Received: 31 December 2020 Revised: 15 April 2021 Accepted: 18 April 2021

DOI: 10.1002/pat.5376

RESEARCH ARTICLE

Highly electro-responsive composite gel based on functionally

tuned graphene filled polyvinyl chloride

Imdad Ali1,2 | Ahsan Ali2 | Ahmed Ali3 | Muhammad Ramzan2 |

Khalid Hussain2 | Li Xudong1 | Zhan Jin1 | Otavio Augusto Titton Dias4 |
Yang Weimin1 | Li Haoyi1 | Zhang Liyan1 | Mohini Sain4

1
College of Mechanical and Electrical
Engineering, Beijing University of Chemical Abstract
Technology, Beijing, P.R. China Electroresponsive devices have attended significant interest for actuators and artifi-
2
Department of Mechanical Engineering,
cial muscles in recent days but are susceptible to low deformation at applied voltages.
QUEST Nawabshah, Sindh, Pakistan
3
Department of Electrical Engineering, Sukkur To address this problem, herein, we have prepared novel flexible composite gel based
IBA University, Sindh, Pakistan on polyvinyl chloride (PVC), dibutyl adipate (DBA), and functionalized reduced
4
Centre for Biocomposites and Biomaterials
graphene oxide (f-rGO) via solution casting technique. The structural, morphological,
Processing, Graduate Department of Forestry,
University of Toronto, Toronto, Ontario, optical, mechanical, and thermal properties of the composite PVC/f-rGO gel were
Canada
characterized by using various techniques. In order to test the usefulness of PVC/f-
Correspondence rGO, we fabricated the new planar PVC/f-rGO-based gel actuator, by holding the gel
Zhang Liyan, College of Mechanical and
between two electrodes. Stimuli-responsive deformation of ~2.7 mm was measured
Electrical Engineering, Beijing University of
Chemical Technology, Beijing 100029, at a voltage of 1200 V for an optimized gel in the designed device. The loading of
P.R. China.
silane-f-rGO greatly enhanced the stimulation, response time and flexibility of the
Email: zhangly@mail.buct.edu.cn
PVC gel. The highest elongation at break of about 433% was achieved for f-rGO-
Mohini Sain, Centre for Biocomposites and
loaded PVC gel owing to strong dipole–diploe interactions between alpha hydrogen
Biomaterials Processing, Graduate Department
of Forestry, University of Toronto, Toronto, of PVC and -NH2 of f-rGO. We believe that highly electro-stimulated, soft and, flexi-
Ontario, Canada.
ble PVC/f-rGO gels could open a new avenue for the fabrication of advanced artifi-
Email: m.sain@utoronto.ca
cial muscles and tunable soft actuators for number of applications.
Funding information
China National Key Research and development KEYWORDS
Plan, Grant/Award Number:
electro-stimulation, flexible actuator, functionalized rGO, physicochemical, PVC gel
2016YFB0302000; Guangdong Provincial
Science and Technology, Grant/Award
Number: 2016B090915001

1 | I N T RO DU CT I O N biological muscles.4,5 EAPs-based gels are characterized as ionic and

Over the last few years, soft stimulated materials which are mechani-
cally responsive toelectric fields have been widely studied as promis-
ing materials for various applications such as micro-electromechanical
systems, artificial muscles, medical implants, actuators, and robotics.1–3
Particularly, soft electro-stimulated materials fabricated from electro-
active polymers (EAPs) have shown remarkable mechanical motion
when energized with electrical energy. The soft electro-stimulated
materials are widely investigated for several applications due to their
rapid response, large displacement, and the high capability to emulate
nonionic. In ionic EAPs gels, such as in polyelectrolytes gels, the evapo-
ration and leakage of solventare hard to control; however, nonionic
EAPs gels do not have such barriers.6,7
Thenon-ionic EAP-based polymers such as polyvinyl chloride
(PVC) have been used for several commercial applications mainly due
to several advantages like biocompatibility, chemical stability and low
cost.8 Several studies suggested that PVC has lower thermal stability,
therefore, it cannot be used for high-temperature applications. Addi-
tionally, the low brittleness and high electrical resistivity of PVC have
restricted its practical usage on large-scale applications. Recent

Polym Adv Technol. 2021;1–10. wileyonlinelibrary.com/journal/pat © 2021 John Wiley & Sons Ltd. 1
2 ALI ET AL.
developments in graphene-based composite material9 have provided
new insight to overcome some of these challenges.
Graphene has been considered a promising material for differ-
ent applications due to its excellent electrical, thermal, and
mechanical properties.10–12 It has been extensively used to
enhance the physical properties of polymer nanocomposites.13,14
However, the synthesis of graphene fillers-based composite mate-
rials still require further research to overcome the aggregation of
graphene and provide better interfacial interactions between poly-
mer and graphene.8,15
8
Vadukumpully et al. studied PVC-graphene nanostructured thin
film prepared by the solution mixing technique. The nanostructured
composition showed excellent electrical, thermal, and mechanical
properties; however, the elongation at break was reduced to 65% due
8,16
to weak interfacial forces between PVC and graphene. Zhao
et al.15 reported the tensile strength and Young's modulus values for
polyvinyl alcohol (PVA)-graphene-based nanostructures. The authors
noted a sharp decrease in elongation at the break due to the irrevers-
ible aggregation of graphene structures.15 Xin et al.17 synthesized
functionalized graphene nanosheets (f-GNS) and water-borne poly-
urethane (WPU)-based nanocomposite coating by sol–gel process.
They reported that f-GNs have good interactions with WPU.17 These
studies clearly indicate the role of interface in further improving
deformation behavior of polymeric gels.
On the other side, PVC has been widely employed due to its
good compatibility with different plasticizers and PVC gels can be
18,19
easily tuned as either stiff or stretchable. Besides, the PVC
gels also have a good response under an applied DC electrical
3,20
source. Bae et al. reported a maximum strain about 300% for
PVC gel.20 Hashimoto et al. fabricated a multilayer actuator by
using PVC gel assembled with electrodes, and the overall contrac-
tion strain was upto 10%–15% underprocess conditions of fre-
quency 3–7 Hz and induced electric potential of 400–600 V.21
Multilayer PVC gel actuators still have certain issues such as poor
stretchability due to their high density, the rigidity of metal elec-
trodes, large size, and heavyweight. Moreover, their properties are
poor compared tobio muscles.22,23
Herein, we have prepared a novel type of gel based on PVC,
dibutyl adipate (DBA), and functionalized reduced graphene oxide
(f-rGO). We found that the optimized concentration of f-rGO as a
nanofiller has enhanced the performance of PVC gel. Moreover,
the dipole–diploe interactions between alpha hydrogen of PVC and
-NH2 from the amino silane moieties of f-rGO improved the
electro-response of fabricated gels. As a proof of concept, to dem-
onstrate how PVC/f-rGO gels can be useful, we fabricated the new
planar PVC/f-rGO-based gel actuator, by holding the gel between
two electrodes. Furthermore, the performance of the composite
gel was studied by measuring deformation, response time, mechan-
ical strength, thermal stability, structural, and morphological char-
acteristics. The prepared PVC/f-rGO-based gel actuator may have
potential applications in the treatment of paralysis patients, artifi-
cial muscle, and various other clinical applications owing to its
excellent performance.
2 | EXPERIMENTAL ANALYSIS
2.1 | Materials
Polyvinyl chloride (degree of polymerization is 2500) was purchased
from Xinjiang Zhongtai Chemical Co., Ltd., Xinjiang, China. Dibutyl
adipate (DBA) plasticizer was obtained from Yingkou Tianyuan Chemi-
cal Research Institute Co. Ltd., Liaoning, China. Organic solvent THF
was purchased from Beijing Century Tuoxin Fine Chemical Co. Ltd.,
Beijing, China. Graphite was purchased from the Aladdin Chemical
Reagents. Other chemicals such as H2SO4, KMnO4, NaNO3, and
H2O2 were purchased from the Beijing Chemical Reagents works.
3-aminopropyltriethoxysilane (APTES) was purchased from Shanghai
Macklin Biochemical Technology Company, Shanghai, China.
2.2 | Preparation of graphene oxide
GO was prepared according to the improved Hummer's method.24
Typically, 2.0 g of graphite and 45.0 ml H2SO4 were added into the
beaker with constant magnetic stirring for 24 hand then 200 mg of
NaNO3 additional added into the reaction mixture for another 30-min
stirring. Further, 6.0 g of KMnO4 was added into the reaction mixture
and maintained at a temperature below 40
C. After sonication at
34
C–40
C, 90 ml of H2O added under stirring for 30 min followed
by further addition of 280 ml of H2O and stirred additionally for
25 min. Obtained mixture centrifuged, neutralized, and the sample
was dried at 60
C vacuum oven.
2.3 | Preparation of f-rGO
150 mg of GO was dispersed in 50 ml of deionized (DI) water and
sonicated for 30 min at 35
C. 2.0 ml of amino silane was addedinto
the mixture with continuous stirring upto 30 min. Further, 1.0 ml of
hydrazine added dropwise with stirring for reduction of GO, equipped
with an oil bath at 80
C for 8 h.25,26 The precipitates off-rGO were
separated by filtration and washed with DI water, dried in a vacuum
oven at 60
C for 12 h and then saved for further use. The synthesis
route of f-rGO is shown in Scheme S1.
2.4 | Preparation of PVC/f-rGOfilm
The gels were prepared with 1:4 w/w% of the PVC:DBA and f-rGO
were added in 4 different compositions at 0.01%, 0.02%, 0.03%, and
0.04% of the total mass.25,27 First, f-rGO dissolved in THF by sonica-
tion for 20 min and then the required quantity of PVC and DBA were
mixed by vigorous stirring at 40
C for 5 h by using a simple solvent
casting technique. After achieving a uniform dispersion, the solution
was poured into a petri dish and dried inan oven and further kept
under the evaporator for 3 days. Finally, after evaporation of the sol-
vent, the concentrated mass is left behind as a soft flexible PVC/f-rGO
ALI ET AL.
composite gel film with thickness of ~0.5 mm. The preparation proce-
dure for PVC/f-rGO composite gel film as illustrated in Scheme 1. The
sample without the f-rGO named Gel-0 and other samples were desig-
nated as Gel-1, Gel-2, Gel-3, and Gel-4 based on the f-rGO contents as
depicted in Figure S1.
2.5 | Characterizations
FT-IR studies were carried out with FTIR spectrometer (Thermo
American type Nicolet 6700) and Raman spectra were recorded on a
Renishaw in Via Raman spectrometer with laser excitation at 785 nm
with the power of 1 mW. X-Ray Diffraction (XRD) study was per-
formed by X-ray Diffractometer (D/mac 2500 VB2+/PC Rigaku) at



the range of 10 –60 the angle 2Ɵ, to investigate the crystalline
nature of PVC/f-rGO gels. The optical properties of the gel samples
were determined by UV–Vis spectrometer (Shimadzu UV-3600).Scan-
ning electron microscopy (SEM, Hitachi-4700) and trinocular met-
alogical microscope (XJ-55C) were used to analyze the surface
morphology of pure PVC and PVC/rGO-based gels. The samples were
freeze-dried for the SEM test. The mechanical properties of the gel
samples were tested by a universal testing machine (UTM INSTRON
5567) with the standard ASTM D638 at a speed of 50 mm/min at
room temperature. The dumb bell-shaped specimens were formed
from the flat drop-casted of gels. The thermal degradation was ana-
lyzed by MettlerToledoSTARe SYSTEM TGA/DSC3+ in the tempera-




ture range of 100 C–500 C in a nitrogen environment of 10 C/min.
The displacement was measured by using a laser displacement meter
(Panasonic industrial devices SUNX Co., Ltd., Suzhou, Jiangsu China).
2.6 | Actuator design setup
The pure PVC gel and the samples with different concentrations of
f-rGO were tested on a self-fabricated setup. This setup was
S C H E M E 1 Schematics for the
preparation of novel flexible polyvinyl
chloride (PVC)/functionalized reduced
graphene oxide (f-rGO) composite gel
3
fabricated from the plastic material and glass strips pasted with cop-
per tape as an electrode as shown in Figure 1(A). Figure 1(B) shows
the schematic illustration of the setup. The deformation of gel sam-
ples was observed by the laser displacement technique.
3 | RESULTS AND DISCUSSION
3.1 | Structural study of pure PVC gel and PVC/
f-rGO gels
Raman scattering-based experiments were carried out to study the
structural features of GO, f-rGO, PVC, and PVC/rGO gels. Figure 2(A)
shows a typical Raman spectrum of GO displayed two main peaks at
1354 cm1 and 1593 cm1 for the D and G bands, respectively. The
D band is attributed to edges, defects, and disordered domains,
whereas the G band is associated with graphitic carbons.28,29 The G
band was at 1593 cm1 for the GO and broadened and shifted to
1603 cm1 for f-rGO, indicating a good exfoliation of graphene layers.
Moreover, the ID/IG ratio for GO was 0.74 that increased to 1.07 for
the rGO due to the reduced oxygen functional groups as compared to
GO.30,31 Furthermore, Figure 2(B), showed the Raman spectrum of
PVC/f-rGO gel samples, the D and G bands peak at 1304 cm1 and
1580 cm1, respectively. The intensity of D band was increased with
the loading of f-rGO, which is a clear indication of the strong interac-
tion between PVC and f-rGO and the increased degree of
defectswithin the f-rGO structure.32 The band at 1580 cm1 in Gel-
1which gradually shifted to 1599 cm1 in Gel-4. This blue shifting
phenomenon of the G peak can be attributed to the occurrence of
greater defects in the f-rGO sheets during the physical cross-linking
reaction between PVC and f-rGO.26,33 In addition, the two major
peaks at 630 and 694 cm1 were detected in the C–Cl stretching
region of pure PVC. According to the results, the plasticizers DBA
bonded to PVC since the peak at 630 cm1 was not blue shifted. The
presence of DBA and f-rGO allowed free rotation of PVC chain
4 ALI ET AL.

segments to respond under induced electric force.34,35 Furthermore,

the intensity of peaks of PVC/f-rGO gels has also increased. This
result implies that good physiochemical interactions occurred among
PVC, DBA, and f-rGO.
The FT-IR techniques were carried out to study the physicochem-
ical interactions of f-rGO with PVC gel. The FT-IR spectra of GO, f-
rGO, and PVC/f-rGO composite gel are shown in Figure 3(A), (B). In
GO spectrum at 3394, 2924, 2850, 1722,1624 cm1 were attributed
to hydroxyl groups (-OH), asymmetrical and symmetrical stretching of
the –CH2 band, carbonyl group (C=O) and C=C, respectively, as
shown in Figure 3(A). Inf-rGO, bands appeared at 3431, 2924, 2856,
F I G U R E 1 Gel deformation and response time experimental
1729, 1649, and 1080 cm1 are assigned to -NH bending, –CH2
setup (A) self-fabricated setup (B) Schematic illustration of setup

F I G U R E 2 Raman spectra of (A) graphene oxide (GO) and functionalized reduced graphene oxide (f-rGO) and (B) pure polyvinyl chloride
(PVC) gel and PVC/f-rGO gels

F I G U R E 3 FTIR spectra (A) graphene oxide (GO) and functionalized reduced graphene oxide (f-rGO) (B) pure polyvinyl chloride (PVC) gel and
PVC/rGO gels
ALI ET AL.
stretching, carbonyl group (C=O), C=C, and Si-O-C, respectively.36–38
The peaks shift in f-rGO was observed from lower to higher values,
indicating the functionalization and reduction of GO. Figure 3(B)
shows FT-IR spectra of pure PVC gel and PVC/f-rGO composite gels.
The main characteristics bands were observed at 3448–3454, 2860–
2970, 1740–1780 cm1, and 750 and 633 cm1 are attributed to
(-NH,-OH), –CH2, carbonyl group (C=O) of DBA and -Cl of PVC, 39–41
respectively. We found that by increasing the loading of f-rGO in the
PVC gel, the peaks havebecome broader and shifted to higher wave
numbers as shown in Figure 3(B). These changes in peaks indicated
the presence of hydrogen bonding and dipole–dipole interactions
between alpha hydrogen of PVC and carbonyl ester group
(RC=OOR0 ) of DBA. The carbonyl group (C=O) of DBA is the main
group that polarized the PVC polymer.40 Besides, the other possible
interactions could be dipole–diploe and hydrogen bonding of -NH
(OH) group of f-rGO with alpha hydrogen of PVC as illustrated in
Scheme 2. From the FT-IR and Raman spectra we concluded that
good physicochemical interactions were present among PVC, DBA,
and f-rGO, which resulted in forming successful physical blending.
Figure 4(A) shows the XRD patterns of GO and f-rGO, that rev-
ealed a strong diffraction peak (001) for GO sheets at 10.5

corresponding tofixed d-spacing of 0.8 nm.42 After reduction/modifi-


cation, the peak at 10 disappeared and a wide peak (002) emerged at
23.5
consistent with an interlayer distance of about 0.4 nm, revealing
a well-oriented structure of graphene.42 The XRD showed a broad
peak at 20.10
for pure PVC gel and PVC/f-rGO gel samples. The
o
weak peaks at 40 have revealed the highly amorphous nature of
composite gels.43 As shown in Figure 4(A), when the concentration
of the f-rGO in PVC gel was increased the peak intensity decreased.
The decrease in the widthand intensity of the peak at 20.10
was
attributed to the presence of amorphous regions in the samples. In
addition, this decrease was a result of gelatinization and cross-linking
during the gel fabrication process.44,45 The absence of small peaks
and reduced fluctuation amplitude confirmed the purity and good dis-
tribution of f-rGOin PVC gels.46
3.2 | Optical and morphological analysis of pure
PVC gel and PVC/f-rGO gels
The onset absorption spectra of the fabricated gels in the range 200–
280 nm was attributed to the π–π* transition of the PVC.47 Both pure
S C H E M E 2 Schematics illustration of
polyvinyl chloride (PVC), dibutyl adipate,
and functionalized reduced graphene
oxide (f-rGO) possible interactions
mechanism
5
PVC gel and PVC/f-rGO composite gels showed high absorbance in
the UV regionas shown in Figure 5(A). The absorbance was increased
with increasing f-rGO content in gels as reported earlier.48 The optical
bandgap of PVC and polymer nanocomposite gels was estimated by
using Tauc's relation.49 The intercept with the x-axis estimates the
optical band gap value. The values of optical band gap were found to
be 4.09, 3.97, 2.89, 2.56 and 2.62 eV for Gel 0, Gel 1, Gel 2, Gel 3, and
Gel 4, respectively. As shown in Figure 5(B), the band gap
decreased with increasing f-rGO loading due to the formation of
new levels in the optical band gap. The slight drop of Eg from 2.62
to 2.56 eV at 0.04 wt.% of f-rGO loading was likely due to light
absorption by nanoparticles.50 It has been previously reported that
the variations in the optical band gap changes the electronic struc-
ture of PVA molecules and there was no effect of higher filler con-
centration on band gap.49
Further, the SEM studies were carried out forcomposite gels
(Figure 6). Figure 6(A) shows the micrograph of Gel-0 withoutany
f-rGO as a control sample. Figure 6(B)–(E) shows SEM images of
Gel-1, Gel-2, Gel-3, and Gel-4 with 0.01%, 0.02%, 0.03%, and 0.04%
concentrations of f-rGO, respectively. We can clearly observe signifi-
cant change in internal structure has occurred due to successful physi-
cal cross-linking between f-rGO nanosheets and PVC gel as shown in
Figure 6. As the f-rGO concentration was increased, interstitial voids
were created between the sidechains of PVC. As a result, the DBA
molecules in turn facilitated f-rGO particles to flow easily through the
PVC chains, resulting in more uniform morphologies for higher f-rGO
concentrations. Moreover, Figure S2(A-D) shows lenticular images of
PVC/f-rGO gel, which can be easily observed from Figure S2(A-D) a
disordered network of f-rGO nanosheets within the gel matrix, which
reveals excellent dispersion and entanglement of f-rGO and PVC gel.
3.3 | Thermal and mechanical properties of pure
PVC gel and PVC/f-rGO gels
The thermogravimetric analysis was carried outto understand the
thermal degradation behavior of gels. Figure 7(A) shows the thermo-
graphs of pure PVC gel and PVC/f-rGO gel samples with different
concentrations of f-rGO. In pure PVC gel, the major weight loss was
occurred at 204
C, mainly due to the loss of HCl from the PVC
chain.51 While for PVC/f-rGO weight loss was occurred at higher
temperature of 220
C–228
C, this was occurred due to the presence
6 ALI ET AL.

F I G U R E 4 X-Ray diffraction patterns of (A) graphene oxide (GO) and functionalized reduced graphene oxide (f-rGO) (B) pure polyvinyl
chloride (PVC) gel and PVC/f-rGO gels

F I G U R E 5 Optical properties of pure polyvinyl chloride (PVC) gel and PVC/functionalized reduced graphene oxide (f-rGO) gels (A) UV–Vis
absorption spectra (B) Band gap energy plots

f-rGO, which also resulted in increased thermal stability. However,
the total weight loss of all gel samples was observed at 481
C. Inter-
estingly, above 380
C there was not much change in terms of thermal
behavior of the gels indicating good compatibility and better interac-
tions among PVC, DBA, and f-rGO.
Stress–strain curves are crucial graphical measure of actuator
flexibility and mechanical properties. Figure 7(B) shows the stress
and strain curves of different gel samples. We found that the addi-
tion of f-rGO has resulted in enhancing the value of strain with
increased stress-bearing capacity. As shown in Figure 9. Gel-1,
Gel-2, Gel-3, and Gel-4 demonstrated higher stress-bearing capa-
bility with higher strain value compared to Gel-0. Gel-4 containing
0.04% of f-rGO has the highest strain of about 433%. The given
results show that with the addition of f-rGO contents the stress
and strain were enhanced and these gels were highly flexible and
could be suitable for actuator applications.20 Moreover, in order to
quantitatively analyzed the interactions among PVC, DBA, and
f-rGO, the areas under the stress–strain curves were calculated,
that indirectly measured the toughness of the gel. We observed
that the amount of energy absorbed by gel during deformation has
varied significantly with the f-rGO contents. For example, for
Gel-1, Gel-2, Gel-3, and Gel-4 the toughness, as a measure of the
amount of energy absorbed before failure, was 46%, 80%, 262%,
and 588%, respectively, these values were dramatically higher than
that of Gel 0. These results have strongly supported our earlier
observation that hydrogen bonding and dipole–dipole interactions
among PVC, DBA, and f-rGO could easily enhance both stress and
strain simultaneously.
ALI ET AL. 7

FIGURE 6 SEM micrographs of (A) Pure polyvinyl chloride (PVC) gel, (B) Gel 1, (C) Gel 2 and (D) Gel 3 (E) Gel-4 (F) Partial enlarged details of
Gel-4

F I G U R E 7 TGA and DTG thermograms (B) Stress–strain curves of pure polyvinyl chloride (PVC) gel and PVC/ functionalized reduced
graphene oxide (f-rGO) gels

3.4 | Deformation and response time of the
electro-stimulated actuator
The deformation act of gel samples was tested on a self-fabricated
setup. Figure 8(A) shows displacement in millimeter of different Gel-0,
Gel-1, Gel-2, Gel-3, and Gel-4 with 0%, 0.01%, 0.02%, 0.03%, and
0.04% concentration of f-rGO, respectively. Initially, the pure PVC
(Gel-0) was tested by applying 800, 1000, and 1200 V, the resulting
displacements were 0.5, 0.65, and 0.8 mm with the response time of
1, 0.9, and 0.8 s, respectively, as shown in Figure 8(A), (B). The defor-
mation occurred due to the Maxwell stress effect and was attributed
to the fact that the plasticizer DBA molecules were charged under
applied voltage and polarized DBA easily facilitated the free dipole
reorientation of the PVC chains from PVC gel network.21 Whenever
voltage was applied, the negative charges of cathode passed from gels
moved toward the anodeand caused bending deformation. This bend-
ing deformation mechanism of pure PVC and PVC/r-rGO composite
gels are depicted in Figure 9(A), (B). Moreover, we found that with the
addition of f-rGO displacements degree was increased with rapi-
dresponse timeas shown in Figure 8(A), (B). The Gel-4 which contains
0.04% of f-rGO experienced displacements of 1.3, 1.5, and 2.7 mm
with response times of Gel-4 of 0.5, 0.4, and 0.3 s, at applied voltages
of 800, 1000, and 1200 V, respectively. The Gel-4 displacement was
highest and response time was shortest as compared to Gel-0, Gel-1,
8 ALI ET AL.
F I G U R E 8 (A) Displacement results of pure polyvinyl chloride (PVC) gel and PVC/functionalized reduced graphene oxide (f-rGO) gels
(B) Response time of pure PVC gel and PVC/f-rGO gels
F I G U R E 9 Bending deformation of (A) pure polyvinyl chloride
(PVC) gel (B) PVC/functionalized reduced graphene oxide (f-rGO) gels
Gel-2, and Gel-3 as shown in Figure 8(B).This high deformation and
fast response signified that there were strong interactions among
PVC, DBA, and f-rGO. Such a high displacement of Gel-4 is adequate
for actuators. Furthermore, this deformation makes PVC/f-rGO actua-
tor good candidates for artificial muscles and soft robotics.
4 | C O N CL U S I O N S
Highly electro-stimulated PVC/f-rGOwas successfully prepared and
tested on aself-fabricated setup that functioned as an actuator. The
pure PVC gel was deformed upto 0.8 mm under an applied voltage of
1200 V, while at the same applied voltage Gel-4 underwent maximum
deformation of about 2.7 mm. Further, the physicochemical interac-
tions of PVC, DBA, and f-rGO was confirmed by Raman, FT-IR, and
XRD techniques. The SEM images showed that the f-rGO was well
incorporated with the PVC gel, andf-rGO contents on the surface of
PVC gel were also observed through lenticular images. The band-gap
energy obtained from UV/Vis measurements decreased with increas-
ing f-rGO content due to the charge transfer processes. Good thermal
stability, increased stress-bearing capacity, and the highest strain
break at about 433% were achieved. This study could inspire the
novel designs of highly electroresponsive, soft, and, flexible actuator
based on PVC/f-rGO gel for the fabrication of advanced artificial mus-
cles and tunable soft actuators for number of applications.
AC KNOW LEDG EME NT S
The work was supported by China National Key Research and Devel-
opment Plan (2016YFB0302000) and Guangdong Provincial Science
and Technology Project (2016B090915001) China.
DATA AVAILABILITY STAT EMEN T
The experimental data cannot be shared at this time because the cur-
rent research work is part of ongoing study.
OR CID
Ahmed Ali https://orcid.org/0000-0002-2645-7258
Otavio Augusto Titton Dias https://orcid.org/0000-0002-2912-
4387
Zhang Liyan https://orcid.org/0000-0001-8485-1061
RE FE RE NCE S
1. Goponenko AV, Dzenis YA. Role of mechanical factors in applications
of stimuli-responsive polymer gels – status and prospects. Polymer
(Guildf). 2016;101:415-449. https://doi.org/10.1016/j.polymer.2016.
08.068.
ALI ET AL.
2. Bar-Cohen Y, Kim KJ, Choi HR, Madden JDW. Electroactive polymer
materials. Smart Mater Struct. 2007;16(2):1-3. https://doi.org/10.
1088/0964-1726/16/2/E01.
3. Ali I, Xudong L, Xiaoqing C, et al. A review of electro-stimulated gels and
their applications: present state and future perspectives. Mater Sci Eng C.
2019;103(May):109852. https://doi.org/10.1016/j.msec.2019.109852.
4. Braudo EE, Vasil'ev VG, Rogovina LZ. Definition of the concept of
polymer gel. Polym Sci Ser C. 2008;50(1):85-92. https://doi.org/10.
1134/S1811238208010050.
5. Terasawa N, Mukai K, Yamato K, Asaka K. Superior performance of
manganese oxide/multi-walled carbon nanotubes polymer actuator
over ruthenium oxide/multi-walled carbon nanotubes and single-
walled carbon nanotubes. Sens Actuators B. 2012;171-172:595-601.
https://doi.org/10.1016/j.snb.2012.05.039.
6. Shin E-J, Park W-H, Kim S-Y. Fabrication of a high-performance bend-
ing actuator made with a PVC gel. Appl Sci. 2018;8(8):1284. https://
doi.org/10.3390/app8081284.
7. Athir N, Shi L, Shah SAA, et al. Molecular dynamics simulation of
thermo-mechanical behaviour of elastomer cross-linked via
multifunctional zwitterions. Phys Chem Chem Phys. 2019;21(38):
21615-21625. https://doi.org/10.1039/c9cp03221e.
8. Vadukumpully S, Paul J, Mahanta N, Valiyaveettil S. Flexible conduc-
tive graphene/poly(vinyl chloride) composite thin films with high
mechanical strength and thermal stability. Carbon. 2011;49(1):198-
205. https://doi.org/10.1016/j.carbon.2010.09.004.
9. Wang H, Xie G, Fang M, Ying Z, Tong Y, Zeng Y. Electrical and
mechanical properties of antistatic PVC films containing multi-layer
graphene. Compos Part B Eng. 2015;79:444-450. https://doi.org/10.
1016/j.compositesb.2015.05.011.
10. Seol JH, Jo I, Moore AL, et al. Two-dimensional phonon transport in
supported graphene. Science. 2010;328(5975):213-216. https://doi.
org/10.1126/science.1184014.
11. Lee C, Wei X, Kysar JW, Hone J. Measurement of the elastic proper-
ties and intrinsic strength of monolayer graphene. Science. 2008;321
(5887):385-388. https://doi.org/10.1126/science.1157996.
12. Ali A, Hwang EY, Choo J, Lim DW. Nanoscale graphene oxide-
induced metallic nanoparticle clustering for surface-enhanced Raman
scattering-based IgG detection. Sens Actuators B. 2018;255:183-192.
https://doi.org/10.1016/j.snb.2017.07.140.
13. Cui Y, Kundalwal SI, Kumar S. Gas barrier performance of
graphene/polymer nanocomposites. Carbon. 2016;98:313-333.
https://doi.org/10.1016/j.carbon.2015.11.018.
14. Zaman I, Kuan HC, Meng Q, et al. A facile approach to chemically
modified graphene and its polymer nanocomposites. Adv Funct Mater.
2012;22(13):2735-2743. https://doi.org/10.1002/adfm.201103041.
15. Zhao X, Zhang Q, Chen D, Lu P. Enhanced mechanical properties of
graphene-based polyvinyl alcohol composites. Macromolecules. 2010;
43(5):2357-2363. https://doi.org/10.1021/ma902862u.
16. Lee KW, Chung JW, Kwak SY. Flexible poly(vinyl chloride)
nanocomposites reinforced with hyperbranched polyglycerol-
functionalized graphene oxide for enhanced gas barrier performance.
ACS Appl Mater Interfaces. 2017;9(38):33149-33158. https://doi.org/
10.1021/acsami.7b10257.
17. Wang X, Xing W, Song L, Yang H, Hu Y, Yeoh GH. Fabrication and
characterization of graphene-reinforced waterborne polyurethane
nanocomposite coatings by the sol-gel method. Surf Coat Technol.
2012;206(23):4778-4784. https://doi.org/10.1016/j.surfcoat.2012.
03.077.
18. Bae JW, Yeo M, Shin EJ, et al. Eco-friendly plasticized poly(vinyl chlo-
ride)-acetyl tributyl citrate gels for varifocal lens. RSC Adv. 2015;5
(115):94919-94925. https://doi.org/10.1039/c5ra15304b.
19. Ali M, Ueki T, Tsurumi D, Hirai T. Influence of plasticizer content on
the transition of electromechanical behavior of PVC gel actuator.
Langmuir. 2011;27(12):7902-7908. https://doi.org/10.1021/
la2009489.
9
20. Bae JW, Shin EJ, Jeong J, et al. High-performance PVC gel for adap-
tive micro-lenses with variable focal length. Sci Rep. 2017;7(1):1-8.
https://doi.org/10.1038/s41598-017-02324-9.
21. Asaka K, Hashimoto M. Electrical properties and electromechanical
modeling of plasticized PVC gel actuators. Sens Actuators B. 2018;
273(March):1246-1256. https://doi.org/10.1016/j.snb.2018.07.037.
22. Li Y, Li Y, Hashimoto M. Low-voltage planar PVC gel actuator with
high performances. Sens Actuators B. 2019;282(September 2018):
482-489. https://doi.org/10.1016/j.snb.2018.11.101.
23. Ariano P, Accardo D, Lombardi M, et al. Polymeric materials as artifi-
cial muscles: an overview. J Appl Biomater Funct Mater. 2015;13(1):1-
9. https://doi.org/10.5301/jabfm.5000184.
24. Marcano DC, Kosynkin DV, Berlin JM, et al. Improved synthesis of
graphene oxide. ACS Nano. 2010;4(8):4806-4814. https://doi.org/10.
1021/nn1006368.
25. Yang C, Liu Z, Chen C, et al. Reduced Graphene oxide-containing
smart hydrogels with excellent electro-response and mechanical
properties for soft actuators. ACS Appl Mater Interfaces. 2017;9(18):
15758-15767. https://doi.org/10.1021/acsami.7b01710.
26. Lei L, Xia Z, Zhang L, Zhang Y, Zhong L. Progress in organic coatings
preparation and properties of amino-functional reduced graphene
oxide / waterborne polyurethane hybrid emulsions. Prog Org Coatings.
2016;97:19-27. https://doi.org/10.1016/j.porgcoat.2016.03.011.
27. Xia H, Takasaki M, Hirai T. Actuation mechanism of plasticized PVC
by electric field. Sensors Actuators A Phys. 2010;157(2):307-312.
https://doi.org/10.1016/j.sna.2009.11.028.
28. Iqbal MZ, Katsiotis MS, Alhassan SM, Liberatore MW, Abdala AA.
Effect of solvent on the uncatalyzed synthesis of aminosilane-
functionalized graphene. RSC Adv. 2014;4(13):6830-6839. https://
doi.org/10.1039/c3ra46586a.
29. Thebo KH, Qian X, Zhang Q, Chen L, Cheng HM, Ren W. Highly sta-
ble graphene-oxide-based membranes with superior permeability.
Nat Commun. 2018;9(1):1-8. https://doi.org/10.1038/s41467-018-
03919-0.
30. Qureshi TS, Panesar DK. Impact of graphene oxide and highly
reduced graphene oxide on cement based composites. Construct Build
Mater. 2019;206:71-83. https://doi.org/10.1016/j.conbuildmat.2019.
01.176.
31. Bagheri M, Jafari SM, Eikani MH. Ultrasonic-assisted production of
zero-valent iron-decorated graphene oxide/activated carbon
nanocomposites: chemical transformation and structural evolution.
Mater Sci Eng C. 2021;118(August 2020):111362. https://doi.org/10.
1016/j.msec.2020.111362.
32. Akhina H, Gopinathan Nair MR, Kalarikkal N, et al. Plasticized PVC
graphene nanocomposites: morphology, mechanical, and dynamic
mechanical properties. Polym Eng Sci. 2018;58:E104-E113. https://
doi.org/10.1002/pen.24711.
33. Sun S, Wu P. A one-step strategy for thermal- and pH-responsive
graphene oxide interpenetrating polymer hydrogel networks. J Mater
Chem. 2011;21(12):4095-4097. https://doi.org/10.1039/
c1jm10276a.
34. Ali M, Hirai T. Effect of plasticizer on the electric-field-induced adhe-
sion of dielectric PVC gels. J Mater Sci. 2012;47(8):3777-3783.
https://doi.org/10.1007/s10853-011-6229-6.
35. Ali I, Weimin Y, Xudong L, et al. Highly electro-responsive plasticized
PVC/FMWCNTs soft composites: a novel flex actuator with func-
tional characteristics. Eur Polym J. 2020;109556:109556. https://doi.
org/10.1016/J.EURPOLYMJ.2020.109556.
36. Akhtar N, Shao H, Ai F, et al. Gelatin-polyethylenimine composite as a
functional binder for highly stable lithium-sulfur batteries. Electrochim
Acta. 2018;282:758-766. https://doi.org/10.1016/j.electacta.2018.
06.101.
37. Pourhashem S, Rashidi A, Vaezi MR, Bagherzadeh MR. Excellent cor-
rosion protection performance of epoxy composite coatings filled
10
with amino-silane functionalized graphene oxide. Surf Coat Technol.
2017;317:1-9. https://doi.org/10.1016/j.surfcoat.2017.03.050.
38. Ali A, Hwang EY, Choo J, Lim DW. PEGylated nanographene-
mediated metallic nanoparticle clusters for surface enhanced Raman
scattering-based biosensing. Analyst. 2018;143(11):2604-2615.
https://doi.org/10.1039/c8an00329g.
39. Seeponkai N, Wootthikanokkhan J, Thanachayanont C. Synthesis and
characterization of fullerene functionalized poly(vinyl chloride) (PVC)
and dehydrochlorinated PVC using atom transfer radical addition and
AIBN based fullerenation. J Appl Polym Sci. 2013;130(4):2410-2421.
https://doi.org/10.1002/app.39443.
40. Coltro L, Pitta JB, Madaleno E. Performance evaluation of new plasti-
cizers for stretch PVC films. Polym Test. 2013;32(2):272-278. https://
doi.org/10.1016/j.polymertesting.2012.11.009.
41. Yadav M, Ahmad S, Chiu FC. Graphene oxide dispersed polyvinyl
chloride/alkyd green nanocomposite film: processing and physico-
mechanical properties. J Ind Eng Chem. 2018;68:246-256. https://doi.
org/10.1016/j.jiec.2018.07.051.
42. Yasin G, Arif M, Shakeel M, et al. Exploring the nickel–graphene
nanocomposite coatings for superior corrosion resistance: manipu-
lating the effect of deposition current density on its morphology,
mechanical properties, and erosion-corrosion performance. Adv
Eng Mater. 2018;20(7):1-12. https://doi.org/10.1002/adem.
201701166.
43. Xiao Y, Chen Z, Xin B, Lin L. Preparation and characterization of
graphene enriched poly(vinyl chloride) composites and fibers. J Text
Inst. 2018;109(8):1008-1015. https://doi.org/10.1080/00405000.
2017.1398059.
44. Hodge RM, Edward GH, Simon GP. Water absorption and states of
water in semicrystalline poly(vinyl alcohol) films. Polymer (Guildf).
1996;37(8):1371-1376. https://doi.org/10.1016/0032-3861(96)
81134-7.
45. Yu C, Tang X, Liu S, Yang Y, Shen X, Gao C. Laponite crosslinked
starch/polyvinyl alcohol hydrogels by freezing/thawing process and
studying their cadmium ion absorption. Int J Biol Macromol. 2018;117:
1-6. https://doi.org/10.1016/j.ijbiomac.2018.05.159.
46. Gaabour LH, Hamam KA. The change of structural, optical and ther-
mal properties of a PVDF/PVC blend containing ZnO nanoparticles.
ALI ET AL.
Silicon. 2018;10(4):1403-1409. https://doi.org/10.1007/s12633-
017-9617-y.
47. Giuffrida S, Condorelli GG, Costanzo LL, Ventimiglia G, Di Mauro A,
Fragalà IL. In situ synthesis of photoluminescent films of PVC, doped
with Ce3+ ion. J Photochem Photobiol A Chem. 2008;195(2):215-222.
https://doi.org/10.1016/j.jphotochem.2007.10.005.
48. Koli VB, Dhodamani AG, Delekar SD, Pawar SH. In situ sol-gel syn-
thesis of anatase TiO2-MWCNTs nanocomposites and their photo-
catalytic applications. J Photochem Photobiol A Chem. 2017;333:40-
48. https://doi.org/10.1016/j.jphotochem.2016.10.008.
49. Prabhakaran T, Mangalaraja RV, Denardin JC, et al. Studies on the
functional properties of free-standing polyvinyl
alcohol/(CoFe2O4/CoFe2) composite films. Mater Sci Eng B. 2017;
226:211-222. https://doi.org/10.1016/j.mseb.2017.09.024.
50. Phin H-Y, Ong Y-T, Sin J-C. Effect of carbon nanotubes loading on
the photocatalytic activity of zinc oxide/carbon nanotubes
photocatalyst synthesized via a modified sol-gel method. J Environ
Chem Eng. 2019;8:103222. https://doi.org/10.1016/j.jece.2019.
103222.
51. Hasan M, Banerjee AN, Lee M. Enhanced thermo-optical perfor-
mance and high BET surface area of graphene@PVC nanocomposite
fibers prepared by simple facile deposition technique: N2 adsorption
study. J Ind Eng Chem. 2015;21:828-834. https://doi.org/10.1016/j.
jiec.2014.04.019.
SUPPORTING INF ORMATION
Additional supporting information may be found online in the
Supporting Information section at the end of this article.
How to cite this article: Ali I, Ali A, Ali A, et al. Highly electro-
responsive composite gel based on functionally tuned
graphene filled polyvinyl chloride. Polym Adv Technol. 2021;
1–10. https://doi.org/10.1002/pat.5376