2/Fe reinforcements and preparation of Al-base nanocomposite.
Results showed that Al2O3TiB2/Fe nanocomposite powders can synthesis by mechanical alloying and
subsequent heat treatment at 700 C. Hot extrusion of powder samples lead to preparation of fully dense
Al-base nanocomposite. With increasing the amount of complex reinforcements, the compression
strength was increased and reached to 560 MPa. Consolidated samples show good ductility related to
the nature of Al2O3TiB2/Fe reinforcements.
2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction
Aluminum-based metal matrix composites (MMCs) have
emerged as an important class of high performance material for
use in aerospace, automobile, chemical and transportation industries due to their high specic modulus and strength, low density,
superior wear and creep resistances [1,2]. Reinforcing the ductile
aluminum matrix with stronger and stiffer second-phase reinforcements provides a combination of properties of both the aluminum matrix and the reinforcement components [3].
Different reinforcement particles such as aluminides (Al4Mo,
Al3Ti, Al3Zr), carbides (SiC, TiC, ZrC), nitrides (AlN, Si3N4), oxides
(Al2O3, SiO2) and borides (TiB2, ZrB2) have been incorporated in
Al MMCs by various methods [16]. Among these reinforcements,
TiB2 comes into prominence with its excellent properties such as
high melting point (3225 C), high hardness (25 GPa), superior
wear resistance, high electrical conductivity and considerable
chemical stability [715]. Recently, new group of TiB2 base composite (multiple complex TiB2-ceramic-metallic component), such
as TiB2TiC/Ni [16], TiB2Al2O3/Al [17], TiB2TiC/Fe [18,19], have
been developed. This new group of composite could be a good candidate for using as reinforcement for improving the mechanical
properties of Al MMCs. It seems that, the ceramic components in
these reinforcements increase the strength and thermal stability
and the metallic component increases the ductility of produced
composite.
Corresponding author.
E-mail address: m.Tavoosi@ma.iut.ac.ir (M. Tavoosi).

Al based MMCs can be fabricated via various techniques such as

reactive squeeze casting and rapid solidication processing, exothermic dispersion, reactive hot pressing, self propagating high
temperature synthesis (SHS) and mechanical alloying (MA).
Mechanical alloying is a solid-state powder processing technique
involving repeated deformation, welding and fracturing of powder
particle. MA has been widely used to synthesize a variety of materials, such as amorphous alloys, nanocrystalline materials, intermetallic compounds, borides, carbides, nitrides and composites.
In almost all cases, the nal product has nanosized structure which
exhibits better properties and performance compared to the conventional coarse-grain materials [2022].
In the present study, Al matrix composite reinforced with complex Al2O3TiB2/Fe particles were fabricated via mechanical alloying
and hot extrusion processes. The effects of complex reinforcement
on the microstructure and mechanical properties of produced composites were investigated.
2. Experimental procedures
The powders of aluminum (99.5% purity, average particle size
45 lm,), ferrotitanium (0.8 wt%Ti0.2 wt%Fe, average particle size
60 mm), and B2O3 (99% purity, average particle size 45 lm) were
used as raw materials. The stoichiometric powders mixture
according to reaction (1) was milled in an attrition ball mill using
hard chromium steel vial and balls, under argon atmosphere. MA
was done with rotation speed of 365 rpm for predetermined hours
without interruption and ball to powder ratio was 10:1. The vial
temperature was maintained at ambient temperature using of

http://dx.doi.org/10.1016/j.apt.2014.06.016
0921-8831/ 2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

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Fig. 1. The XRD patterns of Al, ferrotitanium (Fe and Ti) and B2O3 powder mixture
after different milling times.

Fig. 4. The SEM micrographs of Al, ferrotitanium (Fe and Ti) and B2O3 powder
mixture after 20 h of milling and annealing at 700 C for 90 min.

Fig. 2. The DTA curve of Al, ferrotitanium (Fe and Ti) and B2O3 powder mixture after
20 h of milling process at a constant heating rate of 20 C/min.

Fig. 5. The XRD patterns of Al-base composite with 1.25, 2.5 and 5 vol% of produced
reinforcement (Al2O3TiB2/Fe) after 10 h of milling.

Fig. 3. The XRD patterns of Al, ferrotitanium (Fe and Ti) and B2O3 powder mixture
after 20 h of milling and annealing at 700 C for 90 min.

water circulating system. Stearic acid powder (1 wt%), supplied by

Merck was used as the process control agent (PCA). In order to formation of nal nanocomposites, Al powders were milled with 1.25,
2.5 and 5 vol% of produced reinforcements (Al2O3TiB2/Fe) in a
same condition for 10 h. The produced composite powders with
different vol% of the reinforcements were consolidated with hot
extrusion process (the extrusion ratio, rate and temperature was
about 6:1, 5 mm/s and 500 C, respectively).

Fig. 6. The morphological micrographs of Al-base composite with (a) 1.25, (b) 2.5
and (c) 5 vol% of produced reinforcement (Al2O3TiB2/Fe) after 10 h of milling.

2Al 0:8Ti  0:2Fe 0:8B2 O3

! 0:8TiB2 0:8Al2 O3 0:2Fe

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Table 1
Characteristics of Al (Al2O3TiB2/Fe) nanocomposites after 10 h of milling.
Sample

Al2O3TiB2/Fe (vol%)
Al2O3

TiB2

Fe

1.25
0.75

0.45

0.05

2.5
1.5

0.9

0.1

5
3

1.8

0.2

2
3

Particle size (lm)

Crystallite size (nm)

Microhardness (Hv)

43

40

110

39

40

150

41

40

160

X-ray diffractometry (Philips diffractometer (40 kV) with Cu Ka

radiation) was used to follow the structural changes of samples
during milling and extrusion processes. The XRD patterns were
recorded in 2h range of 10110 (step size: 0.05; time per step
1 s). The crystallite size of produced samples was estimated by analyzing broadening of XRD peaks using Scherrer formula [23]. Microstructural characterizations of synthesized samples were carried
out by scanning electron microscopy (SEM) (Seron AIS-2100, Korea)
at an accelerating voltage of 20 kV. Differential thermal analysis
was done by using Rhemometric STA 1500 differential thermal analyzer. The sample was placed in Al2O3 pans and heating in Ar atmosphere up to 1000 C at heating rate 20 C/min. The compression
test was done according to ASTM E9. The Archimedes technique
was also used to measure the density of consolidated samples.
3. Results and discussion
3.1. Production of Al2O3TiB2/Fe nanocomposite
In fact, Al2O3TiB2/Fe nanocomposite can be synthesized by a
displacement reaction of Al, ferrotitanium and boron oxide according to reaction (1). The Gibbs free energy and enthalpy changing of
this reaction at ambient temperature were about 579 and
600 kJ/mol, respectively. These points illustrated that this
reaction is highly exothermic and can thermodynamically occurs
at room temperature [2022].
The XRD patterns of powder mixture (according to reaction
(1)) after different milling times are shown at Fig. 1. It can be
seen that, in the early stage of milling, only broadening of the
Al, ferrotitanium (Fe and Ti) and B2O3 peaks accompanied with
remarkable decrease in their intensities occurred as a result of
renement of crystalline size and enhancement of lattice strain.
Increasing milling time to 10 h, led to the disappearance of Fe
and Ti peaks. This can be due to the partial dissolution of Fe
and Ti in Al lattice as well as grain boundaries. Another possibility
is that these elements could disappear into the Al as very small
isolated particles which are virtually undetectable by XRD [21].
The results shows that, by milling the powder mixture up to
20 h, gradual grain renement is the only considerable change
that occurs in the powder mixture, and no detectable reaction
takes place.
Fig. 2 has shown the DTA curve of Al, ferrotitanium (Fe and Ti)
and B2O3 powder mixture after 20 h of milling process at a
constant heating rate of 20 C/min. As seen in this gure, only
one exothermic peak appears in the DTA curve at 650 C. To
analyze the reaction responsible for the exothermic peak, the
produced powder sample was annealed in an argon atmosphere
at 700 C for 90 min. The XRD pattern of annealed sample is presented in Fig. 3. As seen, the annealed sample is composed of the
Al2O3, TiB2 and Fe phases. Therefore, the exothermic peak in
Fig. 3 should be attributed to the formation of these phases from
the milled powders. Crystallite sizes of Al2O3, TiB2 and Fe phases
were about 60, 50 and 50 nm, respectively. The morphological

micrographs of milled samples after annealing are presented in

Fig. 4. As seen, the morphology of Al2O3TiB2/Fe nanocomposite
powder (complex reinforcement) is equiaxed and the average particle size of that is about 5 lm.
3.2. Production of Al(Al2O3TiB2/Fe) nanocomposites
The XRD patterns of Al-base composites with 1.25, 2.5 and
5 vol% of produced reinforcement (Al2O3TiB2/Fe) after 10 h of
milling are presented from Fig. 5. As seen, the diffraction peaks
from XRD patterns are related to Al matrix and there are no
any peak related to Al2O3, TiB2 and Fe phases. This result is attributed to the low volume fraction of the Al2O3, TiB2 and Fe phases
and the ne size of these powders in the matrix. The morphological micrographs of produced nanocomposites powder are also
shown in Fig. 6. As can be seen, the powders morphology of produced composites in different volume fraction of complex reinforcement were almost equiaxed and the average size of these
particles were about 40 7 lm. Several characteristics (volume
fraction, particle size, Al crystallite size and microhardness) of
produced nanocomposites are presented in Table 1. As shown,
the hardness value of the samples increase with increasing
amount of Al2O3TiB2/Fe reinforcement from 1.25 to 2.5 and
5 vol%.
3.3. Consolidation processes
The XRD patterns of consolidated samples with different percentage of complex reinforcement (Al2O3TiB2/Fe) are presented
in Fig. 7. Same to XRD results of powder samples, the XRD patterns
of consolidated samples are only contain of Al peaks. The cross-sectional SEM micrographs of the consolidated samples with different
percentage of reinforcements are shown in Fig. 8. According to
these micrographs, a ne and uniform distribution of Al2O3TiB2/
Fe reinforcement particles within the aluminum matrix is obtained
although most of the reinforcement particles appeared to be small
to be observed on SEM.
Table 2 shows the mechanical properties of produced nanocomposite with different percentage of reinforcement. As seen, by
increasing the percentage of reinforcement, compression strength
(and hardness) of samples increase strongly and rich to 560 MPa
(150 Hv) in composite contain 5 vol% of Al2O3TiB2/Fe particles.
The strength of the present study is much higher than those
reported in previous studies [714]. The improved yield strength
of the nanocomposite presented here can be explained by an Orowan strengthening mechanism as a result of presence of ne closely spaced hard particles in the matrix, which hinder the
movement of dislocations [13,14].
Although, the ductility (fracture strain) of produced composites
decreases with increasing the percentage of reinforcements, it is
important to note that the ductility of these samples is higher than
other similar studies (composite with single ceramic reinforcements) [715]. In fact, this effect could be because of the nature

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Fig. 7. The XRD patterns of consolidated samples (hot extruded at 500 C) with
different percentage of complex reinforcement (Al2O3TiB2/Fe).

Fig. 8. The SEM micrograph of consolidated samples with (a) 1.25, (b) 2.5 and (c)
5 vol% of Al2O3TiB2/Fe reinforcement.

of complex Al2O3TiB2/Fe reinforcements. Fig. 9 has shown the

distribution of reinforcement particle in Al matrix at high magnication. As seen, the reinforcements particles are contained of two

separated composed phases (light and gray phases). The EDS

results which taken from these phases (Fig. 9) showed that the
light and gray precipitates related to Fe rich and Al2O3/TiB2 phases,

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Table 2
Characteristics of consolidate Al (Al2O3TiB2/Fe) nanocomposites with different volume percentage of complex reinforcement.
Sample

Relative density (%)

Al crystallite size (nm)

Hardness (Hv)

Compression strength (MPa)

Fracture strain (%)

1
2
3

99.98
99.97
99.91

48
43
45

100
145
155

373
530
560

5
4
3.5

Fig. 9. The SEM micrograph and EDS analysis of separated phases in Al(Al2O3TiB2/Fe) nanocomposite.

respectively. These results show that, during the production of

Al2O3TiB2/Fe reinforcements, Fe atoms reject from ceramic matrix
and form separated Fe rich phase. This phase stick in Al2O3TiB2
ceramic components and can pin them to Al matrix. Moreover,
the wettability and interaction of complex metalceramic reinforcements with Al matrix is higher than ceramics only. With
regard to this point, it is expected that the produced Al(Al2O3
TiB2/Fe) nanocomposite show higher ductility than other similar
composites.
4. Conclusion
In the present paper, the fabrication of Al(Al2O3TiB2/Fe)
nanocomposite by means of mechanical alloying and hot extrusion
methods has been investigated. The achieved results showed that:
1. Al2O3TiB2/Fe nanocomposite powders can synthesis by
mechanical alloying and subsequent heat treatment at 700 C.
The crystalline sizes of Al2O3, TiB2 and Fe in produced nanocomposite were about 60, 50 and 50 nm, respectively.
2. Mechanical alloying of aluminum particles with produced reinforcements for 10 h and then hot extrusion, lead to a more uniform distribution of complex reinforcements and formation of
fully dense Al/(Al2O3TiB2/Fe) nanocomposite.
3. The compression strength of consolidated samples increase
strongly with increasing the percentage of reinforcements and
rich to 560 MPa.

4. Produced bulk samples show good ductility related to the nature of complex Al2O3TiB2/Fe reinforcements.

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