Received: 25 November 2020 Revised: 24 February 2021 Accepted: 27 February 2021

DOI: 10.1002/app.50710

ARTICLE

Ionic liquids enhanced performance of PVC gels actuator

Imdad Ali1,2 | Abdul Laitf2 | Khalid Hussain2 | Farooq Khurum Shehzad3 |

Ahmed Ali4 | Rehman Faisal4 | Li Xudong1 | Otavio Augusto Titton Dias5 |
Yang Weimin1 | Li Haoyi1

1
College of Mechanical and Electrical
Engineering, Beijing University of Abstract
Chemical Technology, Beijing, China Stimulated devices are highly demanded for actuators and artificial muscles in
2
Department of Mechanical Engineering, the recent era but susceptible to low deformation at an applied voltage. In the
QUEST Nawabshah, Nawabshah,
present work, ionic liquids (ILs) based gel films were prepared from the polyvi-
Pakistan
3
Department of Chemistry, Muhammad
nyl chloride (PVC), dibutyl adipate (DBA), 1-butyl, 3-methimidazolium chlo-
Nawaz Sharif University of Engineering ride, and 1-pentyl-3-methylimidazolium hexafluorophosphate by a simple
and Technology, MNSUET, Multan, solvent evaporation method. The structural, morphological, optical, and
Pakistan
4
mechanical properties of the composite PVC/ILs gel were characterized by
Department of Electrical Engineering,
Sukkur IBA University, Sukkur, Pakistan Fourier-transform infrared spectroscopy (FTIR), Large Angle X-ray scattering
5
Centre for Biocomposites and (LAXS), UV–visible (UV–vis) absorption spectroscopy, scanning electron
Biomaterials Processing, John H. Daniels micrpscopy (SEM) and elemental mapping. We found that the displacement of
Faculty of Architecture, Landscape, and
Design, University of Toronto, Toronto,
plasticized PVC gels-based actuator was 0.1 mm with the response time of
Ontario, M5S 3B3, Canada 0.33 s at an induced voltage of 1000 V. The loading of 0.02% of IL (fluorides)
with PVC gel showed maximum deformation of 0.16 mm with a relatively
Correspondence
Li Haoyi, College of Mechanical and
rapid response time of 0.2 s. These high deformation and response time values
Electrical Engineering, Beijing University of IL fluoride-based gels are dramatically higher than reported PVC gels. Like-
of Chemical Technology, Beijing 100029, wise, the loading of IL fluorides in the PVC gel showed a high elongation value
China.
Email: lhy@mail.buct.edu.cn at the break of about 377%. This work suggests that the flexible gel based on IL
fluorides and PVC could be a potential candidate for the fabrication of high-
Funding information
performance artificial muscles and tunable soft actuators.
Guangdong Provincial Science and
Technology Project, Grant/Award
KEYWORDS
Number: 2016B090915001
flexible actuator, mechanical, optical Properties, physicochemical interaction, PVC/IL gel

1 | INTRODUCTION under applied voltage.4 Among many EAPs, PVC is

widely used due to its low cost, high chemical stability,
Recently, soft stimulated materials that can convert good biocompatibility, and excellent stabilizability;
electrical energy into mechanical work have been moreover, PVC has relatively higher compatibility with
shown to be promising for various applications such as different plasticizers.5–7 Likewise, PVC has ability to
robotics, actuators, artificial muscles, and medical form soft or hard structures based on different plasti-
devices.1–3 These devices based on smart polymer gels cizers as compared to other conventional polymers.8,9
have a high actuation degree under the applied voltage. Hashmito et al10,11 prepared a PVC gel using PVC pow-
These soft stimulated materials are usually based on der and DBA as a plasticizer, the prepared gel was sand-
electroactive polymer (EAP) gels, assembled with elec- wiched between two parallel electrodes, and hence the
trodes that function as actuators and can move quickly resulting device functioned as a multi-layer actuator.

J Appl Polym Sci. 2021;e50710. wileyonlinelibrary.com/journal/app © 2021 Wiley Periodicals LLC. 1 of 7

https://doi.org/10.1002/app.50710
2 of 7 ALI ET AL.

Cheng et al prepared a PVC gel using eco-friendly plasti- 2 | MATERIALS AND METHODS
cizer dioctyl terephthalate (DOTP) and PVC powder by
a simple solvent casting method. The authors studied in 2.1 | Materials
detail prepared gel creep deformation and plasticizer
migration towards anode reaction under the applied Polyvinyl chloride (degree of polymerization is 2500) was
voltage.12 Later, the same authors extended their work obtained from the Xinjiang Zhongtai Chemical Co., Ltd.,
and fabricated a tunable-focus negative microlens based Xinjiang, China and Di Butyl adipate (DBA) plasticizer,
on PVC gel and suggested that the prepared device was purchased from Yingkou Tianyuan Chemical
could be used in cell phones.13 Although, PVC has the Research Institute Co. Ltd., Liaoning, China. Organic sol-
limitations of high electrical resistivity, low thermal sta- vent Tetrahydrofuran (THF) was obtained from Beijing
bility, and low brittleness for practical application. Century Tuoxin Fine Chemical Co. Ltd., Beijing, China
Recently reported research studies have suggested that and 1-butyl, 3-methimidazolium chloride and 1-pentyl-3-
the thermal stability, electrical conductivity, and methylimidazolium hexafluorophosphate ionic liquids
mechanical strength of PVC can be easily enhanced by were acquired from Aichun Biological technology
the addition of an appropriate nanofiller.14 Co. Shanghai, China.
Recently, ionic liquids have been widely used as a
green solvent.15 Their intrinsic non-molecular character-
istics have resulted in unique physicochemical character- 2.2 | Preparation of PVC/IL gels
istics, such as high thermal stability, very low volatility,
flammability, negligible vapor pressure, high electric con- The gel samples were prepared with 1:4 w/w% of the
ductivity, simple reusability, and comprehensive electro- PVC: DBA and ionic liquids were loaded in two concen-
chemical window.16,17 Sirisopanaporn and coworkers18 trations at 0.01, and 0.02% of the total mass. First PVC
have prepared transparent, freestanding, and flexible was dissolved in solvents THF by sonication for 20 min
polymer gel-based electrolyte membranes by loading N- and then the required quantity of DBA and IL were
N-bis(trifluoromethane) sulfonamide ionic liquid solu- mixed by vigorous stirring at 30 C for 12 h by a simple
tions in poly(vinylidene fluoride)-hexafluoropropylene solvent evaporation technique. After attaining a homoge-
copolymer (PVdF-co-HFP) media. The prepared gel- nous dispersion, a certain volume of the mixture was
based electrolyte membranes showed high ionic conduc- poured into a petri dish and kept under an evaporator for
tivity ranges from 0.34 to 0.94 m S cm−1 at room temper- 5 days at room temperature. Finally, after evaporation of
ature. Incidentally, these polymer electrolytes the THF, a soft, transparent PVC/IL gel was obtained,
membranes operated normally even at a relatively higher the thickness of the prepared gel was approx. 0.5 mm.
temperature of 110 C, no structural decompositions, and The proposed surface structures in continuous PVC of
IL leakages were observed over an extended period of plasticized PVC and PVC/IL gels are represented in
four months, resulting in excellent stability and shelf Scheme 1. The sample without the IL named as pure
life.18,19 Rahman and his coworkers15 have introduced PVC gel used as a control sample and other samples were
ammonium and phosphonium ionic liquids instead of labelled as PVC/Cl-1, PVC/Cl-2, PVC/F-3, and PVC/F-4
traditional plasticizer (phthalate acid ester) with plasti- based on the IL contents as given in Table S1.
cized PVC, and a lower glass transition temperature of up
to 20% (wt%) of plasticization was observed.15 In another
study, electrochemical properties of PVC gel with IL 2.3 | General characterizations
based on electromechanical model were investigated.20
However, further studies are required to evaluate the In order to develop understanding of the physicochemi-
physicochemical interactions of PVC and IL, which have cal interactions among PVC, DBA, and ionic liquids, the
yet to be established. Furthermore, the parameters, such Fourier-transform infrared spectroscopy (FTIR) spectra
as, large deformation, response time, electrical and were performed, the PVC/IL gel samples were first dried
mechanical need to be enhanced in PVC gel, and only a under vacuum. The FTIR spectra was observed on a FTIR
suitable nanofiller can bring dramatic changes in the spectrometer (Thermo American type Nicolet 6700),
properties of PVC gel. In the current study, a gel film has under the transmission mode. The scan range was from
been prepared, based on PVC, DBA, and IL, the ionic liq- 4000 to 500 cm−1. Surface characteristics and morphol-
uid used as an additive. In addition, the various structural ogies of PVC/IL based gels were recorded by capturing
and morphological characteristics of pure PVC and fluo- scanning electron microscopy (SEM) images using
ride and chloride-based were characterized by FTIR, Hitachi-4700 operated at an accelerating voltage of 0.5 to
LAXS, UV–Vis, SEM, and EDS techniques. 30 kV, samples were freeze-dried on silicon wafers before
ALI ET AL. 3 of 7

S C H E M E 1 Proposed surface
structure of gels (a) plasticized PVC gel,
(b) PVC/IL (Cl) gel, and (c) PVC/IL
(F) gel [Color figure can be viewed at
wileyonlinelibrary.com]

F I G U R E 1 (a) FTIR spectra of

plasticized PVC and PVC/IL gels
(b) LAXS patterns of plasticized PVC
and PVC/IL gels [Color figure can be
viewed at wileyonlinelibrary.com]

carrying out SEM characterization, while elemental com- PVC/Cl-2, PVC/F-1, and PVC/F-2 are shown in the
position and distribution maps were evaluated by energy Figure 1(a). The main absorptions band of pure PVC gel
dispersive spectroscopy (EDS) Structural variations in at 826, 1738, and 2868–2963 cm−1 are allocated to Cl
PVC/IL gels were analyzed by Large Angle X-ray scatter- stretching band, the C O group in the carboxyl and CH
ing (LAXS) analysis technique, using X-ray Diffractome- stretching band respectively. However, similar peaks

ter (D/Mac 2500 VB2+/PC Rigaku) in the range 10–60 . were also observed in PVC/IL gels. Interestingly, the new
UV–visible (UV–Vis) absorption spectroscopy (Shimadzu peak in PVC/IL gels was observed at 1574 cm−1 that
UV-3600, Japan) was used to study the optical properties attributed to C Cl or C F.21
of the PVC/IL gels. All UV–Vis absorption measurements The LAXS patterns of pure PVC gel and PVC/IL gels
were performed in the wavelength range of 350 to are shown in Figure 1(b) The broad halo peak was
600 nm having a fixed slit width of 1 nm in a single observed for pure PVC gel and PVC/IL gels, this halo
10 scan mode with a medium scan speed at room peak representing an amorphous behavior of the flexible
temperature. gel materials. In the LAXS patterns, a high intensity dif-

fraction peak appeared at 2θ =22 for pure plasticized
PVC. Furthermore, the peaks of PVC/Cl-1, PVC/Cl-2,
 
3 | R ESULTS A ND DISCUSSIONS PVC/F-3, and PVC/F-4 were observed at 21.17 , 20.9 ,
 
and 20 and 20.4 respectively. It can also be seen that the
3.1 | Structural studies of plasticized intensity of all the peaks was decreased, and it was
PVC and PVC/IL gels reduced with increasing the IL concentrations in the
PVC gel. This decrease in intensity of gels can be attrib-
FTIR spectra of pure PVC gel and plasticized PVC with uted to the change in the physically cross-linking density
different concentrations of IL named as PVC/Cl-1, of PVC/DBA with the loading of IL contents.19 Likewise,
4 of 7 ALI ET AL.

it is also possible that the decreased intensity of the LAXS the transmittance properties of the PVC gel become
pattern resulted due to the highly amorphous nature of higher than that of pure PVC films. Moreover, the two
the flexible gels. Furthermore, in LAXS data no promi- gel samples (PVC/Cl-2 and PVC/F-4) were compared by
nent peak was noticed for IL vibrations in PVC/IL gels, loading the same concentrations of plasticizer with differ-
which proved that the well dispersion of IL in PVC gel. ent ILs. The transparency values of PVC/Cl-2 and
Figure. 2(a and b) shows the physicochemical interac- PVC/F-4 were observed that of 86% and 93.3% at 573 nm.
tion mechanism of PVC, DBA and IL. The N+…−Cl inter- The PVC/F-4 has the highest transmittance and this
action between the IL and the PVC polymer chain result has been attributed to the conversion of the PVC
promotes dipole–dipole interactions through the coulom- matrix crystalline nature into amorphous nature during
bic interaction.22 Furthermore, the dipole–dipole interac- gel formation.24
tion, between the carbonyl groups (C O) of DBA and the The SEM images of pure PVC gel and PVC/IL gel are
C Cl groups of PVC23 and the DBA and PF6 increases shown in Figure 4(a) and Figure 4(b),(c), which revealed
the spacing between chains of PVC resulting in better
physicochemical interactions among PVC, DBA and fluo-
rides based IL.

3.2 | Optical and morphological analysis

of plasticized PVC and PVC/IL gels

The transmittance spectra of pure PVC and PVC/IL are

shown in Figure 3. The transmittance of pure PVC gel
exhibited a peak at 573 nm with T ≈ 80% as shown in
Figure 3. The PVC/F-2 has the highest transparency of
about 93.3%. However, it was observed that the loading of
ILs with PVC gel greatly enhanced the transmittance
characteristics. Typically, the PVC chain space was
increased by the addition of the plasticizer and therefore
the free volume of the PVC gel was increased. This effect
has improved the physical bonding and entanglement of F I G U R E 3 UV–Vis spectroscopy of pure PVC and
the PVC matrix with plasticizer and changed the crystal- PVC/ILs gels [Color figure can be viewed at
line nature of PVC into amorphous nature. Consequently, wileyonlinelibrary.com]

F I G U R E 2 Illustration of the physicochemical interaction mechanism of PVC/ILs gels (a) PVC, DBA and 1-butyl, 3-methimidazolium
chloride and (b) PVC, DBA and 1-pentyl-3-methylimidazolium hexafluorophosphate
ALI ET AL. 5 of 7

F I G U R E 4 SEM and EDS images of gel samples: (a) Plasticized PVC (b) PVC/Cl-2, (c) PVC/F-4, (d) mapping of PVC/Cl-2 and
(e) mapping of PVC/F-4 [Color figure can be viewed at wileyonlinelibrary.com]

that the micrographs of the PVC loaded with different

contents of ILs have uniform surface morphology. Over-
all, it was observed from SEM images that uniform sur-
face morphology of plasticized PVC with good dispersion
of IL. The EDS mapping of the PVC/Cl-2 and PVC/F-2
showed that the good dispersion of IL in plasticized PVC,
as shown in (Figure 4(d),(e)). The size distribution of
PVC/Cl-2 and (c) PVC/F-4 are given in Figure. S2. Fur-
thermore, the possible interactions of plasticized PVC
and PVC/ILs gel are represented in Scheme S1.

3.3 | Mechanical properties of

plasticized PVC and PVC/IL gels
F I G U R E 5 Stress–strain curves of pure PVC gel and
PVC/IL gels [Color figure can be viewed at wileyonlinelibrary.com]
The mechanical studies were carried out to characterize
the stress and strain properties of the PVC/IL gels. The
stress and strain characteristics of gel samples were that these gels are highly flexible and suitable for the
shown in Figure 5. The elongation at break of pure PVC actuator applications.25
gel and the PVC/Cl-1, PVC/Cl-2, PVC/F-3, and PVC/F-4
were observed at 178, 204%, 210%, 331%, and 373%,
respectively. The PVC/Cl-1, PVC/Cl-2, and PVC/F-3 and 3.4 | Displacement and response time of
PVC/F-4 have high stress and higher strain as compared plasticized PVC gel and PVC/IL gel-based
to the pure plasticized PVC gel. PVC/F-4 contains 0.02% actuator
fluorine that has the highest strain about 373%. The given
results showed that with the addition of ionic liquid con- The displacement and response time of pure PVC gel and
tents, the stress and strain were enhanced and directed the samples, which contain different contents of ILs were
6 of 7 ALI ET AL.

F I G U R E 6 (a) Displacement results of pure PVC gel and PVC/IL gels (b) Response time of pure PVC gel and PVC/IL gels [Color figure
can be viewed at wileyonlinelibrary.com]

F I G U R E 7 Deformation mechanism of actuator (a) PVC gel without applied voltage, (b) PVC gel with applied voltage, (c) PVC/[Cl−],
and (d) PVC/IL[F−] gels [Color figure can be viewed at wileyonlinelibrary.com]

tested by a self-fabricated setup. This self-designed experi- the high deformation and fast response signified that
mental setup is depicted in Figure. S1. The deformation there were strong interactions among PVC, DBA, and
of gels was observed by the laser displacement meter. Ini- IL. Such a high displacement of PVC/F-4 is required for
tially, the pure PVC was tested by applying 1000 V, high-performance actuators and artificial muscles.
resulting in a displacement of 0.1 mm with a response The electrophoretic mobility of ILs is made possible
time of 0.33 s, as shown in Figure 6(a,b). In Figure 6(a), it by chloride and fluoride functional groups. Here, due to
has been depicted that the displacement of PVC/Cl-1, the movements of ILs inside the PVC polymer matrix,
PVC/Cl-2, PVC/F-3, and PVC/F-4 were recorded as 0.11, this mobility allows for contraction deformation of the
0.12, 0.13, 0.16 mm at an applied voltage of 1000 V. At gel. This effect of PVC and ILs are clearly depicted in
the same applied voltage, the PVC/IL-4 was deformed to Figure 7. The polarized ILs and DBA were located in the
a maximum of 0.16 mm and reacted quickly in 0.2 s. This direction of applied electric force. After applying the volt-
high deformation and response time of PVC/F-4 is due to age to the PVC gel, electrostatic forces act on the internal
phosphorous fluoride [PF6]. This deformation occurred structure of the PVC chain therefore the movement and
due to the Maxwell stress effect and is attributed to the orientation of ILs and DBA.20,28
fact that the plasticizer DBA molecules were charged
under applied voltage and polarized DBA easily facili-
tated the free dipole reorientation of the PVC chains from 4 | CONCLUSIONS
PVC gel network.26,27 Whenever the voltage was applied, AND FUTURE WORK
the negative charges of cathode passed from gels moved
and toward the anode and caused contraction deforma- Herein, the pure PVC gel and PVC/ILs based gels were suc-
tion this mechanism is shown in Scheme S1. However, cessfully developed by a simple solvent casting method and
ALI ET AL. 7 of 7

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