Ceramics International 44 (2018) 20774–20781

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effect of nano TiO2 particles on microhardness and microstructural behavior T

of AA7068 metal matrix composites
⁎ ⁎
K. John Joshua , S.J. Vijay , D. Philip Selvaraj
Department of Mechanical Engineering, Karunya Institute of Technology and Sciences, Coimbatore 641114, Tamil Nadu, India

A R T I C LE I N FO A B S T R A C T

Keywords: Present work deals with the fabrication of AA7068 composites reinforced with different percentages of Nano
Compacting TiO2 (3, 6 and 9 wt%) using powder metallurgy technique along with as sintered AA7068 material. The pressure
Sintering applied for compacting the composites was 318 MPa and sintered at 560 °C in a sintering furnace for one hour.
Powder metallurgy Vickers micro hardness test have been conducted for finding the microhardness. Optical Microscopy was carried
FESEM
out to analyze the microstructural behavior. The worn surface was investigated by the Field Emission Scanning
EDS
Electron Microscope (FESEM) after the wear test. The microhardness was found to increase by increasing the
weight percentage of TiO2 particles. It was observed to be a maximum of 68 VHN by adding 9% Nano TiO2
particles. Abrasion, oxidation and delamination were the dominant wear mechanisms present in the composites.
Energy Dispersive Spectroscopy analysis was done to confirm the presence of the TiO2 particles.

1. Introduction composites exhibits higher hardness, lower wear coefficient when

Metal matrix composites (MMCs) that incorporate ceramic particles
as a reinforcement enhances the wear resistance, elasticity and hard-
ness of pure metals. In past few years, researchers has focused attention
on the aluminum alloys, due to their low density, high strength-to-
weight ratio, improved resistance to corrosion and mechanical property
[1,2]. AA7068 alloy provides high mechanical strength and offers
better bulk mechanical properties [3]. AA7068 is the strongest alu-
minum alloy which offers high strength, good workability, high re-
sistance to corrosion and so on [4]. Titanium dioxide (TiO2) has
properties like chemical stability, good optical transparency, high re-
fractive index, low cost, and non-toxicity. TiO2 has been widely used as
in environmental applications, building materials such as tiles, con-
crete, paints and glasses. TiO2 nanoparticles finds its use in industrial
and medical applications. TiO2–Al2O3 nanocomposite materials pro-
vides better wear and corrosion due to their thermal, chemical and
mechanical stability. TiO2–Al2O3 structures are also used in various
applications such as catalysis, solar cells, photocatalytic and self-
cleaning [5,6]. TiO2 is inexpensive and provides better wear resistance,
mechanical and thermal properties [7]. The presence of TiO2 in an
Al2O3 coating has enhanced its mechanical behavior [8]. The toughness
of Ti/TiO2 nanocomposite samples has improved considerably [9]. The
hardness and wear performance of Ni–TiO2 nanocomposite coating are
improved by increasing of TiO2 wt% in coating [10]. Al6061–TiO2
compared with the matrix alloy [11]. The Ni–P–TiO2 nanocomposite
coatings show improved hardness and wear resistance as compared to
that of Ni–P alloy coatings [12]. Other researchers show that the
hardness has been improved by the addition of increase in TiO2 content
[13–16]. Stir casting and powder metallurgy are two widespread
methods used for product manufacturing. Powder metallurgy method is
the most suitable method for making MMCs which has the advantage of
low processing temperature and has better distribution of reinforce-
ment particles in the matrix [17,18].
The fabricated AA7068/TiO2 composites with various compositions
such as 3%, 6% and 9% reinforcement in Al matrix are characterized for
their microhardness and metallurgical properties and their results are
reported. The results of the composites are also compared with as sin-
tered AA7068.
2. Experimental procedure
2.1. Composite preparation
Fig. 1 shows the FESEM images of powders used in this research
work. The AA7068/TiO2 composite samples were produced through
powder metallurgy route. The composition of AA7068 powders were
shown in the Table 1. Shimadzu electronic weighing machine-ATY 224
model with an accuracy of 0.0001 g was used for weighing all the

⁎
Corresponding authors.
E-mail addresses: kjohnjoshua@gmail.com (K.J. Joshua), vijayjoseph@karunya.edu (S.J. Vijay).

https://doi.org/10.1016/j.ceramint.2018.08.077
Received 4 June 2018; Received in revised form 24 July 2018; Accepted 7 August 2018
Available online 09 August 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
K.J. Joshua et al. Ceramics International 44 (2018) 20774–20781

Fig. 1. FESEM image of powders as received a) AA7068 after milling b) Nano TiO2.

sizes [20]. The average particle size of AA7068 powders and Nano TiO2
Table 1 powders were calculated using particle size analyzer which were shown
Composition of AA7068 (% by weight). in Table 2. The powders were cold compacted at a pressure of 318 MPa
Element Si Fe Cu Mn Mg Cr Zn Ti Zr Al using a Universal Testing Machine (UTM) to produce green compacts of
size 20 mm diameter and 30 ± 2 mm height. The green compacts of
Content 0.12 0.15 2 0.1 3 0.05 8 0.01 0.1 Bal the samples were shown in the Fig. 2. The green compacts were sintered
at 560 °C for one hour in a sintering furnace. Similar procedure was
used to fabricate the composites of AA7068 reinforced with Nano TiO2
with 3, 6, 9 wt% and plain AA7068 samples. The samples were allowed
Table 2
to cool at room temperature after sintering. The sintered composites
Average particle size.
and as sintered AA7068 were machined to 10 mm diameter for testing
Powders Average Particle size purpose. The samples were ground using belt grinder with abrasive
AA7068 1.785 µm
papers of grit sizes 600, 800 and 1200. They were finally polished using
TiO2 2.585 nm 2 µm diamond paste and then with 0.5 µm diamond paste in a twin disk
polisher. The samples were etched with Keller's reagent for 10 s to re-
move impurities on the surface and expose the grains. Optical micro-
scopy analysis was done to study microstructural behavior of the
samples. The samples were tested for their wear behavior at 5 N load,
sliding velocity of 1.2 m/s and sliding distance of 2.5 km to study the
dominant wear behavior. Subsequently the worn surface and the wear
debris collected were investigated by the Field Emission Scanning
Electron Microscope (FESEM). Energy Dispersive Spectroscopy (EDS)
analysis was carried out to confirm the presence of combinations of the
worn surface.
The hardness test was conducted using a Vickers microhardness
machine. The results were presented in Fig. 5. Three spots were iden-
tified and Vickers microhardness was measured and the average values
were taken for all the samples.

Fig. 2. Compacted samples of AA7068 reinforced with Nano TiO2. 3. Results and discussion

powders accurately and milled in a ball mill for 40 h. 2% stearic acid
was added to have proper bonding between the particles [19]. Reduc-
tion of reinforcing particle size and matrix grain size to submicron level
was possible by ball milling. Distribution of reinforcing particles during
ball milling depend on ball milling parameters and on initial particle
3.1. Microstructural analysis
Fig. 3(a-d) shows the optical micrographs of AA7068 reinforced
with Nano TiO2 particles. Fig. 3a shows the micrograph of AA7068 base
matrix without reinforcement. It consists of more number of uniformly

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K.J. Joshua et al.
Fig. 3. Optical Micrographs of the processed samples (a) As sintered AA7068 (b) AA7068-3%TiO2 (c) AA7068-6%TiO2 and (d) AA7068-9%TiO2.
distributed spherical shaped pores. This is due to the application of low
pressure (318 MPa) during the compacting process [3]. It is observed
from the Fig. 3(b-d) that TiO2 particles are uniformly distributed
throughout the matrix. The hard TiO2 reinforcement provides strong
bonding with the matrix alloy which enabled uniform load transfer
from the base matrix to the reinforcement [7]. Uniform dispersion of
Nano TiO2 particles effectively prevent the formation of large grains
and grain growth. Smaller sized particle has more pinning effect com-
pared to those of large sized particles [28]. The composites reinforced
with TiO2 are denser compared to the matrix alloy. This is due to the
addition of fine nano-TiO2 particles mixed with the matrix material,
uniform mixing of particles and proper application of compaction
pressure. Fine grain size improves hardness and reduces wear rate.
Porosity formation is highly probable in sintering method compared to
stir casting technique [17]. The presence of porosity is due to the result
of poor mixing of powders or insufficient compaction and sintering
conditions [27].
3.2. EDS analysis
EDS analysis is used to determine the elemental analysis at different
regions [12]. Fig. 4(a-d) Illustrates the EDS pattern for AA7068
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Ceramics International 44 (2018) 20774–20781
reinforced with Nano TiO2 particles. It is noticed that the highest peak
belongs to aluminum for all patterns from the EDS analysis. 7XXX series
alloys are age-hardenable high strength aluminum alloys, which has
zinc as its major element next to aluminum [4,29,30]. The EDS ele-
mental analysis confirms the maximum amount of zinc present next to
aluminum. The EDS pattern in Fig. 4(b-d) confirms the existence of
Nano TiO2 reinforcement particles. All the EDS patterns confirm the
presence of oxide layer. Oxidation occurs due to the frictional heat
generation during sliding surfaces. The oxide layer acts as protective
layer which reduces the wear loss by minimizing the effective area of
contact between the mating surfaces [7].
3.3. Microhardness measurement
Fig. 5 indicates the effect of Nano TiO2 on microhardness for the
composite samples. The graph shows that as the Nano TiO2 content
increases the microhardness also increases. Vickers hardness number
increases from 33 VHN (as sintered AA7068) to 45 VHN (3 wt% TiO2),
indicating an improvement of 36.3%. The maximum hardness is found
to be 68 VHN for an addition of 9% Nano TiO2 reinforcement particles.
The incorporation of hard ceramic particles into an aluminum matrix
results in increase in the bulk hardness of the material [31]. The
K.J. Joshua et al.
Fig. 4. EDS patterns of worn surface (a) As sintered AA7068 (b) AA7068-3%TiO2 (c) AA7068-6%TiO2 and (d) AA7068-9%TiO2.
Fig. 5. Vickers microhardness of AA7068 with increase in TiO2 Reinforcement.
hardness of an aluminum based composite depends on many factors
such as grain size, dislocation density, nano sized reinforcement parti-
cles, heat input [28], porosity [31] and so on depending on the fabri-
cation techniques used. The hardness value is inversely proportional to
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the grain size. Larger grain size reduces the hardness and smaller grain
size increases the hardness. Larger proportions of porosity minimizes
the hardness and lower proportions of porosity increases the hardness
of the composite. Hardness increases due to a better distribution of the
TiO2 nanoparticles and grain refinement in the base matrix [28].
During sliding, an increase in the Nano TiO2 content, increases the
dislocation density there by restricting the plastic deformation. Uniform
distribution of the reinforcement particles in the matrix and the higher
hardness values of TiO2 are the reasons for the increase in the micro-
hardness of the composites [7].
3.4. Interpretation of worn surface
Fig. 6(a-h) shows the FESEM images of worn surfaces of AA7068
reinforced with TiO2. Fig. 6a and b illustrates the FESEM images of
worn surfaces of as sintered AA7068 at lower magnification and at
higher magnification respectively. Wear mechanisms such as abrasion,
delamination and oxidation were predominant mechanisms in the
sample. Fig. 6b shows large number of deep and shallow narrow plastic
grooves present on the worn surface. Grooves are present paralleling to
the sliding direction which is the characteristic of abrasive wear [23].
The presence of deep grooves and plastic flow increases the shear stress
required to peel off the wearing surface and contributes to delamination
wear mechanism. Deep grooves present are due to the formation of
plastic deformation and soft aluminum asperities developed by the
K.J. Joshua et al. Ceramics International 44 (2018) 20774–20781

frictional heat and shear stress [24]. Few pits are found in Fig. 6b which
is due to the pulling out of the particles of the matrix material. Wider
Grooves and scratching becomes more severe at the higher speeds of
1–5 m/s and at higher loads. Such feature is the characteristics of severe
abrasion, where hard asperities on the steel counter face or hard pulled
out particles in between the contacting surfaces, which causes wear
debris [25]. The EDS pattern shown in Fig. 4(a) confirms the presence
of oxide layer. Oxidation occurs during the sliding of surfaces due to
frictional heat generation. The wear loss is reduced due to the protec-
tive oxide layer, which minimizes the effective area of contact between
the mating surfaces [7].
Figs. 6c and 6d illustrates the FESEM images of worn surfaces of
AA7068 reinforced with 3% of nano TiO2 composite at lower magni-
fication and at higher magnification respectively. Adhesion, abrasion
and delamination are the dominant wear mechanisms present in the
sample. Shallow and narrow grooves are present in the sample which
encourages abrasive wear mechanism. This indicates the occurrence of
micro-cutting and micro-ploughing effect of the counter face which are
signs of ductile fracture [12]. The worn surface shows few cavities
which are clearly visible in Fig. 6d. Cavities of rough regions indicate
adhesive wear and smooth regions of fine grooves or ploughing suggest
abrasive wear [21].
Fig. 6e, f and g, h illustrates the FESEM images of worn surfaces of
AA7068 reinforced with 6% and 9% of nano TiO2 particles respectively.
Both worn surfaces shows similar type of wear pattern. Mild abrasion
and oxidation are the dominant mechanisms present in the sample.
Restriction of grooves along the sliding surface can be attributed to the
high dislocation density of the deformed planes and high content of
nano TiO2 (9%). The presence of TiO2 offers extreme hardness to the
composites and reduces loss of material. Evidence of the oxide layer and
the adhesive compacted particles on the worn surface obviously re-
stricts severe plastic deformation thereby lowers the wear loss [7]. The
EDS pattern shown in Fig. 4(b-d) confirms the presence of nano TiO2
particles and the oxide layer present in the composite.
3.5. Examination of wear debris
Fig. 7(a–d) shows the FESEM images of wear debris collected for as
sintered AA7068 and the composites. Fig. 7a shows the bigger deep
groove shaped sheets and irregular shaped particles. During dry sliding,
larger sized wear debris is formed due to large scale plastic deforma-
tion. Presence of grooves can be attributed to abrasive wear

Fig. 6. FESEM micrograph of the worn surface (a) As sintered AA7068 (c) AA7068-3%TiO2 (e) AA7068-6%TiO2 and (g) AA7068-9%TiO2 at lower magnification and
(b) As sintered AA7068 (d) AA7068-3% TiO2 (f) AA7068-6% TiO2 and (h) AA7068-9% TiO2 at higher magnification respectively.

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K.J. Joshua et al.
Fig. 6. (continued)
mechanism, which is due to the hard asperities of the hard counterface
or hard particles which exists between the pin and disk surfaces. This
can be attributed to a combination of delamination and abrasion wear
mechanism [22].
Fig. 7b and c shows large irregular shaped debris particles. The
cutting action of the hard asperities of the counterface creates such kind
of debris. The large sized debris is probably due to the presence of deep
grooves in the worn surface. Presence of large grooves confirms dela-
mination wear mechanism [26].
Fig. 7d shows fine loose particles of wear debris. The image further
shows reduced mean size of particles for an addition of 9% TiO2 com-
pared to other composite combinations. The addition of Nano TiO2
particles in the composite minimizes the plastic deformation due to
increase in dislocation density. Hence the hardness of the composite is
increased and reduces the particle size. The amount of hard TiO2 phases
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dictates the size and morphology of wear debris [7].
4. Conclusions
• AA7068/TiO 2 metal matrix composite was successfully fabricated
using powder metallurgy technique with improved hardness and
better bonding.
• Optical microscopic images, represented a uniform dispersion of
reinforcement particles in the aluminum matrix.
• The microhardness of the composites increased with increase in
TiO2 particles and was found to be having a maximum of 68 VHN for
an addition of 9% Nano TiO2 particles.
• Abrasion, oxidation and delamination were found to be the domi-
nant wear mechanisms in the composites.
K.J. Joshua et al. Ceramics International 44 (2018) 20774–20781

Fig. 7. FESEM images of wear debris (a) As sintered AA7068 (b) AA7068-3%TiO2 (c) AA7068-6%TiO2 and (d) AA7068-9%TiO2.

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