j m a t e r r e s t e c h n o l .

2 0 2 0;9(4):9108–9116

Available online at www.sciencedirect.com

www.jmrt.com.br

Original Article

Experimental investigation on mechanical and

wear properties of nanoclay–epoxy composites

Manjunath Shettar a , C.S. Suhas Kowshik a , Maitri Manjunath b,∗ , Pavan Hiremath a
a Department of Mechanical and Manufacturing Engineering, Manipal Institute of Technology, Manipal, Manipal Academy of Higher
Education, Manipal, Karnataka 576104, India
b Department of Humanities and Management, Manipal Institute of Technology, Manipal, Manipal Academy of Higher Education,

Manipal, Karnataka 576104, India

a r t i c l e i n f o a b s t r a c t

Article history: The work targets to fabricate and characterize “nanoclay–epoxy composites” (NECs) by vary-
Received 2 April 2020 ing weight percentages (wt.%) of nanoclay. Mechanical stirrer and sonicator are used to mix
Accepted 15 June 2020 nanoclay into epoxy resin. The mixture is molded to prepare specimens in accordance with
Available online 26 June 2020 ASTM standards. The addition of nanoclay increased the mechanical properties of fabricated
composites. Scanning Electron Microscopy (SEM) images revealed the causes of specimen
Keywords: failure. Four factors viz., nanoclay wt.%, speed, load, and time at three levels are consid-
Nanoclay ered a wear test on a pin-on-disc machine. The design of experiments (Taguchi design) is
Epoxy applied for the experimentation, and analysis of variance is established through Minitab 19
Mechanical properties software. Results revealed that the nanoclay addition improved the resistance to wear of
Wear epoxy.
© 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

crack initiation & propagation, and inferior fracture toughness

1. Introduction [3]. A new method is suggested to boost the properties of poly-
mers by adding fillers in the polymer matrix. The nanoparticle
Epoxy resin has outstanding features viz., reasonably higher
reinforced polymer matrix has increased attention in compar-
strength & module, limited shrinkage, and exceptional heat
ison with pure polymers due to their outstanding properties
and chemical resistance. Owing to epoxy’s excellent proper-
[4]. Nanoclay is a fine-sheet, crystalline compound. The simple
ties, it is employed in numerous applications viz., adhesives,
structural component of a nanoclays is a sheet, and are typi-
coatings, and composite matrix constituents [1]. A high degree
cally stacked over each other like pages of a book [5]. Nanoclay
of crosslinking and the nature of the interchain bonds give
has gained merit over other nanoparticles, because of its ease
cured epoxies numerous desired features [2]. Cured epoxy
of use, ecological usability and sound explored chemistry [6,7].
structures showed low impact strength, reduced tolerance to
To be consistent with organic polymers, the nanoclay surface
must be modified to organophilic before usage. Ammonium or
phosphonium ion, are commonly used organic modifiers for
∗
Corresponding author. nanoclay. Ammonium salts are utilized for modifying com-
E-mail: maitri.m@manipal.edu (M. Manjunath).
https://doi.org/10.1016/j.jmrt.2020.06.058
2238-7854/© 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):9108–9116
mercially accessible nanoclays and are named as “organically
modified nanoclays or organoclays” [8].
Numerous researchers reported that the presence of nan-
oclay significantly improved tensile, flexural, and impact
strengths. Nanoclay’s high aspect ratio can also enhance
strength by enhancing the contact surface area of the poly-
mer matrix on the nano-filler. Numerous nanoclay particles
present in the matrix serve as active agents of stress-transfer
in the nanocomposite, causing plastic deformation in the
base material and eventually increasing the strength of the
nanocomposites [9,10]. Also, the nanoclay addition increased
fracture toughness of epoxy, as a result of additional crosslink-
ing related to amino groups found on the surface of nanoclay
and the ability of nanoclay to redirect the crack. This implies
that nanoclay areas will survive the spreading of cracks and
thus cause the advancing cracks to adopt a tortuous course.
Further, this leads to higher toughness of the epoxy matrix
reinforced by nanoclay owing to the formation of a higher area
of the surface fracture [11,12].
The wear property of any material is equally important
as mechanical properties for any given application. Wear is
characterized as the material loss when subjected to relative
motion from the contact surface. There are five major forms of
wear that are commonly found with composites of polymers
viz., fretting, fatigue wear, adhesive, erosion, and abrasive
wear [13,14]. The prime focus of the current research work is
to experimentally investigate the mechanical and wear prop-
erties of NECs, with a varied wt.% of nanoclay. The novelty of
present work is to study the effect of nanoclay morphology,
i.e., “layers or stacks morphology” on the tensile and flexural
properties and to use a statistical tool, i.e., “Taguchi design” for
investigating wear properties, which drastically reduces the
number of experiments and gives the regression equation to
predict the mass loss.
2. Methodology
2.1. Specimens preparation and testing
Commercially available Epoxy resin (L-12) and hardener (K-
6) (“Mixing ratio 10:1, supplied by Atul Polymers, Gujarat,
India”) and Nanoclay (“Surface modified contains 25–30 wt.%
trimethyl stearyl ammonium supplied by Sigma Aldrich”),
have been utilized to fabricate NEC specimens. NECs are fab-
ricated through the “general casting technique” by varying
weight percentages of nanoclay (0–5). Nanoclay is mixed in
epoxy by mechanical stirrer and sonicator. The tests for ten-
sile and flexural strengths are conducted on all the specimens
as per the ASTM standards, D-638 and D-790, respectively.
2.2. Wear test
Wear test of the specimens are experimented on a pin-on-disc
machine as per the ASTM standard G-99. The ASTM specifica-
tion is designed to refer to polymeric materials. The machine’s
disk is made of hardened EN 31 steel, with minimal roughness
on the surface (Ra = 5 ␮). With the aid of a specimen holder and
screws, the specimen is kept on the disc, with four screw fas-
teners perpendicular to the spinning disk, and load is added
9109
Table 1 – Levels and factors for the current study.
Sl. no. Factors Unit Levels
1 Nanoclay wt.% 0 2 4
2 Speed RPM 100 200 300
3 Load kg 1 2 3
4 Time min 5 10 15
with a lever connection. Other factors, such as rotation time,
disc rotation speed, and diameter of the track, are set manually
for every test iteration.
2.3. Experimental design
In the current work, 4-continuous factors at 3-levels are used
(Table 1). The sliding diameter of the disc is maintained con-
stant for all the experiments, i.e., 80 mm. For optimization of
the response variable, i.e., mass loss (in mg), “design of experi-
ment (DOE)” with the Taguchi design (L27 ) is applied. For design
and analyses, MINITAB-19 software is utilized.
2.4. SEM analysis
“Scanning Electron Microscope (SEM); Model: EVO18, ZEISS”
is used to capture the morphology of the fracture and worn
surface of the tested specimen. The reasons for specimen’s
failure are studied by the SEM images.
3. Results and discussion
3.1. Mechanical properties
3.1.1. Tensile strength
Fig. 1 shows the tensile properties of NEC specimens. Typi-
cal stress vs. strain behavior from tensile tests is presented
in Fig. 1(a). All the specimens failed instantly after the attain-
ment of the extreme limit of ultimate tensile stress, although
the stress vs. strain plots displayed significant non-linearity
before extreme stress is reached. Nanoclay addition increased
the stress value before failure and declined the strain to break
(%) under tensile load for all the wt.% of nanoclay compared
to neat epoxy.
Nanoclay addition has improved the tensile strength of
NEC. The maximum tensile strength, of 57.4 MPa, is obtained
with 4 wt.% of nanoclay, which is 6% more than the pure
epoxy, as shown in Fig. 1(b). The addition of surface-modified
nanoclay results in an improvement in the epoxy’s crosslink
density, further resulting in improved fracture toughness and
the tensile strength of epoxy as a consequence of the matrix-
to-reinforcement transfer of load interactions. The greater
nanoclay aspect-ratio has improved the results of the ten-
sile strength of NECs by increasing the nanoclay interaction
surface area [6,11]. Nanoclay acts as an effective stress trans-
fer element in NECs, resulting in epoxy’s plastic deformation
and ultimately improved tensile strength [9]. The presence of
nanoclay prohibits the propagation of cracks by producing a
significant volume of plastic deformation [15,16].
9110 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):9108–9116
Fig. 1 – Tensile properties of NEC.
3.1.2. Flexural strength
The nanoclay addition has improved the flexural strength of
neat epoxy, as presented in Fig. 2. The highest flexural strength
of 134 MPa is obtained at 2 wt.% of nanoclay, which is 9% more
compared to pure epoxy. NECs flexural strength enhancement
is due to the enhanced interfacial properties in the presence
of nanoclay particles responsible for the movement of stresses
and elastic deformation. Nanoclay strengthens and stiffens
the surrounding matrix [17].
The maximum flexural strength is attained at 2 wt.% of
nanoclay because of aggregation of the nanoclay at its higher
concentrations, i.e., 3–5 wt.%.
As seen in Fig. 3, nanoclay “layers or stacks morphology”
have been highly important in improving the tensile strength,
thus causing a reduction in flexural strength at 3–5 wt.%
of nanoclays. Flexural properties are greatly subjugated to
the matrix. As a consequence, agglomeration/low dispersion
defects for flexural properties are strongly evident [18]. Sup-
pose the nanoclay layers are situated along the “dumb-bell
axis,” tensile strength may be improved due to the slip of lay-
ers on each other. However, the increase in nanoclay layers
Fig. 2 – Flexural strength of NECs.
(3–5 wt.%) leads to a decrease in flexural strength even though
the layers are highly parallel and situated perpendicular to the
force introduced [19].
3.1.3. SEM analysis
According to microscopic analyses, a major variation can be
noticed among the fracture surfaces of neat epoxy and NECs.
As seen in Fig. 4, the pure epoxy shows an absolutely smooth
surface showing a fast proliferation of cracks and low tough-
ness of fractures [20,21]. The NEC’s SEM micrograph (Fig. 5)
revealed a considerably rougher surface compared with pure
epoxy. Nanoclay in NECs mechanically obstructs and slows
down the propagation of cracks, and the resultant. NEC’s
fractured surface displays a river-surface form. The river-
surface-form gives a strong indication of improved fracture
toughness [15].
Also, SEM micrographs revealed that nanoclay addition
could alter the crack formation mechanism, due to improved
bonding between nanoclay and epoxy owing to the effect of
crosslinking. The nanoclay can knit the epoxy chains and ulti-
mately produce robust barriers to halt the propagation of crack
[21]. The crosslinking reactions produce a growing network
and reduce the mobility of the chain segments. The growth of
the network results in the mechanical stability of the structure
[2]. These are the main reasons for improving the strength of
the NECs compared to pure epoxy. Micro-voids are found in
NECs (Fig. 6) with higher nanoclay, i.e., 5 wt.%, and the failure
pattern is also considerably modified. The failure is triggered
at an area of nanoclay particle aggregate concentration.
3.2. Wear properties
Table 2 gives an experimental Taguchi design. A total of 27
tests are performed, and values of mass loss (mg) are consid-
ered as a variable response. The study is performed using the
software “MINITAB 19.”
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):9108–9116 9111

Fig. 3 – Nanoclay morphology.

Fig. 4 – SEM images of neat epoxy fracture surface.

Fig. 5 – SEM images of NEC (with 2 wt.%) fracture surface.

Fig. 6 – SEM images of NEC (with 5 wt.%) fracture surface.

3.2.1. Analysis of variance (ANOVA) all the factors influence the wear properties of NECs. P-values
The ANOVA general linear model for the response of mass of all the factors are less than 0.05 (95% significance), which
loss (mg) can be seen in Table 3. From Table 3, it is evident that indicates that all the factors contribute to the mass loss. Load
9112 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):9108–9116

Table 2 – Taguchi design with levels, control factors, and response variable.
Nanoclay (wt.%) Speed (RPM) Load (kg) Time (min) Mass loss (mg)

0 100 1 5 64
0 100 1 5 60
0 100 1 5 68
0 200 2 10 111
0 200 2 10 118
0 200 2 10 106
0 300 3 15 180
0 300 3 15 170
0 300 3 15 190
2 100 2 15 94
2 100 2 15 88
2 100 2 15 100
2 200 3 5 98
2 200 3 5 90
2 200 3 5 105
2 300 1 10 70
2 300 1 10 65
2 300 1 10 74
4 100 3 10 83
4 100 3 10 78
4 100 3 10 88
4 200 1 15 57
4 200 1 15 52
4 200 1 15 60
4 300 2 5 67
4 300 2 5 62
4 300 2 5 73

Table 3 – Analysis of variance.

Source DF Adj SS Adj MS F-value P-value % of Contribution

Nanoclay 2 11362.7 5681.37 151.88 0.000 32.55

Speed 2 3006.5 1503.26 40.19 0.000 8.61
Load 2 14567.2 7283.59 194.71 0.000 41.73
Time 2 5291.0 2645.48 70.72 0.000 15.16
Error 18 673.3 37.41
Total 26 34900.7

S = 6.11616, R-sq = 98.07 %, R-sq(adj) = 97.21 %.

(41.73 %) and nanoclay (32.55%) have more influence on mass

loss because of wear tests, compared to speed (8.61%) and time
(15.16%) for the test.

3.2.2. Main effects plots

The main effect plots, which are shown in Fig. 7 indicate
the effect of different process parameters on mass loss in
wear test (higher slope indicates the greater influence). The
slopes of speed, load, and time indicate that the higher the
value, the greater the mass loss. The slope of the load is very
steep, which influences more on mass loss. The slope of nan-
oclay indicates higher the nano clay content lowers the mass
loss. The drastic increase in mass loss found when the speed
increased from 200 to 300 RPM as well as time from 10 to
Fig. 7 – Main effect plots for mass loss.
15 min due to the heat generated as a result of friction between
the disc and specimen. The maximum mass loss resulted in
pure epoxy at 300 RPM speed, 3 kg load, and 15 min of testing
time. The improvement of wear resistance (lower mass loss) logical behavior can also be linked to the enhanced features
can be explained by the reinforcement of pure epoxy by high of the transfer film. Nanoclay offers a lot of load during the
strength and hardness nanoclay. This increase in NECs tribo- wear process and decreases the stress between the epoxy and
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):9108–9116 9113

Fig. 8 – Residual plots for flexural strength.

Fig. 9 – SEM images of worn surface of pure epoxy.

9114 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):9108–9116
Fig. 10 – SEM images of worn surface of NEC (4 wt.% of nanoclay).
nanoclay; thus, the epoxy matrix is effectively secured, and
the wear resistance of NEC is increased [22]. Other studies [23]
have reported that the addition of fillers in an epoxy matrix
forms a protective layer that reduces the wear rate.
3.2.3. Residual plots
As shown in Fig. 8, the normal probability plot indicates that
the residuals are distributed adjacent to the equipped line,
with only a minimal variation from the normal spread. This
determines that there is a regular dispersion of the residuals,
validating the best linear relationship between the response
variable and control factors. The graphs of residual vs. fit-
ted value, residual vs. frequency, and residual vs. observation
order, display little agreement or the residuals show up with
each other haphazardly. This is a crucial organization for rea-
sonable compatibility between the experimental and fitted
value [24,25].
3.2.4. Regression analysis
The regression equation is created by general regression anal-
ysis, depending on different parameters.
MassLoss = 0.35 − 12.417Nanoclay + 0.1267Speed
+ 28.44Load + 3.378Time
The regression Eq. (1) is checked for the following variables:
4 wt. % nanoclay, 250 RPM speed, 2.5 kg load, and 10 min time.
For the above parameters, the predicted mass-loss range in
MINITAB 19 is 71–104 mg. An average experimented mass loss
for the above-said parameters is 89 mg, which very well within
the predicted range.
3.2.5. SEM analysis
Fig. 9 displays the worn surfaces of pure epoxy. At a lower level
(i.e., 100 RPM speed, 1 kg load, and 5 min time), the worn sur-
face (Fig. 9(a)) is relatively rough. At mid-level (i.e., 200 RPM
speed, 2 kg load, and 10 min time), the worn surface is associ-
ated with micro-cracks in the matrix (Fig. 9(b)). At a higher level
(i.e., 300 RPM speed, 3 kg load, and 15 min time), SEM image
(Fig. 9(c)) presents the greater damage of the specimen, viz.,
removal of a higher amount of matrix from the surface. The
contact temperature and the loss in mass are increased con-
siderably, resulting in an accelerated split of the matrix. Due
to this phenomenon, the damage on the surface increased.
Grooves are formed due to matrix removal [26].
The SEM micrograph of the worn-out surfaces of 4 wt.%
nanoclay added NECs are as shown in Fig. 10. In comparison
with pure epoxy (Fig. 9), it is evident that the worn-out sur-
(1) faces are considerably smoother under similar wear factors
and levels, and with the introduction of nanoclay, the matrix
detachment is considerably reduced.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(4):9108–9116
The worn-out surface is relatively smoother. However, the
surface damage is due to fatigue wear, which usually arises at
higher temperatures. The micro-cracks break the layer of the
surface. With the introduction of nanoclay, surface integrity
is retained in the matrix, hindering the crack propagation in
the epoxy matrix [27]. Even under higher-level conditions, the
NECs have improved load-bearing capability in the incremen-
tal wear process [26].
Two wear mechanisms viz., abrasive wear and adhesive
wear can be observed in Figs. 9 and 10. Abrasive wear is
the cutting and plowing of the surface by harder particles.
The adhesive wear process involves the creation of adhesive
bonds, their growth, and breaking when the material is trans-
ferred from one surface to another. It is significant to note that
wear typically results not from a single mechanism but from
a combination of different mechanisms [14].
4. Conclusions
1. The nanoclay addition enhanced the epoxy resin’s tensile
properties.
2. The highest flexural strength is achieved at 2 wt.% of nan-
oclay. Further nanoclay addition has decreased the flexural
strength.
3. SEM image of neat epoxy showed a perfectly smooth sur-
face reflecting the fast proliferation of cracks and low
fracture toughness.
4. NEC’s SEM micrograph shows a far rugged background and
shows river-level design.
5. ANOVA results showcase that load and nanoclay have more
influence on mass loss, compared to speed and time for the
wear test.
6. As per the main effect plots, the slopes of speed, load,
and time indicate higher the value greater the mass loss,
whereas the slope of nanoclay indicates higher the value
lower the mass loss.
7. SEM images of worn-out specimens disclosed the different
types of wear mechanisms responsible for the wear-out of
specimens.
Conflicts of interest
The authors declare no conflicts of interest.
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