polymers
Article
Mechanical Characterization of Graphene—Hexagonal Boron
Nitride-Based Kevlar–Carbon Hybrid Fabric Nanocomposites
Srivatsava Madarvoni and Rama P. S. Sreekanth *
Citation: Madarvoni, S.; Sreekanth,
R.P.S. Mechanical Characterization of
Graphene—Hexagonal Boron
Nitride-Based Kevlar–Carbon Hybrid
Fabric Nanocomposites. Polymers
2022, 14, 2559. https://doi.org/
10.3390/polym14132559
Academic Editor: Jin-Hae Chang
Received: 8 June 2022
Accepted: 16 June 2022
Published: 23 June 2022
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Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2022, 14, 2559. https://doi.org/10.3390/polym14132559
School of Mechanical Engineering, VIT-AP University, Amaravati 522337, Andhra Pradesh, India;
msv354@gmail.com
* Correspondence: happyshrikanth@gmail.com
Abstract: Polymer nanocomposites have been gaining attention in recent years. The addition of
a low content of nanomaterials into the matrix improves mechanical, wear, thermal, electrical,
and flame-retardant properties. The present work aimed to investigate the effect of graphene and
hexagonal boron nitride nanoparticles on Kevlar and hybrid fiber-reinforced composites (FRP).
Composites are fabricated with different filler concentrations of 0, 0.1, 0.3, and 0.5 wt.% by using
a hand layup process. Characterizations like tensile, flexural, hardness, and impact strength were
evaluated separately, heat deflection and viscosity properties of the epoxy composites. The dynamic
viscosity findings indicated that a higher concentration of filler material resulted in nano-particle
agglomeration. Graphene filler showed superior properties when compared to hexagonal boron
nitride filler. Graphene showed optimum mechanical properties at 0.3 wt.%, whereas the hBN filler
showed optimum properties at 0.5 wt.%. As compared to Kevlar composites, hybrid (carbon–Kevlar)
composites significantly improved properties. As compared to graphene-filled composites, hexagonal
boron nitride-filled composites increased scratch resistance. Digimat simulations were performed
to validate experimental results, and it was observed that hybrid fabric composites exhibited better
results when compared to Kevlar composites. The error percentage of all composites are within 10%,
and it was concluded that hybrid–graphene fiber composites exhibited superior properties compared
to Kevlar composites.
Keywords: FRPs; hybrid fabric; mechanical properties; simulation; dynamic viscosity
1. Introduction
Recent scientific advances in composites have opened the way for fiber-reinforced
composites (FRP) for lightweight and imperishable structural applications like aerospace,
automotive, rocket, and sports, which demand multifunctional properties. To achieve
these multifunctional properties, nanoparticles are being added to polymer matrix systems.
Several types of particles, such as silica, carbon nanotube (CNT), and clay have been
added to FRPs. These nanoparticles enhance good mechanical properties but due to an
insulating property of epoxy, thermal properties are poor in FRP composites [1]. To address
this issue, in recent years researchers have been exploring nanomaterials that can exhibit
good mechanical as well as electrical properties. Hexagonal boron nitride (hBN) has
two-dimensional SP2 honeycomb structures similar to graphene, due to which these two
materials have excellent mechanical and thermal properties, which have recently attracted
a lot of interest. Graphite, hexagonal boron nitride (hBN), and graphene nanomaterials are
most suited for improving the mechanical and electrical properties of epoxy composites [2].
Sharma et al. [3] investigated the mechanical properties of multiwalled carbon nan-
otube Kevlar fabric composites. They observed properties at 0.3 wt.%, showing a maximum
tensile strength of 93%; a 56% improvement in tensile strength and Young’s modulus com-
pared to pristine Kevlar. Ahmade et al. [4] investigated the impact and hardness properties
of graphene Kevlar composites and found 0.2 wt.% graphene, showing maximum impact
https://www.mdpi.com/journal/polymers
Polymers 2022, 14, 2559 2 of 22

and hardness values of 1.6 joules and 82, respectively. Hallad et al. [5] investigated the me-
chanical properties of Kevlar composites and reported that tensile strength was increased
by 117% at 0.3 wt.% of graphene compared to pristine Kevlar. They also found that flexural
strength was increased by 48%. From TGA, they observed that up to 330 ◦ C the samples
were thermally stable. Naveen et al. [6] investigated the effect of graphene on the ballistic
performance of a hybrid (Kevlar and Cocos nucifera) composite and found that at 0.25 wt.%,
filler energy absorption increased by 8.5% in a nine-layered composite and by a 12% incre-
ment in twelve-layered composites. It was also observed that at 0.5 wt.%, better interfacial
bonding was displayed. Rahman et al. [7] investigated the effects of graphene and nano
clay on the impact strength of Kevlar epoxy composites and reported that 10 wt.% of nano
clay improved 26% of impact strength compared to pristine Kevlar composites. Graphene
resulted in no improvement in impact strength. The addition of graphene and nano clay
improved damage resistance to UV and water absorption. Truong et al. [8] investigated the
effects of different fillers on carbon fiber composites at elevated temperatures and found
short multiwalled carbon nanotubes functionalized COOH filler, showing a maximum
improvement of 20.7%, 45.7%, and 73.8% in tensile strength, ultimate strain, and toughness
values, respectively, and also found that at 100 ◦ C the tensile strength, ultimate strain,
and toughness were decreased by 36.5%, 37.1%, and 60%, respectively. Tominaga et al. [9]
investigated the influence of exfoliated hexagonal boron nitride particles on mechanical
properties of composites and found that specific strength was increased by 22% and specific
rigidity was increased by 37%. Zhang et al. [10] investigated the effect of boron nitride on
the thermal proprieties of epoxy and found that 40 wt.% boron nitride composite showed a
76% improvement in thermal conductivity and also that the addition of 5–10 wt.% boron
nitride improved glass transition temperature. Pasare et al. [11] investigated the mechanical
and tribological properties of hBN-filled carbon composites and found a 43.1% increase in
tensile modulus. They also found that increasing filler content reduced the specific wear
rate. Ulus et al. [12] investigated the effect of seawater on basalt graphene epoxy composites
by using dynamic mechanical analysis and discovered that 0.5 wt.% graphene improved
glass transition temperature by 107 ◦ C. Wazalwar et al. [13] investigated the mechanical
properties and curing behavior of graphene oxide-incorporated epoxy composites and
discovered an improvement of 26% in fracture energy. Nebe et al. [14] investigated the
flexural properties of composites through experimental and numerical investigations and
discovered that deflection improved by 74%. Bao et al. [15] investigated the tribological
behavior of epoxy composites and discovered that 0.2 wt.% graphene composites exhibited
better wear properties. Raci Aydin et al. [16] investigated the effect of dynamic mechanical
analysis of carbon–glass hybrid laminates in different ply angles and found that 12 layered
0◦ /90◦ angle piles were best suited for natural frequencies, while 30◦ /60◦ laminates were
best suited for damping. Vedanarayanan et al. [17] investigated the mechanical properties
of Kevlar and ramie fiber composites and found that interlaminar shear strength, tensile,
and flexural strength increased by 30%. Yadav et al. [18] investigated the effect of nano SiO2
on the mechanical properties of Kevlar composites and found an increase in hardness and
flexural properties by 29% and 50% for 3 wt.% of composites. Srivatsava et al. [19] investi-
gated the dynamic mechanical analysis of carbon, Kevlar, and hybrid fabric composites
and found that storage modulus, glass transition temperature at 0.3 wt.%, graphene filler
was higher for carbon fabric. They also investigated the circularity index of composites and
found that the composites fabricated were homogeneous, based on the circularity index.
Based on the literature review, it can be observed that several works reported on the
mechanical properties of carbon fabric with MWCNT, silica, clay, graphene, etc. Very few
works reported on Kevlar and hybrid fabric composites to the best of our knowledge. The
novelty of the present work lies in incorporating the hybrid Kevlar–carbon fabric as a
matrix into the 2D nanofillers reinforced epoxy. To the best of authors’ knowledge, such
work has not been reported elsewhere in the literature. The present work aims to study the
effect of different wt.% graphene (0, 0.1, 0.3, 0.5) and hBN (0, 0.1, 0.3, 0.5) fillers on Kevlar
and hybrid (carbon as a wrap and Kevlar weft) fiber on mechanical properties, dynamic
 Polymers 2022, 14, x FOR PEER REVIEW 3 of 25
Polymers 2022, 14, 2559 3 of 22

novelty of the present work lies in incorporating the hybrid Kevlar–carbon fabric as a ma-
trixviscosity,
into the 2Dhardness,
nanofillersand
reinforced epoxy. To the
heat deflection best of authors’
response. Digimat knowledge,
simulations suchwere
work also performed
has not been reported elsewhere in the literature. The present work aims to study the
and compared with the experimental results.
effect of different wt.% graphene (0, 0.1, 0.3, 0.5) and hBN (0, 0.1, 0.3, 0.5) fillers on Kevlar
and hybrid (carbon as a wrap and Kevlar weft) fiber on mechanical properties, dynamic
2. Materials and Methods
viscosity, hardness, and heat deflection response. Digimat simulations were also per-
formed and Bisphenol
compared A with
diglycidyl ether (DGEBA),
the experimental results. commonly named Epoxy Ly556, and Hardener
Hy951 were obtained from Singhal Chemical Corporation, Delhi, India. Kevlar (200 GSM)
2. Materials
and hybridand (aramid
Methods as warp and carbon as weft, 200 GSM) were obtained from Marktech
Bisphenol APvt.
companies diglycidyl ether (DGEBA),
Ltd., Bangalore, commonlyIndia.
Karnataka, namedHexagonal
Epoxy Ly556,boron
and Hard-
nitride (h-BN) was
ener Hy951 were obtained from Singhal Chemical Corporation, Delhi, India.
obtained from Sisco Research Laboratories Pvt. Ltd., Hyderabad,Telangana,India. Kevlar (200 Hexago-
GSM) and hybrid (aramid as warp and carbon as weft, 200 GSM) were obtained from
nal boron nitride (h-BN) platelets had an average particle size of 70 nm and surface area of
Marktech companies Pvt. Ltd., Bangalore, Karnataka, India. Hexagonal boron nitride (h-
19.4 m2 /g. The functionalization of h-BN was performed as described in the literature [20].
BN) was obtained from Sisco Research Laboratories Pvt. Ltd., Hyderabad,Telangana,In-
dia.Functionalized
Hexagonal borongraphene wasplatelets
nitride (h-BN) obtainedhadfrom Adnano
an average Technologies,
particle size of 70 nmMajjigenahalli,
and Kar-
nataka,India. GNP had a surface area of 112 m 2 /g, bulk density of 0.3 g/cc, and an average
surface area of 19.4 m /g. The functionalization of h-BN was performed as described in
2

the diameter of 10–15

literature [20]. microns with
Functionalized a purity
graphene was greater
obtainedthan
from98%.
Adnano Technologies,
Majjigenahalli, Karnataka,India. GNP had a surface area of 112 m2/g, bulk density of 0.3
2.1.
g/cc, andComposite
an averageFabrication
diameter of 10–15 microns with a purity greater than 98%.
Fabrics were washed with acetone to extract dust particles from the fiber’s surface
2.1. Composite Fabrication
and then dried for 24 h at room temperature. After drying, the fibers were subjected to
Fabrics were washed with acetone to extract dust particles from the fiber’s surface
moisture removal in a vacuum oven at 70 ◦ C for 4 h. To ensure that no air bubbles were
and then dried for 24 h at room temperature. After drying, the fibers were subjected to
present
moisture in theinepoxy,
removal a vacuumdegassing
oven at 70was performed
°C for 60 min
4 h. To ensure thatbefore the addition
no air bubbles were of the curing
agent
present in and 5 mindegassing
the epoxy, after thewas
addition of the
performed curing
60 min agent.
before Graphene
the addition of theand hexagonal boron
curing
nitride
agent and 5particles
min after at
thedifferent
addition wt.%
of the (0, 0.1,agent.
curing 0.3, 0.5) were added
Graphene into theboron
and hexagonal epoxy individually.
Ultrasonication
nitride was performed
particles at different wt.% (0, 0.1,on
0.3,different
0.5) were filler
addedconcentrations at a temperature of 80 ◦ C
into the epoxy individually.
Ultrasonication
for 0.5 h. was performed
Hardener on different
HY951 filler concentrations
was added to the epoxy at a with
temperature
a mixingof 80 ratio
°C of 10:1 [21].
for Kevlar
0.5 h. Hardener HY951composites
and hybrid was added towere
the epoxy with a mixing
fabricated by usingratiothe
of 10:1 [21].layup
hand Kevlartechnique, each
and hybrid composites were fabricated by using the hand layup technique, each compo-
composite consisting of nine layers of fibers. Layers were oriented in 0◦ and 90◦ directions.
site consisting of nine layers of fibers. Layers were oriented in 0° and 90° directions. Fab-
Fabricated composites were subjected to the compression molding process. The schematic
ricated composites were subjected to the compression molding process. The schematic
representation
representation of composite
of composite fabrication
fabrication is shown inisFigure
shown 1c. in Figure
Final 1c. Final
composites composites had
had di-
dimensions
mensions of 300 ×of
300300
× 3 mm × 300 mmwere
mm. Composites × 3 coded
mm. according
Composites were
to filler coded according to filler
concentrations
concentrations
listed listed
in Table 1a,b. The TEMinimages
Tableof1a,b. The and
graphene TEM images
hBN fillers of graphene
were shown inand hBN fillers were
Figure
1a,b.
shown in Figure 1a,b.

Polymers 2022, 14, x FOR PEER REVIEW 4 of 25

(c)
Figure 1.Figure
TEM images of (a) images
1. TEM grapheneof
and
(a)(b)graphene
hexagonal boron nitride
and (b) (hBN). (c)boron
hexagonal Composite fabri-(hBN). (c) Composite
nitride
cation process.
fabrication process.
Table 1. (a). Specification material according to GNP wt.%. (b) Specification of material according
to h-BN wt.%.

a
Symbol No of Layers GNP (wt.%)
Polymers 2022, 14, 2559 4 of 22

Table 1. (a). Specification material according to GNP wt.%. (b) Specification of material according to
h-BN wt.%.

a
Symbol No of Layers GNP (wt.%)
GK0 9 0
GK1 9 0.1
GK2 9 0.3
GK3 9 0.5
GH0 9 0
GH1 9 0.1
GH2 9 0.3
GH3 9 0.5
b
Symbol No of Layers GNP (wt.%)
hBK0 9 0
hBK1 9 0.1
hBK2 9 0.3
hBK3 9 0.5
hBH0 9 0
hBH1 9 0.1
hBH2 9 0.3
hBH3 9 0.5

2.2. Tensile Testing

Tensile testing was conducted on a Universal Testing Machine (Tec-sol, Chennai, Tamil
Nadu, India), according to ASTM D 3039 standard, at a crosshead speed of 2 mm/min at
room temperature. The test samples were cut by using a Bosch Jigsaw machine (Bosch,
Guntur, Andhraprdesh, India). The final dimensions of the cut tensile samples were
250 mm × 25 mm × 3 mm. For accuracy and repeatability, 5 samples were tested per each
filler concentration and the average values were reported.

2.3. Flexural Testing

The flexural test was performed on a Tinius Olsen H10KL, Noida, Uttar Pradesh,
India, according to ASTM D7264, at a crosshead speed of 2 mm/min. For accuracy and
repeatability, 5 samples were tested per each filler concentration and the average values
were reported.

2.4. Micro Vickers Hardness

Hardness measured by using Micro Vickers hardness tester supplied by R.S.Scientific
Kolkata, West Bengal, India. ASTM E384-17 standard was used for the measure of micro-
hardness. Hardness was measured at a constant load of 1 kg over a dwell period of 20 s. To
ensure repeatability, 5 readings were taken for each configuration and the average value
was reported.

2.5. Viscosity Measurement

Viscosity measurements were carried out on the Rheometer (MCR 102) model from
Anton Paar India limited, Bangalore, Karnataka, India. A frequency sweep was performed
on the epoxy filled with nanomaterials (graphene and hBN).

2.6. Heat Deflection Test

The heat deflection test is a measure of the ability of a polymer to carry a load at raised
temperatures. The heat deflection apparatus was supplied by S.C.Dey & Co, Kolkata, West
Bengal, India. ASTM D 648 or ISO 75 standards were used for the measuring. Table 2
shows the standard sample dimensions and deflection values as per the ISO standard. The
Polymers 2022, 14, 2559 5 of 22

sample was placed in between two supports and the load was applied to the sample. Then
the sample was dipped into silicone oil and subjected to the heat of 2 ◦ C/minute. As the
temperature increased, the sample began deflection, and when the sample reached the
specified standard deflection, the temperature was recorded. The test was repeated twice,
and the average value was reported.

Table 2. ASTM/ISO standard dimension of the heat deflection test.

ASTM Standard ISO Standard ASTM Sample

Load ISO Sample Dimensions (mm)
Deflection (mm) Deflection (mm) Dimensions (mm)
Method A 1.8 MPa Flat Edge L B H L B H
0.25
Method B 0.45 Mpa 0.32 0.34 50.8 12.6 6.35 Flat 80 10 4
Edge 120 10 4

2.7. Impact Test

The impact test was performed on a Digital Izod/Charpy tester supplied by R.S.Scientific,
Kolkata, West Bengal, India, according to ASTM D256, with sample dimensions of
63.5 mm × 12.7 mm × 3 mm. The prepared sample was placed 2 mm away from stop-
pers with a 21.7 Kg weight hammer at the center of the sample.

2.8. Scratch Test

A scratch test was performed on a Scratch Tester (DUCOM, Bangalore, Karnataka,
India), according to ASTM D7027-05. Experiments were conducted under a constant load
of 150 N, a ramp 30–150 N with a velocity of 1 mm/s, and scratch length of 25 mm.

2.9. Digimat Software

Digimat software was used for linear and nonlinear multiscale material modeling.
Digimat software enables the prediction of the constitutive behavior of heterogeneous
and/or anisotropic materials such as polymer matrix composites (PMC), rubber matrix
composites (RMC), metal matrix composites (MMC), or even nanocomposites. It consists
of different modules, namely, MF, FE, MX, MAP, CAE, RP, VA, HC, and AM. In the
present study, MF and FE modules were used. MF indicates mean-field homogenization,
and it uses Eshelby-based semi-analytical mean-field homogenization approaches and an
analytical description of the material in order to compute the thermo-mechanical, thermal,
or electrical properties of a composite as a function of its microstructure morphology,
i.e., the inclusion of shape, orientation, volume/mass fraction, and micro (i.e., per-phase)
material behavior. Mori–Tanaka homogenization models were used in the present study. In
this uniform model, fiber distribution assumption was taken into consideration to approach
the problem within the micromechanical theory of periodically arranged heterogeneous
materials. The Digimat MF module was used for the evaluation of fiber volume fraction,
and Young’s modulus and Poisson’s ratio of Kevlar- and hybrid fiber-reinforced graphene
filler composites were calculated.
The Digimat FE module was used for the visualization of RVE geometry and the
evaluation the stress–strain analysis. Fabric microstructure was generated by 3D woven
interlock wrap weft phases considered for Kevlar composites and for hybrid composites
with Kevlar as a wrap and hybrid fabric (carbon–Kevlar) as weft phase, with parameters
shown in Tables 3 and 4. The fabric weaving pattern is shown in Figure 2e and the generated
fabric has a unit cell of 9 mm × 9 mm × 1.9 mm. The RVE model of Fabric and filler is
shown in Figure 2.
 Polymers 2022, 14, 2559 6 of 22
PEER REVIEW 6 of 25

Table 3. Parameters for microstructure generation of fabric.

the inclusion of shape, orientation, Woven Pattern

volume/mass Twill per-phase) ma-
fraction, and micro (i.e.,
terial behavior. Mori–TanakaNumber of warp yarns models were used in the9 present study. In
homogenization
Number of weft yarns 9
this uniform model, fiber distribution assumption was taken into consideration
Number of layers 9 to ap-
Warp depth 2
proach the problem within the micromechanical
Weave step
theory of periodically1 arranged hetero-
geneous materials. The DigimatWarp MFyarnmodule
count was used for the evaluation10 of fiber volume
Weft yarn count 10
fraction, and Young’s modulusYarn and Poisson’s ratio of Kevlar- and hybrid
spacing ratio 0
fiber-reinforced
graphene filler composites were calculated.
Yarn crimp 0.1
The Digimat FE module was used for the visualization of RVE geometry and the
evaluation the stress–strain analysis.
Table 4. Fiber Fabric microstructure was generated by 3D woven
yarn phase properties.
interlock wrap weft phases considered Fiber Yarn
for Kevlar composites andKevlar,
for hybrid
Hybrid
composites
with Kevlar as a wrap and hybrid fabric
Yarn linear (carbon–Kevlar) as weft phase,
density with parameters
43.96 tex
shown in Tables 3 and 4. The fabric weaving pattern is shown in Figure
Fiber diameter 0.05 mm2e and the gener-
Fiber volume fraction 0.66
ated fabric has a unit cell of 9 × 9Yarn × 1.9 mm. The RVE model of Fabric0.1and
height mm filler is shown
in Figure 2. Yarn width 0.6 mm

Figure 2. Cont.
ers 2022, 14, x FOR PEER REVIEW 7 of 25
Polymers 2022, 14, 2559 7 of 22

Figure 2. Digimat modeling: (a) RVE of filler and fibers matrix, (b) RVE of matrix and fibers, (c) RVE
Figure 2. Digimat modeling: (a) RVE of filler and fibers matrix, (b) RVE of matrix and fibers, (c) RVE
of filler, (d)of
meshing of RVE, (e) fabric weaving style, (f) Digimat simulation results.
filler, (d) meshing of RVE, (e) fabric weaving style, (f) Digimat simulation results.

Table 3. Parameters for microstructure

The generated generation
RVE model of fabric.to meshing (voxel) with a size of 100 mm,
was subjected
◦
followed by uniaxial loading with 90 theta.
Woven Pattern Twill
Number of warp yarns 9
Number of weft yarns 9
Number of layers 9
Warp depth 2
Weave step 1
 Yarn width 0.6 mm

The generated RVE model was subjected to meshing (voxel) with a size of 100 mm,
followed by uniaxial loading with 90° theta.
Polymers 2022, 14, 2559 8 of 22
3. Results & Discussion
3.1. Tensile Strength
Figure&3a
3. Results shows the stress–strain curves of GK and GH composites. It can be ob-
Discussion
served thatStrength
3.1. Tensile the materials followed a linear pattern, which indicates that the composites
are brittle
Figurein3anature.
showsThe brittleness increased
the stress–strain curves of GK withandfiller
GHcontent. GH composites
composites. exhibited
It can be observed
athat
more
the brittle
materialsnature as compared
followed to GKwhich
a linear pattern, composites.
indicatesGH2 showed
that the a maximum
composites stress
are brittle
value of 780
in nature. TheN/mm 2 compared
brittleness increasedto an all-composite
with filler content.variation, whereasexhibited
GH composites GK0 demonstrated
a more
brittle
the nature
least valueas ofcompared
390.10 N/mm to GK composites.
2. The reason for GH2 showed properties
the superior a maximum stress
of GH value
composites
of attributed 2
780 N/mmtocompared to an all-composite variation, whereas GK0 demonstrated the The
is their better dispersibility and excellent load-carrying capacity [22].
least valuestress
increasing of 390.10 N/mmof2 . all
sequence The reason foristhe
composites as superior
follows: properties
GH2 > GH3 of>GHGH1 composites
> GK2 > GK3
>isGK1
attributed
> GK0.to their better dispersibility and excellent load-carrying capacity [22]. The
increasing stress sequence of all composites is as follows: GH2 > GH3 > GH1 > GK2 > GK3
> GK1 > GK0.

Figure 3. (a). Stress–strain curves of graphene filled composites. (b) Stress–strain curves of hBN-filled
Figure 3. (a). Stress–strain curves of graphene filled composites. (b) Stress–strain curves of hBN-
composites.
filled composites.
Figure 3b shows the stress–strain curves of hBK and hBH composites. It is observed
Figure
that the 3b shows
materials the stress–strain
followed curves
a linear pattern which ofindicates
hBK andthat hBH thecomposites.
compositesItareis brittle
observed
that the materials
in nature. followed
The addition a linear
of filler pattern
materials which
further indicates
increased that the composites
the brittleness are brittle
of the composites.
in
HBHnature. The addition
composites exhibitedof filler
a morematerials furthercompared
brittle nature increasedtothe hBKbrittleness of the
composites. compo-
hBH3
showed a maximum value of 812.08 N/mm 2 , while hBK0 demonstrated the least value
sites. HBH composites exhibited a more brittle nature compared to hBK composites. hBH3
of stress.aThe
showed stress behavior
maximum value ofof812.08
different
N/mm composites in incremental
2, while hBK0 order are
demonstrated theas follows:
least value of
hBH3 >The
stress. hBH2 > hBH0
stress > hBK3
behavior of>different
hBK2 > hBK1 > hBK0.inThe
composites tensile properties
incremental of different
order are as follows:
composites are shown in Table 5a.

Table 5. (a). Tensile values of hBN-filled composites. (b) Tensile values of graphene-filled composites.

a
Young’s
Young’s Ultimate Tensile Young’s
Filler Weight Ultimate Tensile Modulus UTS
Fabric Modulus Strength (MPa) Modulus
Percentage Strength (MPa) (GPa) Error
(GPa) Digimat Error
Digimat
hBK0 390.10 39.31 403.66 44.85 3.3 12.3
hBK1 442.65 49.58 496.61 55.17 10.8 10.1
Kevlar
hBK2 475.44 59.90 513.73 57.08 7.4 4.7
hBK3 488.09 70.20 530.46 58.94 7.9 16.0
hBH0 557.67 71.54 589.92 65.54 5.4 8.3
hBH1 616.13 72.78 681.76 74.54 9.6 2.3
Hybrid
hBH2 676.29 77.46 698.68 77.63 3.2 0.2
hBH3 752.67 85.14 779.15 86.64 3.3 1.7
Polymers 2022, 14, 2559 9 of 22

Table 5. Cont.

b
Young’s
Young’s Ultimate Tensile Young’s
Filler Weight Ultimate Tensile Modulus UTS
Fabric Modulus Strength (MPa) Modulus
Percentage Strength (MPa) (GPa) Error
(GPa) Digimat Error
Digimat
GK0 390.10 39.31 403.66 44.85 3.3 12.3
GK1 463.70 50.29 473.65 52.62 2.1 4.4
Kevlar
GK2 507.40 65.04 541.78 60.13 6.3 7.54
GK3 491.55 57.78 513.10 57.01 4.1 1.3
GH0 557.67 71.54 589.92 65.54 5.4 8.3
GH1 723.89 83.10 732.12 81.34 1.1 2.1
Hybrid
GH2 780.58 89.09 779.12 86.56 0.18 2.83
GH3 746.84 85.70 751.31 83.47 0.59 2.60

Polymers 2022, 14, x FOR PEER REVIEW 9 of 25

The ultimate tensile strength comparison of GK and GH composites are shown in
Figure 4a. The figure indicates that hybrid fiber composites exhibited superior strength
hBH3 > hBH2 > hBH0
compared to> Kevlar
hBK3 > hBK2 > hBK1 > hBK0. The
composites. tensile properties ofthe
Additionally, different
increase in filler content increased
composites are shown in Table 5a.
the
Thestrength ofstrength
ultimate tensile the composites
comparison of GK upandtoGH0.3 wt.% are
composites in shown
both inGH and GK composites, beyond
Figure
which4a. The figure
the indicates that
strength washybrid fiber composites
decreased. exhibited superior
Increments ofstrength
29.80%, 39.97%, and 33.9% for GH1,
compared to Kevlar composites. Additionally, the increase in filler content increased the
GH2, and GH3 composites, as compared to GH0 composites,
strength of the composites up to 0.3 wt.% in both GH and GK composites, beyond which were observed and, similarly,
theincrements
strength was decreased. Increments
of 18.86%, of 29.80%, and
30.06%, 39.97%,26.0%
and 33.9% for GK1,
for GH1, GH2,GK2,and and GK3, as compared to GK0,
GH3 composites, as compared to GH0 composites, were observed and, similarly, incre-
were observed, respectively. Theand ultimate tensiletostrength 2
ments of 18.86%, 30.06%, and 26.0% for GK1, GK2, GK3, as compared GK0, were of 780 N/mm was observed in
observed, respectively. The ultimate tensile strength
the GH2 composite among all composite configurations. of 780
2 N/mm was observed in the
GH2 composite among all composite configurations.

Figure 4. Cont.
Polymers 2022, 14, 2559 10 of 22
Polymers 2022, 14, x FOR PEER REVIEW 10 of 25

Figure 4. Ultimate tensile strength of (a) graphene-reinforced composites, (b) hBN-reinforced com-
Figure 4. Ultimate tensile strength of (a) graphene-reinforced composites, (b) hBN-reinforced com-
posites, Young’s modulus of (c) graphene-reinforced composites, and (d) hBN-reinforced compo-
sites. posites, Young’s modulus of (c) graphene-reinforced composites, and (d) hBN-reinforced composites.

Young’s modulus comparison of GK and GH composites are shown in Figure 4c. it

was observedYoung’s modulus
that GH composites comparison
exhibited ofmodulus
a superior Young’s GK and GH tocomposites
compared GK are shown in Figure 4c. it
composites. GH2 had the highest Young’s modulus of 89.09 GPa, and GK0 had the lowest
was observed that GH composites exhibited a superior
Young’s modulus of 39.31 GPa. The Young’s moduli of different composites are shown in
Young’s modulus compared to GK
Tablecomposites.
5b. The reason forGH2 hadYoung’s
the superior the highest
modulus inYoung’s modulus
GH composites of 89.09 GPa, and GK0 had the lowest
is the presence
of carbon fiber, enabling better bonding energy between carbon atoms of the nano-
Young’s modulus of 39.31 GPa. The Young’s moduli of different composites are shown in
material.
Table 5b. The reason for the superior Young’s modulus in GH composites is the presence of
carbon fiber, enabling better bonding energy between carbon atoms of the nanomaterial.
Figure 4b,d shows the comparison of Young’s modulus and the UTS of hBK and hBH
composites. It is evident that hBH composites exhibit higher values as compared to hBK
and hBH3, showing a 15% improvement in Young’s modulus, i.e., 85.14 GPa. Graphs give
a clear indication of improvement with the addition of hBN filler. The increase is attributed
to the high modulus of hBN filler (400 to 900 GPa) [23]. It was observed that the graphs are
linear, irrespective of materials and filler content. This could be due to the layup sequence
(0◦ , 45◦ , 90◦ ) of composites during fabrication [24,25] as well as the weaving pattern [26].
RVE analysis was performed using Digmat software, and the findings were compared
with the experimental data, as shown in Figure 5. The comparison of the UTS of the
experimental and Digimat values of GK composites is shown in Figure 5a. Table 5b shows
the error percentage between the experimental and Digimat values, which ranges from 2 to
6 percent and is within acceptable bounds.
Figure 5b shows a comparison of the UTS of GH composites produced physically and
via Digimat modeling. Table 5a shows the percentage difference between experimental
and simulation results. The percentage variation is in the 0–5% range, which is within
acceptable bounds. The experimental values of GH composites are almost identical to
Digimat values in the case of GH2 and GH3 composites, with an error rate of less than
0.6%. Figure 5c,d represents a comparison of Young’s modulus of Kevlar and hybrid fiber
composites incorporated with graphene filler.
Polymers 2022,14,
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Figure 5.
Figure 5. Comparison
Comparisonofofexperimental
experimental Digimat graphene-reinforced
Digimat composite
graphene-reinforced system—(a)
composite UTSUTS
system—(a) of
Kevlar composites, (b) UTS of hybrid composites, (c) Young’s modulus of Kevlar composites,
of Kevlar composites, (b) UTS of hybrid composites, (c) Young’s modulus of Kevlar composites, (d)
Young’s modulus of hybrid composites; and comparison of experimental Digimat hBN-reinforced
(d) Young’s modulus of hybrid composites; and comparison of experimental Digimat hBN-reinforced
composite systems—(e) UTS of Kevlar composites, (f) UTS of hybrid composites, (g) Young’s mod-
composite systems—(e) UTS of Kevlar composites, (f) UTS of hybrid composites, (g) Young’s modulus
ulus of Kevlar composites, (h) Young’s modulus of hybrid composites.
of Kevlar composites, (h) Young’s modulus of hybrid composites.
Polymers 2022, 14, 2559 12 of 22

Young’s modulus of Kevlar and hybrid composites incorporated with graphene are
shown in Figure 5c,d. The graphs revealed that the Young’s modulus increased up to the
GH2 and hBH2 composition, beyond which the composites exhibited a sightly decreased
modulus. The variation in simulation results and experimental results observed in the
graphs may be due to many factors, such as the composite fabrication, weather, and mixing
of nanoparticles during experimentation.
The ultimate tensile strength of hBK composites obtained experimentally and those
obtained using Digimat is shown in Figure 5e. Table 5a displays the error percent of
experimental and Digimat results. The error percentage of values ranges between 2 and
10%, which is within acceptable bounds. hBK2 has the lowest mistake rate of 7.4%. Figure 5f
depicts a comparison of the ultimate tensile strength of hBH composites from experimental
and Digimat simulations. Table 5a shows the error percentages of experimental and Digimat
values, which vary from 3 to 10% and are within acceptable ranges; nevertheless, hBH2 has
the lowest error of 3.2%.
Young’s modulus of Kevlar and hybrid composites incorporated with graphene are
shown in Figure 5g,h. It is observed that the Young’s modulus increased up to hBK3
and hBH3. Simulation results revealed that hybrid composites are more accurate when
compared with experimental results.
From the above discussion, it can be observed that 0.3 wt.% graphene exhibits su-
perior UTS and Young’s modulus in all combinations; this may be due to the uniform
dispersion of particles through the fiber surface and epoxy. Uniform dispersion ensures
better interlocking between the fiber and matrix parts, which results in the improvement of
the load-carrying capacity of the composite. At 0.5 wt.%, the UTS and Young’s modulus
decreased because of the agglomeration caused by Van der Waals forces [27]. An increase
in filler content increases the bonding surface area, which in turn results in a decrease in
bonding strength [28]. Inadequate bonding strength leads to reduced loads transferred
from the matrix to the fiber, which also results in crack propagation.
RVE FE analysis of hybrid composites is shown in Figure 2f. It can be observed
from the diagram that the equivalent von Mises stress, maximum principal stress, and the
maximum total strain of the composite are within the acceptable limits, which indicates that
the applied load on the composite was absorbed by the composite without any deformation
or failure.

3.2. Dynamic Viscosity

Viscoelastic materials behave linearly up to the critical strain level, beyond which
the materials behave non-linearly. Therefore, a strain sweep was initially performed to
estimate the linear viscoelasticity of the epoxy-filled graphene and hBN composites. The
dynamic viscosity of epoxy filled with graphene and hBN is shown in Figure 6a,b. The
addition of fillers increased the storage modulus, which led to an increase in the viscosity
of composites.
The dynamic viscosity of pure epoxy incorporated with graphene and HBN filler was
observed to decrease as the angular frequency increased. The behavior of neat epoxy is
similar to a Newtonian fluid at lower frequencies, but as the frequency increases, it shows
a shear-thinning effect. The addition of nanofiller content linearly increased the viscosity
of epoxy. At higher viscosity, it is difficult to mix the nanofillers properly into the epoxy
matrix, which leads to the agglomeration of nanoparticles, leading to the poor strength of
the matrix. Another problem at higher viscosity is that while carrying out the hand layup
process it becomes exceedingly difficult to roll epoxy smoothly over the entire composite
laminate. Up to 0.5 wt.% filler content, the viscosity of filler increases proportionately,
whereas at 0.7 wt.%, the jump in the viscosity is high, which leads to a higher chance of
agglomeration at 0.7 wt.%. Therefore, in the present study, we experimented with up to
0.5 wt.% of filler content.
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Polymers 2022, 14, x FOR PEER REVIEW 15

Table 6. (a). Flexural values of graphene-filled composites. (b) Flexural values of hBN-filled
posites.

a
Filler Weight Per- Ultimate Flexural Flexural Modulu
Fabric
(a) centage (b) Strength (MPa) (GPa)
GK0 158.49 28.33
Figure
Figure6. 6.Dynamic
Dynamicviscosity of epoxy
viscosity of epoxywithwith(a)(a) graphene
GK1 andand
graphene (b) (b)
hBNhBN fillers
165.56
fillers at different
at different loadings.
loadings. 35.83
Kevlar
GK2 287.0 66.66
3.3.The
Flexural Test viscosity of pure epoxy incorporated with graphene and HBN filler was
dynamic GK3 253.35 57.56
observed Figure 7a illustrates
to decrease as thetheangular
stress–strain curve increased.
frequency
GH0 of graphene–Kevlar
The composites.
behavior
369.69 of neatThe epoxy
52.49 is
figure indicates that the addition of
similar to a Newtonian fluid at lower frequencies, filler content
GH1 increased
but as the
the stress
frequency
443.82 of composites,
increases, withit shows
72.72
GK2 showing the maximum Hybrid value of 287 N/mm2 . It should be noted that beyond GK2,
a shear-thinning effect. The addition of nanofiller GH2 content linearly517.96increased the viscosity 99.16
the addition of filler content resulted in decreased values. All composites exhibited no
of epoxy. At higher viscosity, it is difficultGH3 to mix the nanofillers 480.81 properly into the82.89 epoxy
delamination until peak stress but thereafter displayed a significant drop due to crack
matrix, which inside
leads to b
propagation thethe agglomeration
composites, beyondofwhich nanoparticles,
the composite leading to thetopoor
continued bearstrength
load of
thebut
matrix. Another
never achieved peak problem at higherFiller Weight
viscosity Per-
is that Ultimate
while Flexural
carrying
values. Figure 7c,e shows the comparison of Kevlar- and hybrid out theFlexural
hand Modulu
layup
Fabric
process it becomes
fabric-based exceedingly
graphene composites difficult centage
to roll epoxy
with different Strength
smoothly
filler contents. The(MPa)
over the entire
values composite
of flexural (GPa)
laminate. Up to 0.5 wt.%
strength and modulus are
Kevlar filler content, the
listed in Table 6a. It
hBK0 viscosity of filler158.49
should be noted that increases proportionately,
an increment of 38.5%, 28.33
88.91%,at
whereas and
0.757.91%
wt.%,ofthe
GH1, GH2,
jump inand
theGH3 was
viscosity
hBK1 seen
is in the
high, flexural
which modulus
leads
202.71 to aof the
higher hybrid–
chance
36.66 of
graphene composite. Maximum
agglomeration at 0.7 wt.%. Therefore, in the flexural strength was achieved
present study, we by GH2 composites,
experimented with41.54 i.e., up to
hBK2 i.e., 99.6 GPa, for246.22
0.5517.96
wt.%MPa, andcontent.
of filler a maximum flexural modulus, hybrid–graphene-based
composites. The optimum loading was at 0.3 hBK3wt.% graphene, beyond 253.35which the property 55.00
decreased due to the rapid Hybrid aggregation of graphene
hBH0 sheets, which behaved
369.69 like micro fillers52.49
3.3. Flexural Test
with less surface area. These agglomerates behave as an obstacle [29] in polymer flow,
hBH1 439.91 69.63
Figure
which 7a illustrates
results the stress–strain
in voids being created [30] betweencurve ofepoxy graphene–Kevlar
and fiber. Duecomposites.
to these voids, The fig-
ure indicates
when a load that the addition
is applied on to composites hBH2
of filler content
there is aincreased the457.15
chance of zero stress of composites,
load transfer to fibers. 81.10
with
GK2In fiber-reinforced
showing the maximum composites, fibers
value of act
287as hBH3
high 2load
N/mm carriers.
. It should be480.39
However,
noted that inbeyond
the current 97.48the
GK2,
scenario,
addition ofdue to content
filler the non-transfer
resultedofinload, epoxy cannot
decreased values. carry
Allthe load and therefore
composites exhibited results
no delam-
in crack propagation and ultimately in the failure of the composite.
ination until peak stress but thereafter displayed a significant drop due to crack propaga-
tion inside the composites, beyond which the composite continued to bear load but never
achieved peak values. Figure 7c,e shows the comparison of Kevlar- and hybrid fabric-
based graphene composites with different filler contents. The values of flexural strength
and modulus are listed in Table 6a. It should be noted that an increment of 38.5%, 88.91%,
and 57.91% of GH1, GH2, and GH3 was seen in the flexural modulus of the hybrid–gra-
phene composite. Maximum flexural strength was achieved by GH2 composites, i.e.,
517.96 MPa, and a maximum flexural modulus, i.e., 99.6 GPa, for hybrid–graphene-based
composites. The optimum loading was at 0.3 wt.% graphene, beyond which the property
decreased due to the rapid aggregation of graphene sheets, which behaved like micro fill-
ers with less surface area. These agglomerates behave as an obstacle [29] in polymer flow,
which results in voids being created [30] between epoxy and fiber. Due to these voids,
when a load is applied on to composites there is a chance of zero load transfer to fibers. In
Figure 7. Cont. composites, fibers act as high load carriers. However, in the current sce-
fiber-reinforced
nario, due to the non-transfer of load, epoxy cannot carry the load and therefore results in
crack propagation and ultimately in the failure of the composite.
 Polymers 2022, 14, x FOR PEER REVIEW
Polymers 2022, 14, 2559 14 of 22 1

Figure 7. FlexureFigure
response of (a) graphene–Kevlar,
7. Flexure (b) hBN–Kevlar;
response of (a) graphene–Kevlar, (b)ultimate flexural
hBN–Kevlar; strength
ultimate of strength
flexural
(c) graphene system, (d) hBN
graphene system;
system, (d)Flexure modulus
hBN system; of (e)modulus
Flexure graphene
of system, (f) hBN
(e) graphene system.
system, (f) hBN system.

Table 6. (a). FlexuralFigure

values7b
of illustrates
graphene-filled composites. response
the stress–strain (b) Flexural values of hBN-filled
of hBN–Kevlar composites. It sh
composites. be noted that the addition of hBN content increased the flexural modulus and fle
strength, as shown in Table 6b. A comparison of flexural strength and modulus of d
a
ent materials is shown in Figure 7e,f. It can be observed from the graphs that the hy
basedFiller
composites have a maximumUltimate Flexural
flexural strength Flexural Modulusflexural mod
and maximum
Fabric Weight Percentage
Strength (MPa) (GPa)
The addition of hBN filler improved 30% of flexural strength in the hBH3 comp
whereas an 85% GK0of improvement in the 158.49
flexural modulus of the28.33
hBH3 composite wa
Kevlar served. A highGK1modulus indicates that 165.56 35.83and the addition of
the material is tougher [31]
GK2 287.0 66.66
content improved flexural strength and modulus due to the uniform dispersion of
GK3 253.35 57.56
cles [32], resulting
GH0 in good bonding strength
369.69 between the fiber and matrix. Additio
52.49
due to the largeGH1
surface area of hBN particles,
443.82 contact with the 72.72
matrix enables load tra
Hybrid
to the matrix and
GH2fibers [33]. 517.96 99.16
GH3 480.81 82.89
b 3.4. Hardness
The hardness values of graphene-based fiber composites
Ultimate Flexural Flexural are depicted in Figu
Modulus
Fabric KevlarFiller Weight Percentage
composites exhibited lower hardness, whereas carbon composites showed
Strength (MPa) (GPa)
hardness. The highest values of hardness were observed in GK2 composites at 20
hBK0 158.49 28.33
and the least hBK1
at 159 HV in the GK0 composite.
202.71 An increment of 38.36% and 12.20
36.66
Kevlar hardness of Kevlar and hybrid composites can be observed, and
hBK2 246.22 41.54the hardness valu
shown in Table 7.
hBK3 From the figure, it can
253.35be noted that the addition of filler incr
55.00
hBH0 369.69 52.49
hardness up to an optimum value, beyond which a minor drop in hardness values
hBH1 439.91 69.63
Hybrid composites was seen. A direct relationship between stiffness and modulus was e
lished by [31], where the results were presented, following 81.10
hBH2 457.15
the criteria, and maxi
hBH3 480.39 97.48
modulus was observed at 0.3 wt.%. Indent images of graphene and hBN composit
shown in Figure 8c,d.
Figure 7b illustrates the stress–strain response of hBN–Kevlar composites. It should
be noted that the addition of hBN content increased the flexural modulus and flexural
Polymers 2022, 14, 2559 15 of 22

strength, as shown in Table 6b. A comparison of flexural strength and modulus of different
materials is shown in Figure 7e,f. It can be observed from the graphs that the hybrid-
based composites have a maximum flexural strength and maximum flexural modulus. The
addition of hBN filler improved 30% of flexural strength in the hBH3 composite, whereas
an 85% of improvement in the flexural modulus of the hBH3 composite was observed. A
high modulus indicates that the material is tougher [31] and the addition of filler content
improved flexural strength and modulus due to the uniform dispersion of particles [32],
Polymers 2022, 14, x FOR PEER REVIEW 17 of 25
resulting in good bonding strength between the fiber and matrix. Additionally, due to the
large surface area of hBN particles, contact with the matrix enables load transfer to the
matrix and fibers [33].
Table 7. Micro hardness values of hBN and graphene-filled composites.
3.4. Hardness
Filler Weight
Fabric Filler Weight
The hardness values ofPercentage
graphene-basedHardness
fiber composites are depictedHardness
in Figure 8a.
Percentage
Kevlar composites exhibited lower hardness, whereas carbon composites showed high
hBK0 159 GK0 159
hardness. The highest values of hardness were observed in GK2 composites at 200 HV and
the Kevlar hBK1
least at 159 HV in the 177
GK0 composite. An increment GK1 and 12.20% in
of 38.36% 174
hardness
of Kevlar and hybrid composites can be observed, and the hardness values are220
hBK2 187 GK2 shown in
Table 7. From the figure,hBK3 200addition of filler
it can be noted that the GK3increased hardness
186 up to
an optimum value, beyond hBH0which a minor drop 172in hardness values
GH0 in all composites
172 was
hBH1
seen. A direct relationship 176 modulus was
between stiffness and GH1 191 where
established by [31],
Hybrid
hBH2
the results were presented, 183and maximum
following the criteria, GH2 193
modulus was observed at
0.3 wt.%. Indent images hBH3
of graphene and hBN192 composites areGH3shown in Figure170
8c,d.

Figure 8. Cont.
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2522

Figure8.8.Micro-Vickers
Figure Micro-Vickershardness
hardness of
of (a) graphene composites,
(a) graphene composites,(b)
(b)hBN
hBNcomposites,
composites,and
and micro-Vicker
micro-Vicker
hardness images of (c) graphene composites, (d) hBN composites.
hardness images of (c) graphene composites, (d) hBN composites.

Figure
Table 7. Micro8b illustrates
hardness a hardness
values comparison
of hBN and of hBN-filled
graphene-filled Kevlar and hybrid compo-
composites.
sites. The maximum hardness exhibited by a hBK3 composite, i.e., 200 Hv. Hardness val-
ues of all compositesFiller
are Weight 8. The additionFiller
shown in TableHardness Weight
of hBN filler contentHardness
increased
Fabric
Percentage Percentage
hardness due to the high hardness of the hBN filler compared to epoxy. When a high
hBK0 into the epoxy,
hardness filler is incorporated 159 the overall hardness
GK0 of composite159 also in-
creases [34]. The hBK1 of hBN filler 177
addition to increase GK1 was also reported
hardness 174 by
Kevlar
hBK2 187 GK2 220
Alqahtani et al. [35].
hBK3 200 GK3 186
hBH0 172 GH0 172
Table 8. Impact strength values of hBN-filled graphene composites.
hBH1 176 GH1 191
Hybrid
hBH2
Filler Weight Impact Strength 183 GH2 193
Impact Strength
Fabric hBH3 192Filler Weight Percentage
GH3 170
Percentage (J/M) (J/M)
GK0 370 hBK0 370
Figure 8b illustrates
GK1 a hardness520 comparison of hBN-filled
hBK1 Kevlar and hybrid 467 compos-
ites.Kevlar
The maximum hardness exhibited
GK2 800 by a hBK3 composite,
hBK2i.e., 200 Hv. Hardness
598 values
of all composites are
GK3shown in Table6308. The addition of hBN
hBK3 filler content increased
765 hard-
ness due to the highGH0hardness of the hBN
345 filler compared to
hBH0 epoxy. When a high
345hardness
filler is incorporated
GH1into the epoxy, the
480 overall hardness of
hBH1 composite also increases
434 [34].
TheHybrid
addition of hBN filler to increase hardness was also reported by Alqahtani et al. [35].
GH2 650 hBH2 567
GH3 578 hBH3 716
Table 8. Impact strength values of hBN-filled graphene composites.

3.5. Izod Impact Test Filler Weight Impact Strength Filler Weight Impact Strength
Fabric
The impact test Percentage (J/M) to ASTM Percentage
was performed according (J/M)
D 256. The impact strength of
various graphene-based GK0 composites was shown
370 in Figure 9a.hBK0The impact strength370of gra-
phene-filled composites GK1is shown in Table 8.520
Figures indicates superior impact properties
hBK1 467
Kevlar
for Kevlar fiber compositesGK2when compared 800 hBK2
to hybrid fiber composites. 598
It was observed
that 0.3 wt.% of grapheneGK3 630
filler showed maximum hBK3 in all-fiber composites.
impact strength 765
GH0 345
The GK2 composite exhibited maximum impact strength ofhBH0
800 J/m, which was 345
116.2%
GH1 480 hBH1 434
Hybrid
higher than the Kevlar composite without graphene. The impact strength of different gra-
GH2 650 hBH2 567
phene composites in sequential
GH3 order is as follows:
578 GK2 > GH2 > GK3 > GH3 > GK1
hBH3 716> GH1
> GK0 > GH0.
3.5. Izod Impact Test
The impact test was performed according to ASTM D 256. The impact strength
of various graphene-based composites was shown in Figure 9a. The impact strength of
Polymers 2022, 14, 2559 17 of 22

graphene-filled composites is shown in Table 8. Figures indicates superior impact properties

for Kevlar fiber composites when compared to hybrid fiber composites. It was observed
that 0.3 wt.% of graphene filler showed maximum impact strength in all-fiber composites.
The GK2 composite exhibited maximum impact strength of 800 J/m, which was 116.2%
higher than the Kevlar composite without graphene. The impact strength of different
Polymers 2022, 14, x FOR PEER REVIEW 19 of 25
graphene composites in sequential order is as follows: GK2 > GH2 > GK3 > GH3 > GK1 >
GH1 > GK0 > GH0.

Figure
Figure9.9.Izod
Izodimpact
impactstrength
strengthof
of(a)
(a)graphene
graphenecomposites
compositesand
and(b)
(b)hBN
hBNcomposites.
composites.

Theimpact
The impactstrength
strengthofofhBN-filled
hBN-filledcomposites
composites is is shown
shown in in Figure
Figure 9b 9b
andand tabulated
tabulated in
in Table 8. The figure indicates superior impact properties for Kevlar
Table 8. The figure indicates superior impact properties for Kevlar fiber composites when fiber composites
when compared
compared to hybrid to hybrid fiber composites.
fiber composites. It can Itbecan be observed
observed the addition
the addition of hBN of hBN
fillerfiller
in-
increased the impact strength of the composites. The maximum
creased the impact strength of the composites. The maximum impact strength was ob- impact strength was
observed
served at hBK3
at hBK3 composites,
composites, i.e., J/m.
i.e., 765 765 J/m. The addition
The addition of hBNoffiller
hBNresulted
filler resulted in a38%,
in a 51%, 51%,
and 26% increase in GK3, GK2, and GK1 composites, whereas a 51%, 39%, and 20% 20%
38%, and 26% increase in GK3, GK2, and GK1 composites, whereas a 51%, 39%, and in-
increase
crease waswas observed
observed in GH3,
in GH3, GH2, GH2, andand
GH1GH1 composites,
composites, respectively,
respectively, as compared
as compared to
to pure
pure samples.
samples. Graphene-filled
Graphene-filled composites
composites exhibited
exhibited slightly
slightly higherhigher
impactimpact
strengthstrength
com-
compared
pared to hBN-filled
to hBN-filled composites
composites untiluntil optimum
optimum fillerfiller concentration.
concentration.
3.6. Heat Deflection Test
3.6. Heat Deflection Test
Heat deflection curves of graphene-filled composites are shown in Figure 10a, and
Heat deflection curves of graphene-filled composites are shown in Figure 10a, and
the heat deflection temperatures of different composites are listed in Table 9. From the
the heat deflection temperatures of different composites are listed in Table 9. From the
figures it can be observed that the hybrid–graphene fiber composites exhibited superior
figures it can be
temperature observed
compared tothat the hybrid–graphene
Kevlar–graphene fiber composites
fiber composites. exhibited
The addition superior
of graphene
temperature compared to Kevlar–graphene fiber composites. The addition
filler improved temperatures up to GK2, and GH2 composites thereafter decreased. GH2of graphene
filler improved
composites temperatures
showed a maximumup to GK2, and GH2
temperature composites
of 97.65 thereafter
◦ C. The heat decreased.
deflection GH2
temperature
composites showed a maximum temperature of 97.65 °C. The heat deflection temperature
of different composites is shown in the following sequential order: GH2 > GH3 > GH1 >
of
GK2different
> GH0composites
> GK3 > GK1is shown
> GK0.in the following sequential order: GH2 > GH3 > GH1 >
GK2 > GH0 > GK3 > GK1 > GK0.
Table 9. Heat deflection values of graphene- and hBN-filled composites.
Table 9. Heat deflection values of graphene- and hBN-filled composites.
Filler Weight Temperature Filler Weight Temperature
Fabric Filler Weight Filler Percentage
Weight
Percentage (°C) (°C)
Fabric Temperature (°C) Temperature (°C)
PercentageGK0 80.84 Percentage
hBK0 80.64
GK0 GK1 80.84 84.2 hBK0hBK1 80.64
85.36
Kevlar
GK1 GK2 84.2 91.03 hBK1hBK2 87.47
85.36
Kevlar
GK2 GK3 91.03 85.73
hBK2hBK3 89.4
87.47
GH0 87.11 hBH0 87.11
GK3 GH1 85.73 93.71 hBK3hBH1 89.4
89.36
Hybrid
Hybrid GH0 GH2 87.11 hBH0 87.11
97.65 hBH2 91.24
GH1 GH3 93.71 95.38 hBH1hBH3 92.57
89.36
GH2 97.65 hBH2 91.24
GH3 95.38 hBH3 92.57
olymers 2022, 14,2022,
Polymers x FOR14, PEER
2559 REVIEW 18 of 22 20

Figure 10.10.
Figure Heat
Heatdeflection temperature
deflection temperature ofgraphene
of (a) (a) graphene composites
composites andcomposites.
and (b) hBN (b) hBN composites.

Heat deflection curves of hBN-filled composites are shown in Figure 10b, and the heat
Heat deflection curves of hBN-filled composites are shown in Figure 10b, and
deflection temperatures of different composites are listed in Table 9. The figure indicates
heatthat
deflection
hybrid–hBNtemperatures of different
fiber composites composites
exhibited superior are listed
temperatures in Table
compared to 9. The figure i
Kevlar–
cates
hBN that hybrid–hBN
composites. fiber composites
The addition exhibited
of hBN filler resulted in thesuperior
continuoustemperatures
improvement of compare
temperature in composites. hBH3 composites showed a maximum temperature of 92.57 ◦ C.
Kevlar–hBN composites. The addition of hBN filler resulted in the continuous impr
The addition hBN filler resulted in an increase of 5.8%, 4.5%, and 2.5% in hBH3, hBH2,
ment of temperature in composites. hBH3 composites showed a maximum tempera
and hBH1 composites but an increase of 9.7%, 7.8%, and 5.5% in hBK3, hBK2, and hBK1
of 92.57 °C. The
composites, addition
respectively, hBN filler
compared resulted
to pure samples.in an increase of 5.8%, 4.5%, and 2.5
hBH3, hBH2, and hBH1 composites but an increase of 9.7%, 7.8%, and 5.5% in hBK3, h
and3.7.
hBK1Scratch Test
composites, respectively, compared to pure samples.
Figure 11a,b illustrates the relationship between the coefficient of friction and the
scratch length of the graphene-based hybrid fiber and Kevlar fiber composite system. From
3.7. Scratch Test
the figure it can be observed that there is no influence of the scratch length on the coefficient
ofFigure
friction, 11a,b
but the illustrates
coefficient ofthe relationship
friction varies from between
0.3 to 0.6 asthe coefficient
the indenter movesof across
friction and
the surface
scratch length of the composite
of the up to the defined
graphene-based scratch
hybrid length.
fiber andThis is duefiber
Kevlar to the composite
fact that sys
when the indenter applied load on the composite surface for the first time, the coefficient of
From the figure it can be observed that there is no influence of the scratch length on
friction increased linearly and initially fluctuated between certain values because of the
coefficient of friction,
fiber surface. When thebut the coefficient
indenter ofthe
moves, it cuts friction varies from
fiber’s surface, 0.3 to 0.6
and whenever as the inde
it cuts’s
moves across
the fiber the surface
surface, it shows aofhigh
thecoefficient
composite up to the
of friction [36];defined
however,scratch length. This
a low coefficient of is du
the fact that when the indenter applied load on the composite surface for the first t
friction is observed for pure samples. The addition of fillers into composites resulted in
the coefficient of friction increased linearly and initially fluctuated between certain va
because of the fiber surface. When the indenter moves, it cuts the fiber’s surface,
whenever it cuts’s the fiber surface, it shows a high coefficient of friction [36]; howev
low coefficient of friction is observed for pure samples. The addition of fillers into c
 Polymers 2022, 14, 2559 19 of 22

Polymers 2022, 14, x FOR PEER REVIEW the strengthening of the matrix surface, and thereby we can observe less fluctuation of the
21 of 25
coefficient of friction. From the figures, a similar kind of mechanism can be observed in the
HBN-based filler composites shown in Figure 11c,d. Figures showed fluctuations in the
reading and therefore the average coefficient friction was considered. Graphene-based filler
the friction
compositescoefficient.
showed an The addition
optimum of fillers
friction resulted
coefficient inwt.%,
at 0.3 noisewhereas
reduction
boron in nitride
the coefficient
filler
displayed 0.5 wt.% as the optimum concentration for the friction coefficient.
of friction of the materials. The variation of load increased the scratch width and the The addition of dif-
fillers
ficulty of resulted
capturing in noise reduction inimage
the full-width the coefficient
through of friction
the imageof theacquisition
materials. The variation
system, which
of load increased the scratch width and the difficulty of capturing the
resulted in the scratches not looking straight. Some chipping was observed on the scratch full-width image
through the image acquisition system, which resulted in the scratches not looking straight.
line, which indicates that the applied load is higher and looks like a dent on the surface of
Some chipping was observed on the scratch line, which indicates that the applied load is
the composite. The scratch
higher and looks image
like a dent (Figure
on the surface11e) reveals
of the that the
composite. Thescratch looks (Figure
scratch image like a plowing
11e)
mechanism [37] and adhesive failure occurred during the scratch test. The
reveals that the scratch looks like a plowing mechanism [37] and adhesive failure occurred addition of na-
nomaterials
during the increased adhesion
scratch test. [38] between
The addition the fibersincreased
of nanomaterials and matrix, which
adhesion [38]resulted
betweenin thegood
interfacial bonding. Composites that have good interfacial bonding increase
fibers and matrix, which resulted in good interfacial bonding. Composites that have good in resistance
interfacial
to scratch andbonding increase in resistance to scratch and penetration.
penetration.

Figure 11. Cont.

Polymers
Polymers2022,
2022,14,
14,x 2559
FOR PEER REVIEW 2220ofof2522

Figure 11. Scratch test of (a,b) graphene composites and (c,d) hBN composites; (e) sample scratch
Figure 11. Scratch test of (a,b) graphene composites and (c,d) hBN composites; (e) sample scratch
image of graphene composites.
image of graphene composites.
Polymers 2022, 14, 2559 21 of 22

4. Conclusions
In the present research work, a comparative study on the effect of graphene and
hBN fillers on carbon, Kevlar, and hybrid composites and their mechanical properties was
evaluated. Based on the study, the following conclusions can be drawn:
• Hybrid composites show a higher flexural modulus, which demonstrates their usabil-
ity for compressive and bending load applications. The flexural modulus in the HBH3
composite was increased by 85%.
• Hardness, tensile strength, and heat deflection of graphene-based composites exhib-
ited superior properties when compared to HBN-based composites. The optimum
properties were found at 0.3% filler content.
• Digimat simulations were close to experimental results regarding ultimate tensile
strength. Simulation results suggested that the applied load conditions are within
acceptable limits.
• Kevlar’s impact resistance properties were greatly enhanced by the addition of fillers
and thus enhancing their applicability.

Author Contributions: Conceptualization, R.P.S.S.; formal analysis, R.P.S.S.; investigation, S.M.;

resources, S.M.; data curation, R.P.S.S.; writing—original draft preparation, S.M.; writing—review
and editing, R.P.S.S.; supervision, R.P.S.S.; funding acquisition, R.P.S.S. All authors have read and
agreed to the published version of the manuscript.
Funding: The authors acknowledge the funding support received from VIT-AP University through a
project grant VIT-AP/2018/VC/RGEMS/2.
Conflicts of Interest: The authors declare no conflict of interest.

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