Wear 418–419 (2019) 290–304

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Wear
journal homepage: www.elsevier.com/locate/wear

Wear behavior of silica and alumina-based nanocomposites reinforced with T

multi walled carbon nanotubes and graphene nanoplatelets
Nidhi Sharmaa, Syed Nasimul Alama, , Bankim Chandra Raya, Surekha Yadavb, Krishanu Biswasb
⁎

a
Metallurgical and Materials Engineering Department, National Institute of Technology Rourkela, Rourkela, Orissa 769008, India
b
Material Science and Engineering Department, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India

ARTICLE INFO ABSTRACT

Keywords: Spark plasma sintering (SPS) technique has been employed to fabricate silica (SiO2) and alumina (Al2O3) based
Silica nanocomposites having multiwalled carbon nanotubes (MWCNTs) and exfoliated graphite nanoplatelets (xGnPs)
Alumina as reinforcement phase. The influence of MWCNTs and xGnPs on the wear behavior of the nanocomposites is
MWCNTs analyzed. SiO2-MWCNT, SiO2-xGnP nanocomposites having 0.5, 3 and 5 vol% and Al2O3-MWCNT, Al2O3-xGnP
xGnPs
nanocomposites having 0.2, 0.8, 3 and 5 vol% of the respective nanofiller were developed. SiO2-based nano-
Wear resistance
Abrasive wear
composites were fabricated at 1350 °C under a pressure of 40 MPa whereas Al2O3-based nanocomposites were
Adhesive wear prepared at 1450 °C under a pressure of 50 MPa. Experimental results indicate that the wear behavior of various
SiO2 and Al2O3-based nanocomposites improves with the introduction of carbonaceous nanofillers like MWCNTs
and xGnPs. With the addition of these nanofillers, a continuous supply of graphitic reinforcement phase at the
ceramic interface provided a better lubrication to the reinforced nanocomposites, which was not found in the
case of monolithic SiO2 or Al2O3 samples. Both MWCNTs and xGnPs effectively withstand the applied stress
during the wear test owing to their structural morphology once subjected to the wear strain. A remarkably varied
wear behavior of both SiO2 and Al2O3 based nanocomposites was observed. SiO2 based nanocomposites depict
narrower wear tracks with high wear rates whereas Al2O3 based nanocomposites were found to depict broader
wear tracks with low wear rates.

1. Introduction
Ceramics like silica (SiO2) and alumina (Al2O3) serve as the po-
tential candidates for several structural and mechanical applications
owing to their high-temperature stability, high hardness, good com-
pressive strength, exceptional oxidation resistance and relatively low
density [1]. Owing to these remarkable properties, both SiO2 and Al2O3
based materials are used in many applications like valves, cutting tools
and bearings, where friction and wear processes dominate [2]. How-
ever, due to their extreme brittleness, monolithic ceramics are me-
chanically unstable, due to which their use is highly limited in the
applications requiring friction tolerance. This makes wear a crucial
concern for ceramic-based materials due to high energy and material
loss. To reduce the frictional and wear loss in brittle ceramics, various
new lubricants have been developed in recent years. Lubricants mini-
mize the friction between the components in contact and thus sig-
nificantly reduce the energy loss in mechanical and structural assem-
blies [3]. Recently, researchers have made several attempts in
developing new lubricants and coatings which can effectively decrease
the wear loss in ceramic-based materials under varied operating con-
ditions [4]. However, despite the rapid progress, finding solid lu-
bricants which could efficiently enhance the wear resistance of ceramic-
based materials is still a challenge. In the last decade, the addition of
nanoparticles as reinforcing agents into ceramic matrices has emerged
as the latest trend for the production of tougher and wear resistant
ceramic matrix nanocomposites (CMNCs). Nowadays, new functional
CMNCs showing drastic improvement in the dry sliding wear perfor-
mance against metallic and polymeric counterparts are constantly
emerging [5]. It has been found that the addition of nanoparticles into
monolithic ceramics can enhance their load-bearing capacity during
sliding motion and thus decrease the tribological problems like friction,
abrasion and wear. The extremely large surface area of the nanofillers
effectively improves the wear resistance of CMNCs [6]. The sliding
friction coefficient of carbonaceous nanofillers like graphene, graphene
oxide, nano-graphite, carbon fibers and carbon nanotubes (CNTs) is
reported lowest among all existing solids [7]. Graphene and carbon
nanotubes (CNTs) owing to their unrivaled amalgam of mechanical,
thermal, chemical and electrical properties are the ideal choices as

⁎
Corresponding author.
E-mail address: syedn@nitrkl.ac.in (S.N. Alam).

https://doi.org/10.1016/j.wear.2018.10.008
Received 23 July 2018; Received in revised form 12 September 2018; Accepted 9 October 2018
Available online 15 October 2018
0043-1648/ © 2018 Elsevier B.V. All rights reserved.
N. Sharma et al.
nanostructured solid lubricants for a variety of materials [8]. As a re-
sult, numerous studies have been conducted on these unique materials
and impressive improvements in wear, friction, strength and toughness
have been observed [9,10]. A significantly small amount of these solid
lubricants can explicitly affect the friction stability, sliding distance,
wear resistance and torque variation of the CMNCs. A small loading
level of graphene and CNTs could dramatically reduce the wear loss. It
has also been demonstrated that these nanofillers work equally well in
varied environmental conditions (dry as well as humid), which is not
possible for other commonly used solid lubricants [11]. The wear me-
chanism of MWCNTs and graphene is ascribed to the debonding of in-
plane C-C bonds and shear forces acting at the matrix-nanofiller inter-
face [12]. For CMCs which are frequently subjected to high loads and
stresses, self-lubricating solid nanofillers are preferred due to their
ability of automatic self-release during the wear process to reduce the
frictional loss. For tribological components, it is a key necessity to
provide low friction, minimal wear, least deformation and high stress
bearing ability. To achieve these properties in CMNCs, CNTs and gra-
phene effectively work as novel solid lubricants in various operating
conditions. The wear behavior of CMNCs reinforced with these nano-
fillers is mainly effected by two different mechanisms: the enhancement
in mechanical attributes caused by the inclusion of nanofiller in the
ceramic matrices and the emergence of a lubricating tribo-film over the
contact area due to the exfoliation of the nanofillers [13].
Many authors have stated the formation of a tribo-layer during the
wear experiments in CNT and graphene reinforced CMNCs. Belmonte
et al. [14] studied the formed tribo-film using micro Raman and re-
ported it to be comprised of debris consisting of graphitized and de-
formed CNTs pulled out from the Si3N4 based composites. Several
works have documented the high wear performance in graphene and
CNT reinforced CMNCs due to the toughening processes like crack
branching, crack deflection and crack bridging combined with the
evolution of a protective lubricating film on the worn surface [15,16].
At the sliding speed of 100 mm s−1 and load of 25 N, a decrease of
~91.5% in the wear rate of Al2O3-exfoliated graphene composites
having 1.0 vol% of graphene was reported by Kim et al. [17]. A de-
crement of ~50% in the wear rate and ~10% in the coefficient of
friction of SPSed Al2O3-0.22 wt% graphene composite was reported by
Gonzalez et al. [18]. Balani et al. [19] observed a reduction of ~49
times in the sliding wear volume of Al2O3–8 wt% CNT coating against a
ZrO2 pin as compared to pure Al2O3 coating. Similarly, Keshri et al.
[20] also reported a reduction of ~72% in the wear rate of Al2O3–8 wt
% CNT coating against a WC ball as compared to pure Al2O3 coating.
Yazdani et al. [21] examined the tribological behavior of Al2O3 hybrid
CMNCs reinforced with graphene and carbon and reported that gra-
phene nanoplatelets mainly contribute in the formation of lubricating
Fig. 1. Synthesis of xGnPs by acid intercalation method.
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tribofilm whereas CNTs are associated with the improvement in the
fracture toughness of the nanocomposite by preventing the pull-out of
alumina grains during the wear test.
The present work focuses on the study of wear mechanisms in SiO2
and Al2O3-based nanocomposites developed using MWCNTs and xGnPs
as nanofillers and the effect of both nanofillers on the wear behavior of
various SPSed SiO2-MWCNT, SiO2-xGnP, Al2O3-MWCNT and Al2O3-
xGnP composites has been compared. The results suggest that xGnPs
serve as a novel substitute over MWCNTs in improving the mechanical
properties such as hardness and fracture toughness. It has been ob-
served that the Al2O3-based nanocomposites show lower wear rate as
compared to the SiO2-based nanocomposites.
2. Experimental details
2.1. Nanofiller synthesis and preparation of nanocomposite powder mixture
For the fabrication of various SiO2 and Al2O3-based nanocompo-
sites, xGnPs were prepared by acid intercalation method and later ul-
trasonicated for 20 h to avoid the problem of agglomeration during
their dispersion in the respective ceramic matrix. The schematic dia-
gram in Fig. 1 describes the steps followed during the synthesis of
xGnPs.
For the synthesis of MWCNTs, low-pressure chemical vapor de-
position (LPCVD) technique was used. Owing to their high van der
Waals forces and high aspect ratio, an adequate surface modification of
MWCNTs is necessary to overcome the problem of agglomeration and
enhance their homogeneous dispersion in the ceramic matrices. To
achieve this property, MWCNTs were acid functionalized with H2SO4
and HNO3 in the ratio of 3:1. The route followed to synthesize MWCNTs
is illustrated in the schematic diagram in Fig. 2(a) and the process of
acid functionalization of MWCNTs is shown in Fig. 2(b).
For the fabrication of various nanocomposites, SiO2 powder
(100–200 mesh size) was procured from Thermo Fischer Scientific Pvt.
Limited, India and alumina (α-Al2O3) powder was procured from RFCL
Limited, India. Powder metallurgy technique was opted to fabricate
various SiO2-MWCNT, SiO2-xGnP, Al2O3-xGnP and Al2O3-MWCNT na-
nocomposites. For the preparation of nanocomposite powder mixtures,
a Fritsch Pulverisette 5 planetary ball mill was used. The ball milling of
various powder mixtures was carried out at the rotational speed of
2.5 s−1 for 30 min with zirconia (ZrO2) milling media.
2.1.1. Preparation of nanocomposite powder mixtures
Before the introduction into SiO2 or Al2O3 matrix, xGnPs were ul-
trasonicated for 20 h and MWCNTs were acid functionalized as pre-
sented in Fig. 1 and Fig. 2(b) respectively. The steps followed for the
N. Sharma et al.
Fig. 2. (a) The synthesis of MWCNTs by LPCVD method, (b) Process of acid functionalization of MWCNTs.
preparation of various SiO2-MWCNT, SiO2-xGnP, Al2O3xGnP and
Al2O3-MWCNT nanocomposite powder mixtures are as follows:
2.2. Sintering and densification
SiO2-MWCNT, SiO2-xGnP, Al2O3-MWCNT and Al2O3-xGnP nano-
composites were fabricated from their respective milled powder mix-
tures by spark plasma sintering (SPS). SPS was done using Dr. Sinter
515S apparatus (SPS Syntex Inc., Kanagawa, Japan). Pure SiO2, SiO2-
0.5, 3, 5 vol% MWCNT, SiO2-0.5, 3, 5 vol% xGnP and pure Al2O3,
Al2O3-0.2, 0.5, 0.8, 3, 5 vol% MWCNT, Al2O3-0.2, 0.5, 0.8, 3, 5 vol%
xGnP nanocomposites were fabricated. For the fabrication of SiO2-
MWCNT and SiO2-xGnP nanocomposites, SPS was carried out at
1350 °C for the duration of 10 min under a pressure of 40 MPa. SPS of
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Al2O3-MWCNT nanocomposites was carried out at 1450 °C for 10 min
whereas for Al2O3-xGnP nanocomposites, SPS was performed at
1450 °C for the duration of 5 min under a pressure of 50 MPa. The other
sintering parameters maintained during SPS of various SiO2 and Al2O3
based nanocomposites are shown in Table 1.
At the end of the SPS process, the pressure was removed and the
sintered samples were naturally cooled inside the furnace. The SPS
profiles for the fabrication of pure Al2O3 and pure SiO2 samples along
with various SiO2-MWCNT, SiO2-xGnP, Al2O3-MWCNT and Al2O3-xGnP
nanocomposites are shown in Fig. 3.
N. Sharma et al.
Table 1
Sintering parameters during SPS.
Sintering parameter Specification
Heating Rate 100 °C/min
Pulse on-off ratio 12:2
Diameter of graphite die 15 mm
Vacuum in the chamber 6 Pa
Ambience Ar (flow rate ~2 L/min)
Current flow ~1200 A
Voltage 20 V
The Archimedes’ method was used to determine the bulk density of
the sintered nanocomposites and the rule of mixture was followed to
obtain their theoretical density. The density of Al2O3, SiO2, xGnP and
MWCNT was assumed as 3.95 g/cm3, 2.65 g/cm3, 2.26 g/cm3 and
2.6 g/cm3 respectively. The morphological analysis of the polished
SPSed nanocomposites was carried out using SEM. The nanofillers,
milled powder mixtures and various fabricated nanocomposites were
characterized by several techniques like scanning electron microscopy
(SEM), X-ray diffraction (XRD) and high-resolution transmission elec-
tron microscopy (HRTEM) as described elsewhere [22]. The hardness of
SPSed nanocomposites was measured on a polished cross-section using
the Vickers microhardness tester at a load of 500 gf for a period of 10 s.
An average of five indents was considered for each sample and the size
of the samples was 5 mm × 15 mm.
Dry sliding wear test of the fabricated pure SiO2, pure Al2O3 and
various SiO2 and Al2O3-based nanocomposites was performed using a
DUCOM TR208-M1 ball-on-plate type tribometer equipped with a
hardened steel ball (SAE 52100) indenter of 2 mm diameter. The har-
dened steel ball slided unidirectionally on the fixed samples and the
wear test was carried out at the room temperature (~27 °C). The var-
iation of wear depth and wear rate with respect to the sliding time was
investigated for the sintered nanocomposites. The various process
parameters during wear test are shown in Table 2.
3. Results and discussion
3.1. Microstructural analysis
Fig. 4(a) shows the SEM image of pure unmilled Al2O3 particles used
in the fabrication of Al2O3-based nanocomposites. The inset image in
Fig. 4(a) clearly reveals the distinct porous surface of monolithic Al2O3
particles. The average diameter of Al2O3 particles was found in the
range of ~90–150 µm. The SEM micrograph of pure unmilled SiO2
particles used in the fabrication of various SiO2-based nanocomposites
is shown in Fig. 4(b). The irregular shape of SiO2 particles with smooth
surfaces and sharp edges can be confirmed by the inset image in
Fig. 3. SPS profile for the preparation of (a) pure SiO2, SiO2-MWCNT and SiO2-xGnP, (b) pure Al2O3, Al2O3-MWCNT, (c) pure Al2O3, Al2O3-xGnP nanocomposites.
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Table 2
Process parameters during wear test.
Sintering parameter Specification
Diameter of sliding indenter 2 mm
Normal load 9.8 N
Sliding time 10 min
Sliding speed 0.33 s−1
Diameter of wear track 6 mm
Fig. 4(b). The average particle size of SiO2 particles was observed in the
range of ~70–220 µm. From the SEM images, it can be stated that SiO2
particles show a much smoother surface as compared to the Al2O3
particles. The structural morphology of MWCNTs and xGnPs used in the
fabrication of various SiO2 and Al2O3 based nanocomposites is shown in
the HRTEM images in Fig. 4(c, d) and Fig. 4(e, f) respectively. The
HRTEM micrographs in Fig. 4(c, d) confirm the large aspect ratio of
MWCNTs having an outer diameter in the range of ~20–50 nm. The
prominent black dots in Fig. 4(c) correspond to the agglomerates of
MWCNTs adhered to the tubular sidewalls [23]. During HRTEM,
MWCNTs were found stable under the irradiation of the electron beam.
Fig. 4(e) shows a high magnification HRTEM image of xGnPs comprised
of several graphene layers stacked together. The overlapped and su-
perimposed graphite nanoplatelets are clearly evident in Fig. 4(f). The
nanoplatelets were found to be electron transparent [24].
Fig. 5 depicts the SEM micrographs of various SiO2-MWCNT, SiO2-
xGnP, Al2O3-MWCNT and Al2O3-xGnP milled powder mixtures. Ob-
taining near full density, without deteriorating the morphology and
structure of the nanofillers is a key challenge during the fabrication of
CMNCs as most of the mechanical properties of the nanocomposites
depend upon the distribution of the nanofillers in the host matrix.
Homogeneous mixing and uniform distribution of the nanofillers in the
matrix is a prime objective during the processing of CMNCs to ensure
optimum densification [25]. The short milling duration of 30 min re-
sulted in the homogeneous mixing of the nanofillers with SiO2 and
Al2O3 powders. The SEM images in Fig. 5(a, b) and Fig. 5(c, d) show the
adherence of MWCNTs to SiO2 and Al2O3 particles respectively. Due to
their large aspect ratio, MWCNTs tend to entangle and form complex
agglomerates [26]. Dense bundles of MWCNTs deposited on the surface
of milled SiO2 and Al2O3 particles could be easily viewed. The SEM
micrographs of SiO2-xGnP and Al2O3-xGnP powder mixtures in Fig. 5(c,
d) and Fig. 5(g, h) reveal the smooth planar morphology of xGnPs.
Several graphene nanoplatelets stacked together as a sheet-like struc-
ture are evident in Fig. 5(h). This could be ascribed to the adhesion of
thin xGnPs due to stresses caused by ZrO2 balls during milling [27].
The microstructures of various SPSed SiO2 and Al2O3-based com-
posites were analyzed to determine the dispersion of the nanofillers in
the SPSed nanocomposites. Formation of carbides in the form of SiC and
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Fig. 4. SEM images of (a) pure Al2O3 and (b) pure SiO2. HRTEM images of (c, d) MWCNTs and (e, f) xGnPs used in the fabrication of various SiO2 and Al2O3-based
nanocomposites.

Al4C3 nanorods after the high temperature-pressure assisted SPS of
SiO2-MWCNT and Al2O3-MWCNT nanocomposites could be observed in
the SEM images in Fig. 6(a) and Fig. 6(f). The diameter of SiC rods in
SiO2-MWCNT nanocomposites and Al4C3 rods in Al2O3-MWCNT nano-
composites were found to be in the range of ~90–230 nm and
~50–200 nm respectively. The formation of carbide nanorods could be
associated with the carbo-thermal reactions of MWCNTs and the
ceramic matrix. MWCNTs react with the matrix and form carbides in
the vapor phase, depending upon the atmosphere and pressure during
sintering [28]. The extent of carbide formation increased with the in-
crease in the amount of MWCNTs from 0.5 vol% to 5 vol% in both the
SiO2-MWCNT and Al2O3-MWCNT nanocomposites. Irregular cracks and
surface damages can be seen in the SEM micrographs. These surface
defects and cracks deteriorate the mechanical attributes, fracture
toughness and the wear behavior of the nanocomposites [29]. In
Fig. 6(b), well sintered SiO2-MWCNT conglomerate represents the dif-
fusion of MWCNTs with SiO2 grains. In Fig. 6(c, d) xGnPs were found
well dispersed in between the grain boundaries of the SiO2 particles. In
Fig. 6(g), diffused xGnPs with Al2O3 grains, forming well sintered
Al2O3-xGnP conglomerates could be easily seen. Several xGnPs stacked
together to form thick graphene sheets could be observed in Fig. 6(h). It
should be noted that the structure of both the nanofillers was found
well preserved in the SPSed nanocomposites.
XRD analysis was carried out for the SPSed nanocomposites to
analyze the formation of any new phases during sintering. Peaks cor-
responding to (002) plane of xGnP at ~26.43° in SiO2-xGnP and Al2O3-
xGnP nanocomposites and (002) plane of MWCNT at ~26.38° in SiO2-
MWCNT and Al2O3-MWCNT nanocomposites could be seen in the XRD

Fig. 5. SEM images of milled (a, b) SiO2-3 vol% MWCNT, (c, d) SiO2-3 vol% xGnP, (e, f) Al2O3-3 vol% MWCNT and (g, h) Al2O3-3 vol% xGnP powder mixtures.

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Fig. 6. SEM of SPSed (a, b) SiO2-3 vol% MWCNT, (c, d) SiO2-3 vol% xGnP, (e, f) Al2O3-3 vol% MWCNT and (g, h) Al2O3-3 vol% xGnP nanocomposites.
plots in Fig. 7(a, b) which confirm that the crystalline structure of the
nanofillers was well preserved in the ceramic matrix during SPS. The
intensity of (002) peak of xGnPs and MWCNTs increases on increasing
the concentration of the nanofillers in the nanocomposites. From
Fig. 7(a), it is evident that sharper peaks of MWCNTs were found in
SiO2-based nanocomposites as compared to the Al2O3-based nano-
composites. The (002) peak of MWCNT at 2θ ~26.38° in the case of
Al2O3-MWCNT nanocomposites was not as sharp as the peak observed
in the case of SiO2-MWCNT nanocomposites. This could be associated
with the higher thermal conductivity of Al2O3 (12-38.5 W/m K) as
compared to SiO2 (1.3–1.5 W/m K) as a result of which SiO2 could ef-
fectively reduce the MWCNT degradation and preserve its crystallinity
[30]. A slight shift in the XRD peak of Al2O3 was seen only in the case of
the Al2O3-xGnP system. However, any prominent shift in the peaks of
Al2O3 or SiO2 was not observed for other systems due to short sintering
time during SPS, which prevented the carbon diffusion from nanofillers
into the ceramic matrix [31]. Formation of any new phase could not be
traced from the XRD plots of both SiO2 and Al2O3-based nanocompo-
sites when the amount of nanofiller was increased up to 5 vol% in the
ceramic matrices. It should also be noted that several small peaks ob-
served for SiO2-0.5 vol% MWCNT and SiO2-0.5 vol% xGnP nano-
composites diminish on the increment of the loading level of both the
nanofillers from 0.5 vol% to 5 vol% in the SiO2 matrix.
Fig. 7. XRD plots of (a) SiO2-MWCNT, Al2O3-MWCNT and (b) SiO2-xGnP, Al2O3-xGnP nanocomposites.
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3.2. Characteristic properties
Fig. 8 shows the variation of relative density with respect to the
volume fraction of MWCNTs and xGnPs in SPSed SiO2 and Al2O3-based
nanocomposites. Fig. 8(a) indicates that the Al2O3-MWCNT nano-
composites developed at 1450 °C for a holding time of 10 min are
denser as compared to SiO2-MWCNT nanocomposites developed at
1350 °C for a holding time of 5 min. Addition of MWCNTs up to the
concentration of 3 vol% led to the improvement in the relative density
of Al2O3-MWCNT nanocomposites. The maximum relative density of
~99.62% was obtained for Al2O3-3 vol% MWCNT nanocomposites
whereas the density of pure Al2O3 sample fabricated under similar
sintering conditions was found to be ∼99.24%. For SiO2-MWCNT na-
nocomposites, a similar trend in the variation of relative density was
observed. The minimum relative density of ~99.21% was observed for
SiO2-0.5 vol% MWCNT nanocomposite whereas the maximum relative
density of ~99.47% was observed for SiO2-3 vol% MWCNT nano-
composite. The higher relative densities of Al2O3-MWCNT nano-
composites as compared to SiO2-MWCNT nanocomposites suggest that
the addition of MWCNTs is more effective in densification of the Al2O3
matrix as compared to the SiO2 matrix. Further addition of MWCNTs in
Al2O3 and SiO2 matrix beyond 3 vol% led to a decrease in the density of
the Al2O3-MWCNT and SiO2-MWCNT nanocomposites. However, the
N. Sharma et al.
Fig. 8. Variation in the relative density of (a) SiO2-MWCNT, Al2O3-MWCNT and (b) SiO2-xGnP, Al2O3-xGnP composites.
Fig. 9. Variation in the hardness of (a) SiO2-MWCNT, Al2O3-MWCNT and (b) SiO2-xGnP, Al2O3-xGnP composites.
density of all the SiO2-MWCNT and Al2O3-MWCNT nanocomposites
was found much higher as compared to the density of pure SiO2 and
Al2O3 samples. Fig. 8(b) represents the variation in the relative density
of SPSed SiO2-xGnP and Al2O3-xGnP nanocomposites. It is evident from
the plot that the relative density of the nanocomposites increases with
the increase in the xGnP content in the ceramic matrices. For SiO2-xGnP
nanocomposites, the maximum relative density of ~99.77% was ob-
served for SiO2-3 vol% xGnP nanocomposite whereas for Al2O3-xGnP
nanocomposites an optimal loading level of 0.8 vol% xGnP in the Al2O3
matrix resulted in the maximum density of ~99.64%. Any further ad-
dition of xGnPs beyond the optimum loading level results in their ag-
glomeration in the ceramic matrix which deteriorates the densification
of the nanocomposites [32].
Fig. 9 shows the variation in the hardness of various SiO2 and Al2O3-
based nanocomposites with respect to the loading level of MWCNTs and
xGnPs. For MWCNT reinforced nanocomposites (Fig. 9(a)), SiO2-
MWCNT nanocomposites possess better hardness as compared to Al2O3-
MWCNT nanocomposites whereas for xGnP reinforced composites
(Fig. 9(b)) the hardness value of Al2O3-xGnP nanocomposites was found
higher as compared to SiO2-xGnP nanocomposites. However, all the
four nanocomposite systems were found to follow the same pattern in
the increment of the hardness value. The major challenge in the de-
velopment of SiO2-MWCNT and Al2O3-MWCNT nanocomposites is the
homogenous dispersion of MWCNTs in the ceramic matrices due to
their high agglomeration tendency owing to their very high aspect
ratio. Introduction of MWCNTs and xGnPs to monolithic SiO2 and Al2O3
led to a notable improvement in their hardness. However, on the ad-
dition of the nanofillers beyond an optimal loading level of 3 vol%, a
decrease in the value of hardness was observed for all the four nano-
composite systems. It implies that an optimum loading level of nano-
fillers is essential for achieving a significant increase in the hardness of
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CMNCs as beyond the loading level of 3 vol% of both MWCNTs and
xGnPs, they tend to agglomerate and form weak interfaces with the
matrix [33]. However, the hardness value of all the SPSed nano-
composites was found higher than that of pure sintered SiO2 and Al2O3
samples. From Fig. 9(a), the hardness of Al2O3-3 vol% MWCNT nano-
composite was found ∼8.32 GPa which was ~8.06% lower than the
hardness of SiO2-3 vol% MWCNT nanocomposite (∼9.05 GPa). An
overall improvement of ~35.2% in the hardness value of pure Al2O3
sample (∼5.43 GPa) was observed when 3 vol% of MWCNT was added
to it. Similarly, on optimum loading level of MWCNTs (3 vol%), an
increase of ~28.83% in the hardness value of SiO2-3 vol% MWCNT
nanocomposite (~9.05 GPa) was noticed as compared to the pure SiO2
sample (~6.44 GPa). In the case of xGnP reinforced nanocomposites
(Fig. 9(b)), the highest hardness value was obtained for Al2O3-3 vol%
xGnP nanocomposite and SiO2-3 vol% xGnP nanocomposite. The
hardness of Al2O3-3 vol% xGnP nanocomposite and SiO23- vol% xGnP
nanocomposite were observed ∼10.91 GPa and ∼9.74 GPa respec-
tively. An increase in the concentration of xGnPs beyond 3 vol% led to
the decrease in the hardness of the nanocomposites. Nanofillers restrict
the grain growth in the ceramic matrix by enhancing the interfacial
bonding at the matrix-nanofiller interface. Nanofillers like MWCNTs
and xGnPs bridge the grains and pin the grain boundaries which leads
to higher hardness of MWCNT and xGnP reinforced composites caused
by grain boundary pinning. Both xGnPs and MWCNTs prevent the grain
boundary motion by exerting the pinning pressure which impedes the
driving force pushing the grain boundaries [34].
3.3. Wear behavior
Wear in CMNCs is mainly caused due to abrasion, cracks and re-
sidual stresses. The various signs indicating wear in the nanocomposites
N. Sharma et al. Wear 418–419 (2019) 290–304

Fig. 10. SEM micrographs of the wear tracks of (a-c) SiO2-0.5, 3, 5 vol% MWCNT, (d-f) SiO2-0.5, 3, 5 vol% xGnP, (g-i) Al2O3- 0.8, 3, 5 vol% MWCNT and (j-l) Al2O3-
0.8, 3, 5 vol% xGnP nanocomposites.

include increased surface roughness, microscopic changes in surface
morphology, fatigue and micro-cracks. The major factors contributing
towards the wear in CMNCs are material structure, interaction condi-
tions like load, stress, time and surface texture [35].
The sliding wear test of various SiO2 and Al2O3-based nano-
composites was conducted. The wear rate, wear depth, mechanism of
nanofiller pull out during wear test, the morphology of wear tracks and
the effect of the nanofillers on the wear behavior of composites were
analyzed. It has been found that the addition of both MWCNTs and
xGnPs led to the decrement in the diameter of the wear tracks. The
diameter of the wear tracks was found to be decreasing up to the ad-
dition of 3 vol% of both MWCNTs and xGnPs irrespective of the host
matrix. Although, on increasing the concentration of the nanofillers up
to 5 vol%, the diameter of the wear tracks shows an instantaneous in-
crement. Both MWCNTs and xGnPs significantly enhance the wear re-
sistance of the nanocomposites by the formation of a lubricating

Fig. 11. Wear tracks of (a) SiO2-3 vol% MWCNT, (b) SiO2-3 vol% xGnP nanocomposites.

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Fig. 12. Schematic diagrams showing (a) two-body, (b) three-body abrasive wear mechanisms.
tribofilm on the wear tracks. On addition beyond an optimum value,
these graphitic nanofillers tend to agglomerate owing to their high
surface area. This deteriorates the uniformity of the lubricating tribo-
film and ultimately reduces the wear resistance of nanocomposites
containing higher volume fractions of the nanofillers [14,21].
By the SEM micrographs in Fig. 10, it is clear that the width of the
wear tracks for MWCNT reinforced composites is much lower as com-
pared to the width of the wear tracks of CMNCs reinforced with xGnPs.
The wear tracks observed for SiO2-MWCNT (Fig. 10(a-c)) and Al2O3-
MWCNT (Fig. 10(g-i)) nanocomposites depict much lower width than
the wear tracks of SiO2-xGnP nanocomposites (Fig. 10(d-f)) and Al2O3-
xGnP nanocomposites (Fig. 10(j-l)). This variation can be attributed to
the coiling and rolling behavior of MWCNTs when subjected to the wear
stresses.
When MWCNTs come in the contact of sliding indenter, they coil up
and roll over to a different location on the wear tracks without de-
formation and fragmentation of their tubular structure. On the other
hand, xGnPs due to their flake-like morphology, crumple and scroll
along the sliding direction on the application of the wear stresses. This
results in the degradation of xGnPs and decreases their efficiency in
improving the wear resistance of CMCs. Due to the morphological dif-
ference between the two nanofillers, MWCNTs provide a uniform lu-
bricity by the formation of a continuous tribofilm and serve more ef-
ficiently in the wear reduction of the CMNCs as compared to the
protective film formed by the xGnPs [36].
In order to examine the lubricating effects of MWCNTs and xGnPs,
the wear tracks of SiO2-3 vol% MWCNT, SiO2-3 vol% xGnP and Al2O3-
3 vol% MWCNT, Al2O3-3 vol% xGnP nanocomposites were analyzed
using SEM. It is evident from Fig. 11(a, b) and Fig. 14(a, b) that the
width of wear tracks of SiO2-based nanocomposites was much lower as
compared to the width of wear tracks of Al2O3-based nanocomposites,
although the loading level of both MWCNTs and xGnPs was kept same
as 3 vol% for both CMCs. The variation in the morphology of wear
tracks in both matrices could be attributed to the difference in the
alignment of the nanofillers in the host matrix.
For the SiO2 based nanocomposites, delamination was observed as
the major mode of wear. A similar wear phenomenon was observed for
both SiO2-MWCNT and SiO2-xGnP nanocomposites. The abrasive wear
Fig. 13. Schematic diagram of various wear mechanisms.
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was found dominant where the surface layer of SiO2 based composites
was gradually peeled layer-by-layer. The debris obtained from the worn
surface after the sliding wear test acted as a third body collapsed in
between the contact surfaces and changed the wear mechanism from
the two-body abrasion to the three-body abrasive wear. A schematic
diagram illustrating the abrasive wear mechanism is shown in Fig. 12.
This resulted in the galling of the wear track surface. The galling
parallel to the sliding direction created thin deformed flat sheets which
later caused delamination of the wear track. With an increase in the
sliding time compacted thin flat sheets were created which finally led to
the delamination of the track surface [37]. Therefore, galling served as
the mode of material removal in SiO2 based nanocomposites. A sche-
matic diagram illustrating the galling during wear is shown in Fig. 13.
As the sliding duration increased, the wear stresses caused due to
the abrasion of matrix-nanofiller interface increased [38]. The in-
creased stresses reduced the shear forces caused by the frictional heat
induced during the sliding motion. However, as the sliding continued,
the abrasion exceeded the shear and led to the deformation of the
contact surfaces. Due to the applied stresses, the surface layers com-
pressed and deformed, resulting in the emergence of thin plate-like
sheets. With the increase in the accumulated strain, the deformed layers
flattened and ultimately delaminated [39].
The wear mechanism of Al2O3 based nanocomposites have been
analyzed in Fig. 14. The wear tracks of Al2O3-3 vol% MWCNT and
Al2O3-3 vol% xGnP nanocomposites shown in Fig. 14(a, b) depict lower
delamination as compared to the SiO2-based nanocomposites. The wear
tracks having several micro-pits and deep grooves along the sliding
direction could be easily seen. Due to continuous sliding, the composite
surface breaks into smaller abrasive particles which remain entrapped
at the contact junction of the indenter and the sliding surface and thus
promotes the abrasive wear. The entrapment of abrasive Al2O3 particles
on the wear track surface transforms the two-body abrasion into three-
body abrasion, similarly as observed in the case of SiO2-based nano-
composites. The entrapped Al2O3 particles elevate the abrasion and
lead to the formation of deep grooves and pits on the wear track. The
wear mechanism of Al2O3 based nanocomposites was characterized by
two distinct mechanisms: abrasive deformation and adhesive de-
formation. The abrasive wear was caused due to the rolling or sliding of
N. Sharma et al.
Fig. 14. Wear tracks of (a) Al2O3-3 vol% MWCNT, (b) Al2O3-3 vol% xGnP nanocomposites.
abrasive Al2O3 particles on the surface of lubricating nanofillers. During
sliding, the wear track was continuously ploughed by the abrasive
matrix particles and the worn material dislocated towards the sides of
the formed grooves. On further sliding, the similar mechanism repeated
and led to the formation of deep grooves at the edges of the wear tracks.
The formed grooves were continuous, indicating that the tip of the
sliding indenter was firmly embedded in the counterface [40].
Dry sliding in the Al2O3-based nanocomposites also led to the for-
mation of a high-pressure zone between the contacting asperities,
which resulted in their adhesion. These adhesive zones formed due to
the combination of both normal and tangential stresses were later
sheared by the abrasive motion during sliding. Fig. 14(b) shows the
surface of the wear track of Al2O3-3 vol% xGnP nanocomposite, which
confirms that the worn surface was severely deformed due to the in-
tensive adhesion of the contact surface and sliding indenter which re-
sulted in the ploughing and ultimately led to the formation of deep
grooves and micro-pits. The subsequent removal of the excess material
after prolonged sliding caused the visibility of the subsurface on the
wear tracks [41]. A schematic diagram describing the adhesive wear
mechanism is presented in Fig. 15.
Fig. 16 shows the microstructural characteristics of the worn sur-
faces observed on the wear tracks of various SiO2 and Al2O3-based
nanocomposites. Fig. 16(a) shows the surface deformation of the
smooth delaminated wear track of SiO2-3 vol% MWCNT nanocompo-
site. A deep irregular groove having MWCNTs on its edges, formed by
galling could be evidently seen in Fig. 16(b). This suggests the occur-
rence of MWCNT pull-out during the galling (Fig. 13). The morphology
of the wear track of SiO2-3 vol% xGnP nanocomposite is shown in
Fig. 16(c, d). The worn surface was comprised of two distinct regions:
(i) areas revealing the scratches caused by the deformation during
ploughing and (ii) the areas depicting a large amount of removed ma-
terial due to xGnP pull-out. Continuous surface scratches could be ea-
sily observed in Fig. 16(d) which indicate that the tip of the sliding
indenter was firmly embedded in the counterface. Fig. 16(e, f) show the
Fig. 15. Schematic diagram illustrating the adhesive wear mechanism.
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surface topography of the wear track of Al2O3-3 vol% MWCNT nano-
composite. The deformed wear track is evident in Fig. 16(e). The worn
surface exhibits continuous shallow grooves suggesting that the applied
load was accumulated at the contact surfaces. Densely packed Al2O3
particles are visible on the worn surface in Fig. 16(f). Fine debris ac-
cumulated on the edges of the wear track could be observed on the
worn surface of Al2O3-3 vol% xGnP nanocomposite in Fig. 16(g). This
suggests that the xGnP pull-out was caused during the sliding wear.
Formation of lateral cracks due to material removal and fracture during
plastic deformation is evident in Fig. 16(h). As the sliding distance in-
creased, the majority of xGnPs were pulled out from the wear track, as
seen in Fig. 16(h) [42].
Fig. 17 illustrates the SEM micrographs of the wear debris obtained
from the wear tracks of SiO2-3 vol% MWCNT, SiO2-3 vol% xGnP, Al2O3-
3 vol% MWCNT and Al2O3-3 vol% xGnP nanocomposites. MWCNTs
adhered to the SiO2 particles are clearly visible in Fig. 17(a). A con-
siderably large volume of MWCNTs in the wear debris suggests that the
interfacial bonding between the MWCNTs and SiO2 matrix was weak
which promoted the easy pull out of the nanofiller from the host matrix
during the wear test. Flower-like SiC nanostructures were noticed in the
wear debris collected from the SiO2-3 vol% MWCNT nanocomposite.
SiC nanorods were also observed in the SEM micrographs of the SiO2-
MWCNT nanocomposite in Fig. 6(a). The SEM image in Fig. 17 (b)
shows the wear debris obtained from the wear track of SiO2-3 vol%
xGnP nanocomposite. The agglomerate of diffused SiO2 and fine xGnPs
adhered to the SiO2 particles could be observed. It is well known that
the grain boundaries in the monolithic ceramics remain under tensile
stresses which are responsible for the crack propagation between the
grains and promote their pull out. These tensions thereby are the major
cause for the generation of the wear debris. The incorporation of the
nanofillers like xGnPs and MWCNTs reduce the stresses between the
grains and thus reduce the pullout phenomenon [43]. Fig. 17(c) is the
SEM image of the wear debris collected from the wear track of Al2O3-
3 vol% MWCNT nanocomposite. It could be observed that the wear
N. Sharma et al. Wear 418–419 (2019) 290–304

Fig. 16. Surface topography of the worn surfaces on the wear tracks of (a, b) SiO2-3 vol% MWCNT, (c, d) SiO2-3 vol% xGnP, (e, f) Al2O3-3 vol% MWCNT, (g, h) Al2O3-
3 vol% xGnP nanocomposites.

debris consists of both MWCNTs and Al2O3 particles. Agglomerates of
sintered Al2O3 with MWCNTs adhered to its surface could be easily
seen. The weakly bonded grains in the Al2O3 matrix chipped off during
the wear test. In Fig. 17(d), the sintered aggregate of Al2O3 and xGnPs
in the form of a lump pulled out from the wear track of Al2O3-3 vol%
xGnP nanocomposite could be seen. These adhered xGnPs act as self-
lubricating layers between the nanocomposite surface and the sliding
indenter. xGnPs form a lubricating tribofilm between the indenter and
the composite surface which not only lowers the wear rate but also
reduces the sliding abrasion during the initial wear stage [18]. How-
ever, when the sliding distance increased, the majority of xGnPs were
worn-out from the wear track (Fig. 14(g, h)).
Fig. 18 depicts the variation in the wear rate of various SiO2 and
Al2O3-based nanocomposites. It is clear that the Al2O3-based nano-
composites show better wear resistance than the SiO2-based nano-
composites. It implies that the Al2O3 matrix serves as a better host for
both MWCNTs and xGnPs in the formation of lubricating tribofilm as
compared to the SiO2 matrix. For SiO2 based nanocomposites, the ad-
dition of both MWCNTs and xGnPs up to 3 vol% reduced the wear rate
of both SiO2-MWCNT and SiO2-xGnP nanocomposites. However, the
wear rate again increased on the addition of both the nanofillers up to
5 vol% loading level. The minimum wear rate observed for SiO2-3 vol%
xGnP composites was ~0.265 × 10−4 g/Nm which was ~33.4% times
lower than the wear rate observed for SiO2-3 vol% MWCNT composite

Fig. 17. Wear debris obtained from the wear tracks of (a) SiO2-3 vol% MWCNT (b) SiO2-3 vol% xGnP (c) Al2O3-3 vol% MWCNT and (d) Al2O3-3 vol% xGnP
nanocomposite.

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Fig. 18. Variation of wear rate in (a) SiO2-MWCNT, Al2O3-MWCNT and (b) SiO2-xGnP, Al2O3-xGnP nanocomposites.

(~0.398 × 10−4 g/Nm) when developed under similar sintering con-
ditions. In the case of Al2O3-based composites, the effect of both
MWCNTs and xGnPs on the variation of wear rate was found different
than that observed for SiO2-based composites. On the introduction of
MWCNTs in the Al2O3 matrix, wear rate continuously decreased up to
the 3 vol% concentration of the nanofiller. The wear rate for pure sin-
tered Al2O3 was found ~0.437 × 10−4 g/Nm whereas the wear rate of
Al2O3-3 vol% MWCNT composite was found ~0.238 × 10−4 g/Nm. It
implies that an optimal loading level of 3 vol% MWCNT provided an
improvement of ~45.5% in the wear rate of the composites. However,
the addition of 5 vol% MWCNT in the Al2O3 matrix increased the wear
rate (~0.318 × 10−4g/Nm). On the other hand, the nature of variation
in wear rate of Al2O3-xGnP composites was quite different. The wear
rate of Al2O3-xGnP composite first decreased on a small loading level of
0.2 vol% xGnP in the host matrix and was found ~0.065 × 10−4 g/Nm.
On further addition of xGnPs up to 0.8 vol%, the wear rate slightly
increased and attained a value ~0.195 × 10−4 g/Nm. However, on the
further increment of xGnPs up to 3 vol%, the wear rate showed a de-
crease and was observed ~0.143 × 10−4 g/Nm. This confirms that
there was an enhancement of ~26.6% in the wear rate of Al2O3-3 vol%
xGnP nanocomposite over Al2O3-0.8 vol% xGnP nanocomposite. Fur-
ther addition of xGnPs up to 5 vol% in the Al2O3 matrix deteriorated the
wear resistance of the Al2O3-xGnP composites. The wear rate of
Al2O3–5 vol% xGnP nanocomposite was observed ~0.16 × 10−4 g/Nm
which was ~10.6% higher than that observed for Al2O3-3 vol% xGnP
nanocomposite. However, it is noteworthy that the wear rate of all SiO2
and Al2O3-based nanocomposites was found lower as compared to pure
sintered SiO2 and Al2O3 samples. The improvement in the wear re-
sistance of the nanocomposites could be associated with the emergence
of a protective tribofilm on the wear tracks by the nanofillers, which

Fig. 19. Variation in the wear depth of (a) SiO2-MWCNT, (b) Al2O3-MWCNT, (c) SiO2-xGnP and (d) Al2O3-xGnP nanocomposites.

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N. Sharma et al.
Fig. 20. Variation in the fracture toughness of (a) SiO2-MWCNT, Al2O3-MWCNT and (b) SiO2-xGnP, Al2O3-xGnP composites.
Fig. 21. Toughening mechanisms in (a) SiO2-3 vol% MWCNT, (b) Al2O3-3 vol% MWCNT, (c) SiO2-3 vol% xGnP and (d) Al2O3-3 vol% xGnP nanocomposites.
provided the lubricating effect to the CMNCs [21].
The variation in the wear depth of various SiO2 and Al2O3-based
nanocomposites with respect to time is shown in Fig. 19. It is evident
from Fig. 19(a) that on increasing the concentration of MWCNTs from
0.5 vol% to 3 vol%, the wear resistance of the SiO2-MWCNT nano-
composites improves. However, a decrease in the wear resistance of
SiO2-MWCNT nanocomposites was observed when the MWCNT content
was increased up to 5 vol%. A similar phenomenon was observed for
Al2O3-MWCNT nanocomposites in Fig. 19(b). The wear depth of Al2O3-
based composites was found to be decreasing when MWCNT loading
level in the Al2O3-MWCNT nanocomposites was increased from 0.2 vol
% to 3 vol%. However, on further addition of up to 5 vol% MWCNT, the
wear depth increased. The decrement in the wear resistance of the
nanocomposites beyond 3 vol% loading level of MWCNTs can be as-
sociated with the agglomeration of the nanofiller in the ceramic matrix.
It should be noted that the pattern of wear depth variation in the case of
Al2O3-MWCNT nanocomposites was much smoother than the pattern
observed for SiO2-MWCNT nanocomposites. This suggests that more
uniform densification was achieved for Al2O3-MWCNT nanocomposites
than the SiO2-MWCNT nanocomposites. This could be ascribed to the
fact that SPS of Al2O3-MWCNT nanocomposites was done at elevated
sintering temperature for longer holding time unlike the SiO2-MWCNT
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nanocomposites (Fig. 3). The fluctuations in the wear depth of SiO2-
MWCNT nanocomposites can be associated with their non-uniform
densification. The wear depth of SiO2-0.5 vol% MWCNT and SiO2-3 vol
% MWCNT nanocomposites in Fig. 19(a) were found to be stable up to
the initial 500 s of the sliding wear test but depicted a sudden fluc-
tuation after that. The outer surface having higher wear resistance was
removed first during the wear test followed by the material removal
from the inner subsurface having comparatively lesser density and
lower wear resistance [44]. The increase in the wear depth of Al2O3-
based nanocomposites noticed during the earlier stage of the wear test
could be associated with the eviction of the rough irregular surface.
Further, due to the lubricating behavior of the nanofillers, the friction
reduced and the wear tracks became much smoother. It is noteworthy,
that in the case of various SiO2-xGnP and Al2O3-xGnP nanocomposites,
a comparatively smoother variation of wear depth was observed as
xGnPs show a much lesser tendency to agglomerate than MWCNTs. The
efficacy of the nanofillers in enhancing the wear resistance of the na-
nocomposites depends upon the relative tangential stresses applied on
the matrix grains which leads to the decrement of the grain pull out in
the wear test [17]. The wear depth of SiO2-based nanocomposites was
found much lower as compared to the wear depth observed in the
Al2O3-based nanocomposites.
N. Sharma et al.
3.4. Matrix-nanofiller interface and toughening mechanisms
The fracture toughness of various SiO2 and Al2O3-based nano-
composites was investigated using single-edge notched beam method
and KIC values were calculated by the Shetty equation, using the
Palmqvist crack model as described elsewhere by Alam et al. [45]. The
variation in the value of fracture toughness of various SiO2 and Al2O3-
based nanocomposites with respect to the concentration of the nano-
fillers is shown in Fig. 20. The fracture toughness of Al2O3-0.2 vol%
MWCNT and Al2O3-0.2 vol% xGnP composites was found to be
~3.17 MPa m1/2 and ~3.91 MPa m1/2 respectively, corresponding to an
increase of ∼8.39% and ∼25.72% respectively to the fracture tough-
ness value of pure Al2O3 sample (~2.9 MPa m1/2) developed under the
similar sintering conditions. Results suggest that due to its two-di-
mensional geometry, higher surface area and better interfacial bonding
with the matrix, xGnPs are more efficient than MWCNTs in improving
the fracture toughness of the ceramic-based nanocomposites. Contra-
rily, due to their tendency to form clustered agglomerates, MWCNTs
deteriorates the fracture toughness of the nanocomposites [46]. The
SiO2-MWCNT nanocomposites show the maximum fracture toughness
value of ∼0.68 MPa m1/2 for SiO2-3 vol% MWCNT nanocomposite
which is ~22.72% lower than that observed for SiO2-3 vol% xGnP
composite (∼0.88 MPa m1/2) in Fig. 20(a). The decrement in the frac-
ture toughness of SiO2-MWCNT and Al2O3-MWCNT nanocomposites
can be ascribed to the emergence of brittle SiC and Al4C3 nanorods at
the matrix-nanofiller [47]. The formation of carbide nanorods was not
observed in the xGnP reinforced nanocomposites. Although, the addi-
tion of both MWCNTs and xGnPs, beyond their optimum loading level,
deteriorated the fracture toughness of both SiO2 and Al2O3-based na-
nocomposites. This can be associated with the non-uniform distribution
of MWCNTs and xGnPs in the respective matrices, resulting in their
agglomeration. With the increase in the concentration of the nanofillers
in the ceramic matrix, they overlap and form an interlinked mesh of the
agglomerates, which acts as a frail interface at the grain boundaries.
The fracture toughness of various SiO2-based nanocomposites shows a
remarkable improvement up to the addition of 3 vol% of both nano-
fillers while for Al2O3-based nanocomposites, the same could be seen up
to the addition of 0.8 vol% of both nanofillers. Various toughening
mechanisms such as crack deflection, crack bridging and crack
branching contribute in increasing the fracture toughness of the nano-
composites (Fig. 21) [48]. The highest value of fracture toughness in
the case of Al2O3-based composites was observed as ~4.15 MPa m1/2
for Al2O3-0.8 vol% xGnP nanocomposite which corresponds to an in-
crement of ∼7.22% when compared to the value of fracture toughness
observed for Al2O3-0.8 vol% MWCNT nanocomposite (~3.85 MPa m1/
2
). Similarly, the value of fracture toughness of SiO2-MWCNT nano-
composites was observed much lower than that of SiO2-xGnP nano-
composites.
The matrix-nanofiller interface plays a vital role in the toughening
of CMNCs. The applied stress during sliding wear test is transferred to
the high strength nano-sized reinforcement at the interface. Thus, a
strong interface imparts better toughness to the composites whereas a
weak interface leads to inefficient utilization of the nanofiller properties
due to their pull-out. Microstructural flaws in CMNCs act as a point of
concentration for the wear stresses which leads to the crack propaga-
tion resulting in the material eviction during wear. The damaged sur-
faces observe higher loads due to the small area in contact and thus
create fractured zones in the composites. This implies that the wear
resistance of the nanocomposites could only be enhanced if the inter-
facial bonding between the host matrix and the nanofiller is improved
[49]. Microcracks on the surface of various SiO2 and Al2O3-based na-
nocomposites were observed to determine the mechanism by which
nanofillers arrest the crack propagation in CMCs. The SEM images in
Fig. 21 show the various toughening mechanisms which contribute in
improving the fracture toughness of the nanocomposites. The SEM
images imply that at an optimum concentration of 3 vol%, both
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Wear 418–419 (2019) 290–304
MWCNTs and xGnPs are highly efficient in hindering the path of the
crack propagation. Crack deflection, crack bridging, crack branching
and crack blunting were found to be as the major toughening me-
chanisms in all the nanocomposite systems.
The improvement in the fracture toughness of both SiO2 and Al2O3-
based nanocomposites is credited to the drag provided by the nano-
fillers. A high energy is required to pull out the nanofillers from the host
matrix due to their large surface area. Close contact and better inter-
facial bonding between the nanofillers and matrix enable firm an-
choring of the nanofillers to the matrix grains [50]. In the case of
MWCNT reinforced nanocomposites, a significant number of nanorods
in the form of SiC and Al4C3 for SiO2-MWCNT and Al2O3-MWCNT
composites could be evidently seen in Fig. 21(a, b). The carbide rods
remain embedded in the ceramic matrix and deflect the cracks, hence
refine the fracture toughness of the nanocomposites [51,52].
4. Conclusions
Various SiO2 and Al2O3 based nanocomposites reinforced with na-
nofillers like xGnPs and MWCNTs were fabricated through the SPS
technique. Mechanical properties such as hardness and fracture
toughness of the developed nanocomposites were investigated. The
sliding wear test was conducted on the SPSed composites to determine
their wear resistance and involved wear mechanisms. The prime con-
clusions acquired from this work can be outlined as-
1. A uniform dispersion of the nanofillers like xGnPs and MWCNTs is a
key necessity to obtain the desired properties in the sintered com-
posites. The structure of both nanofillers were maintained after SPS
as confirmed by the SEM and XRD analysis.
2. The emergence of carbide nanorods was observed in MWCNT re-
inforced nanocomposites. SiC nanorods in SiO2-MWCNT and Al4C3
nanorods in Al2O3-MWCNT nanocomposites were observed in the
SEM micrographs of the sintered nanocomposites.
3. The relative density of the SPSed nanocomposites improved on the
addition of the nanofillers up to 3 vol%. Further addition of nano-
fillers beyond 3 vol% up to 5 vol% causes the agglomeration, which
deteriorates the relative density of CMNCs.
4. At an optimum loading level of 3 vol%, SiO2-MWCNT nanocompo-
sites were found to possess better hardness as compared to the
Al2O3-MWCNT nanocomposites whereas in the case of xGnP re-
inforced nanocomposites, the hardness of Al2O3-xGnP nanocompo-
sites was found higher than the SiO2-xGnP nanocomposites.
5. The fracture toughness of both SiO2 and Al2O3-based nanocompo-
sites increased with the addition of the nanofillers in the respective
matrix only up to an optimum value. In the case of Al2O3-based
nanocomposites, the loading level of 0.8 vol% of both MWCNTs and
xGnPs provided the maximum fracture toughness values whereas in
the case of SiO2-based nanocomposites, the maximum value of
fracture toughness was observed on the addition of 3 vol% of both
the nanofillers in the host matrix.
6. Crack deflection, crack blunting, crack branching and crack bridging
were observed as the major toughening mechanisms in all the
composite systems.
7. Both MWCNTs and xGnPs improved the wear resistance of the na-
nocomposites due to the formation of a protective lubricating tri-
bofilm on the wear tracks. The addition of MWCNTs and xGnPs led
to the reduction in the width of the wear tracks. A decrease in the
width of the wear track was observed up to the addition of 3 vol% of
both the nanofillers irrespective of the host matrix.
8. In the case of SiO2 based nanocomposites, galling was found to be
the major mode of wear whereas Al2O3 based composites exhibited
both abrasion and adhesion wear mechanisms.
9. The wear rate of Al2O3-based nanocomposites was found much
lower as compared to the wear rate of SiO2-based nanocomposites.
N. Sharma et al.
Acknowledgments
We sincerely appreciate the assistance provided by the SEM la-
boratory of Metallurgical and Materials Engineering Department,
FESEM laboratory of Ceramic Engineering Department, HRTEM la-
boratory of Chemical Engineering Department and XRD laboratory of
Physics Department, NIT Rourkela. We are grateful to IIT Kanpur, for
providing the SPS facility, procured with partial funding from CARE
Funding, IIT Kanpur and Department of Science and Technology,
Government of India. We are also thankful to the Materials Science
Laboratory, Physics Department, Jamia Millia Islamia for the help
provided in the synthesis of MWCNTs.
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