Interactive Effects of Carbon Nanotube and Montmorrilonite
Reinforcement Polyvinyl Alcohol Composite System
Soo-Tueen Bee ,1 Lee Tin Sin ,1 Nicole Ooi Ker Qi,1 Chantara Thevy Ratnam,2 A. R. Rahmat3
1
Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku
Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor, Malaysia
2
Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor, Malaysia
3
Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310
UTM Skudai, Johor, Malaysia
This work was conducted to investigate the interactive
effect of carbon nanotubes (CNTs) and montmorillonite
(MMT) on the mechanical–physical properties of the poly-
vinyl alcohol (PVOH) nanocomposites. The increasing of
CNTs amounts from 0.5 phr to 1 phr has gradually
increased tensile strength and Young’s modulus of all
PVOH/MMT blends due to good interaction effect
between MMT and CNTs with PVOH matrix especially for
2 phr MMT added PVOH blends. Besides, the addition of
low CNTs amounts (≤1 phr) in PVOH matrix has signifi-
cantly weakened the hydrogen bonding polymer matrix
of all PVOH/MMT blends as evaluated in FTIR analysis.
This is attributed to the good of dispersion of low
amounts of CNTs could disturb the hydrogen bonding
between PVOH molecules and thus induced the strength
of O H stretching in PVOH matrix. However, higher
amounts of CNTs (≥1.5 phr) have significantly increased
hydrogen bonding in PVOH matrix due to the agglomera-
tion of higher amounts of CNTs particles in PVOH matrix
as observed in Fourier transform infrared spectroscopy
and scanning electron microscopy analysis. From X-ray
diffraction and transmission electron microscopy obser-
vation, the MMT particles were found to effectively exfoli-
ate in PVOH matrix of 2 phr MMT (low amounts) added
PVOH/MMT/MCNTs composites, indicates that low MMT
amounts could improve the interaction effect between
PVOH matrix and CNTs particles. In conclusion, the
incorporation of lower amounts of CNTs has effectively
improved on the mechanical and physical properties
of all PVOH and PVOH/MMT blends. J. VINYL ADDIT.
TECHNOL., 2019. © 2019 Society of Plastics Engineers
INTRODUCTION
Polyvinyl alcohol (PVOH) is a biodegradable, biocompati-
ble, water-soluble, nontoxic and odorless polymer and it is
Correspondence to: S-T. Bee; e-mail: direct.beest@gmail.com; L. T. Sin;
e-mail: direct.tinsin@gmail.com
Contract grant sponsor: MOSTI; contract grant number: 03-02-11-SF0196.
DOI 10.1002/vnl.21717
Published online in Wiley Online Library (wileyonlinelibrary.com).
© 2019 Society of Plastics Engineers
Journal of Vinyl and Additive Technology—2019
commonly used in paper coating, textile sizing, and food
packaging due to its harmless biodegradability characteristic
[1,2]. Furthermore, the good flexibility and gas barrier charac-
teristics of PVOH have also attracted more attention in the
field of food packaging and biomedical application [3,4].
Besides, the characteristics of PVOH with water-soluble,
hydrophilic, and biodegradable have almost similar physical
properties with human tissues in resulting commonly used in
biomedical applications. The applications of PVOH in bio-
medical field such as wound dressing, artificial organs, and
drug delivery systems have been widely developed in current
century [5,6]. This is due the biocompatible structure of
PVOH, which able to attract the protein molecules and binds
with the human cell without producing toxic effects [7].
However, the relatively weak mechanical properties of PVOH
have significantly limited the application in the field of bio-
medical, food packaging, and so on[8]. Due to this problem,
several investigations have been conducted by various
researchers in order to overcome the weak mechanical proper-
ties of PVOH [8–10]. In recent, the incorporation of rein-
forcing fillers, such as montmorillonite (MMT), in PVOH has
been widely conducted to induce the mechanical properties
such as tensile strength and modulus of PVOH [11].
Recently, many research and reports have been reported on
the addition of MMT with high modulus behavior in polymer
matrix could effectively enhance the mechanical properties of
polymer nanocomposite [12–14]. This is because the hydro-
philic characteristics of MMT platelets could help in promoting
the MMT particles to be homogenous dispersed in polymer
matrix especially hydrophilic polymers such as PVOH [13].
MMT is the most commonly used reinforcing filler to achieve
desired mechanical properties of polymer composites [9,11].
Various researches have been conducted to investigate the
effect of MMT amounts on the thermal, mechanical, and phys-
ical properties of polymer nanocomposites [14–16]. The dis-
persion state of nanoparticles of MMT in polymer matrix
(exfoliation, intercalation or phase separated) has played an
important role to achieve better mechanical properties of
polymer nanocomposites. The effective intercalation and exfo-
liation effect of MMT particles in polymer matrix could signifi-
cantly improve the mechanical properties by providing
reinforcement effect to polymer matrix under straining [14,17].
On the other hand, carbon nanotubes (CNTs) have also
been developed in the past few decades as effective reinforcing
filler in polymer matrix due to its high surface area, high aspect
ratio, and low-density properties in order to improve the
mechanical properties of polymer nanocomposites [18,19].
CNT can be described as graphite sheet in the form of rolled
up tiny tube form with the carbon structures building up from
sp2 carbon units [20]. CNTs are mainly divided into two
groups, which are single-walled carbon nanotube (SWCNTs)
and multi-walled carbon nanotube (MCNTs) [21]. The CNTs
can be incorporated into polymer matrix through various types
of methods such as melt blending, in situ polymerization and
solution mixing. CNTs are widely developed as filler in poly-
mer matrix because of its superior enhancement effect on elec-
trical properties, fire resistance, and mechanical properties such
as high Young’s modulus, stiffness, and tensile strength
[19,22]. According to our previous works [9,17], the addition
of low amounts of MMT had gradually enhanced the mechani-
cal properties of PVOH. However, higher amounts of MMT
loading level was found to provide inferior effect on the
mechanical properties of PVOH. In this work, CNTs were
selected as additional reinforcing filler due to its excellent per-
formance in enhancing the mechanical properties of various
types of polymer blends [22,23]. It is expected that the addition
of CNTs into PVOH/MMT nanocomposites can further pro-
vide the enhancement effect on mechanical and physical prop-
erties of PVOH/MMT nanocomposites. Up to date, there is no
paper reported to investigate the interactive effect of CNTs and
MMT particles on the physical–mechanical properties of
PVOH. Therefore, this work was conducted to investigate the
interactive effect of CNTs and MMT on mechanical and physi-
cal properties of PVOH nanocomposites.
EXPERIMENTAL
Materials
In this work, the fully hydrolyzed PVOH was used as
sole polymer base. The Sekisui Selvol™ 325 grade of
PVOH was supplied by Sekisui Specialty Chemicals Amer-
ica, LLC. MCNTs with diameter of 50 nm was supplied by
Ant Spirits Sdn Bhd and used as primary reinforcing addi-
tive in this study. On the other hand, MMT with 0.5–5 wt%
of aminopropyltriethoxysilane and 15–35 wt% of octa-
decylamine was secondary reinforcing additive and it was
manufactured by Sigma-Aldrich (M) Sdn. Bhd.
Preparation of PVOH/CNT/MMT Composites
All the samples of PVOH/MCNTs/MMT composites
were prepared via solution casting method by dissolving
100 phr of PVOH, various loading levels of MMT (0, 2,
and 4 phr), and MCNTs (0.5, 1.0, 1.5 and 2.0 phr) into dis-
tilled water in hot water bath. First, 100 phr of PVOH resin
2 Journal of Vinyl and Additive Technology—2019
was added and dissolved into distilled water by using water
bath at the temperature of 97
2 C. The mixture of
PVOH and distilled water was stirred using a motor-driven
stirrer at a rotation speed of 800 rpm until all the PVOH
resin was fully dissolved into the hot distilled water. After
that, the MMT and MCNTs powder were added into the
PVOH solution and the mixture of PVOH solution and
MMT-MCNTs powder was further stirred and heated in
water bath at temperature of 97
2 C for another 30 min
until all the MMT and calcined eggshell powder was fully
dispersed in the PVOH solution. The mixture of
PVOH/MCNTs/MMT solution was then cast into film form
by using a Teflon mold. The Teflon mold with cast solu-
tion was placed and dried in a vacuum oven at the tempera-
ture of 50 C for 24 h. The dried sample was then put into
the sealed plastic bags and stored in a desiccator cabinet
under room temperature at 25 C.
Characterization Testing
X-Ray Diffraction Test. X-ray diffraction (XRD) analysis
test was conducted to determine the dispersion state of MMT
and MCNTs particles in the sample using Shimadzu XRD
6000 XRD. The XRD spectra of all samples of pristine
MMT, pristine MCNTs, and PVOH/MCNTs/MMT compos-
ites were recorded with the diffractometer using Cu-Kα radi-
ation generator (λ = 1.542 Å) at scan rate of 1.2  min−1.
The operation current and acceleration voltage of the Cu-Kα
radiation generator were set at 30 mA and 40 kV, respec-
tively. The interlayer spacing (or also known as d spacing),
d was calculated according to Bragg’s equation as shown
in 1. The inter-chain separation, R was determined by using
Klug and Alexander equation as shown in 2.
λ
d= ð1Þ
2 sin θ
5λ
R= ð2Þ
8 sinθ
where λ is 1.542 Å and θ is the Bragg angle in radians.
Tensile Test. Tensile properties were determined using an
Instron Tensile Microtester with model of 5848 in accor-
dance to ASTM D882 (apply for the rectangular film with
thickness <1 mm). The cast sample of PVOH/MCNTs/MMT
composites was cut into standard rectangular shape according
to the ASTM D882 with 6 mm width and 60 mm length.
The thickness of each specimen was measured using measur-
ing instrument before proceed to the tensile testing. The ten-
sile test was conducted with the straining rate and cell load
of 50 mm/min and 5 kN, respectively. The tensile strength
and Young’s modulus of each sample formulation were
recorded as an average of five specimens.
Fourier Transform Infrared Spectroscopy Analysis.
Fourier transform infrared (FTIR) analysis was conducted
using a Nicolet model of IS10 FTIR spectrometer to
DOI 10.1002/vnl
determine the presence of specific chemical groups. The
samples of PVOH/MCNTs/MMT composites were directly
placed on the diamond crystal in the center of the ATR
plate. The IR beam with 0.1 mm diameter of the FTIR
instrument was focused at the center of the diamond. Pres-
sure was applied to the sample in order to scan it by lower-
ing the press of the ATR. Then, the dial of the ATR was
turned until the click was heard. The samples were scanned
under the region of 4,000 cm−1 to 400 cm−1.
Scanning Electron Microscopy Analysis. The fractured
surface morphologies of the PVOH/MCNTs/MMT com-
posites were observed by using a Hitachi S3400N SEM
machine. The applied electron beam voltage of the SEM
machine was set at 15 kV. First, the fractured surfaces of
all PVOH/MCNTs/MMT composites were cut into smaller
portion. The cut samples were then mounted onto specimen
stub using double-sided carbon tape with the fractured sur-
face of the cut samples was placed facing up. The mounted
samples were then coated with a layer of gold and palla-
dium using EMITECH SC7620 Sputter Coater. The coated
samples on stubs were loaded into SEM chamber and
scanned with electron beam voltage of 30 kV. The SEM
micrographs were recorded at the magnification of 1,000
times, 3,000 times, and 10,000 times.
RESULTS AND DISCUSSION
Tensile Properties
Tensile Strength. By referring to Fig. 1a, the increasing
of CNTs loading level from 0.5 phr to 1 phr has gradually
decreased the tensile strength of non-MMT added PVOH
composites. This observation indicates that the increasing of
CNTs amount up to 1 phr did not provide strengthening
effect to PVOH matrix. This might be due to the moderate
loading level of CNTs particles (1 phr) with hydrophobic
behavior were poorly interacted with PVOH matrix and
these particles tended to interact to each others in PVOH
matrix. This has significantly reduced the effective amounts
of CNTs, which are well disperse in PVOH matrix and thus
reduced the effective reinforcement effect of CNTs to the
PVOH matrix. However, further increasing the loading
levels of CNTs from 1 phr to 1.5 phr has rapidly induced
the tensile strength of non-MMT added PVOH composites.
This might be attributable to higher amount of CNTs (≥1.5
phr) in PVOH matrix could provide higher amounts of
effective local reinforcing points and show a rapid increment
of ~40% in tensile strength of non-MMT added PVOH com-
posites. Besides, the higher amounts of CNTs also increased
the specific surface area of CNTs in PVOH matrix, which
could further promote the Van der Waals binding in PVOH
matrix [24]. The presence of Van der Waals binding could
increase interfacial adhesive effect and interaction bonding
between CNTs particles and PVOH matrix by restricting the
mobility of PVOH chains at the CNTs/PVOH interfaces
[24]. Subsequently, this has further induced the efficiency of
stress transferring of between the PVOH matrix and CNTs
DOI 10.1002/vnl
FIG. 1. Effect of CNT and MMT loading level on (a) tensile strength
and (b) Young’s modulus of all PVOH nanocomposites.
particles [24,25]. However, the tensile strength of non-MMT
added PVOH composites was found to marginally decrease
when the loading level of CNTs increased from 1.5 phr to
2 phr as shown in Fig. 1a. Higher amounts of CNTs with
hydrophobic behavior in PVOH matrix tended to interact to
each others in PVOH matrix with hydrophilic nature. This
has significantly caused the agglomeration of CNTs particles
in PVOH matrix and thus slightly reduced the effective
localized reinforcing effect of CNTs particles in PVOH
matrix [26].
For low loading level of CNTs (≤ 0.5 phr), the increasing of
MMT amounts up to 4 phr has gradually decreased the tensile
strength of PVOH/MCNTs/MMT composites as shown in
Fig. 1a. This indicates that the addition of MMT particles did
not provide reinforcement effect to polymer matrix of low load-
ing level of CNTs added PVOH composites. This is mainly
attributable to the poor interaction effect of low loading level of
CNTs and MMT particles in PVOH matrix, which lead to inef-
ficient local reinforcing effect of CNTs and MMT particles in
the PVOH matrix [24]. The poor local reinforcing effect of
CNTs and MMT particles also unable to provide effective
micromechanical interlocking of CNTs and MMT particles in
PVOH matrix by restricting the movement of PVOH chains
under straining [24,26]. Thus, this has further reduced the trans-
mission of straining stress between the CNTs and MMT parti-
cles with PVOH matrix [27]. However, the addition of 2 phr
MMT has rapidly increased the tensile strength of higher load-
ing levels (≥1 phr) of CNTs added PVOH composites as
depicted in Fig. 1a. This indicates that the presence of MMT
particles in polymer matrix of PVOH composites reinforced
with higher CNTs amounts could further provide synergistic
reinforcement effect to PVOH matrix. This could be due to the
good interaction effect between MMT particles and higher
amounts of CNTs particles in PVOH matrix has remarkably
Journal of Vinyl and Additive Technology—2019 3
induced the interfacial adhesion between the particles with
PVOH matrix as illustrated in Fig. 2. Subsequently, this could
enhance the stress transmission between the particles and
PVOH matrix by preventing the propagation of breakage along
the interfaces between the particles and PVOH matrix under
straining [28]. Furthermore, higher loading level of CNTs could
also promote the intercalation effect of MMT particles in PVOH
matrix and further induce the resistance ability to the slippage
effect of PVOH chains under straining. Besides, the hydropho-
bic end of MMT particles tends to form bonding with CNTs
particles with similar nature, while the hydrophilic side would
interact well with PVOH matrix, which is hydrophilic in nature
[9]. This could further improve the surface wettability of the
CNTs particles by PVOH matrix by introducing the formation
of more micro interface and thus enhance the tensile strength of
PVOH/MCNTs/MMT composites. However, further increasing
the MMT loading level from 2 phr to 4 phr has gradually
decreased the tensile strength of PVOH/MCNTs/MMT com-
posites reinforced with higher amounts of CNTs as shown in
Fig. 1a. This might be due to higher amount of MMT particles
(≥ 4 phr) tended to agglomerate together into larger MMT
agglomerates and weaken the interfacial adhesion and interac-
tion effect of MMT particles with CNTs and PVOH matrix
[19,20]. The irregular shapes of the MMT and CNTs agglomer-
ates particles have significantly weakened the interfacial adhe-
sion effect between the MMT and CNTs agglomerates with
PVOH matrix [9,11]. Furthermore, the poor interaction between
MMT and CNTs particles also led to reduce the specific surface
area of CNTs and MMT in PVOH matrix and thus further
weakened the Van der Waals binding in PVOH matrix [24].
This has further reduced the bonding effect between the
agglomerated MMT and CNTs particles and PVOH matrix at
interface and thus highly reduced the local strengthening effect
of CNTs particles in PVOH matrix [28]. As results, the stress
transmission with the particles and PVOH matrix also signifi-
cantly reduced during straining.
Young’s Modulus. By referring to Fig. 1b, the Young’s
modulus of non-MMT added PVOH composites was observed
to gradually increase when the loading level of CNTs increased
FIG. 2. Mechanism diagram of PVOH/MCNTs/MMT composites.
4 Journal of Vinyl and Additive Technology—2019
from 0.5 phr to 1.5 phr. This is noted that the addition of CNTs
particles into PVOH matrix could significantly induce the
rigidity of PVOH matrix. The presence of CNTs particles in
PVOH matrix could provide local stiffening effect of polymer
matrix at the CNTs–matrix interfaces by toughening the PVOH
matrix under straining [24,28]. Furthermore, the higher specific
area of CNTs could also induce the interfacial frictional effect
and further resist the slippage ability of PVOH chains when
subjected to straining, thus higher straining stress is required to
break the PVOH matrix [25]. On the other hand, the increasing
of CNTs loading level up to 2 phr has gradually increased the
Young’s modulus PVOH/MCNTs/MMT composites added
with 2 and 4 phr MMT as depicted in Fig. 1b. This also indi-
cates that the presence of MMT particles in polymer matrix of
CNTs added PVOH composites would further promote the
local stiffening effect of polymer matrix by inducing inter-
locking of CNTs particles and PVOH matrix [28]. Subse-
quently, the movement of PVOH chains was highly restricted
by the presence of CNTs and MMT particles and higher
straining stress is needed to break the PVOH/MCNTs/MMT
composites. Thus, the rigidity also significantly induced.
On the other hand, it can be clearly observed that the addi-
tion of 2 phr MMT has highly increased the Young’s modu-
lus of all CNTs added PVOH/MCNTs/MMT composites
especially higher loading levels of CNTs (≥1 phr) as observed
in Fig. 1b. This indicates that the low loading level of MMT
could interact well with CNTs particles in polymer matrix by
effectively intercalating into PVOH matrix. This has further
increased the amounts of effective interface-localized particles
(CNTs and MMT) in PVOH matrix by forming higher num-
bers of micro-interface in PVOH matrix. The presence of
effective micro interface-localized particles in PVOH matrix
could remarkably induce the interfacial adhesion effect of
filler’s particles in PVOH matrix and subsequently resist the
crack propagation of PVOH matrix when subjected to
straining stress [28,29]. However, the Young’s modulus of all
PVOH/MCNTs/MMT composites was severely decreased
when the MMT loading level increased from 2 phr to 4 phr
as illustrated in Fig. 1b. This is due to the MMT particles
unable to disperse and interact well with CNTs particles at
higher loading level in PVOH matrix. The poor dispersion
and interaction effect of MMT particles with CNTs and
PVOH matrix has caused the MMT particles to form MMT
agglomerates in PVOH matrix and severely weakened the
interfacial adhesion effect between the fillers’ particles and
PVOH matrix. The formation of MMT agglomerates has also
significantly induced irregularity of MMT particles inside
polymer chain arrangement and thus weakened the movement
restriction of polymer chains when subjected to extension
[30]. Furthermore, the formation of MMT agglomerates with
larger in size and irregular in shape could also decrease the
local stiffening effect by weakening the mechanical inter-
locking of CNTs and MMT particles in PVOH matrix [24].
The MMT agglomerates act as stress concentration point
under straining by further promoting the crack propagation
and thus weaken the Young’s modulus of
PVOH/MCNTs/MMT composite added with higher MMT
amounts (4 phr) [24,31].
DOI 10.1002/vnl
FTIR Analysis
Figures 3–5 illustrate the infrared spectrum of all
PVOH/MCNTs/MMT composites added with increasing load-
ing level of CNTs and MMT. By referring to Figs. 3–5, two
prominent peaks can be clearly noticed to occur on the FTIR
spectrum of all the PVOH composites at wavenumber bands of
3,200 cm−1 to 3,600 cm−1 and 2,800 cm−1 to 3,000 cm−1,
respectively, which are attributed to the stretching of hydroxyl
group (O H) and C H bond [2,10]. The changes in the
wavenumbers of the stretching of O H and C H bonds repre-
sent that the incorporation of CNTs and MMT particles into
PVOH could change the bonding strength within the lattice
structure. The effect of incorporating CNTs and MMT particles
on wave numbers of O H stretching and C H stretching of
PVOH matrix was summarized in Table 1. From Table 1, the
increasing of CNTs loading level from 0.5 phr to 1 phr has sig-
nificantly increased the wavenumber of the hydroxyl group
(O H) stretching band of all PVOH/MCNTs/MMT composites
to higher wavenumber value. The increasing of wave number of
hydroxyl group (O H) stretching band shows that the addition
of CNTs up to 1 phr could slightly weaken the hydrogen bond-
ing inside the polymer matrix of PVOH/MCNTs/MMT com-
posites [9,17]. This also indicates the presence of CNTs particles
up to 1 phr in polymer matrix of PVOH/MCNTs/MMT compos-
ites could effectively interact with PVOH matrix and induce the
interfacial adhesion effect with PVOH matrix. The good interac-
tion effect between CNTs particles and PVOH matrix could
marginally reduced the hydrogen bonding between the PVOH
macromolecular chains in polymer matrix. However, the
wavenumber of hydroxyl group (O H) stretching of all
PVOH/MCNTs/MMT composites was observed to marginally
decrease when the loading level of CNTs increased from 1 phr
to 2 phr as shown in Table 1. The decrement in wave number of
the hydroxyl group (O H) stretching indicates the presence of
higher loading level of CNTs (≥1.5 phr) could slightly increase
of the hydrogen bonds inside PVOH matrix [32]. This also
shows that the interaction effect between the CNTs particles and
MMT-PVOH matrix was significantly weakened at higher load-
ing level of CNTs. This is due to the higher amounts of CNTs
particles tended to agglomerate together due to theirs hydropho-
bic behavior into larger CNTs agglomerates. The agglomeration
of CNTs particles in polymer matrix could further reduce the
effective amounts of dispersed CNTs particles in PVOH matrix,
which would disturb the hydrogen bonding in PVOH matrix
[32,33]. Furthermore, the presence of larger CNTs agglomerates
with shape irregularity in PVOH matrix has significantly weak-
ened the interaction effect between the CNTs particles and
PVOH matrix and thus induced the hydrogen bonds in PVOH
matrix.
By referring to Table 1, the addition of low amount of
MMT particles (≤2 phr) into polymer matrix of
PVOH/MCNTs/MMT composites added with lower loading
level of CNTs (≤1 phr) has significantly shifted the wave num-
ber of hydroxyl group (O H) stretching band to higher value.
This indicates that the occurrence of low amounts of MMT
particles in PVOH matrix has significantly increased the
strength of O H bonds of PVOH chains by reducing the
DOI 10.1002/vnl
hydrogen bonding in polymer matrix of all PVOH composites.
This observation also indicates that the combination of low
loading level of CNTs at 1 phr and low amount of MMT at
2 phr could achieve a synergistic interaction effect with PVOH
matrix by inducing the interfacial adhesion between the CNTs
and MMT particles and PVOH matrix. This is due to the
PVOH matrix with hydrophilic behavior would intercalate into
interlayer galleries of MMT particles which is hydrophilic in
nature, while the hydrophobic end of MMT particles would
attach with CNTs particles with hydrophobic behavior [34,35].
The synergistic interaction effect of MMT and CNTs particles
with PVOH could hinder and weaken the hydrogen bonding
between PVOH chains in polymer matrix [32]. However, the
wave number of hydroxyl group (O H) stretching of all low
loading level of CNTs (≤1 phr) added PVOH/MCNTs/MMT
composites was gradually decreased when the MMT loading
level further increased from 2 phr to 4 phr as shown in Table 2.
At higher loading level of MMT particles (≥4 phr), the MMT
particles tended to agglomerate together to form larger agglom-
erates particles in PVOH matrix due to poor interfacial adhe-
sion effect of MMT particles with CNTs particles and PVOH
matrix. The presence of MMT agglomerates could signifi-
cantly weaken the interaction effect of MMT particles with
CNTs-PVOH matrix and thus increase the hydrogen bonds in
PVOH matrix. For PVOH/MCNTs/MMT composites added
with higher loading level of CNTs (≥1.5 phr), the increasing of
MMT particles has gradually reduced the hydroxyl group
(O H) stretching with increasing of MMT loading level up to
4 phr. This is because the higher loading level of CNTs and
MMT particles tended to agglomerate together into larger
agglomerates particles due to their poor interaction effect with
PVOH matrix when added in high amount. This has further
reduced the interfacial adhesion effect between CNTs and
MMT particles and PVOH matrix and thus induced the hydro-
gen bonds of PVOH chains in polymer matrix. The strengthen-
ing of hydrogen bonding in PVOH matrix could significantly
weaken the strength of O H stretching [32].
On the other hand, the presence of C H stretching at the
band region of 2,900 cm−1 can be clearly observed on the
FTIR spectrum as shown in Figs. 3–5. The increasing of
CNTs loading level up to 1 phr has slightly increased the
wavenumber of C H stretching of non-MMT added
PVOH/MMT blends from 2,921.21 cm−1 to 2,922.39 cm−1.
This shows that the addition of CNTs particles up to 1 phr
could improve the structure of PVOH matrix by strengthen-
ing the structure of PVOH matrix. Besides, the good disper-
sion effect of CNTs in PVOH matrix could induce the
specific surface area of CNTs particles interacted with
PVOH matrix and thus induce the Van der Waals binding in
PVOH matrix [24]. The increasing of Van der Waals bind-
ing within the PVOH matrix has induced changes in
the intermolecular vibrations and thus induced the C H
stretching in the PVOH matrix [24]. Such increment in the
C H bonding wavenumber also indicates that the weakening
of hydrogen bonds between CNTs and PVOH matrix that has
increased the force constant. However, the C H stretching of
non-MMT added PVOH composites was found to marginally
decrease when the loading level of CNTs increased from
Journal of Vinyl and Additive Technology—2019 5
FIG. 3. FTIR spectrums of PVOH composites added with (a) 0 phr MMT and 0.5 phr MCNTs, (b) 0 phr MMT and 1.0 phr MCNTs, (c) 0 phr MMT and
1.5 phr MCNTs and (d) 0 phr MMT and 2.0 phr MCNTs. [Color figure can be viewed at wileyonlinelibrary.com]

1 phr to 2 phr as summarized in Table 1. This is due to the PVOH matrix by forming CNTs agglomerates. This has fur-
poor interaction effect of CNTs in PVOH matrix could ther reduced the Van der Waals binding in PVOH matrix by
reduce the effective specific surface area of CNTs particles in strengthening the hydrogen bonds in PVOH matrix and thus

6 Journal of Vinyl and Additive Technology—2019 DOI 10.1002/vnl

FIG. 4. FTIR spectrums of PVOH composites added with (a) 2 phr MMT and 0.5 phr MCNTs, (b) 2 phr MMT and 1.0 phr MCNTs, (c) 2 phr MMT and
1.5 phr MCNTs and (d) 2 phr MMT and 2.0 phr MCNTs. [Color figure can be viewed at wileyonlinelibrary.com]

weakened the interaction of CNTs with C-H stretching. On C-H stretching band into higher value as shown in Table 1.
the other hand, the addition of MMT particles into polymer This is due to the presence of MMT particles with polar and
matrix of PVOH/MCNTs/MMT composites added with 0.5 non-polar ends into PVOH matrix could harmonize the inter-
and 2.0 phr CNTs has slightly shifted the wavenumber of action effect between the CNTs and PVOH matrix and thus

DOI 10.1002/vnl Journal of Vinyl and Additive Technology—2019 7

FIG. 5. FTIR spectrums of PVOH composites added with (a) 4 phr MMT and 0.5 phr MCNTs, (b) 4 phr MMT and 1.0 phr MCNTs, (c) 4 phr MMT and
1.5 phr MCNTs and (d) 4 phr MMT and 2.0 phr MCNTs. [Color figure can be viewed at wileyonlinelibrary.com]

8 Journal of Vinyl and Additive Technology—2019 DOI 10.1002/vnl

TABLE 1. Effects of loading level of carbon nanotubes and MMT on 1400000 Pristine Carbon Nanotube 0.5 phr CNT (0 phr MMT)
the wavenumber of O H stretching and C H stretching of all PVOH 1200000 1.0 phr CNT (0 phr MMT) 1.5 phr CNT (0 phr MMT)
nanocomposites. 1000000 2.0 phr CNT (0 phr MMT)

Intensity, a.u.
−1 800000
PVOH nanocomposites added with Wave number, cm
600000
Loading level of Loading level of 400000
CNTs (phr) MMT (phr) O H stretching C H stretching
200000
0
0.5 0 3,264.71 2,921.21
1.0 0 3,266.45 2,922.39 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
o
2 Theta,
1.5 0 3,266.12 2,920.82
2.0 0 3,265.10 2,920.67 (a)
0.5 2 3,266.33 2,921.90 1400000 Pristine Carbon Nanotubes Pristine MMT
1.0 2 3,266.79 2,921.13 1200000 0.5 phr CNT (2 phr MMT) 1.0 phr CNT (2 phr MMT)
1.5 2 3,262.68 2,921.24 1.5 phr CNT (2 phr MMT) 2.0 phr CNT (2 phr MMT)

Intensity, a.u.
1000000
2.0 2 3,260.31 2,922.01
800000
0.5 4 3,259.72 2,922.82
600000
1.0 4 3,261.66 2,922.53
400000
1.5 4 3,261.07 2,922.10
200000
2.0 4 3,260.52 2,921.77
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
phr, parts per hundred resin. o
2 Theta,
(b)
improve the polymer structure of PVOH/MCNTs/MMT com-
1400000 Pristine Carbon Nanotubes Pristine MMT
posites by increasing of the C H stretching of PVOH matrix. 1200000 0.5 phr CNT (4 phr MMT) 1.0 phr CNT (4 phr MMT)
1000000 1.5 phr CNT (4 phr MMT) 2.0 phr CNT (4 phr MMT)
Intensity, a.u.

Dispersion Effect of MMT and Carbon Nanotubes 800000

Particles
A deflection peak can be found to occur on the XRD
curves of pristine CNTs and all PVOH/MCNTs/MMT
composites at 2θ range of 0.89–0.91 as depicted in Fig. 6.
By observing the Fig. 6b, two deflection peaks were
observed to occur at 2θ of 0.400 and 1.099 , respectively,
on XRD curve of pristine MMT. By referring to Fig. 6, the
deflection peak appeared on XRD curve of pristine MMT
at 2θ = 0.400 was found to be disappeared from the XRD
curves of all PVOH/MCNTs/MMT composites after adding
MMT particles into polymer matrix of PVOH/MCNTs
composites. This indicates that the layered structure of
MMT particles could well interact with CNTs particles in
polymer matrix of PVOH matrix by dispersing uniformly
in PVOH matrix [14,36]. This observation can be further
confirmed by the conducted TEM analysis as shown in
Fig. 7a–c, which the MMT stacked layers were observed to
disappear from the TEM micrographs of 2 phr MMT added
PVOH/MCNTs composites [36]. At low loading level of
MMT (2 phr), the layered structure of MMT particles were
separated and well dispersed in polymer matrix of
PVOH/MCNTs composites and optimized the interfacial
interaction with PVOH matrix and CNTs particles as
depicted in Fig. 7a–c. In other words, the layers of MMT
particles were effectively exfoliated in polymer matrix of
PVOH/MCNTs/MMT composites added with low MMT
amount (2 phr). However, the deflection peak of MMT par-
ticles appeared at 2θ = 1.099 on XRD curves of all
PVOH/MCNTs/MMT composites was observed to be hin-
dered by the presence of CNTs particles in PVOH matrix.
However, the incorporation of higher loading level of
MMT particles up to 4 phr were found to disperse poorly
in polymer matrix of PVOH composites with the presence
600000
400000
200000
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
o
2 Theta.
(c)
FIG. 6. Effect of increasing CNT loading levels on X-ray diffraction cur-
ves of (a) 0 phr MMT, (b) 2 phr MMT and (c) 4 phr MMT added polyvi-
nyl alcohol (PVOH) nanocomposites. [Color figure can be viewed at
wileyonlinelibrary.com]
of MMT agglomerates as shown in Fig. 7d. From Fig. 7d,
the agglomeration of MMT stacked layers can be clearly
observed on the TEM micrograph of 4 phr added
PVOH/MCNTs/MMT composites. This has further indi-
cated that the MMT particles pose poor interfacial interac-
tion effect with CNTs particles and PVOH matrix when
added with higher amount (4 phr).
On the other hand, the increasing of CNTs from 0.5 phr to
1 phr has marginally increased the d-spacing and interchains
separation of the deflection peak of all PVOH/MCNTs and
PVOH/MCNTs/MMT composites as tabulated in Table 2.
This indicates the good dispersion effect of CNTs particles in
polymer matrix of all PVOH composites, which the distance
gap between the carbon nanotubes particles has been increased
due to the increased interfacial adhesion effect between the car-
bon nanotubes and PVOH matrix. The good dispersion of
CNTs particles at loading level of 1 phr can be further con-
firmed with the TEM micrograph as shown in Fig. 7c. The par-
ticles of CNTs were observed to well interfacial adhere with
PVOH matrix without entanglement effect, which indicates the
good dispersion effect of carbon nanotubes particles. Further
increasing the CNTs amounts from 1 phr to 2 phr was found to

DOI 10.1002/vnl Journal of Vinyl and Additive Technology—2019 9

FIG. 7. TEM morphologies observation for the samples of 0.5 phr MCNTs +2 phr MMT added PVOH/MCNTs/MMT composites under magnification
of (a) 15,000 times; (b) 150,000 times; (c) 1 phr MCNTs +2 phr MMT added PVOH/MCNTs/MMT composites and (d) 2 phr MCNTs +4 phr MMT under
magnification of 15,000 times. [Color figure can be viewed at wileyonlinelibrary.com]

TABLE 2. 2 Theta (2θ), d-spacing and interchain separation (R) of pristine carbon nanotubes, pristine MMT and PVOH nanocomposites reinforced with
various loading levels of CNTs and MMT

Samples 2 Theta ( ) d-spacing, Ǻ Interchain separation (R), Ǻ

Pristine CNTs 0.9112 96.873 121.04

Pristine MMT 1.2458 70.900 88.53

PVOH Nanocomposites reinforced with:

Loading level of CNT (phr) Loading level of MMT (phr) 2 Theta ( ) d-spacing, Ǻ Interchain separation (R), Ǻ

0.5 0 0.8990 98.188 122.69

1.0 0 0.8918 98.980 123.68
1.5 0 0.8984 98.253 122.77
2.0 0 0.9018 97.883 122.31
0.5 2 0.9014 97.926 122.36
1.0 2 0.8997 98.111 122.59
1.5 2 0.8979 98.308 122.84
2.0 2 0.9163 96.334 120.37
0.5 4 0.9008 97.992 122.44
1.0 4 0.9049 97.548 121.89
1.5 4 0.9049 97.548 121.89
2.0 4 0.8963 98.484 121.04

10 Journal of Vinyl and Additive Technology—2019 DOI 10.1002/vnl

FIG. 8. SEM micrographs of 0.5 phr CNTs reinforced PVOH nanocomposites added with (a) 0 phr MMT; (b) 2 phr MMT; (c) 4 phr MMT and 2.0 phr
CNTs reinforced PVOH nanocomposites added with (d) 0 phr MMT; (e) 2 phr MMT; 4 phr MMT.
pose insignificant effect on the d-spacing and interchains sepa-
ration of the deflection peak of all PVOH composites as tabu-
lated in Table 2. This indicates that the addition of higher
loading level (>1 phr) of CNTs particles did not provide any
significant improvement effect on the dispersion effect of
CNTs particles in PVOH matrix. As shown in Fig. 6d, the
higher loading level of CNTs particles did not provide signifi-
cant enhancement effect in interfacial interacting effect with
MMT agglomerates particles and PVOH matrix.
Surface Morphologies Observation
Figure 8 illustrates the fracture structure and surface
morphologies of all PVOH/MCNTs/MMT composites after
conducted tensile test by using SEM observation test. By
referring to Fig. 8a and b, the addition of MMT loading
level up to 2 phr has significantly induced the tearing effect
on the fracture surface of PVOH composites. This is due to
the presence of MMT particles in polymer matrix of
PVOH/MCNTs composites has increased the numbers of
DOI 10.1002/vnl
stress concentration points in PVOH matrix during
straining and caused the tearing of PVOH matrix at these
stress concentration points [14,24]. This also indicates that
the addition of 2 phr MMT particles has marginally weak-
ened the tensile strength of 0.5 phr MCNTs added
PVOH/MCNTs/MMT composites as discussed earlier. As
shown in Fig. 8c, the agglomeration of MMT particles can
be clearly observed to occur on the fracture surface of 0.5
phr MCNTs added PVOH/MCNTs/MMT composites when
the MMT loading level was further increased from 2 phr to
4 phr. This indicates the poor dispersion effect of MMT
particles in polymer matrix of PVOH/MCNTs/MMT com-
posites, which led to poor interfacial adhesion effect
between the particles and PVOH matrix. By comparing the
Figs. 8d–f, the tearing effect on fracture surface of 2 phr
MCNTs added PVOH/MCNTs composites was observed
to be less continuous, shorter and lower elongation ability
in compared to all MMT (2 phr and 4 phr) added
PVOH/MCNTs/MMT composites. This observation indi-
cates that the addition of MMT particles into polymer
Journal of Vinyl and Additive Technology—2019 11
matrix of high CNTs (2 phr) added PVOH/MCNTs/MMT
composites have significantly improved the interfacial
interaction effect of particles and PVOH matrix. This is
due to the good interaction effect between the MMT parti-
cles, CNTs particle and PVOH matrix have further pro-
moted the effectiveness in transferring of the applied
straining stress from particles to polymer matrix, thus
strengthened the polymer matrix [28].
By comparing Fig. 8b and e, the increasing of CNTs parti-
cles from 0.5 phr to 2 phr was observed to significantly induce
the continuity and extendibility of the tearing effect on fracture
surface of 2 phr MMT added PVOH/MCNTs/MMT compos-
ites. Furthermore, the tearing effect on fracture surface of 2 phr
MCNTs added PVOH/MCNTs/MMT composites added with
2 phr MMT also observed to be longer as illustrated in
Fig. 8e. This indicates that higher loading level of CNTs could
effectively strengthen the polymer matrix by evenly distribut-
ing the applied load throughout the whole polymer matrix.
Similar observation can also be observed on the fracture sur-
faces of 4 phr MMT added PVOH/MCNTs/MMT composites
when the loading level of CNTs was increased from 0.5 phr to
2 phr as depicted in Figs. 8c and f.
CONCLUSIONS
In this work, the interactive effect of adding CNTs and
MMT on the physical–-mechanical properties of PVOH
blends have been intensively investigated. The tensile
strength of non-MMT added PVOH blends was marginally
decreased when the CNTs loading level increased from 0.5
phr to 1 phr. This is due to the poor dispersion and interfa-
cial adhesion effect between CNTs particles (hydrophobic
nature) and PVOH matrix (hydrophilic behavior) has weak-
ened the interfacial adhesion effect of CNTs and PVOH
matrix. However, the increasing of CNTs from 0.5 phr to
1.5 phr has gradually increased the tensile strength and
Young’s modulus of all MMT added PVOH blends. This
observation indicates that the presence of MMT particles
could promote the interaction effect between CNTs parti-
cles and PVOH matrix and lead to efficient localized rein-
forcement of CNTs particles. From FTIR analysis, the
increasing of CNTs amounts from 0.5 phr to 1 phr has sig-
nificantly induced the strength of O H stretching in all
PVOH blends, indicates the presence of low amounts of
CNTs could disturb and weaken the hydrogen bonding
between PVOH macromolecules in PVOH matrix. How-
ever, higher amount of CNTs (>1 phr) was found to
slightly reduce the O H stretching in PVOH matrix of all
PVOH blends due the agglomeration of CNTs in polymer
matrix as evidenced in SEM analysis. On the other hand,
the addition of low amount of MMT (2 phr) has slightly
increased the wavenumber of O-H stretching of low
amount of CNTs added PVOH blends. However, the
wavenumber of O H stretching was significantly
decreased when the MMT loading level increased from
2 phr to 4 phr. This indicates that the low amount of MMT
particles could reduce the hydrogen bonding in PVOH
matrix by promoting the interaction effect between the
12 Journal of Vinyl and Additive Technology—2019
CNTs and PVOH matrix of low CNTs added PVOH
blends. The addition of low amount of CNTs (≤1 phr) has
significantly increased the wavenumber of C H stretching
of all PVOH blends, which indicates the structure strength-
ening of PVOH matrix. This is due to the good dispersion
of CNTs at low loading level could induce the specific sur-
face area of CNTs particles and thus induce the Van der
Waals binding with PVOH matrix. According to XRD
analysis, the deflection peak at 1.2458 was found to disap-
pear from XRD curves of all MMT added PVOH blends,
which indicates the efficient exfoliation of MMT particles
in PVOH matrix of 2 phr MMT added PVOH/MCNTs
composites. The exfoliation of MMT particles can be fur-
ther proved by the TEM analysis. On the other hand, the
increment of d-spacing and interchain separation for deflec-
tion peak occurred at 2θ0.89 of all PVOH/MCNTs com-
posites indicates the good dispersion of CNTs particles in
polymer matrix of all PVOH blends. The good dispersion
of CNTs particles in PVOH matrix can be further evident
by the TEM analysis. In overall, the incorporation of CNTs
up to 1.5 phr could significantly enhance the physical–
mechanical properties of 2 phr MMT added PVOH blends.
ACKNOWLEDGMENTS
The authors gratefully acknowledge the Minister of Sci-
ence, Technology, and Innovation, Malaysia (MOSTI) of
The Federal Government of Malaysia-Putrajaya under Sci-
ence Fund (03-02-11-SF0196) for the financial support.
NOMENCLATURE
CNTs carbon nanotubes
d interlayer spacing
FTIR Fourier transform infrared spectroscopy
MMT montmorillonite
MCNTs multi-walled carbon nanotubes
phr parts per hundred resin
PVOH polyvinyl alcohol
R interchain separation
SEM scanning electron microscopy
TEM transmission electron microscopy
XRD X-ray diffraction
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