Journal of Alloys and Compounds 769 (2018) 713e724

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Synthesis, mechanical properties and wear behavior of hybrid

Al/(TiO2 þ CuO) nanocomposites
M. Ahmadi*, M.H. Siadati
Faculty of Materials Science and Engineering, K. N. Toosi University of Technology, Tehran, Iran

articleinfo abstract

Article history: One of the relatively new but affordable reinforcements that can be used to effectively enhance the
Received 5 April 2018 mechanical properties and wear behavior of particularly light metals is oxide nanoparticles. In this study,
Received in revised form hybrid TiO2 - CuO nanoparticles as the reinforcing materials were mixed with aluminum (Al) powder
30 July 2018
using a planetary ball mill, then consolidated by uniaxial pressing at 450 MPa, and finally sintered at
Accepted 31 July 2018
Available online 1 August 2018
400 ○C for 90 min in order to produce hybrid aluminum matrix nanocomposites (HAMNCs). Between a
total of 7 and 5 wt%, the optimum amount of nanoparticles was found to be 5 wt% (2.5 wt% each). The
results of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spec -
Keywords:
trometry (EDS) examinations revealed that the ceramic nanoparticles were distributed uniformly in the
Hybrid nanocomposites
Nanoparticle reinforcements Al matrix. The microhardness and compression tests indicated that the addition of TiO 2 and CuO
Mechanical properties nanoparticles to Al matrix resulted into a nanocomposite with superior mechanical properties. Micro -
Wear behavior hardness, yield and compression strengths values were obtained to be 73 HV, 250, and 278 MPa,
Mechanical milling respectively. Compared to the Al matrix, the percent increases are 83, 187 and 167, respectively for
Scanning electron microscopy microhardness, yield and compression strengths. Wear tests revealed a lower coef ficient of friction (0.27)
for the HAMNCs than for the milled and compacted pure Al sample (0.575). The wear resistance
increased as indicated by the reduction in the wear volume to approximately half as compared to the
pure aluminum. SEM observations of the worn surfaces revealed that the controlling wear mechanisms
were a mixture of abrasive and adhesive, and some delamination.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction single reinforcement composites as they combine the advantages of

Among the different types of nanostructures, nanocomposites
are of special importance. Metal matrix nanocomposites (MMNCs)
have shown considerably superior properties compared with their
corresponding metal matrix composites (MMCs), even when con-
taining lower volume fraction of reinforcing nanoparticles [1].
Higher surface area exposed by nano-size reinforcements at the
matrix interface has been the main cause to their superior prop-
erties such as mechanical strength, fatigue life, and wear resistance.
Nonetheless, the final properties of MMNCs are strongly influenced
by the shape, size, distribution pattern, production process, and
thermal stability of the nano-size reinforcements. Furthermore,
hybrid metal matrix composites (HMMCs) have been investigated
by various researchers [2e4] due to their improved properties over
* Corresponding author.
E-mail addresses: m.ahmadi@kntu.ac.ir (M. Ahmadi),
(M.H. Siadati).
their constituent reinforcements. Needless to mention that
aluminum (Al) matrix composites (AMCs) have constituted the
most famous category of MMCs as they offer higher and better
functionalities than those of the Al alloys [3,5]. As matrix materials,
Al and its alloys have drawn much attention due to their low
density, strength enhancement by precipitation hardening, corro-
sion resistance, higher thermal and electrical conductivity, and
attenuation (vibratory motion prevention via friction, etc.). AMCs
have been widely investigated since the 1920's [6], and are appli-
cable for many industries such as sports, electronics, arms, and
automotive. The reinforcements for AMCs should satisfy the re-
quirements including low density, thermal expansion coefficient
matching to the Al matrix, chemical acclimation, thermal stability,
high elastic modulus, high tensile and compression strengths, and
suitable fabrication feasibility.
Melting approaches for fabricating composites and nano-
composites have some weaknesses such as non-wetting of re-
inforcements (especially ceramic types) by the matrix, generation
siadati@kntu.ac.ir
of casting defects (porosity and shrinkage), and inappropriate

https://doi.org/10.1016/j.jallcom.2018.07.363
0925-8388/© 2018 Elsevier B.V. All rights reserved.
714 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724
Table 1
Characteristics of nanoparticles.
Nanoparticle Powder size (nm) Purity (%) Color Powder morphology
TiO2 30 <99.9 White Semi-spherical
CuO 40 <99 Black Semi-spherical
connection between the reinforcements and the matrix or
damaging of reinforcements due to excessive reactions. Thus, solid
state processes like mechanical milling (MM) have also been under
investigation. MM is a powder process, which generates a ho-
mogenous mixture of materials from the initial powders [7].
The most important difference between sintered parts and fully
dense materials is the existence of pores remained after the
consolidation and sintering stages. Pores contribute in reducing the
wear resistance. They also play a significant role in removing wear
debris from the sliding surfaces. Consequently, tribological treat-
ment of sintered materials is so complex and depends on many
factors mainly wear conditions [8].
Benjamin et al. [9] introduced MM for the first time in the early
1966, intending to produce Nickel based superalloys. Since then
MM has been used for making composites, too. Rajmohan et al. [10]
synthesized and characterized hybrid-AMCs reinforced with nano-
CuO and micro-SiC particles, and indicated that the microhardness
of the samples improved with increase of nano-CuO content from
140 up to 147 VHN. Furthermore, it was observed that the nano-
CuO addition increased the density from 2.9 to 3.06 g/cm 3, which
also improved the mechanical properties of the hybrid-AMCs.
Microstructure and mechanical properties of aluminum hybrid
nanocomposite (Al-5wt.% SiC-Graphite) were investigated by Rav-
indran et al. [11]. Although adding graphite to the nanocomposite
decreased the density and hardness, the wear rate decreased by the
solid lubrication of graphite particles released during sliding and
formation of a tribo layer at the contact surface.
Sobhani et al. [12] investigated Al titanate composite prepared
with TiO2 powder. The results demonstrated that the KIC value
pffi ffiffiffi
increased from the initial value of 2.6e5.5 MPa m at the
maximum load for the nanocomposite. The microstructural ob-
servations indicated that bridging and microcracking were the
main toughening mechanisms in the Al titanate composite.
In this study, the effects of adding nanoparticles of TiO2 and CuO
on the microstructure and tribological behavior of pure Al powder
were investigated. The main aim of this study was to produce
Fig. 1. (a) SEM micrographs of as-received TiO2 nanoparticles (b) TEM micrographs of as-received CuO nanoparticles.
Specific Surface Area (m2/g) Melting Point (○C) Elastic modulus (GPa)
35 1843 240
20 1326 81
hybrid Al matrix nanocomposites (HAMNCs) and investigate the
relationship between microstructure and mechanical as well as
wear properties of the resulting HAMNCs.
2. Experimental procedure
2.1. Materials
Pure Al powder (purity 99.9%) with particle size of 63 mm was
used as the composite matrix. Nanoparticles of TiO2 and CuO were
used as the reinforcements. Table 1 shows the characteristics of the
nanoparticles used in this research. Stearic acid with chemical
composition of CH3(CH2)16CO2H was used as a process controller
agent (PCA) for nanocomposite fabrication.
2.2. Milling conditions
The milling process was conducted using a high-energy plane-
tary ball mill with cups (250 ml) and balls of hardened steel. The
rotation speed was adjusted to 250 rpm and the ball to powder
ratio was kept 12:1 for all milling processes [7,13]. At first, pure Al
powder, along with 2 wt% PCA, was milled for 20 h in argon at-
mosphere. Then 2.5 wt% nanoparticles of each TiO 2 and CuO were
added to the milled Al powder and the mixture was milled for
another 5 h. The total milling time was 25 h for producing the
nanocomposite powder. Time intervals of 30 min for milling and
30 min for resting were used to avoid temperature rise inside the
cups.
2.3. Powder compaction and density measurement
The mixed powders were consolidated using cold and hot uni-
directional pressing. First, 3 g of powders were poured into in a
cylindrical tool steel die and cold pressed into disk-shaped com-
pacts with diameter and length of 10 and 15 mm, respectively. The
compacts were then hot pressed at 400 ○C under pressure of
 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724 715

450 MPa for 90 min. The density of all compacted samples was
measured according to ASTM: B328. The bulk density of all samples
was also measured in pure water by the Archimedes buoyancy
method.

2.4. Microstructure evaluation

Low rates and pressures were used to mechanically polish the

hot-pressed samples. Metallographic observations were carried out
using an optical microscope (LOM) IMI-420. Samples were etched
for 5 s with Modified Keller (20 ml HNO3, 2 ml HF, 3 ml HCl
175 ml H2O) [14]. Observations were made on un-etched and
etched surfaces in order to identify and observe the porosity levels
and microstructure conditions. Before mixing, the size,
morphology, and distribution of the nanoparticles were examined
by transmission electron microscopy (TEM -LEO/ZIESS, Germany)
operated at 80 kV. Also, the microstructure of the mixed powder
particles as well as the compacted samples were examined using
scanning electron microscopy (SEM - VEGA/TESCAN) equipped Fig. 3. XRD patterns of pure Al powder, milled for various times of 0, 10, 20, 30 h, and
with an energy dispersive spectrometry (EDS). To explore the ef- one Al powder milled 20 h then milled 5 h more after addition of 5 wt% (TiO 2 þ CuO)
nanoparticles.
fects of work hardening on the final morphology, crystalline size,
and phase transformation of the powders upon ball milling, X-ray
diffraction (XRD) was conducted. The XRD was done using Equinox
bs $cos q ¼ Kl=d þ 2 ε sin q (1)
3000 (Inel, France) with Cu Ka1l ¼ 1.54056 Å radiation. The XRD
scan rate was set at 0.2○/s and its range was between 0○ and 90○. Moreover, to assess the lattice parameter, Nelson-Riley
The Average crystallite size parameter and lattice strain were approach (Eq. (2)) was applied [16]:
calculated by Williamson-Hall formula (Eq. (1)) as follows [15]: .. Σ . ΣΣ.
NR ¼ cos2q=sin q þ cos2q=q 2 (2)

2.5. Mechanical test

Uniaxial compression test via Zwick/Reoll Z050 was performed

on cylindrical shaped specimens (10 mm in diameter and 14 mm in
height) at room temperature and constant strain rate of 1 mm/
min, according to ASTM E9-89a [17] standard. At least three
compression tests were performed for each sample. Vickers
microhardness (Wolpert Instron) was used to determine the
hardness of compacted composites according to ASTM E384 [18]
standard. The microhardness measurements were conducted at 50
gf for 10 s. A minimum of five indentations were measured per
condition.

2.6. Wear test

Dry wear testing was carried out according to ASTM standard

G99 [19] at room temperature by unidirectional pin-on-disk
aperture with a counter face of AISI 52100 steel which was
hardened to 62 HRC. Consolidated pin shape samples with 10 mm
in diameter and 15 mm in length were grinded with 1000 grit SiC
paper. Worn samples were cleaned after the tests and then
weighed to determine the wear weight loss using an electronic
balance (GR200-AND) with an accuracy of 0.1 mg. Eq. (3). calcu-
lated the volume loss of samples through the mass loss divided by
the Archimedes density of the nanocomposite, and the friction
coefficient (m) values were measured by a load cell equipped with
the pin-on-disk apparatus. Moreover, the wear rate was calcu-
lated by Eq. (4). Normal load, velocity and wear distance were set
at 30 N, 350 RPM at 0.8 mm diameter track, and 1000 m,
respectively.
. Σ weight loss ðgÞ
Volume loss mm3 ¼ . Σ × 1000 (3)
g
density
3
cm
Fig. 2. XRD patterns of TiO2 and CuO nanoparticles (inset pictures are ICSD 1 card of
each phase).
716 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724
Fig. 4. (a) Crystalline size and lattice strain of Al powder, (b) variation of Al lattice parameter as a function of milling time.
Fig. 5. Morphology variation in Al powder (a) as-received Al powder, (b) Al powder after 20 h of milling, (c) after addition of TiO 2 and CuO nanoparticles and milled for another 5 h.
. mm3 Volume loss.mm3 Σ
Wear rate ¼ × 1000
km sliding distanceðkmÞ
Σ the nanoparticles were observable in the diffraction patterns. In
For accuracy, each wear test was repeated 3 times and the
average was taken into consideration. The morphology of the worn
surfaces and debris were analyzed by SEM-line scan and SEM-MAP.
3. Results and discussion
The SEM and TEM images of the nanoparticles used in this study
are shown in Fig. 1. The average sizes of TiO2 and CuO nanoparticles
were determined to be around 30 nm and 40 nm, respectively. The
morphology of both nanoparticles was semi-spherical. Fig. 2 illus-
trates the XRD patterns belonging to TiO2 and CuO nanoparticles. In
both cases, the peaks widening was due to the existence of nano-
structure [20].
3.1. Optimal nanoparticles amount and milling time for Al matrix
Mechanical milling containing 3.5 wt% of each TiO 2 and CuO
nanoparticles led to powder adhesion in the system of balls and
cups. However, the sample containing 2.5 wt% of each TiO2 and CuO
nanoparticles turned out very good. Hence, it was used as the ideal
sample for characterizing mechanical properties and microstruc-
ture examination.
Fig. 3 exhibits the XRD patterns of the pure Al powder, milled for
various times of 0, 10, 20, 30 h, and also one containing 5 wt%
(TiO2 þ
CuO) nanoparticles. As it is obvious in Fig. 3, increase in the
milling time led to decrease in the Al peaks intensities and their
1
Inorganic Crystal Structure Database.
widening, as a result of microstructural alteration. With increase in
milling time, Al crystallite size decreased and lattice strain
(4)
increased. Because of their small amount, no diffraction peaks for
order to determine the optimal time duration of MM for the Al
powder, 6 diffraction planes of its FCC lattice including (111), (200),
(220), (311), (222), and (400) were considered as the main
diffraction planes for calculation. By applying the Williamson-Hall
equation, crystallite size and lattice strain were measured for
different durations of MM.
The Williamson-Hall diagram for Al powder, milled for various
time durations, is illustrated in Fig. 4 (a). It was found that by
increasing the milling time beyond 20 h, the crystals did not get any
finer. In other words, the milling process was not useful beyond
20 h. Hence the milling time of 20 h was taken as the optimal
milling time, at which the crystals reached their optimal nano-size
of around 10 nm. Regarding the Al lattice parameter (0.4046 nm),
the values calculated for every peak at various milling times ac-
cording to Nelson-Reilly equation are shown in Fig. 4 (b). At 20 h of
milling, the lattice parameter increased by 2%, and afterwards the
lattice parameter reduced again due to perhaps dislocation satu-
ration and other atomic phenomena.
3.2. SEM analysis
Morphology variation versus milling time is shown in Fig. 5 for
the Al powder before and after milling. At short durations of MM,
the soft Al particles became polygon in shape due to cold welding.
In time, they became smaller and more spherical particles. After the
addition of TiO2 and CuO nanoparticles, they got refined and uni-
form. In other words, upon reaching the optimal time (25 h), the
balance between repeated cold welding and fracturing processes
 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724 717

Fig. 6. SEM micrographs in accordance with MAP analyses for the milled powders at different milling times, (a) Al powders, Al/(TiO 2 þ CuO) milled for (b) 1 h and (c) 5 h.
718 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724
Fig. 7. Optical microscopy images indicating porosity percent in HAMNCs calculated by Motive Image Advance software 3.2 at two various parts of samples A and B.
resulted in spherical nanostructured composite powder. The
elemental distribution within the powder, using EDS-Map analysis
is shown in Fig. 6. After the addition of nanoparticles, followed by
1 h of mechanical milling, the distribution of Ti and Cu elements
and oxygen within the Al matrix can be observed. Increasing the
milling time up to 5 h assisted in more uniform distribution.
3.3. Density measurement
The average density of the hot pressed Al/(TiOþ 2 CuO) com-
posite was measured to be 2.46 g/cm3. After hot pressing, the
density decreased around 8e10%. This density drop was due to the
hard nature and size of TiO2 and CuO nanoparticles [8]. In other
words, the presence of nanoparticles helped the process of pore
reduction/elimination by readjusting and realigning themselves
from their position.
Optical microscopy images of the hot pressed HAMNCs before
etching are shown in Fig. 7. The porosity calculation was performed
by Motive Image Advance software marked in green color. Nu-
merical properties determined by the software from Fig. 7 are
presented in Table 2. The density value conforms to the value ob-
tained by the densitometry results.
3.4. Microstructure examination
The dispersion of nanoparticles in the Al matrix is illustrated in
Fig. 8. Nanoparticles have aggregated mainly within the porosities
due to their tiny size. The signs refer to the porosities, inside which
the oxygen element was identified. This element proves the pres-
ence of TiO2 and CuO reinforcement nanoparticles. Of course, the
nanoparticles have been uniformly distributed in the Al matrix,
however, in some regions (e.g., porosities), the tendency to clus-
tering and agglomeration seems to be higher. The uniformity of
elements as shown in the map analysis of Fig. 8 confirmed that
milling followed by hot pressing were performed properly and
adequately. Furthermore, the presence of nanoparticles in the Al-
based nanocomposites led to the formation of finer grains, which
is attributed to two factors:
Table 2
Results of porosity characteristics of hot pressed HAMNC specimens in Fig. 7 con-
ducted by Motive Image Advance software.
Figure A B
Characteristic
Average surface of pores (m m2) 16.90
Average pore size ( mm) 25.20
Total pores percentage 11.76
Density of samples 2.38
● Nanoparticles act as abrasive agents during the milling of
composite powder mixture.
● Nanoparticles prevent grain growth during sintering.
3.5. Mechanical properties
Microhardness and compression as two representative me-
chanical properties were conducted on the HAMNCs. Table 3
compares the hardness of the HAMNC in this research with those
of other related studies. It is evident that addition of nanoparticles
in the Al matrix almost doubled its hardness. According to the rule
of mixtures (Eq. (5)) [21]:
Hc ¼ Hmfm þ Hrfr (5)
where Hc, Hm, and Hr stand for hardness of the composite, matrix,
and reinforcement, respectively, and fm and fr represent the volume
fraction of the matrix and reinforcement, respectively. This increase
in the hardness can certainly be attributed to the size and the
presence of the reinforcement nanoparticles. In other words, the
nano-size of both reinforcing particles and matrix increased the
interfacial contact between the particles and the matrix during the
milling process, leading to hardness elevation.
In Fig. 9, compression test result of the HAMNC is presented as a
true strain-strain curve. In Table 4, the values extracted from the
compression test results are compared with another related study.
As can be observed, the final synthesized nanocomposite sample
has a high strength, and its failure occurred at a 45-degree angle.
The corresponding ultimate strength is approximately 70% more
than that of the pure Al sample. Moreover, its strength is nearly 50%
more than that of the sample containing 2 weight percent of only
CuO nanoparticles.
The strengthening mechanism in these nanocomposites in-
volves formation of Orowan dislocation rings, which leads to
strength elevation. As described by Eq. (6), increasing the rein-
forcement volume fraction leads to reducing the distance between
the reinforcement nanoparticles, which in turn helps to enhance
the strength by means of preventing motion of dislocations [22].
Hence, the required tension for dislocation motion would increase.
Ds ¼ 2Gb=l (6)
where G is shear modulus, and b is the Burgers vector.
3.6. Wear test
18.30
28.40
12.16
In order to investigate the effect of nanoparticles on the wear
2.37 behavior of HAMNCs, including weight and volume loss and
 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724 719

Fig. 8. SEM-MAP analysis of the compacted Al nanocomposite containing 5 wt% (TiO 2 þ CuO) nanoparticles (circles show porosities inside which contain agglomerated
nanoparticles).

determine the wear mechanisms, the pin on disk test was per-
formed. The contributing factors in wear resistance such as the
applied force, sliding speed, and distance were set constant. Both
quantitative and qualitative studies were performed on the HAMNC
samples.

3.6.1. Quantitative studies

The weight loss in time versus distance up to 1000 m is reported
in Table 5. Some information regarding the overall scheme of the
wear test are presented in Table 6. Fig. 10 illustrates the curves
regarding the results of weight and volume loss of the HAMNC

Table 3
Hardness of HAMNC in comparison to other related studies.

Sample Hardness value Hardness scale

Pure milled Al powder [23] 40 HV0.05

71 70 74 74 76
Al/(2.5TiO2 þ 2.5CuO) 73 HV0.05
Al- 2.5TiO2 [5] 79 (83 HV) BHN
Fig. 9. True stress-strain curves for the Al nanocomposite reinforced with TiO 2 and
Al- 10SiCp [24] 61 HV
CuO nanoparticles.
720 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724

Table 4 of the soft material in kg/mm 2, and a constant called wear coeffi-
Compression test results of HAMNC compared with other related studies.
cient, respectively.
Sample Ultimate strain Compression strength Yield stress According to Eq. (7), hardness is inversely proportional to the
r sUTS (MPa) sy (MPa) wear rate, indicating that samples with higher hardness experience
Pure milled Al Powder [23] 0.8 104 87 lower wear rate. Fig. 11 shows the friction coefficient variation vs.
Al/(2.5TiO2 þ 2.5CuO) 0.04 278 250 distance for the HAMNCs, whose average friction coefficient is
Al- 2CuO [10] e 147 e approximately 0.27, which for pure milled Al powder was about
0.575 [23]. This increase is mainly due to the presence of hard
nanoparticles of TiO2 and CuO inside the microstructure. These
Table 5 hard and brittle particles are responsible for withstanding against
Weight and volume loss amounts at different distances for HAMNC sample.
applied force on the material. According to Fig. 11, it can be found
Material loss Wear Sample weight (g) Weight loss (g) Volume loss (mm3 ) that the friction coefficient decreases as the wear distance in-
distance (m) creases, as a result of nanoparticles agglomeration between the pin
0 2.1408 0 0 and the hard disk. With increase of the wear distance, these par-
250 2.1345 0.0063 2.5610 ticles prevent the part from further cleavage and wear, and improve
500 2.1275 0.0070 2.8455
the part properties by changing the wear mechanism. It is note-
750 2.1174 0.0101 4.1057
1000 2.1051 0.0123 5
worthy that in accordance with quantitative information gathered
Total 0.0375 14.5122 in Table 6, which indicates considerable weight loss of the nano-
composite sample, it is predictable that the main wear mechanism
is adhesive wear. Hence, to prove the above hypothesis, SEM
Table 6
Wear test results.
equipped with EDS analyzer was used, the results of which are in
the following.
Unit Amount Characteristic

Millimeter 11.2480 Initial length of pin 3.6.2. Qualitative investigation

10.7570 Final length of pin
SEM examinations of the worn surfaces of the nanocomposites
0.4910 Pin length loss
Gram 47.7426 Initial weight of disk
were conducted in order to specify the wear mechanism, wear
47.7441 Final weight of disk surface quality, and chemical composition of the worn surfaces.
0.0015 Disk weight loss Fig. 12 illustrates the wear surfaces of Al base nanocomposite
samples at different magnifications. Wear mechanism is influenced
samples versus the wear distance. Moreover, due to density dif- by several factors such as the applied force and the sliding speed.
ference between the matrix and the reinforcements, calculations This study only focused on investigating the effect of nanoparticles
were done based on the volume loss of the samples (Eq. (3)). For on wear mechanism, while maintaining other factors constant. Two
this purpose, Archimedes density (counting the porosity of the wear mechanisms were observed for Al base nanocomposite
nanocomposite) was used in the calculations. Wear rate can be samples:
expressed in terms of volume (mm3) loss versus wear distance
(km). Hence, wear rate of the HAMNC sample was calculated to be 1 Abrasive
14.5122 (mm3/km). 2 Delamination (of type adhesive)
The effect of reinforcement nanoparticles on mechanical prop-
erties such as hardness can be attributed to the smaller size of the In fact, delamination wear mechanism of pure Al is the main
matrix particles/grains and lower amount of porosity [23]. Relative erosion cause at lower applied forces, due to its low hardness. By
density and hardness are two contributing factors in the wear rate adding hard nanoparticles, the wear mechanism shifts to abrasive
of HAMNCs. The relationship between hardness and wear rate can or combination of abrasive/adhesive wear mechanisms by
be expressed using Archard's relation [24] in terms of Eq. (7): improving the strength and hardness of the sample. Increasing the
wear distance leads to situation in which the nanoparticles extend
W the zones under abrasive wear and consequently the weight loss
Q¼K (7) and sample destruction decreases. In many slipping cases, while a
H
hard rough surface moves over another hard and tough surface, the
where Q, W, H, and K represent the wear rate (volume of eroded slipping occurs on the tips of the contact nodes. These nodes
material during sliding), applied force in Newton, Vickers hardness basically experience plastic deformation. Although the total contact

Fig. 10. Curves of wear volume (a) and weight loss (b) for Al nanocomposite samples according to wear distance.
 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724
Fig. 11. Friction coefficient variation vs. distance for a typical Al-based nanocomposite
sample.
tension may be less than the yield stress of the materials involved
in the contact, the local tensions at small regions of the contact
nodes are much higher, which leads to plastic deformation [8]. High
contact tensions can result in generation and accumulation of
dislocations and crack initiation in regions close to the surface.
Limited amount of plastic deformation of Al base nanocomposite
sample is attributed to the presence of TiO 2 and CuO nanoparticles.
In fact, with limited deformation, creating grooves on the sample is
Fig. 12. SEM images of worn surfaces of Al-based nanocomposite: (a) at low magnification. (b) areas with abrasive morphology, and (c) peeling/adhesive.
721
accompanied by elongation, at medium and mild forces. This
phenomenon was observed for the sintered nanocomposite in this
research. Fig. 12 (b, c) demonstrates SEM images of the surface of
the composite sample. It can be seen that because of the limitations
on plastic deformation of composites due to the presence of
nanoparticles, elongation is observable in addition to the abrasive
wear that leads to a reduction in weight loss of the sample and
compensates the effect of generated grooves on the weight loss. It
means that the materials are worn by rubbing against each other. As
it is demonstrated in Fig. 12 (b) parallel grooves can be observed on
the worn surface of the nanocomposite. On the other hand,
regarding the observations during the experiment, it seems that this
wear is of type three body abrasions. In fact, these grooves are
created due to the separation of some particles from the sample
surface and staying between the surfaces on the abrasion path. The
detached Al particles in the middle of the wearing surfaces and the
reinforcement nanoparticles separated from the matrix form these
grooves. Since the porosities are of high importance in composite
samples, elements including Al, Ti, Cu, and O were examined by
EDS analyzer in order to scrutinize the chemical nature around a
porosity. The image of the mentioned region is demonstrated in
Fig. 13, and the results of chemical composition test are presented
in Table 7. The results reveal that the oxygen concentration is higher
in zone A in which the particles ejection occurs, indicating the
presence of additive oxide nanoparticles. At the surface of the
722 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724

Fig. 13. EDS analysis of the areas around a porosity of the abrasive surfaces. Fig. 15. SEM image of nanocomposite debris.

Table 7 lines have identified significant variations of copper and titanium

Spot analysis report with respect to Fig. 13.
amounts. Hence, the abrasive wear mechanism is dominant when
Element wt.% Oxygen Titanium Copper Aluminum TiO2 and CuO nanoparticles resist against the applied force simul-
Area
taneously and display their impact on the whole microstructure. In
A 1.17 3.63 2.62 Res accordance to the microstructure examination results obtained
B 0.1 0.34 0.55 Res from SEM-MAP test and qualitative wear properties, it is concluded
C 2.54 3.23 2.82 Res
that the additive nanoparticles have been distributed uniformly
throughout the microstructure and therefore improved the wear
properties. Improved properties, confirmed by extracted quantita-
samples, the material strength against the abrasive object increases tive results of wear test including wear rate or friction coefficient,
as a result of the stretching of nanoparticles from the cavities edges justify this phenomenon. The intensity of the changes of three el-
(zone C) into the surface environs. ements (oxygen, titanium, and copper) in Fig. 14 (a) is almost
To have a better understanding of the governing mechanisms, equivalent which again indicates their desirable dispersion within
SEM linear chemical analyzer was used, whose results are pre- the microstructure.
sented in Fig. 14. As it is demonstrated in Fig. 14 (a), the dominant Weight or volume loss rate of the material is caused by occur-
wear mechanism is abrasive, from which the chemical analysis rence of delamination or adhesive wear mechanism, and linear

Fig. 14. SEM-line scans analysis on the worn surfaces (a) abrasive and (b) adhesive/delamination.
 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724 723

chemical analysis on crack route generated by abrasion is presented
in Fig. 14 (b). According to the graph, illustrating the distance as a
function of the elements concentrations in the sample, only the
oxide particles and Ti element involve in determining the mecha-
nism. High oxygen concentration is due to the oxidation phenom-
enon and Ti oxide nanoparticles. As it is clear, oxygen concentration
and variation in the micrograph differ from those of the initial
image in which the abrasion wear mechanism was dominant. In
both linear chemical analysis in Fig. 14 (a) and (b), little amount of
iron was identified, as a consequence of slight penetration of iron
element from the container and the balls into the nanocomposite
powder.
To get a better perception of wear mechanism in nanocomposite
sample, SEM analysis along with MAP and linear chemical analysis
were conducted on wear debris. An overall scheme of the wear
debris is presented in Fig. 15. Because of little plastic deformation of

Fig. 16. MAP analysis: (a) along with EDS linear analysis, (b) wear swarfs of nanocomposite sample.
724 M. Ahmadi, M.H. Siadati / Journal of Alloys and Compounds 769 (2018) 713e724
the surfaces, many cracks initiate before a wear particle is created.
Particles generated by delamination are laminar and shell shaped
with a length of few hundred micrometers.
Fig. 16 demonstrates MAP analysis and EDS linear analysis re-
sults of the wear debris of nanocomposite sample. The MAP anal-
ysis of wear debris (Fig. 16 a) reveals that all the additive
nanoparticles have provided an identical distribution in wear
debris to that of the microstructure. This also confirms the abrasion
wear mechanism justification, mentioned earlier. The EDS linear
analysis (Fig. 16 b) indicates clearly that oxygen element is domi-
nant at adhesion point of the wear debris, and actually the oxida-
tion (adhesive mechanism) caused this phenomenon to happen. It
is noteworthy that the variation intensities of Cu and Ti elements
within the central parts of the debris are approximately equal,
showing the presence of oxide nanoparticles in the debris. Indeed,
presence of nanoparticles inside the nanocomposite structure has
led to particles integrity, and has prevented inter-granular fracture,
which is a weakness point of composite parts.
4. Conclusions
In this work, the effects of additions of TiO 2 and CuO nano-
particles on mechanical properties (microhardness and compres-
sion strength) and microstructure of pure Al powder which was
initially milled mechanically for 20 h were investigated. 2.5 wt% of
each TiO2 and CuO nanoparticles with average sizes of 30 nm and
40 nm, respectively, was added to the milled Al powder. Then the
final mixture was milled for another 5 h in order to make the
nanocomposite powder mixture followed by hot pressing and
sintering. The following conclusions were drawn:
1 Initial Al powder as matrix with semispherical morphology can
be synthesized after 20 h of mechanical milling at speed of 250
RPM, and BPR of 12 to 1.
2 Nano-crystallite size and lattice strain of the Al powder at
optimal milling time of 20 h were calculated to be around 10 nm
and 0.258%, respectively.
3 Between a total of 7 and 5 wt%, the optimum amount of nano-
particles was found to be 5 wt% (2.5 wt% each).
4 The microstructure MAP analysis revealed uniform dispersion of
the nanoparticles within the nanocomposites structure. Also,
the agglomeration of the reinforcement nanoparticles was
negligible.
5 Mechanical properties improved by adding nanoparticles, such
that the yield strength increased from 87 MPa for pure Al to
250 MPa for the nanocomposite.
6 Addition of reinforcement nanoparticles improved the com-
posite hardness up to about twice the pure Al. The hardness
increased from approximately 40 for pure Al to 73 Vickers for
the nanocomposite.
7 Adding oxide nanoparticles improved the wear resistance
considerably, so that the wear coefficient of the nanocomposite
was about half that of pure Al.
8 The main wear mechanisms were a mixture of abrasive and
adhesive, and some delamination.
Acknowledgement
K. N. Toosi University (KNTU) of Technology supported this
project by providing some equipment and laboratory space.
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