materials

Article
Effect of Milling Time on the Microstructure,
Physical and Mechanical Properties of Al-Al2O3
Nanocomposite Synthesized by Ball Milling and
Powder Metallurgy
Meysam Toozandehjani 1,† ID , Khamirul Amin Matori 2, *, Farhad Ostovan 3,† ,
Sidek Abdul Aziz 2 and Md Shuhazlly Mamat 2
1 Materials Science and Characterization Laboratory, Institute of Advanced Technology,
Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia; Toozandejani.meysam@yahoo.com
2 Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia;
Sidek@upm.edu.my (S.A.A.); Shuhazlly@upm.edu.my (M.S.M.)
3 Department of Material Science and Engineering, Bandarabbas Branch, Islamic Azad University,
Bandarabbas 7915893144, Iran; F.ostovan@gmail.com
* Correspondence: khamirul@upm.edu.my; Tel.: +60-03-8946-6653; Fax: +60-03-8945-4454
† These authors contributed equally to this work.

Received: 7 June 2017; Accepted: 1 August 2017; Published: 26 October 2017

Abstract: The effect of milling time on the morphology, microstructure, physical and mechanical
properties of pure Al-5 wt % Al2 O3 (Al-5Al2 O3 ) has been investigated. Al-5Al2 O3 nanocomposites
were fabricated using ball milling in a powder metallurgy route. The increase in the milling time
resulted in the homogenous dispersion of 5 wt % Al2 O3 nanoparticles, the reduction of particle
clustering, and the reduction of distances between the composite particles. The significant grain
refining during milling was revealed which showed as a reduction of particle size resulting from
longer milling time. X-Ray diffraction (XRD) analysis of the nanocomposite powders also showed
that designated ball milling contributes to the crystalline refining and accumulation of internal stress
due to induced severe plastic deformation of the particles. It can be argued that these morphological
and microstructural variations of nanocomposite powders induced by designated ball milling time
was found to contribute to an improvement in the density, densification, micro-hardness (HV),
nano-hardness (HN), and Young’s modulus (E) of Al-5Al2 O3 nanocomposites. HV, HN, and E values
of nanocomposites were increased by ~48%, 46%, and 40%, after 12 h of milling, respectively.

Keywords: Al-Al2 O3 nanocomposites; ball milling; microstructure; physical properties; mechanical

properties

1. Introduction
Application of Al-Al2 O3 composites has been extended into the aerospace and automotive
industries because of improved mechanical, tribological, and high-temperature properties [1–5].
Alumina (Al2 O3 ) has been most widely used as ceramic reinforcement particulates in aluminum
matrix composites (AMCs) due to the availability of different types, shapes, and sizes, its low cost and
overall good properties [4–9].
During synthesizing Al-Al2 O3 nanocomposites, like other metal matrix composites (MMCs),
achieving a uniform dispersion of Al2 O3 reinforcement particles and avoiding clustering of the Al2 O3
reinforcement particles, particularly those at the nano-scale, would be a significant constraint. This is
due to the fact that the enhancement of physical and mechanical properties is potentially decided
by a uniform dispersion of Al2 O3 reinforcement particles within the matrix. Then, reinforcing the

Materials 2017, 10, 1232; doi:10.3390/ma10111232 www.mdpi.com/journal/materials

Materials 2017, 10, 1232 2 of 17

Materials 2017, 10, 1232 2 of 17

aluminum matrix, particularly with Al2 O3 nanoparticles, necessitates a proper technique to obtain a
uniform dispersion
a uniform of Al2of
dispersion O3Al nanoparticles.
2O3 reinforcement Mechanical
particlesmilling
withinthrough ball Then,
the matrix. milling enables uniform
reinforcing the
dispersion
aluminumof reinforcements into the
matrix, particularly withaluminum matrix, which
Al2O3 nanoparticles, avoids the
necessitates agglomeration
a proper technique and clustering
to obtain a
of the reinforcement
uniform dispersion particles
of Al2O3[1,10,11].
nanoparticles. Mechanical milling through ball milling enables uniform
dispersion
Accordingoftoreinforcements
the literature,into Al-Althe2 Oaluminum
3 compositesmatrix, which avoidssynthesized
are successfully the agglomeration and ball
using the
clustering of the reinforcement particles [1,10,11].
milling and powder metallurgy route. The homogenous dispersion of Al2 O3 nanoparticles and
improved According
mechanical to the literature, of
behaviour Al-Al 2O3 composites are successfully synthesized using the ball
Al-Al 2 O3 nanocomposites is reported [1,2,4,7,9]. However,
Al-Al2 O3 nanocomposites are synthesized by thehomogenous
milling and powder metallurgy route. The dispersion
powder metallurgy of Al
route, 2O3 nanoparticles and
but the powder metallurgy
improved mechanical behaviour of Al-Al2O3 nanocomposites is reported [1,2,4,7,9]. However,
parameters, like densification, porosity, and physical dimensional change (PDC%) of bulk specimens,
Al-Al2O3 nanocomposites are synthesized by the powder metallurgy route, but the powder
are not fully investigated. As a well-known fact, porosity is an inevitable part of the powder metallurgy
metallurgy parameters, like densification, porosity, and physical dimensional change (PDC%) of bulk
(PM) product which, in turn, affects the final properties of composites.
specimens, are not fully investigated. As a well-known fact, porosity is an inevitable part of the
In our metallurgy
powder previous work [1], the which,
(PM) product effectiveness of the the
in turn, affects milling process inofproviding
final properties composites.homogenous
dispersion of 1 wt % Al
In our previous2 workO3 nanoparticles is reported. Therefore, the first objective
[1], the effectiveness of the milling process in providing of the investigation
homogenous
was dispersion
to ensure the
of 1 efficiency
wt % Al2Oof designated ball
3 nanoparticles millingTherefore,
is reported. processesthe
onfirst
the objective
incorporation of 5 wt % Al2 O3
of the investigation
nanoparticles
was to ensurewithin a pure aluminum
the efficiency of designated matrix. Secondly,
ball milling the on
processes effect of designated
the incorporation of milling
5 wt % Altime
2O3 on

morphology, microstructure,
nanoparticles within a pure densification
aluminum matrix.behaviour and, finally,
Secondly, mechanical
the effect behaviour
of designated millingoftime
Al-5Alon 2 O3
morphology,
has been microstructure, densification behaviour and, finally, mechanical behaviour of Al-
investigated.
5Al2O3 has been investigated.
2. Results and Discussion
2. Results and Discussion
It is well known that milling processes yield a significant change in the morphology of composite
powdersItas is well known
a result that milling
of severe processes
plastic yield a significant
deformation change within
of the particles in the morphology
the millingofprocess
composite
[1,12].
powders as a result of severe plastic deformation of the particles within the milling process [1,12].
Upon milling of Al-5Al2 O3 nanocomposite powders, aluminum particles are welded and fractured
Upon milling of Al-5Al2O3 nanocomposite powders, aluminum particles are welded and fractured
until reaching a steady state where equiaxed particles are formed in the presence of Al2 O3 nanoparticles.
until reaching a steady state where equiaxed particles are formed in the presence of Al2O3
The morphology of Al-5Al2 O3 nanocomposite powders at the beginning and the end of milling time is
nanoparticles. The morphology of Al-5Al2O3 nanocomposite powders at the beginning and the end
shown in Figure
of milling time1.is shown in Figure 1.

Figure 1. SEM micrographs of Al-5Al2O3 powder mixtures ball milled for (a) 2 h and (b) 8 h, showing
Figure 1. SEM micrographs of Al-5Al2 O3 powder mixtures ball milled for (a) 2 h and (b) 8 h, showing
the morphology of powder mixtures. FESEM micrographs of Al-5Al2O3 powder mixtures ball milled
the morphology of (d)
for (c) 0.5 h and powder mixtures.
8 h, showing the FESEM micrographs
dispersion uniformity of Al-5Al
of Al 2 O3 powder mixtures ball milled
2O3 powders.
for (c) 0.5 h and (d) 8 h, showing the dispersion uniformity of Al2 O3 powders.
Materials 2017, 10, 1232 3 of 17

A short milling time of 0.5 h was found to have no significant effect on the morphology of powders
except partial deformation of aluminum particles. At this stage, aluminum particles have kept their
initial shape wherein the extreme clustering of Al2 O3 nanoparticles could be observed. Figure 1c
illustrates the presence of large amounts of Al2 O3 clusters on the surface of aluminum particles as
pointed out inside Figure 1c. As the milling time increased up to 2 h, cold welding of particles was
activated and ductile aluminum particles started to flatten due to the high impact collision of the
balls. The lamination of particles of soft aluminum was observed in some areas. Figure 1a shows that
flake-shaped particles having large particle size are formed at this stage under deformation and cold
welding of the particles. At the early stage of milling, up to 2, Al2 O3 nanoparticles can rarely reside
within the flattened aluminum particles and Al2 O3 nanoparticle clusters are observed, but they are
smaller and fewer in number than in powders milled for 0.5 h. Certainly, such microstructures have
undesirable effects on mechanical properties. Flattening of the Al particles provides more sites for
Al2 O3 dispersion, which facilitates the uniform distribution of Al2 O3 within the Al matrix.
The particles’ deformation was found to be more pronounced at longer milling times and a
considerable change in morphology of nanocomposite powders was observable after 2 h of milling.
Excessive work hardening and an increment of brittleness of soft aluminum powders activate the
fracture mechanism; particles are fractured until reaching a steady state. Fracturing of work-hardened
and brittle aluminum powders results in the formation of irregular-shaped powders and particles
with smaller particle sizes until 8 h of milling. The progressive decrease in the particle size to Al2 O3
particles encourage Al2 O3 particles to be dispersed and embedded into the ductile aluminum particles
more homogenously due to intense and repeated collision between the balls and the work-hardened
powder. In fact, the finer matrix powder sizes, the more uniform the dispersion [13].
When the powder mixture reaches a steady state after 8 h, the particles’ morphology stabilizes and
particles are in an equiaxed shape and certain size, which are randomly oriented as shown in Figure 1b.
It is anticipated that in the steady state, the milling time is sufficient that no considerable change in the
morphology of the powders is observable. At the steady state stage, Al2 O3 nanoparticles are uniformly
dispersed and the distance between Al2 O3 nanoparticles is reduced; representing a tight bonding of
the matrix and reinforcement at the steady state (Figure 1d). It can be inferred that the steady state
can be achieved with the attainment of a full homogeneity of Al2 O3 nanoparticles throughout the
Al matrix [14]. A low amount of the Al2 O3 nanoparticles can be observed because the remaining
Al2 O3 nanoparticles are embedded in the Al particles after reaching the steady state. At longer milling
times, up to 12 h, the steady state is still predominated and milling has no considerable effect on the
morphology of the powders, however, grain refinement is expected. The similar finding was found
for Al-1 wt % Al2 O3 in the authors’ previous study [1]. However, the deformation of the particles
is more prominent in this study revealing the efficiency of the milling process in the presence of a
larger content of Al2 O3 nanoparticles. Alizadeh and Mirzaei Aliabadi [12] also reported a large Al2 O3
content, and the contribution of the fracture mechanism increases and leads to a decrease in the particle
size of the composite powder even with low milling time.
As can be observed in Figure 1c,d, Al2 O3 nanoparticles which appear in large clusters
(as highlighted in the Figure 1c) start to disperse within pure aluminum particles with a better
homogeneity and smaller interparticle space by increasing the milling time. Figure 2 shows the
dispersion uniformity of Al2 O3 nanoparticles within the Al matrix particles more precisely at different
milling times.
Materials 2017, 10, 1232 4 of 17
Materials 2017, 10, 1232 4 of 17

Figure 2. TEM micrograph of Al-5 wt % Al2O3 powder mixture milled for different times (a) 0.5 h; (b)
Figure 2. TEM micrograph of Al-5 wt % Al2 O3 powder mixture milled for different times (a) 0.5 h;
2 h; (c) 5 h; (d) 8 h; and (e) 12 h.
(b) 2 h; (c) 5 h; (d) 8 h; and (e) 12 h.
The dispersion of Al2O3 nanoparticles within the aluminum matrix increases by increasing the
The dispersion
milling time until aofwell-homogenous
Al2 O3 nanoparticles withinisthe
dispersion aluminum
obtained at thematrix
steadyincreases
state afterby
8 hincreasing
of milling.the
milling time
A short untiltime
milling a well-homogenous dispersion
of 0.5 h has no noticeable is on
effect obtained at the steady
the dispersion of 5 wtstate
% Alafter 8 h of milling.
2O3 nanoparticles

withinmilling
A short the Al time
matrix. It can
of 0.5 be no
h has seen that Al2Oeffect
noticeable 3 nanoparticles are heterogeneously
on the dispersion of 5 wt % Aldispersed on the
2 O3 nanoparticles
within the Al matrix. It can be seen that Al2 O3 nanoparticles are heterogeneously dispersed on the
Materials 2017, 10, 1232 5 of 17
Materials 2017, 10, 1232 5 of 17

surfaces of
surfaces of Al
Al particles.
particles. Al Al22O
O33 nanoparticles
nanoparticles appear appear in in aa clusters
clusters andand most
most of of the
the AlAl surface areas are
surface areas are
not fully
not fully covered
covered (Figure
(Figure 2a).
2a). These
These independent
independent clusters
clusters of of Al
Al22O
O33 nanoparticles,
nanoparticles, as as shown
shown by by circles,
circles,
are effectively broken up and start to disperse with better homogeneity
are effectively broken up and start to disperse with better homogeneity throughout the Al matrix by throughout the Al matrix by
increasing the
increasing the milling
milling time
time to to 88 h.h. Although
Although some some clusters
clusters of of Al
Al22O
O33 particles
particles cancan still
still bebe observed
observed in in
some areas,
some areas, they
they are
are smaller
smalleras ascompared
comparedwith withthe theshort
shortmilling
millingtime.
time.A A homogeneous
homogeneous dispersion
dispersion of
Al2Al
of O23 O nanoparticles throughout microstructure is observed after 8 h of milling (Figure 2d). It also
3 nanoparticles throughout microstructure is observed after 8 h of milling (Figure 2d). It also
seems that
seems that 88 h h of
of milling
milling is is sufficient
sufficient to to disperse
disperse 55 wt wt % % ofof Al
Al22O
O33 nanoparticles
nanoparticles withinwithin the the aluminum
aluminum
matrix (Figure 2d). Milling times longer than 8 h results in no considerable
matrix (Figure 2d). Milling times longer than 8 h results in no considerable changes in the dispersion changes in the dispersion
of Al O nanoparticles at the steady state. Figure 2e shows the adhesion
of Al2 O3 nanoparticles at the steady state. Figure 2e shows the adhesion of Al2 O3 nanoparticles
2 3 of Al 2 O 3 nanoparticles to the
to
surface
the surface of aluminum
of aluminum particles
particles after
after1212 h hofofmilling,
milling,representing
representingaa good bonding between
good bonding between Al Al22O
O33
nanoparticles and
nanoparticles and aluminum
aluminumparticles.
particles.Ostovan
Ostovanetetal.al.[8] [8]also
alsoreported
reported the
thehomogenous
homogenous dispersion
dispersion of
Al2Al
of O32 Onanoparticles after 8 h of milling in the case of 1 wt % Al2O3. In fact, as milling proceeds, clusters
3 nanoparticles after 8 h of milling in the case of 1 wt % Al2 O3 . In fact, as milling proceeds,
of Al2O3ofnanoparticle
clusters disappear,
Al2 O3 nanoparticle Al2O3 Al
disappear, nanoparticles disappear throughout the matrix, and the
2 O3 nanoparticles disappear throughout the matrix, and
distances between particles reduces
the distances between particles reduces [3,7,8,12–14]. [3,7,8,12–14].
The variation
The variation of of particle
particle size
size andand apparent
apparent density
density of ofAl-5Al
Al-5Al22O O33 nanocomposite
nanocomposite powders powders as as aa
function of the milling time is shown in Figure 3. The average particle
function of the milling time is shown in Figure 3. The average particle size Al-5Al2 O3 nanocomposite size Al-5Al 2O 3 nanocomposite
powders increases
powders increases in in the
the first
first 22 hh of
of milling
milling and
and reaches
reaches aa maximum
maximum of of 165.3
165.3 ((± 10.8) μm
± 10.8) µm due due to
to the
the
predominance of
predominance of cold
cold welding.
welding. Cold Cold welding,
welding, along
along with work-hardening of
with work-hardening aluminum particles,
of aluminum particles,
leads to the formation of large particles with increased average particle
leads to the formation of large particles with increased average particle size. This is similar to size. This is similar to other
other
composite systems
composite systems as as reported
reported in in the
the literature
literature [8,13].
[8,13]. Razavi
Razavi TousiTousi etet al.
al. [14]
[14] reported
reported aa continuous
continuous
decrease in particle size of Al-Al O composites in the presence of
decrease in particle size of Al-Al2 O3 composites in the presence of the high volume fraction of
2 3 the high volume fraction ofAl
Al22O
O33
(20 vol %) where 20 vol % Al O prevents cold welding from occurring.
(20 vol %) where 20 vol % Al2 O3 prevents cold welding from occurring. After 2 h of milling, the average
2 3 After 2 h of milling, the
average size
particle particle size progressively
progressively decreases, decreases, representing
representing the onset theofonset of the fracture
the fracture mechanism, mechanism,
until 8until
h of
8 h of when steady state is reached. Fracturing of work-hardened
when steady state is reached. Fracturing of work-hardened and brittle aluminum powders results in and brittle aluminum powders
results
the in the reduction
reduction of the averageof theparticle
average particle
size size of aluminum
of aluminum particles. At particles.
the steadyAt the
state steady
stage,state stage,
a balance
a balancecold
between between
weldingcoldandwelding and fracturing
fracturing is achieved is whereby
achieved the whereby
particlethesize
particle
is kept size is kept
almost almost
constant.
constant. Although the variation of average particle size in the steady
Although the variation of average particle size in the steady state is not significant, it decreases from state is not significant, it
decreases
20.58 (±7.34 from
) µm20.58 (±7.34) μm
to the lowest value to the of lowest
17.82 (± value
6.45)of µm 17.82 (±6.45) μm
at the end of ball atmilling.
the end The of ball milling.
results are
The results are in appropriate accordance with the morphology of
in appropriate accordance with the morphology of the mixtures during milling where three differentthe mixtures during milling where
three different
stages stagesprocess
of the milling of the milling
could be process could be identified.
identified.

Particle Size Apparent Density

200 2
Apparent Density (gcm-3)

160 1.8
Particle Size (μm)

120 1.6

80 1.4

40 1.2

0 1
0.5 2 5 8 12
Milling Time (h)

Figure 3. The variation of particle size and apparent

apparent density
density of
of Al-5Al
Al-5Al22O33 nanocomposite powders as
a function of the milling time.
Materials 2017, 10, 1232 6 of 17

Dissimilar to the variation of particle size, the apparent density of Al-5Al2 O3 nanocomposite
Materials 2017, 10, 1232 6 of 17
powders initially decreases at an early stage of milling, up to 2 h, then increases as the milling time
increases,Dissimilar
as showntointhe Figure 3. Atofearly
variation stages
particle size,ofthe
milling,
apparentup density
to 2 h, the apparent
of Al-5Al density decreases
2O3 nanocomposite
due to the formation of large flake-shaped particles as a result of the
powders initially decreases at an early stage of milling, up to 2 h, then increases as the millingcold welding of particles
time to a
minimum of 1.36 ( ± 0.05 ) g · cm −3 . The apparent density of Al-5Al O nanocomposite powders start
increases, as shown in Figure 3. At early stages of milling, up to 2 h,2 the 3 apparent density decreases
to improve
due to theprogressively
formation ofafter large2flake-shaped
h of milling,particles
as ascribed by the
as a result offracturing of large
the cold welding of particles
particles to anda the
minimum
formation of 1.36irregular
of small, (±0.05) g·cm −3. The apparent density of Al-5Al2O3 nanocomposite powders start to
shapes. The apparent density of Al-5Al2 O3 nanocomposite powders
vary improve progressively
in consistency with the aftervariation
2 h of milling,
in theasmorphology
ascribed by the fracturing
of Al particles,of large
which particles
variesandfrom thelarge
formation of small, irregular shapes. The apparent density of Al-5Al 2O3 nanocomposite powders vary
flake-shaped particles at early stages of milling to more or less quasi-spherical particles having small
in consistency with the variation in the morphology of Al particles, which varies from large flake-
particle sizes. Generally, flake-shaped particles indicate the worst packing properties of the powders,
shaped particles at early stages of milling to more or less quasi-spherical particles having small
while spherical powders show better packing properties due to the relatively good mobility of particles
particle sizes. Generally, flake-shaped particles indicate the worst packing properties of the powders,
and awhile
lowerspherical
tendency to formshow
powders bridges [11,15,16].
better packing Beyond
properties8 hdue
of milling, in the steady
to the relatively good state,
mobilityformation
of
of equiaxed particles improves the apparent density slightly to a maximum
particles and a lower tendency to form bridges [11,15,16]. Beyond 8 h of milling, in the steady state, of 1.65 ( ± 0.02 ) g·cm−3 .
The slight variation
formation in apparent
of equiaxed density
particles in the steady
improves state isdensity
the apparent attributed to thetoslight
slightly variationofin the
a maximum
particle
1.65size of powders.
(±0.02) g·cm −3. The slight variation in apparent density in the steady state is attributed to the

slight variation
Figure 4 presents in the
theparticle size of powders.
X-ray diffraction patterns of Al-5Al2 O3 nanocomposite powders ball milled
Figure 4 presents
for various times. There are four sharpthe X-ray diffraction
detectedpatterns of Al-5Al
diffraction 2O3 nanocomposite powders ball milled
peaks corresponding to the FCC structure
for various times. There are four sharp detected diffraction peaks corresponding to the FCC structure
of aluminum along with small Al2 O3 peaks in XRD diffraction patterns of nanocomposite powders.
of aluminum along with small Al2O3 peaks in XRD diffraction patterns of nanocomposite powders.
The fewer Al2 O3 peaks and their lower intensity in the diffraction pattern might be due to the low
The fewer Al2O3 peaks and their lower intensity in the diffraction pattern might be due to the low
content of the Al2 O
content of the
phase and/or the fine size of the powder in the Al-5Al O3 powder
Al3 2O3 phase and/or the fine size of the powder in the Al-5Al2O32powder
mixture [9,17].
mixture [9,17].
Additionally,
Additionally, neither
neitherthethe presence
presence ofofunwanted
unwanted phases northe
phases nor theimpurity
impurity phases,
phases, such such asFe,
as Si, Si,and
Fe, and
Al4 C3Al
, was revealed
4C3, was revealed in the XRD
in the XRD diffraction
diffractionpattern.
pattern. TheTheresults
resultsare
are inconsistent
inconsistent withwith previous
previous findings
findings
by Zebarjad
by Zebarjad et al.et[15] andand
al. [15] Prabhu
Prabhu et et
al.al.
[9].
[9].The
Theabsence
absence ofof impurities
impurities or orunwanted
unwanted phases
phases indicates a
indicates
a clean interface between particles and the matrix. According to the literature,
clean interface between particles and the matrix. According to the literature, Al2 3 is so stablethat Al 2 O 3 is so stable that no
no unwanted
unwanted solid-statesolid-state
reaction reaction
occurs occurs
during during
the the milling
milling of aluminumand
of aluminum andAlAl22O
O33 [18].
[18].

Figure 4. XRD
Figure diffraction
4. XRD patterns
diffraction ofofAl-5Al
patterns Al-5Al22O nanocompositepowders
O33 nanocomposite powders milled
milled for different
for different times.
times.

An increase in the milling time, up to 12 h, results in a definite shift in the position of the related
An increase in the milling time, up to 12 h, results in a definite shift in the position of the related
peaks. An enlarged view of the shift position of the first peak corresponding to the crystalline plane
peaks.ofAn enlarged
(111) view is
of aluminum ofshown
the shift position
in the of the of
right corner first peak4.corresponding
Figure to the crystalline
The shift in the position plane of
of peaks may
(111) be
of due
aluminum is shown in the right corner of Figure 4. The shift in the position of peaks
to the dissolution of minor alloying elements, impurities, and reinforcement particles in the may be
due to the dissolution of minor alloying elements, impurities, and reinforcement particles in the lattice
Materials 2017, 10, 1232 7 of 17

Materials 2017, 10, 1232 7 of 17

of the aluminum matrix during milling [16,18]. As is also shown in the right corner of Figure 4, the
intensity
latticeofofthe
thefirst peak (111)
aluminum matrixin Al-5Al O3 is decreased
during 2milling [16,18]. Asand its shown
is also width inbroadened. By proceeding
the right corner of Figure the
milling timeintensity
4, the up to 12ofh, the
peakfirst
intensities
peak (111)reduce and relative
in Al-5Al peaks become
2O3 is decreased and slightly
its width broadened
broadened. at the
full-width at half-maximum
By proceeding the milling (FWHM).
time up to In fact,
12 h, theintensities
peak higher weight
reducefraction of Alpeaks
and relative O
2 3 nanoparticles
become slightlyleads
broadened
to higher at the full-width
peak intensities and theat half-maximum
finer particle (FWHM).
size results In in
fact,
thethe higher weight
broadening fraction
of the peaksofand
Al2Olower
3

nanoparticles leads to higher

peak intensities (smaller peak height) [9].peak intensities and the finer particle size results in the broadening of
the
Peak peaks and lowerofpeak
broadening the intensities
ball-milled (smaller
Al-5Al peak height) [9].
2 O3 powders is corresponding to the crystalline size
Peak broadening of the ball-milled Al-5Al2O3 powders is corresponding to the crystalline size
(or grain size) refinement and enhancement of lattice strain [2]. The Williamson-Hall method was used
(or grain size) refinement and enhancement of lattice strain [2]. The Williamson-Hall method was
to analyse the relative peaks in order to relate the broadening in the XRD patterns to the crystalline
used to analyse the relative peaks in order to relate the broadening in the XRD patterns to the
size (d) and lattice strain (η ) of Al-5Al2 O3 nanocomposite powder mixtures. As shown in Figure 5, the
crystalline size (d) and lattice strain ( ) of Al-5Al2O3 nanocomposite powder mixtures. As shown in
crystalline
Figure size
5, theofcrystalline
aluminum sizeparticles generally
of aluminum decreases
particles generally asdecreases
the milling time
as the increases,
milling while lattice
time increases,
strainwhile
increases. The crystalline size of aluminum particles powders decreases
lattice strain increases. The crystalline size of aluminum particles powders decreases(± from 39.10 2.2) nm
from
h to (±2.2) nm
at 0.539.10 19.53 (±2)atnm 0.5 h to 19.53 (±2) nm at 12 h of milling, while the lattice strain increases from ) to
at 12 h of milling, while the lattice strain increases from 0.0026 ( ± 0.019
0.0048 (±0.016
0.0026 ) at the 0.0048
(±0.019) to end of(±0.016) at
the milling theprocess.
end of the milling process.

Crystalline Size Lattice Strain

60 0.5

50
Crystalline Size (nm)

Lattice Strain (%)

0.4
40

30
0.3
20

10 0.2
0.5 2 5 8 12
Milling Time (h)

Figure
Figure 5. Variation
5. Variation of crystalline
of crystalline size
size andlattice
and latticestrain
strain of milled
milled Al-5Al
Al-5Al2OO
2 3 as a function
3 as of milling
a function time.time.
of milling

The significant variations in the crystalline size (or grain size) and in the lattice strain of
The significant variations in the crystalline size (or grain size) and in the lattice strain of aluminum
aluminum particles is attributed to severe plastic deformation and grain size refinement occuring in
particles is attributed
the presence of Al2to
O3severe plastic within
nanoparticles deformation and process
the milling grain size refinement
[19,20]. The mainoccuring in thetopresence
contribution the
of Aldecrement
O
2 3 nanoparticles within the milling process [19,20]. The main contribution to the
of crystalline size is the generation of dislocations as a result of local plastic deformationdecrement of
crystalline size is thework
and accelerated generation
hardeningof of
dislocations as a [14,21,22].
Al2O3 powders result of local plastic deformation
The interaction between hard andandaccelerated
non-
workdeformable
hardeningAlof 2OAl 2 O3 powders
3 nanoparticles and[14,21,22]. The
dislocations interaction
accelerates the between hardmechanism
grain-refining and non-deformable
[16]. In
Al2 Othe presence of and
3 nanoparticles Al2O 3 nanoparticles,
dislocations the Orowan
accelerates bowing mechanism
the grain-refining mechanism results
[16]. in dislocation
In the presence of
multiplication, as reported by Razavi Hesabi et al. [16]. By increasing the
Al2 O3 nanoparticles, the Orowan bowing mechanism results in dislocation multiplication, as reported milling time, the
dislocations are rearranged to a lower energy state and the low angle sub-boundaries
by Razavi Hesabi et al. [16]. By increasing the milling time, the dislocations are rearranged to a are formed.
lowerThe severestate
energy plastic
anddeformation
the low angleandsub-boundaries
generation of more aredislocations
formed. The at longer
severe milling
plastic times leads to and
deformation
the increased misorientations between subgrains at their boundaries. Finally, low angle sub-
generation of more dislocations at longer milling times leads to the increased misorientations between
boundaries turn into high angle boundaries and become grains with nano-scale sizes [17]. On the
subgrains at their boundaries. Finally, low angle sub-boundaries turn into high angle boundaries and
other hand, the interaction of Al2O3 nanoparticles with dislocations hinders the movement of
become grains with
dislocations nano-scale
resulting sizes [17].
in an increase On the other
in dislocation hand,
density andtheaninteraction
accumulationof Al O3 nanoparticles
of 2stresses in the
with aluminum
dislocations hinders the movement of dislocations resulting in an increase in dislocation
lattice. In addition, the distortion of the lattice structure and formation of other lattice density
and an accumulation of stresses in the aluminum lattice. In addition, the distortion
defects, like vacancies and impurities within the milling process, results in the accumulation of of the lattice
structure and
internal formation
stress of otherlattice.
in the aluminum latticeTherefore,
defects, like
latticevacancies and impurities
strain gradually increases by within the milling
increasing the
process, results in the accumulation of internal stress in the aluminum lattice. Therefore, lattice strain
gradually increases by increasing the milling time [14,23]. Ahmad et al. [18] have also reported the
Materials 2017, 10, 1232 8 of 17

Materials 2017, 10, 1232 8 of 17

increase in the lattice strain as a result of less dissolution of alloying elements and reinforcement in the
milling time [14,23]. Ahmad et al. [18] have also reported the increase in the lattice strain as a result
matrix at longer milling times.
of less dissolution of alloying elements and reinforcement in the matrix at longer milling times.
Figure 6 presents experimental density and porosity of sintered Al-5Al2 O3 nanocomposites with
Figure 6 presents experimental density and porosity of sintered Al-5Al2O3 nanocomposites with
respect to milling time. The theoretical density of Al-5Al O was also calculated according to the rule
respect to milling time. The theoretical density of Al-5Al22O33was also calculated according to the rule
of mixtures and and
found to beto2.743 g·cm −3
of mixtures found be 2.743 g·cm.−3The
. Thesmall
smallincrease
increaseofofthe thetheoretical
theoretical density
density is
is due
due toto the
the fact
that fact
the density − 3
g·cm(3.95) isg·cm (2.7 g·cm−3 ).
that theofdensity
Al2 O3 particles
of Al2O3 (3.95
particles slightly
−3) is higher
slightlythan thatthan
higher of aluminum
that of aluminum
It can(2.7
be g·cm
seen−3that
). Itthe
canexperimental
be seen thatdensity (ρ) increasesdensity
the experimental from 2.62 ±0.03) tofrom
(ρ) (increases ±0.015
2.71 (2.62 ) g·cmto−3 by
( ±0.03)
increasing milling time
2.71 (±0.015) g·cm from
−3 by 0.5 h tomilling
increasing 12 h. Although,
time from 0.5 there
h tois12
a h.
slight drop in
Although, theisdensity
there a slightvalues
drop inafter
2 h ofthe densityas
milling, values
shown after
in2Figure
h of milling,
6. as shown in Figure 6.

Density (ρ) Porosity

3 6.5

2.9 5.5
Density (g.cm-3)

Porosity (%)
2.8 4.5

2.7 3.5

2.6 2.5

2.5 1.5
0.5 2 5 8 12
Milling Time (h)

Figure 6. Variation
6. Variation of density
of density andporosity
and porosityof
ofmilled
milled Al-5Al
Al-5Al2O 3 as a function of milling time.
Figure 2 O3 as a function of milling time.

As a matter of fact, the sintered density is dependent on the morphology of the powders after
As a matter of fact, the sintered density is dependent on the morphology of the powders after
milling, size, and distribution of the nano-reinforcement within the matrix, as well as compaction and
milling, size,parameters
sintering and distribution of the
[24]. Lower nano-reinforcement
density withinis the
at early stages of milling duematrix, as wellofas
to the presence compaction
aluminum
and agglomeration
sintering parameters [24]. Lower density at early stages of milling
and Al2O3 clusters in the microstructure. Agglomeration and clustering of is due to the presence
Al2O3 of
aluminum agglomeration
nanoparticles andthat
act as barriers Al2 O
slow3 clusters
down the in the microstructure.
diffusion process which Agglomeration
is needed for the and clustering
sintering
of Alprocess.
O
2 3 nanoparticles
The incrementactofas barriers
density is that slow
attributed down
to the the
better diffusion
dispersion process
of Al 2 O 3which is needed
nanoparticles for the
within
the matrix
sintering process. at The
longer milling of
increment times.
density At longer milling
is attributed to times,
the better Al2Odispersion
3 nanoparticles of Al2are dispersed
O3 nanoparticles
homogeneously
within the matrix at(Figure
longer2d,e), which
milling accelerates
times. the diffusion
At longer milling rate
times,during
Al2 Osintering, as reported
3 nanoparticles areby [25].
dispersed
These uniformly-dispersed
homogeneously Al2O3 particles
(Figure 2d,e), which accelerates arethe
embedded
diffusioninratethe during
grain boundaries
sintering, and surfacesby
as reported of [25].
aluminum particles and hinder the grain growth by a pinning mechanism,
These uniformly-dispersed Al2 O3 particles are embedded in the grain boundaries and surfaces resulting in an increase in of
the density. On the other hand, more grain refining, which is showed as a reduction of the particle
aluminum particles and hinder the grain growth by a pinning mechanism, resulting in an increase in
size resulting from longer milling time, further increases the diffusion rate.
the density. On the other hand, more grain refining, which is showed as a reduction of the particle size
It can also be noticed that the values of experimental densities are lower than that of the
resulting from longer milling time, further increases the diffusion rate.
theoretical densities indicating the presence of some amount of porosity in nanocomposite
It can also be
specimens, as noticed
shown that the values
in Figure of experimental
7. The amount of densities
porosity are lower
in the than that
sintered bulk of the theoretical
Al-5Al 2O3
densities indicating the presence of some amount of porosity in nanocomposite
nanocomposites is found to decrease significantly from 3.76% (±0.04) at 0.5 h to 1.85% (±0.03) at specimens, as shown in
Figure 7. As
12 h. Thea amount
well-known of porosity in theissintered
fact, porosity bulkpart
an inevitable Al-5Al 2 O3 nanocomposites
of powder metallurgy (PM) is product
found towhich decrease
significantly
is inverselyfrom 3.76% (±0.04
proportional ) at 0.5 hAttoearly
to density. (±0.03
1.85%stages of)milling,
at 12 h.nanocomposite
As a well-known fact, porosity
specimens containis an
larger part
inevitable amounts of residual
of powder porosity(PM)
metallurgy as a product
result of which
clustered Al2O3 areas,
is inversely which are to
proportional thedensity.
sites where
At early
cracks and porosities are formed, as reported by Zebarjad et al.
stages of milling, nanocomposite specimens contain larger amounts of residual porosity [26]. Figure 7 shows the opticalas and
a result
FESEM micrographs
of clustered Al2 O3 areas,ofwhich
Al-5Alare
2O3 milled for 2 h, indicating the presence of porosities and voids
the sites where cracks and porosities are formed, as reported by
formed
Zebarjad et on
al. the polished
[26]. Figuresurface
7 shows of the
the composite.
optical andIt FESEM
can be seen that Al2O3 nanoparticles
micrographs of Al-5Al2 O3accumulate
milled for 2 h,
in the void formed on the surface of the nanocomposite (Figure 7b).
indicating the presence of porosities and voids formed on the polished surface of the composite. It can
be seen that Al2 O3 nanoparticles accumulate in the void formed on the surface of the nanocomposite
(Figure 7b).
Materials 2017, 10, 1232 9 of 17
Materials 2017, 10, 1232 9 of 17

Materials 2017, 10, 1232 9 of 17

Figure 7. (a) Optical micrograph and (b) FESEM micrograph of the surface of Al-5Al2O3
Figure 7. (a) Optical micrograph and (b) FESEM micrograph of the surface of Al-5Al2 O3 nanocomposite
nanocomposite milled for 2 h.
milled for 2 h.
Figure 7. (a) Optical micrograph and (b) FESEM micrograph of the surface of Al-5Al2O3
nanocomposite
In addition, milled for 2 h. mechanism shows a similar trend, as observed in the density.
the densification
In addition,
Densification decreases in the first 2 mechanism
the densification h of milling,shows
reachinga similar
a minimumtrend,of as observed
94.13%, in the
and then density.
increasing
In addition, the densification mechanism shows a similar trend, as observed in the density.
Densification
to 98.15% decreases
at 12 h of in the
milling. first 2 h of milling, reaching a minimum of 94.13%, and then increasing
Densification decreases in The densification
the first 2 h of milling,curve of athe
reaching Al-5Alof2O
minimum 3 nanocomposite
94.13%, (Figure 8) is
and then increasing
to 98.15%
similar to at 12
to 98.15% h of
the apparent milling.
density
at 12 h of
The densification
milling.curve
curve
(Figure 3) curve
The densification
of the Al-5Al
whichofcorresponds O
the Al-5Al2O3 to
2 3 nanocomposite
the powder(Figure
nanocomposite
(Figure
morphology
8) is
8) is
and
similar to the
particlesimilar apparent density curve (Figure 3) which corresponds to the powder
to the apparent density curve (Figure 3) which corresponds to the powder morphology and
size variations. morphology and
particle particle
size variations.
size variations.

Densification
Densification
Expansion
Expansion
99 99 3 3
98 98 2.8 2.8
Densification (%)
Densification (%)

97 97
Expansion (%)

Expansion (%)

96 2.6
96 2.6
95 2.4
95 2.4
94
94 93 2.2
2.2
93 92 2
0.5 2 5 8 12
92 2
Milling Time (h)
0.5 2 5 8 12
Milling Time (h)
Figure
Figure 8. The 8. Theof
variation variation of densification
densification and expansion
and expansion of Al-5Al
of Al-5Al 2O3 composites as a function of
2 O3 composites as a function of milling time.
milling time.
Figure 8. The variation of densification and expansion of Al-5Al2O3 composites as a function of
As discussed earlier,
As discussed at early
earlier, stage
at early ofofmilling
stage milling up up 22h,h,nanocomposite
nanocomposite powders
powders showing showing the worst
the worst
milling time.
packingpacking properties
properties dueformation
due to to formation ofoflarge
largeflake-shape
flake-shape particles as aasresult
particles of theofcold
a result thewelding of
cold welding of
particles. Cold-welded and work-hardened powders decrease the pressing
particles. Cold-welded and work-hardened powders decrease the pressing capacity of the specimens. capacity of the specimens.
AsThe
discussed earlier, at
nanocomposites early stage
containing largeofparticles
millingcannot
up 2 h, nanocomposite
reach the full density. powders showing
In contrast, the worst
particles
The nanocomposites containing large particles cannot reach the full density. In contrast, particles
packingwithproperties
small sizesdue to formation
are easily densified of large
rather thanflake-shape
large particlesparticles
under theas a result
same of theconditions.
compaction cold welding of
with small sizes are heterogeneous
Additionally, easily densified ratherofthan
dispersion Al large particlesand
2O3 nanoparticles
underformation
the sameofcompaction conditions.
particles. Cold-welded and work-hardened powders decrease thethe pressing capacity clustered regions
of the specimens.
Additionally, heterogeneous dispersion of Al 2 O3 nanoparticles andaluminum
the formation of clustered regions
at this stage lead to the lack of bonding between Al
The nanocomposites containing large particles cannot reach the full density. In contrast,theparticles
2O3 clusters and at the surface of
at this stage lead
sintered to the lack
composites. of bonding
These between
microstructural featuresAl2lead
O3 clusters
to higher and aluminum
plastic at the surface
strain in clustered region of the
with small sizes are easily densified rather than large particles under the same compaction conditions.
sinteredand favors the These
composites. formation of voids and features
microstructural cracks, and leadconsequently-reduced
to higher plastic strain mechanical properties.
in clustered region and
Additionally,
Uniform heterogeneous
distribution of Aldispersion of Al2O3 nanoparticles and the formation of clustered regions
2O3 nanoparticles within the aluminum matrix at longer milling time and
favors the formation of voids and cracks, and consequently-reduced mechanical properties. Uniform
at this stage
shorterlead to the
distance lack ofnanoparticles
between bonding between Al2O3 bonding
provide tighter clustersbetween
and aluminum at the surface
Al2O3 nanoparticles and of the
distribution of Al2 O3 nanoparticles within the aluminum matrix at longer milling time and shorter
sinteredmatrix,
composites. Theseinmicrostructural
which results the denser sintered features leadConversely,
composite. to higher as plastic strain of
the bonding in particles
clustered is region
distanceincreased,
betweenthenanoparticles
amount of provide tighter bonding between Al2 O nanoparticles and matrix,
is 3obtained.
and favors the formation ofporosities
voids and is decreased,
cracks, so andthatconsequently-reduced
a more dense part mechanical properties.
which results in the denser sintered composite. Conversely, as the bonding of particles is increased,
Uniform distribution of Al2O3 nanoparticles within the aluminum matrix at longer milling time and
the amount of porosities is decreased, so that a more dense part is obtained.
shorter distance between nanoparticles provide tighter bonding between Al2O3 nanoparticles and
matrix, which results in the denser sintered composite. Conversely, as the bonding of particles is
increased, the amount of porosities is decreased, so that a more dense part is obtained.
Materials 2017, 10, 1232 10 of 17

Materials 2017, 10, 1232 10 of 17

The variation of physical dimensional changes (or expansion) of Al-5Al2 O3 nanocomposite
specimens Theis variation
shown inofFigure 8. Itdimensional
physical can also be changes
seen that(or dimensional
expansion) expansion
of Al-5Al2Oincreases in the early
3 nanocomposite
stagespecimens
of milling, is up to 2 in
shown h. Figure
Nanocomposites
8. It can alsomilled
be seenfor 2 hdimensional
that show the maximum
expansionexpansion
increases in due
thetoearly
the cold
welding
stageofofparticles.
milling, up Attoearly stages of milling,milled
2 h. Nanocomposites the presence of cold-welded
for 2 h show the maximum (work-hardened)
expansion due toparticlesthe
and cold welding
clustered Al2ofO3particles. At early
areas hinder the stages of milling,
diffusion the presence
of aluminum of cold-welded
particles to form tighter (work-hardened)
bonds, resulting
particles
in greater and clustered
expansion (grainAl2growth)
O3 areas hinder the diffusion
of specimens and of aluminum
a poor particles to
densification form tighter
process [14]. Asbonds,
milling
resulting in greater expansion (grain growth) of specimens and a poor
time proceeds, dimensional expansion decreases, indicating less grain growth during the sintering densification process [14].
As milling
process time proceeds,
as milling dimensional
time increases (Figure expansion
8). Thedecreases,
dispersion indicating less grain
homogeneity of growth
Al2 O3 during the
nanoparticles
sintering process as milling time increases (Figure 8). The dispersion homogeneity of Al2O3
increases by increasing the milling time and a better bonding of particles can be obtained resulting in
nanoparticles increases by increasing the milling time and a better bonding of particles can be
less dimensional expansion of nanocomposite specimens during the sintering process. According to
obtained resulting in less dimensional expansion of nanocomposite specimens during the sintering
Millsprocess.
[27], dimensional
According to changes of composites
Mills [27], dimensionalare highlyofdependent
changes compositestoare thehighly
compaction
dependentpressure,
to thetime
and compaction
temperature of sintering, physical properties of the initial powder and the
pressure, time and temperature of sintering, physical properties of the initial powder and homogeneity of the
reinforcement powder.
the homogeneity of the reinforcement powder.
The Thevariation of micro-hardness
variation of micro-hardness (HV)
(HV)and andnano-hardness
nano-hardness (HN) (HN) ofof Al-5Al
Al-5Al2O 2O 3 nanocomposites
3 nanocomposites as as a
function of milling
a function timetime
of milling is presented
is presentedin Figure
in Figure9. It
9. is seen
It is seenthat
thatasasmilling
milling time proceeds,HV
time proceeds, HVvalues
values of
of Al-5Al
Al-5Al 2O3 nanocomposite
2 O3 nanocomposite specimens
specimens increase.However,
increase. However, it can canbe benoticed
noticed that
thatthetheimprovement
improvement of of
hardness at early stages of milling, up to 2 h, is not significant, whereas it is
hardness at early stages of milling, up to 2 h, is not significant, whereas it is more profound at longermore profound at longer
milling
milling times.times. HV values
HV values werewere
foundfound to increase
to increase sharply, sharply,
as it isas
theitexpected
is the expected
trend, from trend, from
60.25 (±3.6)
60.25 (±3.6) HV after 2 h of milling to a maximum value of 111.20 (±5.1) HV at the end of milling,
HV after 2 h of milling to a maximum value of 111.20 (±5.1) HV at the end of milling, corresponding
corresponding to an improvement of about 46%. Similarly, HN values of nanocomposite specimens
to an improvement of about 46%. Similarly, HN values of nanocomposite specimens increases by
increases by increasing the milling time. The enhancement of HN values in the milling time longer
increasing the milling time. The enhancement of HN values in the milling time longer than 2 h is also
than 2 h is also noticeable. Al-5Al2O3 nanocomposites milled for 12 h showed HN of about twice
noticeable.
(1.12 GPa) Al-5Al
that 2ofOthe
3 nanocomposites
HN of nanocompositesmilledmilled
for 12 for
h showed HN
0.5 h (0.61 of about
GPa), twicethe
indicating (1.12 GPa) that
profound of the
effect
HN of nanocomposites milled for 0.5 h (0.61 GPa), indicating the profound
of the milling process in the improvement of the mechanical behaviour. The results are in agreement effect of the milling process
in the improvement
with previous studies of thewhere
mechanical
hardness behaviour.
of Al-5Al2O The results are in increases
3 nanocomposite agreement bywith previous
increasing studies
milling
where hardness
process of Al-5Al2 O3 nanocomposite increases by increasing milling process [17,26,28,29].
[17,26,28,29].

1.2
HV HN
110
1
95
HN (GPa)
HV

0.8
80

0.6
65

50 0.4
0.5 2 5 8 12
Milling Time (h)

Figure
Figure 9. Variation
9. Variation of micro-hardness(HV)
of micro-hardness (HV)and
and nano-hardness
nano-hardness (HN)
(HN)ofofAl-5Al
Al-5Al2O3 O
2 composites as a as a
3 composites
function
function of milling
of milling time.
time.

In both micro- and nano-hardness measurements, the increment f HV and HN values of milled
In both
Al-5Al micro- and nano-hardness measurements, the increment f HV and HN values of milled
2O3 nanocomposites is attributed to the presence of Al2O3 nanoparticle reinforcements and
Al-5Al
microstructural variation is
2 O3 nanocomposites attributed
within millingtoprocess
the presence
of Al-5Alof2O
Al3 2
O3 nanoparticle
nanocomposite reinforcements
as also reported by and
microstructural variation within milling process of Al-5Al
Zebarjad et al. [26] and Mazilkin et al. [28]. Recall that, at early 2 3 stages of milling, up to 2reported
O nanocomposite as also h, cold by
Zebarjad
weldinget al. [26] and isMazilkin
of particles et al. [28].
predominated Recall that,
and hardening at early stages
is expected becauseofofmilling, up to 2 h,ofcold
work-hardening
welding of particles
particles is predominated
while milling. Within the andmilling
hardening is expected
process of Al-5Al because of work-hardening
2O3 nanocomposites, severeof local
particles
deformation
while of Al particles
milling. Within in theprocess
the milling vicinity of Al 2O3 nanoparticles
Al-5Al O
2 3 result
nanocomposites, in the cold-working
severe local and grain-
deformation of
Al particles in the vicinity of Al2 O3 nanoparticles result in the cold-working and grain-refining of Al
Materials 2017, 10, 1232 11 of 17

particles which consequently increases the hardness of the powders. In addition, at this stage, Al2 O3
nanoparticles are heterogeneously dispersed and mostly clustered, wherein the distance between
composite particles is large (Figures 1a and 2a), resulting in poor sintering. During sintering processes,
Al2 O3 nanoparticle clusters interrupt the diffusion bonding of particles, resulting in large amounts
of residual porosity in bulk nanocomposites and, consequently, poor consolidation. Then, this
microstructural state contributes to the lower hardness of nanocomposites due to poor sintering
in the presence of Al2 O3 clusters.
After 2 h of milling, both HV and HN values increase when dispersion of Al2 O3 nanoparticles
becomes more homogeneous and significant grain size refining occurs. Enhancement of the
homogeneous dispersion of Al2 O3 nanoparticles by increasing the milling time decreases the distance
between nanocomposite particles so that further sintering processes will result in better bonding and,
consequently, enhanced strength properties. Homogeneity of Al2 O3 nanoparticles in the sintered
composites has been directly related to the homogeneity of nanoparticles before sintering [1,26,29].
These small Al2 O3 nanoparticlesm which have a short distance from each other, act like a barrier;
thus, grain growth will be postponed in milled nanocomposite specimens [15]. By increasing the
milling time, the average particle size of aluminum particles profoundly decreases, which results in
a significant increase in the hardness of the matrix particles. The Al2 O3 nanoparticles, by pinning
the grain boundaries, can also hinder the grain growth mechanism and improve the strengthening
mechanism. Moreover, the pure Al-5Al2 O3 nanocomposites are comprehensively strengthened by
the generation of high-density dislocations and the formation of fine sub-grains within the milling
process, as mentioned earlier. At longer milling times, severe particle deformation, however, yields a
homogeneous dispersion of Al2 O3 nanoparticles within the Al matrix, but introduces strain hardening
to the matrix particles through the generation of a large amount of high-density dislocations [28,29].
In fact, dispersed Al2 O3 nanoparticles inhibit dislocation movement resulting in the generation of a
large amount of high-density dislocations around the particles. Grain refinement is accelerated when a
high dislocation density is present in the microstructure, which contributes to formation of extensive
fine sub-grains in the matrix. Then, grain refinement through sub-grain formation strengthens the
nanocomposites [29–31]. Different orientations of adjacent sub-grains and the high lattice disorder
characteristic of the boundary regions hinder dislocation movement in a continuous slip plane and
consequently harden the nanocomposites [32].
An upward trend in the variation of E values of Al-5Al2 O3 nanocomposites was also obtained by
increasing the milling time up to 12 h (Figure 10). Nanocomposites milled for a short milling time of
0.5 h have the lowest E values of 37.1 (±4.81) GPa. The E values of nanocomposites increase linearly
to 52.50 (±2.24) GPa after 8 h of milling at a steady state. The upward increasing trend of the Young’s
modulus extends to the longer milling time of 12 h in the steady state stage where the maximum value
of the Young’s modulus value of 53.12 (±2.53) GPa, representing an increase in E values of about 28%.
A representative load-displacement curve of Al-5Al2 O3 with respect to milling time at a peak
load of 100 µN is shown in Figure 11. In nanoindentation measurement, elastic modulus is a function
of the slope of the unloading curve. It can be seen that nanocomposites milled for the shortest time
of 0.5 h shows the highest displacement, attributed to the lowest Young’s modulus. Conversely,
nanocomposites milled for the longest milling time of 12 h shows the lowest displacement, indicating
the maximum Young’s modulus under the same indentation conditions. The lower displacement or
lower indention depth in nanoindentation measurements represents the strengthening of the matrix in
the presence of Al2 O3 nanoparticles [33]. Then, the load-displacement curve of Al-5Al2 O3 shifts toward
the left and lower displacements by increasing the milling time due to strengthening of the matrix.
Materials 2017, 10, 1232 12 of 17
Materials
Materials 2017,
2017, 10,
10, 1232
1232 12
12 of
of 17
17

Young's
Young's modulus
modulus (E)
(E)
60
60

(GPa)
Modulus(GPa)
50
50

Young'sModulus
40
40
Young's

30
30

20
20
0.5
0.5 22 55 88 12
12
Milling
Milling Time
Time (h)
(h)

Figure
Figure 10.10.
Figure The
10. The variation
variationofof
variation
The ofEE values
Evalues of
valuesof Al-5Al
ofAl-5Al O333 nanocomposites
Al-5Al222O nanocompositesas
nanocomposites asasaaafunction of
function
function milling
ofof time.
milling
milling time.
time.

60
60

50
50

40
40
(μN)
Load(μN)

30 0.5
30 0.5 hh
Load

22 hh
20
20
55 hh
10
10 88 hh
12
12 hh
00
00 11 22 33 44
Displacement
Displacement (nm)
(nm)

Figure
Figure 11.11.
Figure 11. Load–displacement curves
Load–displacementcurves
Load–displacement of
curvesof Al-5Al
Al-5Al222O
ofAl-5Al O333 nanocomposite
O nanocompositeat
nanocomposite atatdifferent
different
differentmilling
milling
millingtime.
time.
time.

Similar
Similar toto HV
HV and and HN,
HN, thethe variation
variation of of the
the Young’s
Young’s modulus
modulus is is attributed
attributed to to the
the state
state ofof
Similar to
dispersion of HV
Al O and HN, the variation
nanoparticles and the of the
grain Young’sofmodulus
refinement particles is attributed
within the to the
milling state of
process.
dispersion of Al2O3 nanoparticles and the grain refinement of particles within the milling process.
2 3
dispersion
At
At shorter
ofmilling
Al2 O3 times,
shorter milling
nanoparticles
times, heterogeneous
and the
heterogeneous dispersion
grain refinement
dispersion and
of particles
and clustering
clustering of of Al
Al22O
within the milling
O33 nanoparticles
nanoparticles and
process.
and larger
larger
At particle
shorter milling
sizes of times,
particles heterogeneous
contributes to dispersion
the lower and clustering
Young’s modulus of Al
of
particle sizes of particles contributes to the lower Young’s modulus of Al-5Al2O3 nanocomposites. O
Al-5Al
2 3 nanoparticles
2O 3 and
nanocomposites. larger
particle
By sizes
By increasing of
increasing theparticles
the milling contributes
milling time,
time, the to
the Young’s the lower
Young’s modulus Young’s
modulus of of Al-5Almodulus
Al-5Al22O of Al-5Al
O33 nanocomposites
nanocomposites O nanocomposites.
2 3increases,
increases, owing
owing
Bytoincreasing
to aa more the milling time,
more homogenous
homogenous the Young’s
dispersion
dispersion of
of Al Al22modulus
O of Al-5Al
O33 nanoparticles
nanoparticles and2 O3along
and nanocomposites
along with
with thethe grain increases,
grain refining
refining owing
of
of
to aluminum
a more particles.
homogenous
aluminum particles. dispersion of Al 2 3O nanoparticles and along with the grain refining of
aluminum As a matter of
particles. fact, the Young’s modulus, or resistivity of material to being
As a matter of fact, the Young’s modulus, or resistivity of material to being elastically deformed, elastically deformed,
of powder
of As metallurgy
a matter
powder of fact, the
metallurgy is
is significantly affected
Young’s modulus,
significantly affectedor by the
the amount
byresistivity
amount of
of porosity
of material
porosity to and
and cracks
being present
elastically
cracks present in
in the
deformed,
the
of sintered
sintered compacts.
powder metallurgy
compacts. The
Theis presence
presence of
of porosities
significantly affectedand
porosities cracks
by the
and in
in the
amount
cracks sintered
the of porosity
sintered compacts
and cracks
compacts noticeably
present
noticeably lowers
in the
lowers
the
the Young’s
sintered Young’s
compacts. modulus
modulus of
of MMCs
The presence MMCs [9,34].
[9,34]. Heterogeneous
of porosities Heterogeneous
and cracks in the dispersion
dispersion and
and clustering
sintered compacts clustering of
of Al
noticeably Al 22O
O33
lowers
nanoparticles
thenanoparticles
Young’s modulus result
resultofin the
inMMCs formation
the formation of
[9,34]. of more porosity and
more porositydispersion
Heterogeneous cracks
and cracks and after the sintering
afterclustering
the sintering process.
of Alprocess. Resultant
Resultant
2 O3 nanoparticles
residual
residual
result porosities
in theporosities
formation cause
causeof stress
more concentrations
stress concentrations
porosity and cracks and
and unexpected
after the fractures,
unexpected sinteringthus,
fractures, thus, lowering
lowering
process. the
the strength.
Resultant strength.
residual
In
In contrast,
contrast, homogeneous
homogeneous dispersion
dispersion Al
Al 22O
O 33 nanoparticles
nanoparticles provide
provide aa better
better bonding
bonding of
of particles
particles during
during
porosities cause stress concentrations and unexpected fractures, thus, lowering the strength. In
Materials 2017, 10, 1232 13 of 17

Materials 2017, 10, 1232 13 of 17

contrast, homogeneous dispersion Al2 O3 nanoparticles provide a better bonding of particles during
the sintering process.
process. The
The homogeneously-dispersed
homogeneously-dispersed Al Al22O33 nanoparticles
nanoparticles andand very short distances
between Al2O O33 nanoparticles
nanoparticles prevent
prevent crack
crack extension
extension and
and their interconnection
interconnection and reduce stress
concentration, therefore,
therefore, enhancing
enhancing the
the strength
strength properties
properties of of the
the nanocomposites.
nanocomposites.
Finally, it
it should be mentioned that there are some mechanisms which
should be mentioned that there are some mechanisms which may
may simultaneously
simultaneously be
activated that enhance the strength properties of the the Al-5Al
Al-5Al22O33 nanocomposites
nanocomposites like like other
other MMCs.
MMCs.
These mechanisms are include
include Orowon
Orowon strengthening
strengthening as as aa result
result of
ofthe
theuniform
uniformdispersion
dispersionof ofAl
Al22O
O33
particles, solid solution hardening, work work hardening
hardening as a result of the strain misfit between the
reinforcement and andmatrix
matrixparticles,
particles, grain
grain andand substructure
substructure strengthening
strengthening following
following the classical
the classical Hall-
Hall-Petch
Petch relationship, quench hardening due to the dislocations generated to accommodate the
relationship, quench hardening due to the dislocations generated to accommodate
differential thermal
thermal contraction
contraction between
between reinforcement
reinforcement andand matrix
matrix particles,
particles,and
andthermal
thermalmismatch.
mismatch.

3. Materials and
3. Materials and Methods
Methods
Flake
Flake shape
shapeofoffine aluminum
fine aluminum (Al) (Al)
powder supplied
powder by Merck
supplied by (Merck
Merck KGaA,
(MerckDarmstadt, Germany,
KGaA, Darmstadt,
99% purity,99%
Germany, 200 µm) and200
purity, spherical
μm) andnano-alumina (Al2 O3 , Sigma(Al
spherical nano-alumina Aldrich, St. Louis, MO, USA, 200 nm)
2O3, Sigma Aldrich, St. Louis, MO,
were used as a raw material to fabricate Al-5 wt %
USA, 200 nm) were used as a raw material to fabricate Al-5 Al O nanocomposites. Figure 12 shows
2 3 wt % Al2O3 nanocomposites. Figurethe
12
surface morphology
shows the of the as-received
surface morphology of the powders. The
as-received as-received
powders. Theatomized aluminum
as-received atomizedpowders are
aluminum
predominantly equiaxed andequiaxed
powders are predominantly irregular and
in shape.
irregular in shape.

Figure 12. Surface morphology

Figure 12. morphology of
of the
the as-received
as-received (a)
(a) pure
pure Al
Al and
and (b)
(b) Al
Al22O33 powders.

Nanocomposite powder
Nanocomposite powder mixtures
mixtures containing
containing 55 wt wt %% Al
Al2OO3 nanoparticles were prepared along
2 3 nanoparticles were prepared along
with 22 wt
with wt %% stearic
stearic acid
acid as
as aa process
process control
control agent
agent (PCA)
(PCA) to to prevent
prevent excessive
excessive cold
cold welding
welding of of the
the
particles within milling. However, stearic acid stearic acid will then be vaporized
particles within milling. However, stearic acid stearic acid will then be vaporized during sintering during sintering
before the
before the temperature
temperature of of 361
361 ◦°C
C [21].
[21]. The
The nanocomposite
nanocomposite powder powder mixtures were placed
mixtures were placed inin aa tungsten
tungsten
carbide jar with the ball-to-powder weight ratio (BPR) of 8:1. Argon (Ar) was purged
carbide jar with the ball-to-powder weight ratio (BPR) of 8:1. Argon (Ar) was purged into the confined into the confined
and sealed
and sealed jar
jar before
beforemilling
millingtotocarry
carryoutoutthe ball
the milling
ball millingunder an an
under Ar Ar
atmosphere.
atmosphere. A planetary
A planetaryball
milling
ball machine
milling machine(PM(PM 100,100,
Retsch,
Retsch,Haan,
Haan, Germany)
Germany) waswas used
usedtotoball
ballmill
mill Al-5
Al-5 wtwt % % AlAl2OO3
2 3
nanocomposites powder. The powder mixtures were ball milled for various milling
nanocomposites powder. The powder mixtures were ball milled for various milling time from 0.5 to time from 0.5 to
12 h. The rotational speed of the ball milling machine was maintained constant
12 h. The rotational speed of the ball milling machine was maintained constant at 300 rpm. Afterwards, at 300 rpm.
Afterwards, nanocomposite
nanocomposite powders were powders were compacted
compacted using a cold
using a uniaxial uniaxial cold
press at press at a pressure
a pressure of 150ofMPa.
150
MPa. Sampling was accurately done in the glove box under argon atmosphere
Sampling was accurately done in the glove box under argon atmosphere to avoid oxidation and to avoid oxidation and
obtain sound
obtain sound bulk
bulk nanocomposite
nanocomposite specimens
specimens with with free,
free, or
or the
the least
least amount,
amount, ofof pores.
pores. Nanocomposite
Nanocomposite
compacts were finally sintered at 580 ◦°C for 45 min under an
compacts were finally sintered at 580 C for 45 min under an Ar atmosphere. Ar atmosphere.
The morphology
The morphology and and dispersion
dispersion uniformity
uniformity observation
observation of of ball-milled
ball-milled powders
powders waswas initially
initially
performed using scanning electron microscopy (SEM Hitachi S-3400, Tokyo, Japan),
performed using scanning electron microscopy (SEM Hitachi S-3400, Tokyo, Japan), and transmission and transmission
electron microscopy
electron microscopy (TEM,(TEM, LEO
LEO 912AB,
912AB, Zeiss,
Zeiss, Germany).
Germany). The surface of
The surface of the
the bulk
bulk nanocomposites
nanocomposites
were prepared by following standard metallographic techniques. Field emission
were prepared by following standard metallographic techniques. Field emission scanning electron scanning electron
microscopy (FESEM, 7600F, JEOL, Tokyo, Japan) and a Leica light microscope (Leica, Wetzlar,
Germany) equipped with a Qwin image analyser was used to observe the carefully-polished surface
of specimens in the case of porosities.
Materials 2017, 10, 1232 14 of 17

microscopy (FESEM, 7600F, JEOL, Tokyo, Japan) and a Leica light microscope (Leica, Wetzlar, Germany)
equipped with a Qwin image analyser was used to observe the carefully-polished surface of specimens
in the case of porosities.
The particle size of composite powders was measured in each step of milling with MasterSizer
analyser2000 (Malvern Instruments Ltd, Worcestershire, UK), using laser light diffraction. The mean
size of the volume-weighted particles was reported. Phase analysis of nanocomposite powders within
the milling process was performed by a Shimadzu XRD-6000 (Shimadzu Corporation, Osaka, Japan)
using 0.1542 nm CuKα 181 radiation at 4.8 kW with the voltage of 40 kV and a current of 120 mA.
Individual phases were identified by matching the characteristic XRD peaks against ICCD data.
Present peaks in the XRD patterns of nanocomposite powders were indexed using Xpert Highscore
plus software (PANalytical, Almelo, The Netherlands). Crystalline size (d) and lattice strain (η)
of aluminum particles were determined using the Williamson and Hall method and based on the
following equation:
0.9 λ
b cos θ = + 2η sin θ (1)
d
where b, θ, λ, d, and η are the full-width of the peak at half maximum intensity (FWHM), the Bragg
angle, X-ray wavelength used, crystalline size, and lattice strain of the nanocomposite powders,
respectively [35].
The experimental density of the nanocomposites was measured was measured according to the
Archimedes principle at room temperature:

Wa
ρ= × ρb (2)
Wa − Wb

where Wa is the weight of specimens in air, Wb the weight of specimens in buoyant and ρb is the
density of the buoyant, respectively. The average of three density measurement was reported as the
density value. The theoretical density of the nanocomposites was obtained according to using the rule
of mixture. According to the rule of mixture if reinforcement particle of volume fraction νr is now
added to aluminum matrix, the effective density of the composite, ρc , is given by:


ρc = ρr νr + ρstd 1 − νp (1 − νr ) (3)

where ρr and ρstd are the density of the reinforcement particles and standard pore free density of the
matrix material, respectively [36]. The amount of porosities of the nanocomposites was measured from
the difference between the expected and the observed density of each sample.
The physical dimensional changes (PDC) of the nanocomposite specimens were determined
according to ASTM B610 standard using the following equation:

Ds − D g
% PDC = × 100 (4)
Dg

where Dg and Ds are the dimension of the samples before and after sintering, respectively. A positive
% PDC value indicates the growth of the samples, and a negative % PDC values reflects shrinkage of
the specimens [37].
The microindentation hardness was determined using a Mitutoya HV-112 Vickers hardness
measurement machine (Mitutoyo Corporation, Kanagawa, Japan). Ten Vickers indents at a load of
100 gf and a dwell time of 10 s was applied on the polished cross-section of bulk nanocomposite
specimens and the average reported for HV values. Nanoindentation was performed by a Micro
Materials Nanotest™ indenter (Micro Materials, Wrexham, UK) equipped with a standard Berkovich
geometry tip indenter, at a maximum load of 50 µN and dwell time of 5 s applied to 20 different
locations of the polished surface of the nanocomposites. The indentations were made at constant
loading rates of 0.5 µN/s until reaching the maximum load of 50 µN and before being unloaded
Materials 2017, 10, 1232 15 of 17

gradually to zero. The HN and E of values of the nanocomposites were calculated according to the
Oliver–Pharr method [38]. The average values of HN and E values of a total of 20 indents made at
different locations and peak load were reported.

4. Conclusions
This study was conducted to investigate the effect of milling time on morphology, microstructure,
and consequent physical and mechanical behaviour of pure Al-5Al2 O3 . It was found that increasing the
milling time contributes to the homogenous dispersion of 5 wt % Al2 O3 nanoparticles, the reduction
of particle clustering, and the reduction of distances between the composite particles. The increase
of the milling time also leads to grain refining due to induced severe plastic deformation of the
particles within milling, as shown by particle size reduction. These morphological and microstructural
variations at longer milling time enhance the HV, HN, and E values of Al-5Al2 O3 nanocomposite
by ~48%, 46%, and 40%, after 12 h of milling, respectively. Experimental density, densification, and
physical dimensional changes of nanocomposites were also found to increase with an increase in
the milling time. The enhanced physical and mechanical behaviour of Al-5Al2 O3 nanocomposites is
attributed to the increase in the milling time where a homogenous dispersion of Al2 O3 nanoparticles
was obtained along with grain refining, whereas agglomeration of Al particles and clustering of Al2 O3
at shorter milling times contribute to the formation of porosities and cracks which weaken the sintering
process and, thus, finally, the physical and mechanical behaviour of Al-5Al2 O3 nanocomposites.

Acknowledgments: The authors gratefully acknowledge the financial support for this study from the Malaysian
Ministry of Higher Education (MOHE) through the Fundamental Research Grant Scheme and Exploratory
Research Grant Scheme.
Author Contributions: Farhad Ostovan and Meysam Toozandehjani conceived and designed the experimental
procedure. Khamirul Amin Matori supervised the entire research work. Farhad Ostovan and Meysam
Toozandehjani carried out the experimental procedure. Sidek Abdul Aziz and Md Shuhazlly Mamat provided
valuable scientific advice for the entire experiment and assisted the research in analyzing data and manuscript
preparation. Farhad Ostovan and Meysam Toozandehjan wrote the paper, while the final manuscript was revised
by Khamirul Amin Matori and Md Shuhazlly Mamat.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Ostovan, F.; Matori, K.A.; Toozandehjani, M.; Oskoueian, A.; Yusoff, H.M.; Yunus, R.; Ariff, A.H.M.
Microstructural evaluation of ball-milled nano Al2 O3 particulate-reinforced aluminum matrix composite
powders. Int. J. Mater. Res. 2015, 106, 636–640. [CrossRef]
2. Wagih, A. Mechanical properties of Al–Mg/Al2 O3 nanocomposite powder produced by mechanical alloying.
Adv. Powder Technol. 2015, 26, 253–258.
3. Lloyd, D.J. Particle reinforced aluminium and magnesium matrix composites. Int. Mater. Rev. 1994, 39, 1–23.
[CrossRef]
4. Casati, R.; Vedani, M. Metal matrix composites reinforced by nanoparticles—A review. Metals 2014, 4, 65–83.
5. Poirier, D.; Drew, A.R.L.; Trudeau, M.L.; Gauvin, R. Fabrication and properties of mechanically milled
alumina/aluminium nanocomposites. Mater. Sci. Eng. A 2010, 527, 7605–7614.
6. Wessel, J.K. The Handbook of Advanced Materials: Enabling New Designs, 1st ed.; John Wiley & Sons: New York,
NY, USA, 2004; pp. 65–88.
7. Jeyasimman, D.; Sivaprasad, K.; Sivasankaran, S.; Ponalagusamy, R.; Narayanasamy, R.; Iyer, V.
Microstructural observation, consolidation and mechanical behaviour of AA 6061 nanocomposites reinforced
by γ-Al2O3 nanoparticles. Adv. Powder Technol. 2014, 26, 139–148. [CrossRef]
8. Pournaderi, S.; Mahdavi, S.; Akhlaghi, F. Fabrication of Al/Al2 O3 composites by in-situ powder metallurgy
(IPM). Powder Technol. 2012, 229, 276–284. [CrossRef]
9. Prabhu, B.; Suryanarayana, C.; An, L.; Vaidyanathan, R. Synthesis and characterization of high volume
fraction Al–Al2 O3 nanocomposite powders by high-energy milling. Mater. Sci. Eng. A 2006, 425, 192–200.
[CrossRef]
Materials 2017, 10, 1232 16 of 17

10. Suryanarayana, C. Recent developments in mechanical alloying. Rev. Adv. Mater. Sci. 2008, 18, 203–211.
11. Razavi Hesabi, Z.; Hafizpour, H.R.; Simchi, A. An investigation on the compressibility of
aluminum/nano-alumina composite powder prepared by blending and mechanical milling. Mater. Sci. Eng.
A 2007, 454–455, 89–98. [CrossRef]
12. Hossein-Zadeh, M.; Razavi, M.; Mirzaee, O.; Ghaderi, R. Characterization of properties of Al–Al2O3
nano-composite synthesized via milling and subsequent casting. J. King Saud Univ. Eng. Sci. 2013, 25, 75–80.
[CrossRef]
13. Heydarzadeh Sohi, M.; Hojjatzadeh, S.M.H.; Moosavifar, Sh.S.; Heshmati-Manesh, S. Liquid phase surface
melting of AA8011 aluminum alloy by additionof Al/Al2 O3 nano-composite powders synthesized by
high-energy milling. Appl. Surf. Sci. 2014, 313, 76–84. [CrossRef]
14. Razavi Tousi, S.S.; Yazdani Rad, R.; Salahi, E.; Mobasherpour, I.; Razavi, M. Production of Al–20 wt % Al2 O3
composite powder using high energy milling. Powder Technol. 2009, 192, 346–351. [CrossRef]
15. Zebarjad, S.M.; Sajjadi, S.A. Dependency of physical and mechanical properties of mechanical alloyed
Al–Al2 O3 composite on milling time. Mater. Des. 2007, 28, 2113–2120. [CrossRef]
16. Razavi Hesabi, Z.; Simchi, A.; Seyed Reihani, S.M. Structural evolution during mechanical milling of
nanometric and micrometric Al2 O3 reinforced Al matrix composites. Mater. Sci. Eng. A 2006, 428, 159–168.
[CrossRef]
17. Safari, J.; Akbari, G.H.; Shahbazkhan, A.; Delshad Chermahini, M. Microstructural and mechanical properties
of Al–Mg/Al2 O3 nanocomposite prepared by mechanical alloying. J. Alloys Compd. 2011, 509, 9419–9424.
[CrossRef]
18. Ahamed, H.; Senthilkumar, V. Role of nano-size reinforcement and milling on the synthesis of
nano-crystalline aluminium alloy composites by mechanical alloying. J. Alloys Compd. 2010, 505, 772–782.
[CrossRef]
19. Mobasherpour, I.; Tofigh, A.A.; Ebrahimi, M. Effect of nano-size Al2 O3 reinforcement on the mechanical
behavior of synthesis 7075 aluminum alloy composites by mechanical alloying. Mater. Chem. Phys. 2013, 138,
535–541. [CrossRef]
20. Zawrah, M.F.; Zayed, H.A.; Essawy, R.A.; Nassar, A.H.; Taha, M.A. Preparation by mechanical alloying,
characterization and sintering of Cu–20 wt % Al2 O3 nanocomposites. Mater. Des. 2013, 46, 485–490.
[CrossRef]
21. Suryanarayana, C. Mechanical alloying and milling. Prog. Mater. Sci. 2001, 46, 1–184. [CrossRef]
22. Suryanarayana, C.; Gerant Norton, M. X-ray Diffraction: A Practical Approach; Plenum: New York, NY, USA, 1998.
23. Tavoosi, M.; Karimzadeh, E.; Enayati, M.H. Fabrication of Al–Zn/α-Al2 O3 nanocomposite by mechanical
alloying. Mater. Lett. 2008, 62, 282–285. [CrossRef]
24. German, R.M. Sintering Theory and Practice, 1st ed.; Wiley-VCH: New York, NY, USA, 1996; p. 568.
25. Kök, M. Abrasive wear of Al2 O3 particle reinforced 2024 aluminium alloy composites fabricated by vortex
method. Compos. Part A Appl. Sci. Manuf. 2006, 37, 457–464. [CrossRef]
26. Zebarjad, S.M.; Sajjadi, S.A. Microstructure evaluation of Al–Al2 O3 composite produced by mechanical
alloying method. Mater. Des. 2006, 27, 684–688. [CrossRef]
27. Mills, K. Metals Handbook Volume 7: Powder Metallurgy, 9th ed.; American Society for Metals: Metals Park,
OH, USA, 1984; p. 897.
28. Mazilkin, A.A.; Myshlyaev, M.M. Microstructure and thermal stability of superplastic aluminium-lithium
alloy after severe plastic deformation. J. Mater. Sci. 2006, 41, 3767–3772. [CrossRef]
29. Wang, H.M.; Li, G.; Zhao, Y.; Chen, G. In situ fabrication and microstructure of Al2 O3 particles reinforced
aluminium matrix composites. Mater. Sci. Eng. A 2010, 527, 2881–2885. [CrossRef]
30. Zhang, Z.; Chen, D.L. Contribution of Orowan strengthening effect in particulate reinforced metal matrix
nanocomposites. Mater. Sci. Eng. A 2008, 483–484, 148–152. [CrossRef]
31. Karbalaei Akbari, M.; Baharvandi, H.R.; Mirzaee, O. Fabrication of nano-sized Al2 O3 reinforced casting
aluminum composite focusing on preparation process of reinforcement powders and evaluation of its
properties. Compos. Part B. Eng. 2013, 55, 426–432. [CrossRef]
32. Casati, R.; Wei, X.; Xia, K.; Dellasega, D.; Tuissi, A.; Villa, E.; Vedani, M. Mechanical and functional properties
of ultrafine grained Al wires reinforced by nano-Al2 O3 particles. Mater. Des. 2014, 64, 102–109. [CrossRef]
Materials 2017, 10, 1232 17 of 17

33. Ostovan, F.; Matori, K.A.; Toozandehjani, M.; Oskoueian, A.; Yusoff, H.M.; Yunus, R.; Ariff, A.H.M.
Nanomechanical behavior of multi-walled carbon nanotubes particulate reinforced aluminum
nanocomposites prepared by ball milling. Materials 2016, 9, 140. [CrossRef] [PubMed]
34. Zhang, X.C.; Xu, B.S.; Xuan, F.Z.; Tu, S.T.; Wang, H.D.; Wu, Y.X. Porosity and effective mechanical properties
of plasma-sprayed Ni-based alloy coatings. Appl. Surf. Sci. 2009, 255, 4362–4371. [CrossRef]
35. Williamson, G.K.; Hall, W.H. X-ray line broadening from filed aluminium and wolfram. Acta Metall. 1953, 1,
22–31. [CrossRef]
36. Bindumadhavan, P.N.; Wah, H.K.; Prabhakar, O. Assessment of particle–matrix debonding in particulate
metal matrix composites using ultrasonic velocity measurements. Mater. Sci. Eng. A 2002, 323, 42–51.
[CrossRef]
37. Ostovan, F.; Matori, K.A.; Yusoff, H.M.; Yunus, R.; Ariff, A.H.M.; Toozandehjani, M.; Fadaeifard, F.;
Meschian, M.R. Occurrence of pattern formation of microstructural, physical and mechanical properties
of sintered pm steels containing pre-alloyed Astaloy E powder. Trans. Indian Inst. Met. 2014, 67, 881–888.
[CrossRef]
38. Oliver, W.C.; Pharr, G.M. An improved technique for determining hardness and elastic modulus using load
and displacement sensing indentation. J. Mater. Res. 1992, 7, 1564–1583. [CrossRef]

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