nanomaterials
Article
Assessment of Graphene Oxide and Nanoclay Based Hybrid
Filler in Chlorobutyl-Natural Rubber Blend for Advanced Gas
Barrier Applications
Jibin Keloth Paduvilan 1,2,† , Prajitha Velayudhan 1,2,† , Ashin Amanulla 3 , Hanna Joseph Maria 4 ,
Allisson Saiter-Fourcin 5, * and Sabu Thomas 1,2,4, *






Citation: Keloth Paduvilan, J.;
Velayudhan, P.; Amanulla, A.; Joseph
Maria, H.; Saiter-Fourcin, A.; Thomas,
S. Assessment of Graphene Oxide
and Nanoclay Based Hybrid Filler in
Chlorobutyl-Natural Rubber Blend
for Advanced Gas Barrier
Applications. Nanomaterials 2021, 11,
1098. https://doi.org/10.3390/
nano11051098
Academic Editor: Teresa Cuberes
Received: 11 February 2021
Accepted: 20 April 2021
Published: 23 April 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Nanomaterials 2021, 11, 1098. https://doi.org/10.3390/nano11051098
1 International and Interuniversity Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University,
Kottayam 686560, Kerala, India; jibin@mgu.ac.in (J.K.P.); prajitha@mgu.ac.in (P.V.)
2 School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686560, Kerala, India
3 Amity Institute of Nanotechnology, Amity University, Noida 201313, Uttar Pradesh, India;
ashin.jnv@gmail.com
4 School of Energy Materials, Mahatma Gandhi University, Kottayam 686560, Kerala, India; hanna@mgu.ac.in
5 Normandie Université, UNIROUEN, INSA Rouen, CNRS, GPM, 76000 Rouen, France
* Correspondence: allison.saiter@univ-rouen.fr (A.S.-F.); sabuthomas@mgu.ac.in (S.T.);
Tel.: +91-944-722-3452 (S.T.)
† These authors contributed equally to this work.
Abstract: Nanomaterials have engaged response from the scientific world in recent decades due to
their exceptional physical and chemical properties counter to their bulk. They have been widely
used in a polymer matrix to improve mechanical, thermal, barrier, electronic and chemical properties.
In rubber nanocomposites, nanofillers dispersion and the interfacial adhesion between polymer
and fillers influences the composites factual properties. In the present work, a comparison of the
hybrid effects of carbon black with two different nanofillers (graphene oxide and nanoclay) was
studied. The 70/30 composition of chlorobutyl rubber/natural rubber elastomer blend was taken
as per the blend composition optimized from our previous studies. The hybrid effects of graphene
oxide and nanoclay in dispersing the nanofillers were studied mainly by analyzing nanocomposite
barrier properties. The results confirm that the combined effect of carbon black with graphene
oxide and nanoclay could create hybrid effects in decreasing the gas permeability. The prepared
nanocomposites which partially replace the expensive chlorobutyl rubber can be used for tyre inner
liner application. Additionally, the reduction in the amount of carbon black in the nanocomposite
can be an added advantage of considering the environmental and economic factors.
Keywords: rubber; nanocomposite; graphene oxide; nanoclay; carbon black; permeation; mechani-
cal properties
1. Introduction
Ever since the popularity of nanotechnology has grown in recent decades, nanoma-
terials have been widely used as a reinforcing agent in a polymer matrix to improve the
overall properties of polymer composites [1]. Nanomaterials, which essentially have at
least one dimension less than 100 nm and a high surface to volume ratio is a prominent
substitute to conventional fillers due to significant output with lower filler loading [2–4].
Natural rubber (caoutchouc) is organic latex which is extensively used in many in-
dustries due to its unique chemical and mechanical properties. Natural rubber is widely
exploited by tyre industries because it improves their excellent mechanical properties upon
vulcanizing. Chlorobutyl rubber (CIIR) is an isobutylene-isoprene copolymer which is
used to make tyre inner liners and gas masks due to its low gas permeability [5,6]. It has
been reported that a blend of chlorobutyl rubber and natural rubber (NR) can significantly
https://www.mdpi.com/journal/nanomaterials
Nanomaterials 2021, 11, 1098 2 of 14

reduce the cost of inner liners in a tubeless tyre. Many industries use nanomaterials as
fillers in rubber to improve the mechanical, barrier and thermal properties of materials [7,8].
In tyre technology, carbon black with particle size in the 15–200 nm range is widely
used as a reinforcing agent to improve mechanical properties. Although there are reports
on nano-silica as an alternative, the overall filler interaction with rubber matrix and the
economy makes carbon black (CB) a favorite in the tyre industry [9]. Nanoclays (NC)
are yet other nanomaterials that are widely used in polymer technology due to the 2D
structure [10]. Many researchers have already reported that nanoclays act as gas barrier
agents in polymer nanocomposites [11–17]. Evenly nanoclay dispersion creates a tortuous
path in the polymer matrix so that it hinders the movement of gas molecules through the
material [18]. Recent research shows graphene oxide (GO) can also be used in a polymer
matrix to improve the mechanical and barrier properties due to its high aspect ratio and
high Young’s modulus in the range of 200 GPa [19–22]. The high aspect ratio of GO can
create very good interfacial interactions between GO and polymer matrix even in lower
filler loading thus reducing overall polymer composites’ weight to a greater extent. The
2D structure of GO can also create a tortuous path to the gas molecule to pass through the
polymer composite [16,23–25]. Ratnayake et al. successfully dispersed the montmorillonite
into the natural rubber latex matrix and got a tremendous increase in the mechanical
properties with high interfacial compatibility [26]. Yang et al. modified the graphene
oxide with octadecylamine (ODA) and reinforced into brominated butyl rubber (BIIR)
This modification helps to improve the dispersion of the filler in rubber matrix and results
excellent tortuous diffusion pathway for enhanced barrier properties [27]. Zhong et al.
improved the gas barrier properties by introducing sulfur–graphene oxide hybrids to
the styrene butadiene rubber matrix. They have managed to obtain excellent interfacial
interactions between the hybrid filler and the rubber matrix. This strong interface restricts
the chain mobility and thereby reduces the free volume which inhibits the gas molecules
to penetrate through rubber matrix [28]. Alipour et al. discussed the oxygen diffusion
rate and penetrability of the polyethylene and EVOH-based multilayered films having
5- and 19-layer C-films of thicknesses 150 nm or even bigger. They have studied the
crystallization behavior of the polymer layers using a synchrotron wide-angle/small-angle
X-ray scattering technique and correlated these with the permeability and mechanical
strength. It was evident from the work that the various multilayer films having the same
oxygen diffusion ability [29]. Numerous studies were reported on hybrid filler technology
in rubber, but a little has been based on GO and nanoclay hybrid rubber [26,30,31].
In the present work, we have studied the effect of nanofiller (NF) dispersion in rubber
matrix with various amounts of GO and nanoclay. Additionally, we studied how the
synergistic hybrid effects of CB with GO and nanoclay work in the 70/30 composition
of CIIR/NR blend, which has a variety of industrial applications, including the tyre
industry. This work’s prime motive is to analyze the influence of hybrid fillers in the air
permeability characteristics.

2. Materials and Methods

2.1. Materials
NR was provided by the Rubber Research Institute, Kottayam, and Kerala, India. CIIR
from ExxonMobil was provided kindly by Apollo Tyres Pvt Ltd., Kalamassery, Kerala,
India. GO was prepared by the oxidation of 99% unadulterated graphite flakes purchased
from Sigma Aldrich, Ernakulam, Kerala, India. Cloisite 10A with an average size of
1.93 nm was obtained from Southern Clay Products, Mumbai, India. Cloisite 10A is an
organically modified montmorillonite with dimethyl, benzyl, and hydrogenated tallow
(HT), quaternary ammonium salt (125 meq/100 g of clay, moisture <2%). Carbon black
(HAF N330) was supplied by AB Brothers, Mumbai, India. All other vulcanizing agents
were obtained from Apollo tyres (Kalamassery, Kerala, India).
 (HAF N330) was supplied by AB Brothers, Mumbai, India. All other vulcanizing agent
were obtained from Apollo tyers (Kalamassery, Kerala, India).

Nanomaterials 2021, 11, 1098 3 of 14

2.2. Methods
2.2.1. Synthesis of Graphene Oxide
Graphene
2.2. Methods oxide was synthesized by using an improved Hummers method [32].The
detailed
2.2.1. schematic
Synthesis ofof the synthesis
Graphene Oxide route is explained in Figure 1. A total of 2 g of graphite
2 g of sodium
Graphene nitrate
oxide and 90 mL of sulfuric
was synthesized by using acid (98% HHummers
an improved 2SO4) were added together in a
method [32].The
1000detailed
mL Florence
schematic flask and
of the stirredroute
synthesis for 2ish.explained
The temperature
in Figure 1.was kept
A total of less
2 g ofthan 20 °C. Then
graphite,
12 g2 of potassium
g of permanganate
sodium nitrate and 90 mL of was added
sulfuric to(98%
acid the solution slowly.
H2 SO4 ) were added After one in
together hour, 184
◦
mL aof1000 mL Florence
deionized water flask andwas
(DI) stirred for 2slowly
added h. The temperature
and stirredwas for kept
1 h atlessroom
than 20 C.
temperature
Then, 12 g of potassium permanganate was added to the solution slowly.
The temperature of the mixture was maintained at 35 °C and was stirred for 2 h. The tem After one hour,
184 mL of deionized water (DI) was added slowly and stirred for 1 h at room temperature.
perature was increased up to 98 °C for 20 min. The ◦heater was turned off and 40 mL o
The temperature of the mixture was maintained at 35 C and was stirred for 2 h. The
H2Otemperature
2 was added to the solution by
was increased up to 98 ◦ Cwhich the color
for 20 min. changes
The heater to yellow.
was turned off andAfter
40 mLadding
of 400
mL Hof2 O
DI water
2 was thetosolution
added wasbyfurther
the solution which the stirred for 1 h.toThe
color changes product
yellow. After mixture
adding 400was mL washed
withof10% HCl the
DI water andsolution
then withwas DI water
further for many
stirred for 1 h.times until the
The product pH value
mixture between 6 and
was washed
with it
7. Then 10%wasHCl and then withplaced
subsequently DI waterinfor many times
a vacuum oven until
andthedried
pH value
at 100between
°C. The6 and
schemati
7. Then it was subsequently placed in a vacuum oven and dried at 100 ◦ C. The schematic
representation of synthesis is given below.
representation of synthesis is given below.

Figure 1. Schematic representation of graphene oxide synthesis.

Figure 1. Schematic representation of graphene oxide synthesis.
2.2.2. Preparation of CIIR/NR Blend Nanocomposites
2.2.2. Preparation of CIIR/NR Blend Nanocomposites
The polymer nanocomposites were prepared through a melt mixing method on a
The polymer
laboratory nanocomposites
two-roll mill [28]. NR waswere prepared
masticated through
for about two toathree
meltminutes
mixingand method
the on a
masticated NR was then mixed with CIIR trailed by addition of the curing agents
laboratory two-roll mill [28]. NR was masticated for about two to three minutes and the as per the
protocol given
masticated NR wasin Table
then1.mixed
Cure characteristics were deliberated
with CIIR trailed by employing
by addition a Prescott’s
of the curing agents as pe
Rheoline moving Die Rheometer (ASTMD 5289), at a temperature of 160 ◦ C, frequency of
the protocol given in Table 1.◦ Cure characteristics were deliberated by employing a Pres
1.67 Hz and strain rate of 0.5 arc. The mixes were cured at their particular cure times by
cott’s Rheoline
means movingpress
of a hydraulic Dieunder
Rheometer (ASTMD
a pressure of about5289),
120 barat
at a160
temperature of 160 °C, fre
◦ C. The formulation
quency
usedof
for1.67 Hz and strain
the preparation rate
in phr of 0.5°
is given in arc.
TableThe
2. mixes were cured at their particular cure
times by means of a hydraulic press under a pressure of about 120 bar at 160 °C. The
formulation used for the preparation in phr is given in Table 2.
Nanomaterials 2021, 11, 1098 4 of 14

Table 1. Compounding materials used for the preparation of CIIR/NR blend nanocomposites. *
Phr—parts per hundred rubber by weight.

Amount
Materials
(Phr) *
Curing Agent (Phenol Formaldehyde resin) 6
Homogenizing Agent (Struktol 40 MS) 6
Zinc oxide 3
Stearic Acid 1
MBTS (Accelerator) 1.25
Sulphur 0.5

Table 2. The formulations used for the preparation of polymer nanocomposites. * Phr—parts per
hundred rubbers by weight.

Sl. No. CIIR * NR * CB * NC * GO *

1 100 - - - -
2 - 100 - - -
3 70 30 - - -
4 70 30 20 - -
5 70 30 20 2 -
6 70 30 20 3 -
7 70 30 20 5 -
8 70 30 20 - 0.1
9 70 30 20 - 0.2
10 70 30 20 - 0.5

2.3. Characterizations
Transmission electron microscopy (TEM) is deliberated to be the utmost widespread
modus operandi in characterizing nanomaterials in electron microscopy. The information
about chemical constituents and imaginings of nanomaterials at a specific resolution
equivalent to atomic magnitudes are provided using TEM JEM-2100 HRTEM (Musashino,
Akishima, Tokyo, Japan) by means of a point to point steadfastness of 0.194 nm and a speed
up voltage of 200 kV was used to evaluate the graphene oxide sheet structure. From the
TEM images we can confirm the morphology of GO, how it exfoliated and the variation
from graphitic structure.
The Fourier Transform Infra Red spectrum is an active tool to elucidate both covalent
and non-covalent interactions of GO. The fundamental details of graphene oxide together
with polymer nanocomposites were dogged by Fourier Transform Infra Red spectroscopy
(Shimadzu IR Tracer-100, Nishinokyo Kuwabara-cho, Kyoto, Japan). From the FTIR we can
analyze the efficient groups responsible for the copious properties which are present in the
sample and we can ascertain the establishment of hydrogen bonding. In polymer analysis,
the exploration of structures, details about composition, density features, crystallinity data,
magnitude of oxidative degradation, extent of functionalization and blend compatibility
are common deliverables of IR spectroscopy. The Fourier transform infrared spectroscopy
peaks were obtained by Shimadzu IR Tracer-100 by collecting 32 shots extending from 500
to 4000 cm−1 , with a resolution of 0.4 cm−1 .
The mechanical properties of the nanocomposite were quantified by with a Tinius
Olsen H 25 K-L Universal Testing machine (UTM), Surrey RH1 5DZ, UK (ASTM D412).
Sample was prepared as per ASTM die C, the dumbbell shaped samples with a gauge
Nanomaterials 2021, 11, 1098 5 of 14

length of 30 mm and the thickness of 2 mm were used at a testing crosshead speed of

500 mm/minute with the cell load of 1KN. We have taken the average of five readings not
varying within broad limits and the results on these average values, with corresponding
values
Nanomaterials 2021, of standard deviations mentioned in the graph.
11, 1098 5 of 1
Prescott’s Rheoline Moving Die Rheometer, Gloucestershire, UK was utilized to ac-
complish the rheological study as per the ASTM D 5283 standard at a frequency of 1.67 Hz,
and 0.5 arc strain readings
rate. Gasnot
permeability studies
varying within were
broad doneand
limits by the
using Gas Permeability
results Tester
on these average values, wit
from ATS FAAR corresponding
S.p.A, Segrate,values
Italy, of
using oxygen
standard as per the
deviations ASTM D1434-82
mentioned standard.
in the graph.
Prescott’s Rheoline Moving
Prescott’s Die Rheometer,
Rheoline Moving DieGloucestershire, UK was utilized
Rheometer, Gloucestershire, UnitedtoKingdom
ac- wa
utilized to
complish the rheological accomplish
study theASTM
as per the rheological study
D 5283 as per at
standard thea ASTM
frequencyD 5283 standard
of 1.67 Hz, at a fre
and 0.5 arc strain quency of permeability
rate. Gas 1.67 Hz, and 0.5 arc strain
studies wererate.
doneGas permeability
by using studies were
Gas Permeability done by usin
Tester
from ATS FAAR Gas Permeability
S.p.A, Tester
Segrate, Italy, fromoxygen
using ATS FAAR S.p.A,
as per Segrate,
the ASTM Italy, using
D1434-82 oxygen as per th
standard.
ASTM D1434-82 standard.
3. Results and Discussions
3. Results
3.1. Characterizations and Discussions
of Synthesized Graphene Oxide
3.1. Characterizations
3.1.1. Morphological Analysis of Synthesized Graphene Oxide
The prepared 3.1.1.
GOMorphological
was observedAnalysis
(Figure 2) to have a wrinkled sheet-like structure and
The prepared
the size of the sheet is in the nano GO wasTEM
range. observed
image (Figure 2) to havethat
also describes a wrinkled sheet-like structur
the synthesized
graphene oxide is amorphous in nature. The morphology of GO, comprising ofthat
and the size of the sheet is in the nano range. TEM image also describes thinthe synthe
stacked flakes of shapes and having well distinct multilayered structure at the edge, of thi
sized graphene oxide is amorphous in nature. The morphology of GO, comprising
can be undoubtedlystacked flakes
seen of shapes
in Figure 2. and having
It was well distinct
anticipated multilayered
that structure at the
the electronegativity of edge, ca
oxygen atom of –OH and –COOH groups on GO layer surface eased the further oriented of oxyge
be undoubtedly seen in Figure 2. It was anticipated that the electronegativity
accumulation ofatomcationof –OH and –COOH groups on GO layer surface eased the further oriented accumu
radical of carbon. The diffraction pattern from the TEM analysis
lation of cation radical of carbon. The diffraction pattern from the TEM analysis show
shows amorphous nature of the synthesized GO. The wrinkled structure and amorphous
amorphous nature of the synthesized GO. The wrinkled structure and amorphous natur
nature of the synthesized sample confirm the successful oxidation of graphite flakes into
of the synthesized sample confirm the successful oxidation of graphite flakes into gra
graphene oxide nanosheets.
phene oxide For the preparation
nanosheets. of nanocomposites,
For the preparation it is advisable
of nanocomposites, it is to have to hav
advisable
rough surface of rough
GO assurface
it will of
decrease the restacking tendency [32].
GO as it will decrease the restacking tendency [32].

Figure 2. Transmission electron microscopy (TEM) image of synthesized graphene oxide (GO) and Selcted Area Electron
Figure 2. Transmission electron microscopy (TEM) images of synthesized graphene oxide (GO) and
Diffraction pattern.
Selcted Area Electron Diffraction pattern.
 3.1.2. Fourier Transform Infrared Spectra of Synthesized Graphene Oxide
Nanomaterials 2021, 11, 1098 The FTIR spectra of graphite and GO is specified in Figure6 of3.14Peaks
well-designed groups can be understood in the FTIR spectrum of GO. T
of oxygen functionalities existing in GO might be seen from the spectra
graphite, GO
3.1.2. Fourier illustrates
Transform Infrarednew peaks
Spectra at 3400Graphene
of Synthesized cm−1 which
Oxide is owing to the
The FTIRwhereas
vibrations, spectra of graphite
at 1720andcmGO isis
−1 it specified in Figure
attributed to 3.the
Peaks for a number
stretching of
vibrations
well-designed groups can be understood in the FTIR spectrum of GO. The various sorts
atof 1600
oxygencm
−1 is from the skeletal vibrations of un-oxidized graphitic st
functionalities existing in GO might be seen from the spectra. Contrasted to
−1 which is owing to the O–H stretching
stretching
graphite, GOvibrations
illustrates newatpeaks
1220atcm
3400 and
−1 cm C–O stretching vibrations at 1060
− 1
vibrations, whereas at 1720 cm it is attributed to the stretching vibrations from C=O,
perceived from the FTIR spectra. By analyzing the FTIR spectra it is evid
peak at 1600 cm−1 is from the skeletal vibrations of un-oxidized graphitic state. The C–OH
isstretching
successfully
vibrationssynthesized
at 1220 cm−1 andand
C–Oshows
stretchingall characteristic
vibrations at 1060 cm−peaks especially
1 also can be
perceived from the FTIR spectra. By analyzing the FTIR spectra it is evident that the GO is
peaks.
successfully synthesized and shows all characteristic peaks especially C=O and O–H peaks.

Figure 3. FTIR Fourier Transform Infra-Red spectra of prepared GO and Graphite.

Figure 3. FTIR Fourier Transform Infra-Red spectra of prepared GO and Graphite
3.2. Characterizations of Polymer Nanocomposites
3.2.1. FTIR Spectra of Polymer Nanocomposites
3.2. Characterizations of Polymer Nanocomposites
The FTIR analyses give information about the role of filler in the polymer and the
type ofFTIR
3.2.1. filler interactions
Spectra of in Polymer
the blend nanocomposites.
Nanocomposites Figure 4 shows the FTIR spectra
of polymer nanocomposites before vulcanization. The distinctive peaks of cis-1,4 poly-
TheatFTIR
isoprene, analyses
2960, 2927 and 2852 give
cm−1information
is assigned to C–H about the role
stretching, 1661 of
cm−filler in the p
1 credits

the presence of C=C stretching, 1448 cm − 1 due to C–H deformation of –CH –moiety, the
type of filler −interactions in the blend nanocomposites. Figure 2 4 shows the
peak at 1376 cm 1 . On account of C–H deformation of –CH3 and 835 cm−1 owing to C–H
polymer
deformation nanocomposites before vulcanization.
of C=C–H, could be recognized to NR molecules. The Thesame distinctive
was observedpeaks
in of
prene,
the case at 2960,
of CIIR 2927
where and 2852
characteristic cm and
symmetric –1 is assigned to C–Hvibrations
asymmetric stretching stretching,
were 1661
observed. The CH2 (2875 cm−1 ) and CH3 (2951 cm −1 ), 2894 cm−1 , (C–H stretching of CH )
presence of C=C stretching, 1448 cm due to C–H deformation of 3–CH2–m
–1
Also the bending vibrations of C–H were witnessed at CH3 : 1472 cm−1 , CH3 : 1388 cm−1 ,
atCH1376 cm
3 : 1366 cm−.1 On
–1
(C–Haccount
deformationofofC–H
–CH3 ).deformation
The peak differences of –CH andand835
of 1003 NR 100 cm
CIIR owin
–1

is due to of
mation the C=C–H,
chemical composure
could be of each material. Itto
recognized is clear
NR from the FTIR analysis
molecules. The samethat was
the hybrid filler has no chemical bonding with the rubber, it only has physical interactions.
case
If thereofare
CIIR whereinteractions
no chemical characteristic
betweensymmetric
filler and rubber andtheasymmetric
basic structure stretching
of the
observed. The CH (2875 cm −1) and CH (2951
matrix is not altered it will be beneficial to end product application.
2 3 cm −1), 2894 cm −1 , (C–H str
Also the bending vibrations of C–H were witnessed at CH3: 1472 cm−1,
CH3: 1366 cm−1 (C–H deformation of –CH3). The peak differences of 100 N
is due to the chemical composure of each material. It is clear from the FT
the hybrid filler has no chemical bonding with the rubber, it only has phys
Nanomaterials 2021, 2021,
Nanomaterials 11, 1098
11, 1098 7 of 14

Figure 4. FTIR spectra of polymer nanocomposites.

Figure 4. FTIR spectra of polymer nanocomposites.
3.2.2. Morphological Analysis
3.2.2. Morphological
Figure Analysis
5a shows 3 phr nanoclay reinforced in CIIR/NR blend composite and the
Figure 5b shows 0.1 phr graphene oxide reinforced in CIIR/NR blend composite. The
Figure
TEM pictures 5a shows 3 phr
of nanocomposites appearnanoclay
the nature reinforced
of the scattering inofCIIR/NR blend
nano-clays and GO comp
within
ure 5b the shows
mixes. Figure
0.1 5a
phrappears a total scattering
graphene oxide ofreinforced
nano-clay over inthe inspected range.
CIIR/NR blend com
The nano-clays are dispersed within the nanocomposites in the form of tiny nano-units.
pictures
The of from
researchers nanocomposites
different parts of appear
the world the
as ofnature of the
now detailed thesescattering
micro-units, of na
within
named as the mixes.andFigure
nano-units, 5a appears
the collected works areasaying
totalthatscattering
a vigorousof nano-clay ov
interaction
between the elastic chains, carbon black, and the nanofillers
range. The nano-clays are dispersed within the nanocomposites are required to make such
in the fo
units. The researchers claim that the arrangement of such units can slow down the diffusion
units.
of Thethrough
gas atoms researchers
the mixes. from different ofparts
The foundation of the world
such nano-units within as
theof now deta
rubber
units, namedwill
nanocomposites asfurther
nano-units,
uphold the and the collected
interactions works
between the rubber are saying
mixes that a vig
and nano-
clays/GO. The dark portions of the TEM images imply NR phase and the bright portions
between the elastic chains, carbon black, and the nanofillers are requir
entail CIIR phase of blend nanocomposites (Figure 5a,b). From Figure 5a, it is evident
units.
that Thehas
nanoclay researchers claim that
significant interaction with the
both arrangement
CIIR and NR matrix. of But
such units
in the case can
of slow
graphene oxide, the interaction is less compared to that of nanoclay
sion of gas atoms through the mixes. The foundation of such nano-units due to the polar nature
of graphene oxide. Even though the nanoclay platelets have more affinity towards the NR
nanocomposites
matrix, they show goodwill further
dispersion uphold
in both phasesthe interactions
leading between
to strong interface. The the
TEMrubber
clays/GO.
images The dark
of composites furtherportions of thestructure
affirms the layered TEM images of nano-clayimply NR phase
and graphene oxide.and th
entail
3.2.3. CIIR phase
Rheological Studiesof blend nanocomposites (Figure 5a,b). From Figure 5a
nanoclay has significant
The rheological interaction
study was done with
at 160 ◦ C and both
the data CIIRare
obtained and NRin matrix.
given Table 3. But
phene
Cure timeoxide, the
is the time interaction
taken is toless
for 90% curing compared
occur tocure
[30]. From the that ofcharacteristics,
time nanoclay due to
it is very clear that the time taken to cure pure CIIR is very high when compared to NR.
of graphene oxide. Even though the nanoclay platelets have more affinit
matrix, they show good dispersion in both phases leading to strong interf
ages of composites further affirms the layered structure of nano-clay and
 Nanomaterials
Nanomaterials 2021,2021, 11, 1098
11, 1098 8 of 14 8 of 15

Figure
Figure 5. TEM
5. TEM images
images of (a,b)
of (a,b) nanoclayininchlorobutyl
nanoclay chlorobutyl rubber
rubber(CIIR)/natural
(CIIR)/naturalrubber (NR)
rubber andand
(NR) (c,d)(c,d)
graphene oxideoxide
graphene in in
CIIR/NR.
CIIR/NR.
Table 3. Cure characteristics of polymer nanocomposites.
3.2.3. Rheological Studies
Sl No. study was done at Samples
The rheological Cure Time
160 °C and the data obtained are(min:s)
given in Table 3.
Cure time is the 1time taken for 90% curing
100to
CIIR
occur [30]. From the cure11:37
time characteristics,
it is very clear that
2 the time taken to cure100
pure
NR CIIR is very high when compared to NR.
5:47
3 70/30 CIIR/NR 17:26
Table 3. Cure characteristics
4 of polymer nanocomposites.
70/30/20CB 16:33
Sl No. 5 Samples70/30/20CB/2NC Cure Time 14:33(min:s)
1 6 100 CIIR 70/30/20CB/3NC 11:37
16:20
2 7 100 NR 70/30/20CB/5NC 5:47
16:57
3 8 70/30 CIIR/NR
70/30/20CB/0.1GO 17:26
15:16
4 9 70/30/20CB70/30/20CB/0.2GO 16:33
14:40
5 10 70/30/20CB/2NC
70/30/20CB/0.5GO 14:33
15:16
6 70/30/20CB/3NC 16:20
7 In the case of CIIR/NR
70/30/20CB/5NC
blend it can be observed that the cure time 16:57is increased as
compared
8 to neat NR. This can be due
70/30/20CB/0.1GO to the incompatibility of the system
15:16a result of the
as
migration of curatives towards to more unsaturated NR phase. We also have to consider
9 70/30/20CB/0.2GO 14:40
another important point, i.e., upon the addition CIIR to NR the overall unsaturation of the
W10 component is70/30/20CB/0.5GO
resulting lower than the neat NR. The factors affecting the 15:16
curative migration

In the case of CIIR/NR blend it can be observed that the cure time is increased as
compared to neat NR. This can be due to the incompatibility of the system as a result of
the migration of curatives towards to more unsaturated NR phase. We also have to con-
Nanomaterials 2021, 11, 1098 9 of 14

are the degree of unsaturation, viscosity and polarity of the polymers. Curative migration
occurs from highly unsaturated rubber to lower unsaturation. Additionally, the faster cure
rate in highly unsaturated rubber makes the imbalance more prominent [31,32]. Here in
NR, the number of unsaturation is very high compared to CIIR and curing is very fast but
in CIIR the unsaturation is less as a result, CIIR takes more time to get cured. In the case of
70/30 CIIR/NR blend system; the possibility for preferential migration can occur due to
the variation in polarity, viscosity and unsaturation. Additionally, the high incompatibility
between CIIR/NR can reduce the interphase crosslinking thereby increasing the cure time.
It is very evident that after adding the fillers the cure time decreased compared to the
neat blend up to a certain limit this could be due to the cure activating result as result of a
complex reaction which is already reported. However, further loading of filler marginally
increases the cure time on account of the accelerator absorption by the graphene oxide
surfaces. In the case of both the hybrid nanocomposites a hybrid effect can be observed. The
presence of two fillers such as carbon black and nanoclay (70/30/20CB/2NC) and carbon
black and graphene oxide (70/30/20CB/0.2GO) composition reduces the agglomeration
and facilitate the crosslinking thereby reducing the cure time.

3.3. Mechanical Properties

The Figure 6a,b shows modulus of blend nanocomposites with different loading of
nanoclay and GO at 100, 200 and 300% elongation. The moduli of the nanocomposites were
found to increase on adding the nanofiller (Figure 6a,b). The effect was more prominent in
the case of nanoclay. This may be due to the greater number of polymer–filler interactions
than filler–filler interactions. The slightly polar nature of nanoclay and the presence of rich
alkyl groups in nanoclay help to create an interaction with both CIIR and NR matrix when
compared to GO. Graphene oxide is highly polar in nature due to the presence of oxygen
functionalities, so it has better interaction with polar CIIR [33]. The presence of CB should
have a profound effect on improving the dispersion of nanofillers in the rubber matrix. It
reduces the possibilities of filler–filler interaction. From Figure 7, it is clear that the effect of
CB in dispersing the nanofiller is more efficient in the case of nanoclay. This can be due
to the relatively less polar–polar interaction between the nanoclay compared to GO–GO
interaction which is having strong polar nature. The elongation at break for composites
with both nanofiller shows a decrease with increase in filler loading. This is due to the
restriction imparted by filler to the flexibility. The CB plays a major role to disperse the
GO and nanoclay in the CIIR/NR matrix (Figure 7), it is also very effective in preventing
the restacking or agglomeration tendency of both the nanofillers thereby increases the
possibility of better polymer–filler interactions.

3.4. Gas Permeability Study

The permeability of the prepared composites was studied using oxygen as per the
ASTM D1434-82 standard. It was observed that the permeability values of the CIIR/NR
blend nanocomposites with CB is much lower than that of blend with CIIR/NR (Figure 8a).
When we add 0.1 phr of GO to CIIR/NR/CB blend the permeability of air again decreases
drastically, this is because of the hybrid filler effect of CB/GO [34,35]. GO creates an
effective tortuous path for oxygen to permeate through the rubber matrix. CB also plays
an important role in preventing the restacking or agglomeration nature of GO. In fact, CB
effectively interacts with GO and reduces the filler–filler interaction as well as increases the
filler–matrix interaction.
At the same time by the addition of nanoclay to the CIIR/NR/CB blend, we can
observe the same decreasing trend in air permeability up to 3 phr loading, at higher
loading the effect of hybrid nanofillers in lowering the permeability of the air is poor due
to the agglomeration of nanofillers, (Figure 8b). The reduction in permeability of air at
lower loading can be attributed to the better dispersion of nanofillers and the tortuous
path created by them and also the added CB is enough to reduce the filler–filler interaction.
The effect of hybrid filler in reducing the oxygen permeability values could be clearly
Nanomaterials 2021, 11, 1098 10 of 14

Nanomaterials 2021, 11, 1098

established through this. The gas permeability value of the blend decreased after the
addition of layered fillers such as graphene oxide and nanoclay. A 14% and 9% decrease in
permeability values are observed for 70/30/20/0.1 GO and 70/30/20CB/2NC respectively.

Figure 6. (a,b) Effect of nanoclay and graphene oxide on modulus of prepared nanocomposites at
Figure 6. (a,b) Effect
100%,of nanoclay
200% andelongation.
and 300% graphene oxide on modulus of prepared nanocomposites at 100%, 200% a
elongation.
Nanomaterials 2021, 11, 1098Nanomaterials 2021, 11, 1098 11 of 14
11 of 15

Nanomaterials 2021, 11, 1098 12 of 15

Figure 7. Schematic representation showing the interaction of GO and nanoclay with carbon black
Figure 7. Schematic representation showing the interaction of GO and nanoclay with carbon black (CB) and the difference
(CB) and
in dispersion of the
bothdifference
the fillers inin dispersion
presence of CB.of both the fillers in presence of CB.

3.4. Gas Permeability Study

The permeability of the prepared composites was studied using oxygen as per the
ASTM D1434-82 standard. It was observed that the permeability values of the CIIR/NR
blend nanocomposites with CB is much lower than that of blend with CIIR/NR (Figure
8a). When we add 0.1 phr of GO to CIIR/NR/CB blend the permeability of air again de-
creases drastically, this is because of the hybrid filler effect of CB/GO [34,35]. GO creates
an effective tortuous path for oxygen to permeate through the rubber matrix. CB also
plays an important role in preventing the restacking or agglomeration nature of GO. In
fact, CB effectively interacts with GO and reduces the filler–filler interaction as well as
increases the filler–matrix interaction.

Figure 8. (a,b) Gas permeability values of CB/GO and CB/nanoclay hybrid nanocomposite.
Figure 8. (a,b) Gas permeability values of CB/GO and CB/nanoclay hybrid nanocomposite.

At the same time by the addition of nanoclay to the CIIR/NR/CB blend, we can ob-
serve the same decreasing trend in air permeability up to 3 phr loading, at higher loading
the effect of hybrid nanofillers in lowering the permeability of the air is poor due to the
agglomeration of nanofillers, (Figure 8b). The reduction in permeability of air at lower
loading can be attributed to the better dispersion of nanofillers and the tortuous path cre-
Nanomaterials 2021, 11, 1098 13 of 15

Nanomaterials 2021, 11, 1098 12 of 14

of layered fillers such as graphene oxide and nanoclay. A 14% and 9% decrease in perme-
ability values are observed for 70/30/20/0.1 GO and 70/30/20CB/2NC respectively.
On comparing the
On comparing theresults
resultsobtained
obtainedforforGO
GOandand nanoclay,
nanoclay, It isItwell
is well established
established thatthat
the
the interaction
interaction of CBof and
CB and nanoclay
nanoclay is more
is more effective
effective whenwhen related
related to thetointeraction
the interaction
of CBofand
CB
and GO (Figure
GO (Figure 9). permeability
9). The The permeability
valuesvalues also show
also show that CB/nanoclay
that CB/nanoclay hybrid
hybrid filler filler
is veryis
very effective
effective due toduethetobetter
the better interaction
interaction between
between them.them.

Figure 9. Comparison of permeability values of CB/GO

CB/GOand
andCB/nanoclay
CB/nanoclaynanocomposite.
nanocomposite.

4. Conclusions
4. Conclusions
CIIR/NR blend was prepared at 70/30 composition and the effect of hybrid filler was
CIIR/NR blend was prepared at 70/30 composition and the effect of hybrid filler was
studied using CB/NC, as well as CB/GO. The GO used was synthesized via modified hum-
studied using CB/NC, as well as CB/, GO. The GO used was synthesized via modified
mer’s method, characterized using FTIR and TEM analysis and confirmed the formation of
hummer’s method, characterized using FTIR and TEM analysis and confirmed the for-
pristine graphene oxide. Rheological study of CIIR/NR polymer blend nanocomposites
mation of pristine graphene oxide. Rheological study of CIIR/NR polymer blend nano-
indicates that cure time decreases at filler loading. The prepared nanocomposites show
composites indicates that cure time decreases at filler loading. The prepared nanocompo-
an increase in modulus when GO and nanoclay are added to the CIIR/NR matrix along
sites show an increase in modulus when GO and nanoclay are added to the CIIR/NR ma-
with CB. The composites with CB and nanoclay show a gradual increase in modulus with
trix along with CB. The composites with CB and nanoclay show a gradual increase in
filler loading while in the case of CB/GO there is no regular trend in the modulus of the
modulus with filler loading while in the case of CB/GO there is no regular trend in the
composite. Addition of optimum amount of nanoclay or graphene oxide in CIIR/NR blend
modulus of the composite. Addition of optimum amount of nanoclay or graphene oxide
can improve the gas impermeability of the system due to the tortuous path created by the
in CIIR/NR blend can improve the gas impermeability of the system due to the tortuous
layered structure of nanofillers with the help of CB. The interaction of CB and dispersion
path created byinto
of nanofillers thethe
layered structure
matrix is veryof nanofillers
effective with
in the theofhelp
case of CB. The
nanoclay interaction
compared of
to GO.
CB and dispersion of nanofillers into the matrix is very effective in the
Such materials find potential applications in tubeless tyres and other gas-impermeable case of nanoclay
compared
appliancesto GO.
like Suchand
masks materials
sports find potential
utilities. applications
However, it is alsoinobserved
tubeless tyers andhigher
that the other
gas-impermeable appliances like masks and sports utilities. However, it is
loading of fillers reduces its overall gas impermeability property due to the agglomeration also observed
that the higher Thus,
of nanofillers. loading of fillers
adding reducesto
nanofillers itsthe
overall gas impermeability
CIIR/NR blend can helpproperty
to improveduethe
to
the agglomeration of nanofillers. Thus, adding nanofillers to the CIIR/NR
properties and can obtain the polymer nanocomposites with the desired combination blend can help
to improve the properties and can obtain the polymer nanocomposites with the desired
of properties.
combination of properties.
Author Contributions: The first and second authors have equal contributions. Conceptualization,
Author Contributions:
S.T.; methodology, TheP.V.,
J.K.P., firstA.A.
and second authors
and H.J.M.; have equal
validation, contributions.
J.K.P., Conceptualization,
P.V. and H.J.M.; S.T.;
formal analysis,
methodology, J.K.P., P.V., A.A. and H.J.M.; validation, J.K.P., P.V. and H.J.M.; formal analysis,
J.K.P., P.V., A.A. and H.J.M.; investigation, J.K.P., P.V., A.A. and H.J.M.; resources, S.T.; data curation, J.K.P.,
P.V., A.A.A.S.-F.;
S.T. and and H.J.M.; investigation,draft
writing—original J.K.P., P.V., A.A. and
preparation, H.J.M.;
J.K.P. resources,
and P.V.; S.T.; data curation,
writing—review S.T.
and editing,
and A.S.-F.;
J.K.P., writing—original
P.V., H.J.M., draftsupervision,
S.T. and A.S.-F.; preparation,S.T.
J.K.P.
andand P.V.; project
A.S.-F.; writing—review and editing,
administration, J.K.P.,
S.T.; funding
P.V., H.J.M., S.T.
acquisition, S.T. All
andauthors
A.S.-F.; have
supervision,
read andS.T. and A.S.-F.;
agreed project administration,
to the published version of theS.T.; funding acqui-
manuscript.
sition, S.T. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by Department of Science and Technology (DST), New Delhi,
Funding:
DST NanoThis research
Mission was(SR/NM/NT-1054
Project funded by Department of Science and Technology (DST), New Delhi,
(G)-2015).
DST Nano Mission Project (SR/NM/NT-1054 (G)-2015).
Data Availability Statement: Data can be available upon request from the authors.
Nanomaterials 2021, 11, 1098 13 of 14

Acknowledgments: The authors are thankful to Department of Science and Technology (DST), New
Delhi, for providing financial support through DST Nano Mission Project (SR/NM/NT-1054 (G)-
2015). First and second authors likes to acknowledge Abitha V.K., Sisanth K.S. and Anu A.S. (TEM
analysis) for their instrumental help and support.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or
in the decision to publish the results.

References
1. Abraham, J.; Thomas, J.; Kalarikkal, N.; George, S.C.; Thomas, S. Static and Dynamic Mechanical Characteristics of Ionic Liquid
Modified MWCNT-SBR Composites: Theoretical Perspectives for the Nanoscale Reinforcement Mechanism. J. Phys. Chem. B
2018, 122, 1525–1536. [CrossRef] [PubMed]
2. Song, K. 2. Micro- and Nano-Fillers Used in the Rubber Industry; Elsevier Ltd.: Amsterdam, The Netherlands, 2017; ISBN 9780081004098.
3. Stöckelhuber, K.W.; Das, A.; Jurk, R.; Heinrich, G. Contribution of physico-chemical properties of interfaces on dispersibility,
adhesion and flocculation of filler particles in rubber. Polymer 2010, 51, 1954–1963. [CrossRef]
4. Patanair, B.; Thomas, S.; Abitha, V.K.; Saiter-Fourcin, A. Confinement effects at nanoscale in natural rubber composites: Influence
on macroscopic properties. J. Appl. Polym. Sci. 2021, 138, 1–8. [CrossRef]
5. Felix, D.G.; Kumar, D.G.S. Nano particles in Automobile Tires. IOSR J. Mech. Civ. Eng. 2014, 11, 7–11. [CrossRef]
6. Da Rocha, E.B.D.; Linhares, F.N.; Gabriel, C.F.S.; de Sousa, A.M.F.; Furtado, C.R.G. Stress relaxation of nitrile rubber composites
filled with a hybrid metakaolin/carbon black filler under tensile and compressive forces. Appl. Clay Sci. 2018, 151, 181–188.
[CrossRef]
7. Ma, W.; Li, J.; Deng, B.; Lin, X.; Zhao, X. Properties of functionalized graphene/room temperature vulcanized silicone rubber
composites prepared by an In-situ reduction method. J. Wuhan Univ. Technol. Mater. Sci. Ed. 2013, 28, 127–131. [CrossRef]
8. Bhadran, B.; Vijayan, D.; George, N.; Julie Chandra, C.S.; Sabura Begum, P.M.; Joseph, R. Reinforcing effect of organoclay in nitrile
rubber—Effect of mill mixing and latex stage mixing. Appl. Clay Sci. 2018, 165, 91–102. [CrossRef]
9. Kraus, G. Degree of Cure in Filler-Reinforced Vulcanizates by the Swelling Method. Rubber Chem. Technol. 1957, 30, 928–951.
[CrossRef]
10. Galimberti, M.; Cipolletti, V.R.; Coombs, M. Applications of Clay–Polymer Nanocomposites, 2nd ed.; Elsevier Ltd.: Amsterdam, The
Netherlands, 2013; Volume 5, ISBN 9780080982595.
11. Bordes, P.; Pollet, E.; Avérous, L. Nano-biocomposites: Biodegradable polyester/nanoclay systems. Prog. Polym. Sci. 2009,
34, 125–155. [CrossRef]
12. Picard, E.; Espuche, E.; Fulchiron, R. Effect of an organo-modified montmorillonite on PLA crystallization and gas barrier
properties. Appl. Clay Sci. 2011, 53, 58–65. [CrossRef]
13. Jia, Q.X.; Wu, Y.P.; Xiang, P.; Ye, X.; Wang, Y.Q.; Zhang, L.Q. Combined effect of nano-clay and nano-carbon black on properties of
NR nanocomposites. Polym. Polym. Compos. 2005, 13, 709–719. [CrossRef]
14. Majeed, K.; Jawaid, M.; Hassan, A.; Abu Bakar, A.; Abdul Khalil, H.P.S.; Salema, A.A.; Inuwa, I. Potential materials for food
packaging from nanoclay/natural fibres filled hybrid composites. Mater. Des. 2013, 46, 391–410. [CrossRef]
15. Cui, Y.; Kundalwal, S.I.; Kumar, S. Gas barrier performance of graphene/polymer nanocomposites. Carbon N. Y. 2016, 98, 313–333.
[CrossRef]
16. Zachariah, A.K.; Chandra, A.K.; Mohammed, P.K.; Thomas, S. Vulcanization kinetics and mechanical properties of organically
modified nanoclay incorporated natural and chlorobutyl rubber nanocomposites. Polym. Test. 2019, 76, 154–165. [CrossRef]
17. Choudalakis, G.; Gotsis, A.D. Current Opinion in Colloid & Interface Science Free volume and mass transport in polymer
nanocomposites. Curr. Opin. Colloid Interface Sci. 2012, 17, 132–140. [CrossRef]
18. Kuilla, T.; Bhadra, S.; Yao, D.; Kim, N.H.; Bose, S.; Lee, J.H. Recent advances in graphene based polymer composites. Prog. Polym.
Sci. 2010, 35, 1350–1375. [CrossRef]
19. Potts, J.R.; Dreyer, D.R.; Bielawski, C.W.; Ruoff, R.S. Graphene-based polymer nanocomposites. Polymer 2011, 52, 5–25. [CrossRef]
20. Wu, J.; Huang, G.; Li, H.; Wu, S.; Liu, Y.; Zheng, J. Enhanced mechanical and gas barrier properties of rubber nanocomposites
with surface functionalized graphene oxide at low content. Polymer 2013, 54, 1930–1937. [CrossRef]
21. Mensah, B.; Gupta, K.C.; Jeong, K.; Nah, C.; Kim, H.; Wang, W. Graphene-reinforced elastomeric nanocomposites: A review.
Polym. Test. 2018, 68, 160–184. [CrossRef]
22. Maurer, F.H.J.; Arza, C.R. Dispersion and interaction of graphene oxide in amorphous and semi-crystalline nano-composites: A
PALS study. J. Phys. Conf. Ser. 2015, 618. [CrossRef]
23. Yoo, B.M.; Shin, H.J.; Yoon, H.W.; Park, H.B. Graphene and graphene oxide and their uses in barrier polymers. J. Appl. Polym. Sci.
2014, 131, 1–23. [CrossRef]
24. Cao, Y.; Feng, J.; Wu, P. Preparation of organically dispersible graphene nanosheet powders through a lyophilization method and
their poly(lactic acid) composites. Carbon N. Y. 2010, 48, 3834–3839. [CrossRef]
25. Alwis, G.M.C.; Kottegoda, N.; Ratnayake, U.N. Facile exfoliation method for improving interfacial compatibility in
montmorillonite-natural rubber nanocomposites: A novel charge inversion approach. Appl. Clay Sci. 2020, 191, 105633. [CrossRef]
Nanomaterials 2021, 11, 1098 14 of 14

26. Yang, X.; Zhang, Y.; Xu, Y.; Gao, S.; Guo, S. Effect of octadecylamine modified graphene on thermal stability, mechanical properties
and gas barrier properties of brominated butyl rubber. Macromol. Res. 2017, 25, 270–275. [CrossRef]
27. Zheng, L.; Jerrams, S.; Xu, Z.; Zhang, L.; Liu, L.; Wen, S. Enhanced gas barrier properties of graphene oxide/rubber composites
with strong interfaces constructed by graphene oxide and sulfur. Chem. Eng. J. 2020, 383, 123100. [CrossRef]
28. Alipour, N.; Gedde, U.W.; Hedenqvist, M.S.; Yu, S.; Roth, S.; Brüning, K.; Vieyres, A.; Schneider, K. Structure and properties
of polyethylene-based and EVOH-based multilayered films with layer thicknesses of 150 nm and greater. Eur. Polym. J. 2015,
64, 36–51. [CrossRef]
29. Gaidukovs, S.; Kampars, V.; Bitenieks, J.; Bochkov, I.; Gaidukova, G.; Cabulis, U. Thermo-mechanical properties of polyurethane
modified with graphite oxide and carbon nanotube particles. Integr. Ferroelectr. 2016, 173, 1–11. [CrossRef]
30. Lisuzzo, L.; Cavallaro, G.; Milioto, S.; Lazzara, G. Effects of halloysite content on the thermo-mechanical performances of
composite bioplastics. Appl. Clay Sci. 2020, 185, 105416. [CrossRef]
31. Alam, S.N.; Sharma, N.; Kumar, L. Synthesis of Graphene Oxide (GO) by Modified Hummers Method and Its Thermal Reduction
to Obtain Reduced Graphene Oxide (rGO)*. Graphene 2017, 6, 1–18. [CrossRef]
32. Joseph, R.; George, K.E.; Francis, D.J. Studies on the cure characteristics of elastomer blends. Int. J. Polym. Mater. Polym. Biomater.
1986, 11, 205–209. [CrossRef]
33. Kim, H.; Miura, Y.; MacOsko, C.W. Graphene/polyurethane nanocomposites for improved gas barrier and electrical conductivity.
Chem. Mater. 2010, 22, 3441–3450. [CrossRef]
34. Thuruthil Raju, A.; Dash, B.; Dey, P.; Nair, S.; Naskar, K. Evaluation of air permeability characteristics on the hybridization
of carbon black with graphene nanoplatelets in bromobutyl rubber/epoxidized natural rubber composites for inner-liner
applications. Polym. Adv. Technol. 2020, 31, 2390–2402. [CrossRef]
35. Jibin, K.P.; Prajitha, V.; Thomas, S. Materials Today: Proceedings Silica-graphene oxide reinforced rubber composites. Mater. Today
Proc. 2020. [CrossRef]