Accepted Manuscript

Development of conductive poly(vinylidene fluoride) (PVDF) nanocomposite

membrane reinforced with ionic liquid (IL) & carbon nanofiber (CNF)

Brijesh Prasad, Fateh Singh Gill, Varij Panwar, Gopinathan Anoop

PII: S1359-8368(19)31800-1
DOI: https://doi.org/10.1016/j.compositesb.2019.106990
Article Number: 106990
Reference: JCOMB 106990

To appear in: Composites Part B

Received Date: 25 April 2019

Revised Date: 27 May 2019
Accepted Date: 27 May 2019

Please cite this article as: Prasad B, Gill FS, Panwar V, Anoop G, Development of conductive
poly(vinylidene fluoride) (PVDF) nanocomposite membrane reinforced with ionic liquid (IL) & carbon
nanofiber (CNF), Composites Part B (2019), doi: https://doi.org/10.1016/j.compositesb.2019.106990.

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 ACCEPTED MANUSCRIPT

1 Development of conductive Poly(Vinylidene Fluoride) (PVDF) nanocomposite

2 membrane reinforced with Ionic Liquid (IL) & Carbon nanofiber (CNF)

3 Brijesh Prasad1, Fateh Singh Gill1, Varij Panwar1*, Gopinathan Anoop2

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4 Graphic Era deemed to be University, Bell Road, Clement Town, Dehradun-248002, India.
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5 School of Materials Science and Engineering, Gwangju Institute of Science and

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6 Technology Oryong-Dong, Buk-Gu, Gwangju 61005, South Korea.
7 *Corresponding author: varijpanwarcertain@gmail.com

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9 Abstract

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10 High sensitivity and good mechanical strength are required for conductive polymer nano-
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11 composites (CPNC) based flexible strain sensors. Here we have developed CPNC

12 membranes using PVDF as a base polymer along with carbon nanofiber (CNF) and ionic
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13 liquid (IL) as conducting fillers exhibiting good thermal stability, high sensing voltage, and

14 mechanical performance for strain sensors. The IL infiltration in PVDF and CNFs
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15 composition resulted in micro-porous morphology that exhibited stretchability (maximum

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16 elongation = 5.8 mm) and a high gauge factor (4.08) (property of a good strain sensor).

17 Further, infiltration of IL in PVDF/CNF membrane brings microstructural changes (α to β

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18 phase) of PVDF and provides an electrolyte mixture of CNF and IL for the facile flow of
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19 ions through it. The CNFs in CPNC having IL helped in maintaining the crack initiation
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20 during strain. Hence, the deformed CNFs across the pores or within the PVDF act as an

21 interlinking agent and provides an electrical conduction pathway in the shrink lattice of the

22 composite.

23 .

24 Keywords: Flexible composite, Conducting polymers, Nanocomposite, Sensitivity.

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25 1. Introduction

26 The sensing properties of conductive CPNC are widely used in health care monitoring,

27 flexible wearable electronic devices and soft robot applications [1]. Generally, the CPNCs

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28 are developed using metal particles and the nano conducting derivatives of carbons such as

29 carbon nanotubes (CNTs), carbon black (CB) and CNFs in a polymer matrix [2]. Electronic

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30 devices with flexible and low power consumption have been created by cost-effective

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31 fabrication techniques of CPNC [3]. CPNC are widely studied due to the advantage of high

32 mechanical strength of polymers to conjugate with electrical charge carriers to detect the

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33 stimuli [4]. The CPNC shows high deformation, fast response to stimuli, low density,
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34 tunable morphology, low cost, thin, high mechanical flexibility, resilience and ease of

35 fabrication, environmental stability, chemical stability, high electrical conductivity and high
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36 compatibility with the organic and inorganic solvents for chemical modification [5, 6].

37 Different carbon-based nanofillers such as CNTs (single/multiwall), CNFs, Graphene, CB,

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38 and its derivatives [7, 8] have been used with the elastomeric polymer matrix like PEDOT,
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39 styrene-ethylene-butadiene-styrene (SEBS), PVDF, polydimethylsiloxane (PDMS),

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40 polypropylene (PP), ethylene-propylene-diene rubber (EPDM) [9 - 11] for the development

41 of CPNC in the form of pallets, sheets, membranes, and thin films depending on the
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42 applications [12]. CPNC show more flexibility than the semiconductors and their
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43 sensitivity is higher to the commercial metallic foils [13]. The thin films of the CPNCs are

44 appreciated for the sensor applications because of the high sensitivity obtained with

45 variable strain [14]. Among the sensors carbon-based conducting piezoresistive polymer,

46 sensors have also been studied by several workers [15-17].

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47 Luanda et al. [18] studied the chemical nature of IL playing a key role in improving the

48 morphology and crystalline behavior by providing stronger molecular bonds in the blend.

49 IL trapped in the voids contributed to stretching of PVDF chain and attracted the negatively

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50 charged atoms leading to enhancing the mechanical performance. Salazer et al. [19] studied

51 the distribution of MWCNTs in ionic liquids. The polarization of MWCNT is due to weak

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52 van der Walls force by the cations of IL resulted in increased conductivity. Further,

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53 Ezquerra et al. [20] studied the increase in dc conductivity with improved dielectric

54 behavior by producing a change in phase (α→β) using the CNF acting as the nucleating

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55 agent for crystallization. Zheng et al. [21] developed flexible Nanogenerator using the
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56 CNF/PDMS film sandwiched between the PDMS layers which exhibited high piezoelectric

57 signals. The power generated by the nanogenerator turned on the LED and charged 3.7 V
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58 capacitor. Xu et al. [22] investigated the effect of PVDF with poly(ethylene glycol) and IL

59 to study the dielectric behavior using complex permittivity and electric modulus by thermal
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60 treatment transforming the nonpolar phase (α) to polar phase (β and γ). The increased
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61 temperature resulted in higher charge movement resulting in increased conductivity. Zhang

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62 et al. [ 23] purposed the island bridge structure of CNF with HDPE and PVDF. The HDPE-

63 CNF-PVDF island bridge network showed a positive temperature coefficient with the
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64 increase in resistivity. The expansion and contraction of the membrane greatly improved
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65 the reproducibility of the polymer membrane. Kim et al. [24] developed CNF-HEP

66 composite as fabric heating element. The surface resistivity was observed from 1.01 × 103

67 to 1.65 × 103 Ω sq-1 and confirmed excellent electrical characteristics. The mechanical

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68 properties of the CNF-HEP coated samples showed higher values than the uncoated

69 samples.

70 The Piezoresistive sensors work on the principle of resistance change with deformation or

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71 strain. Low sensitivity of piezoresistive sensors have been observed because of its high

72 modulus of the elastomeric layer and restricted compressive stress [15]. The sensitivity of

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73 the CPNC is enhanced by uniform infiltration of the carbon-based conductive in the

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74 polymer matrix [16]. Researchers have been successful in achieving high sensitivity but

75 lacked in maintaining the mechanical strength for repeatability [17]. The sensitivity and

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76 gauge factor (G) are the two parameters which are used for analyzing piezoresistive
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77 behavior of the CPNC. The sensitivity of the composite is calculated using the formula

78 (Sensitivity =∆R/Ri). Where ∆R represents the change in resistance obtained on bending the
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79 CPNC film and Ri the initial resistance without bending. The G is defined as the ratio of the

sensitivity to strain (ε) [16] and is calculated using equation (1).

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80
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81 (1)

82 CPNC show high mechanical deformation range under cyclic and static loading conditions
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83 while maintaining the piezoresistive properties [25]. The CPNCs show relative low yield

84 strength and short elastic region in comparison to thermoplastics. Mechanical measurement

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85 for strain sensing is an important component, as the strain sensing range is limited by the
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86 yield strength. Uphold back forth deformation of the polymer composite ensures the stable

87 sensing ability for the real application of the strain sensor. Dielectric properties and AC

88 conductivities are important factors of the CPNC when it comes to the exploration in the

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89 application of EMI and for sensing applications. In the case of polymers, it is necessary for

90 sensor applications that dielectric constant should be high with the minimum loss [26].

91 Therefore, the development of new flexible CPNC membrane is required for high

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92 sensitivity and enhanced mechanical property. To the best of our knowledge very less work

93 has been conducted on tailoring the piezoresistivity by maintaining mechanical strength for

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94 the piezoresistive sensor. The strengthened CPNC matrix is supposed to facilitate the

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95 transfer of stress from the polymer to the conductive carbon nanofiller network, resulting in

96 an increase in toughness and sensitivity.

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97 In the present manuscript, a highly sensitive and flexible CPNC piezoresistive sensor of
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98 PVDF (matrix) and CNF (conducting filler) developed using solvent casting technique has

99 been reported, which exhibit enhanced electrical and mechanical properties. The PVDF has
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100 been used for various applications of automobile, infrastructures, aerospace, and human

101 health because of its remarkable properties as high strain rate, good workability, chemical
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102 resistant, resistant to ultraviolet radiation [27, 28]. The CNTs are short in size as compared
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103 to 20–200µm long threads of CNFs, therefore, shows less connectivity of conducting
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104 channels in a polymer matrix. Moreover, the CNFs offer high fractal groups in a polymer

105 matrix therefore; the possibility of conduction through the tunnel effect in close fibers is
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106 very high. This ensures enhanced electrical property by mechanical mixing [ 14, 29, 30].
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107 1-Butyl-3-methylimidazolium hydrogen sulfate [BMIM][HSO4] is used as ionic liquid (IL)

108 for interface linking, enhancing the conducting network and mechanical strength of the

109 CPNC strain sensor [30, 31]. In this work, the membranes formed using PVDF, CNF, and

110 IL at different concentration of CNF and IL were studied. The Field emission scanning

111 electron microscopy (FESEM), The X-Ray Diffraction (XRD), Fourier-transform infrared

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112 spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermo Gravimetric

113 Analysis (TGA), tensile test and AC analysis of the fabricated CPNC were conducted to

114 explore the surface morphology, the presence of functional groups, thermal stability,

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115 mechanical strength, and electrical property respectively.

116 In this work, we have been able to develop a flexible conductive membrane with higher

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117 electrical conductivity with minimum dielectric loss using the IL and CNF. Further, it

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118 exhibited enhanced mechanical strength (toughness) which is very difficult to achieve with

119 the carbon-based fillers due to nonuniform dispersion and hence the uneven distribution of

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120 stress. IL helped in dispersion and increased the conductivity but with that also improved
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121 the thermal stability of the nanocomposite membrane.

122 These advances in the production of cheap piezoresistive conductive polymer composite
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123 surely extend the reach of possible applications as sensors in flexible wearable devices,

124 actuators in the form of strain and pressure sensors for the biomedical devices, in
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125 automotive industry and robotics. Further, the conductive nanocomposite membrane can be
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126 used as the conductive substrate which can withstand high voltage up to 32V. The
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127 developed CPNC nanocomposite membrane can also be used as electrode material for

128 capturing the analytes for various biomedical sensor applications.

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129 Materials and method of development of CPNC membranes:

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130 The ingredients of CPNC were purchased from Sigma Aldrich i.e. PVDF (trade name

131 182702), CNF (719781) and [BMIM][HSO4] as ionic liquid (IL). To disperse the CNFs in

132 PVDF, the N N-Dimethylformamide (DMF) was used as solvent supplied by Sigma

133 Aldrich (trade name 57457).

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134 The CPNC membranes were developed using a solvent casting technique. The PVDF,

135 CNF, and IL were mixed and DMF was added to produce a total solution of 10 wt%. The

136 final blend was prepared by mixing the concentration of 10% solute in 90% solvent to form

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137 a 100% solution. The blended solution was heated at ~50 oC on a magnetic stirrer and

138 simultaneously mixed together using a magnetic bead (at 400 rpm) for 5 hours. The mixed

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139 solution was then poured onto a glass petri dish (90 mm diameter) and again heated at 80

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140 C in a vacuum oven for ~12 hours to evaporate the solvent from the membrane. After

141 evaporation of the solvent, the glass petri dish was cooled at room temperature and finally,

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142 the CPNC membrane was peeled off from the glass petri dish. Having optimized the
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143 electrical and mechanical property several varied compositions of PVDF, CNF and IL were

144 developed (refer table 1).

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145 1.1. Characterization and Measurement of CNPC membrane

146 The microstructures of the fractured thin composite films were characterized using FESEM
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147 (MIRA3b TESCAN, USA). The diffraction patterns were collected by XRD Rigaku Ultima
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148 IV (Japan) using Cu Kα radiations (λ = 0.154 nm) at a scan speed of 2° min-1 between 5o-
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149 90°. The organic functional groups in the composite membrane were detected by FTIR

150 (Perkin Elmer L160000V). To study the thermal behavior of fabricated membranes, ~15mg
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151 quantity was taken for the study of DSC and TGA by EXSTAR Model-SII 6300 EXSTAR.
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152 The DSC and TGA were done in a nitrogen ambient at a flow rate of 200 ml min-1 at a

153 heating rate of 5 oC min-1. The mechanical properties such as tensile strength, young’s

154 modulus, and tensile strain were determined by Instron 3366 universal tensile testing

155 machine. The sample sizes were prepared according to ASTM D638. To study the

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156 mechanical behavior, the tensile test at 10 mm min-1 stretching was performed and the

157 bending test was performed at 5 mm min-1 which produced a bending radius of 10mm.

158 The bending strain was calculated using bending strain = L/2r. Here L denotes the thickness

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159 and r the bending radius of the nanocomposite membrane strip. The dielectric behavior of

160 CPNC was studied from measurements taken by E4900A impedance analyzer (Keysight

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161 technologies Germany) in the frequency range 20Hz to 1MHz at room temperature. The

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162 data was recorded using 16451B Teflon coated stainless steel parallel plate probes.

163 2. Results and Discussion

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164 3.1 Morphological characterization of conductive nanocomposite.
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165 The morphological analysis of P-C, P-C-I (1), P-C-I (2), P-C-I (3) and P-C-I (4) the

166 CPNC’s was done by SEM images. Fig. 2(a) represents a pure PVDF membrane and Fig.
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167 2(b) shows the blended PVDF/CNF membrane without IL. Further, Fig. 2(c) shows an

168 enlarged image of a portion from such membrane exhibiting distributed CNF in the PVDF
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169 matrix. Further, Fig. 2(d) shows IL-containing membranes. The cross section of such
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170 images exhibits the porous structures. Such porous structures developed due to the presence
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171 of IL have already been discussed in the literature [30-32]. It must be mentioned that

172 basically the pore-like structures in SEM images (Fig. 2 (d)) are not exactly the voids but
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173 are filled with electrolyte mixture of CNFs and IL (discussed in detail further in next
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174 paragraph) [33]. The sizes of the pores have been found dependent on the heating rate. In

175 the process of drying the blended solution at slow heating, rate leads to larger pore size as

176 compared to the high heating rate. In Fig. 2(d), the thickness of a sample has been depicted.

177 Moreover, the conductivity due to conducting channels of connected CNF’s can be realized

178 in Fig. 2(e) &(f).

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179 It was reported by Salazar et.al. that addition of carbon filler to the imidazolium-based ILs

180 increases the interfacial polarization of carbon filler due to weak van der Waal interactions between

181 CNFs and the cations in carbonaceous-IL mixtures [19]. This decreased the bulk resistance of

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182 the composite membrane hence increased the electrical conductivity of the electrolyte

183 mixture in the composite membrane [19, 34]. Conclusively, conduction in the composite

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184 membrane takes place due to the connected CNF’s present in the web structure (shrink

185 lattice of composite developed due to the presence of IL) and due to a facile flow of ions

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186 through electrolyte mixture CNFs and IL (Fig. 2 (e) & (f)) [34].

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188 3.2 X-Ray Diffraction

189 The FWHM has been found using Gaussian fitting in Origin 12 software. The x-ray
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190 diffraction (XRD) follows Bragg’s law (2d sin θ = nλ), Here, it must be mentioned that

191 slight increase or decrease in angle 2θ refers to decrease or increase in spacing (d-spacing)
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192 respectively between molecular planes whereas the FWHM values correspond the
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193 alignment (arrangement) of molecular planes. And the decrease in intensity of x-ray in a

194 polymers composite system may be due to absorption of x-ray by polymers composite
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195 system.
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196 The various XRD spectra peaks of PVDF have been reported by various researchers as
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197 17.8°, 18.6°, 19.18°, 26.62° and 38.2° corresponding to planes (100), (110), (020), (021)

198 and (002), respectively [35 - 37]. These peaks referred to the presence of the α phase in

199 pure PVDF. In Fig. 3(a), the XRD peaks of sample P-C at 18.32° (α phase), 20.6° (β phase)

200 and 26.4° (α phase) corresponds to PVDF whereas a peak at 26.14° corresponds to CNF.

201 The change in phase from α to β that occurred due to the infiltration of IL in the PVDF

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202 matrix acted as the plasticizer and considered responsible for higher conductivity and

203 mechanical strength in PVDF [38, 39]. It is to be mentioned here that in sample P-C there

204 were nearby two peaks at 18.34° and 20.05° but with the inclusion of IL (samples

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205 containing IL i.e. P-C-I (1), P-C-I (2), P-C-I (3) and P-C-I (4)) the peak seems to combine

206 and only a peak at 2θ = 20.68° has been observed confirming the change in phase from α to

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207 β of the PVDF . The peak at an angle ~20.57o (as 20.67 o, 20.67 o and 20.47 o) corresponds

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208 to the PVDF (β phase), the general behavior of FWHM has been found to decrease which

209 corresponds to more alignment of molecular planes of the PVDF (β phase) in composite

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210 membranes. So, it is concluded IL brings structural changes in PVDF because there is a
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211 possibility of interaction between PVDF and IL due to the presence of C-O-C group present

212 in the IL at the temperature treatment of mixture ∼154-163oC (melting point of PVDF). At
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213 the melting point of PVDF, the molecular chains of the amorphous phase are mobile and
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214 hence due to electrostatic interaction between PVDF and IL it results in the β phase of

215 PVDF [40]. The three common types of interactions occurring due to the IL are (i)
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216 interaction of hydrogen atoms, (ii) polarity and (iii) basicity and acidity interaction for
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217 PVDF/IL interactions have been discussed in following references [41, 42]

218 Further, the peak at an angle 26.44o corresponds to CNF, the FWHM has been found to
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219 decrease which corresponds to a decrease in d-spacing but it might be due to the slight
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220 difference in the arrangement (configuration) of CNFs in a batch (lot), not due to the

221 attachment of IL on the surface of the CNF. It is so because the literature survey reveals

222 that only high temperature near 800 oC or above brings structural changes like a decrease in

223 d-spacing of CNF [14]. The temperature of treatment in our experimentation was ~80 oC.

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224 So, it is concluded that the decrease in d-spacing of CNF is not due to the attachment of IL

225 on the surface of the CNF. Hence, IL inclusion seems to convert into a β phase of PVDF

226 which is also responsible for the enhanced conductivity. These obtained peaks confirm the

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227 presence of α phase crystals having nonpolar TGTG (trans-gauche-trans gauche). At low

228 temperatures around 50-70 oC, the thermal energy is enough to rotate the CNF group, due

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229 to which changes take place in trans-gauch [43].

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230 3.3 FTIR

231 In Fig 3(b), the transmittance spectra of samples P-C, P-C-I (1), P-C-I (2) and P-C-I (4)

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232 along with a spectrum of pure PVDF and IL are shown. Here the peaks obtained at 1678
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233 cm-1, 1408cm-1, 1173cm-1 and 878cm-1 correspond to C=O, C-F, C-C and =C-H

234 respectively of pure PVDF. Whereas, a broad spectrum at 3500cm-1 was observed in IL
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235 which correspond to O-H and were absent in pure PVDF [38]. Further, it was observed that

236 similar peak (3500cm-1) was also observed in other samples which contained CNF and IL
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237 i.e. sample P-C-I (1), P-C-I (2), P-C-I (3) and P-C-I (4) respectively. It is to be mentioned
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238 here that the peaks obtained at 531 cm-1, 764 cm-1, and 989 cm-1 corresponds to the α phase

and 839 cm-1, 1129 cm-1, 1276 cm-1and 1282 cm-1 corresponds to the β phase of the PVDF
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240 [43, 44]. The signatures of the β phase were obtained when IL and CNF were introduced in
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241 the PVDF matrix which signifies the interaction between CNF and PVDF [29]. The
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242 conversion of PVDF from α to β phase assures the enhancement of mechanical property

243 and electrical conductivity.

244 3.4 Thermal analysis:

245 Thermal stability is an important factor for the sensor application as the small change in

246 temperature can affect the working of a sensor. As the temperature plays a crucial role in

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247 structural arrangement especially in case of polymers with IL inclusion which is

248 temperature dependent.

249 3.4.1 DSC

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250 The DSC heating thermographs for the P-C and IL doped P-C-I (1), P-C-I (2), and P-C-I

251 (4), are shown in Fig. 3(c). From literature, the melting point of pure PVDF is at 168oC

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252 having melting enthalpy of 58.08 Jg-1. With the infiltration of CNF in the PVDF matrix, the

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253 melting point remained nearly the same, but the melting enthalpy decreased from 58.08 Jg-1

254 to 11.8 Jg-1. This refers to no change in crystallinity of the PVDF/CNF polymer membrane

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255 with temperature. Further with the infiltration of IL in the PVDF/CNF matrix, a decrease
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256 was observed in the melting point of the composite matrix from 168 °C to 163 °C i.e.

257 sample P-C-I (1). The melting and curing temperature of sample P-C was observed at 160
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258 °C and 168 °C respectively. The melting temperature of as purchased PVDF was found to

259 be 163 °C, while the CNF remains unaffected at this temperature because the structural
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260 changes have been found at ~800 °C [44, 45]. In Fig. 3(c) the DSC spectrum graph of
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261 samples P-C-I (2) and sample P-C-I (4), the melting peak is observed at ~164 °C but there

is difference in their melting enthalpy as 10.1 mJmg-1 and 20.2 mJmg-1 respectively. This
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263 increase in melting enthalpy signifies the effect CNF (carbon content) in composite system.
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264 Hence, it is concluded that different compositions of CNF and IL in composite (CPNC)
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265 brings no major change in the crystallization points of PVDF but the only slight change in

266 enthalpy of the system. This property is useful for the application of the sensor.

267 3.4.2 TGA

268 The TGA thermographs of samples P-C, P-C-I (1), P-C-I (2) and P-C-I (4) are shown in

269 Fig. 3(d). The transition temperature and melting temperature index of PVDF is at 135-

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270 140oC and 230oC respectively at the temp of 30 -300 °C at 5 °C min-1 rate (Sigma Aldrich).

271 The samples containing IL show transition temperature of PVDF ~163 °C as found in

272 following [46]. One of the samples, due to the higher part of the polymer in composition,

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273 shows greater weight loss (marked) than others (see Table 1). This sample also exhibits the

274 maximum elongation as compared to sample P-C as well the SEM shows membrane

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275 surface with pores. The discussion on reason is under heading mechanical properties.

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276 3. Mechanical Properties:

277 The pores have been an attribute of infiltration of IL in the PVDF matrix. Generally, the

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278 pores are the crack initiating sites but reinforcing CNF in the PVDF matrix helps withstand
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279 the tension forces at the time of elongation. The deformed pattern of CNF dispersed across

280 or within the pore helps the PVDF to adhere to the reinforcing CNF surface hence enhances
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281 stretchability of CPNC membranes [44, 45] and is shown by Fig.4 (a). Hence, the

282 incorporation of CNFs in IL composition provides strength to the pores at the time of
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283 elongation [43, 45].

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284 The mechanical properties of the CPNC were investigated using the ultimate tensile
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285 testing machine. Generally, the inclusion of carbon content increases hardness and

286 strength and improves hardenability. The following samples of P-C and P-C-I in Table
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287 1were under test and their corresponding tensile strength, Young’s modulus and
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288 elongation at breaks are mentioned. The stress-strain diagram of the same samples is also

289 shown in Fig. 4(b). A comparison among mechanical parameters of P-C and samples

290 containing the IL (i.e. sample P-C-I (1), P-C-I (2), P-C-I (3) and P-C-I (4)) clearly shows

291 that P-C composition has high modulus of 48 MPa with tensile strength of 5 MPa and

292 small elongation of 0.4 mm (at break) as compared to the samples containing the IL.

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293 Among the samples containing the IL (P-C-I (1), P-C-I (2), P-C-I (3) and P-C-I (4) of

294 different composition), sample P-C-I (2), exhibited maximum elongation (5.8309 ± 2 mm)

295 although corresponding SEM image in Fig. (SEM) exhibit pores.

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296 4. Electrical and sensing property

297 Carbon based CPNCs are highly appreciated for the piezoresistive strain sensing

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298 application because of their ability to work in both macro and micro level strain sensing,

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299 with controllable sensitivity, flexibility, thermal stability with maintained ductility and

300 durability.

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301 The sensitivity and gauge factor (G) of the composites were evaluated using equation (1).
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302 The values obtained before bending and after bending in the CPNC membrane with initial

303 resistance (Ri), final resistance (Rf), change in resistance (∆R). The sensitivity and gauge
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304 factor (G) of the blended CPNCs are shown in Table 2. Samples P-C-I (1), P-C-I (2), P-C-I
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305 (3), and P-C-I (4) containing the IL showed higher gauge factor comparing to the sample P-

306 C without IL (Table 2). The sample P-C-I (2) has the highest gauge factor (4.08) which is
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307 near to gauge value exhibited by metals [46] due to the uniform distribution of CNF using
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308 IL. Here IL acted as a catalyst for uniform dispersion of CNF in the PVDF polymer matrix.

309 The sensitivity and gauge factors are the two important parameters responsible for
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310 determining the efficiency of any piezoresistive sensor. With this, the sample P-C-I (3)
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311 showed high toughness which is responsible for good repeatability of the flexible

312 conductive polymer sensor.

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313 The values of capacitance (C) and dielectric loss (tanδ) were directly recorded from the

314 impedance analyzer (E4900A) for frequency ranging 20 Hz -1 MHz. To determine the

315 dielectric constant ε′, the eq. (2) was used.

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316 (2)

Where ε′ represents the dielectric constant, l defines the thickness, εo shows the dielectric

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317

318 permittivity in the air (8.85x10-12 Fm-1) and A defines the cross-sectional area. The

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319 conductivity of the samples was obtained by σ = ω × ε × εo × Tanδ.

320 Here σ defines the conductivity, ω = 2× π × f is the angular frequency and tanδ is the

321
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dielectric loss. In Fig. 5(a) comparing the dielectric behavior of sample containing P-C and
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322 samples containing the IL (i.e. (P-C-I (1), P-C-I (2), P-C-I (3) and P-C-I (4) it is clearly
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323 observed that sample P-C has the lowest dielectric constant being a more dielectric medium

324 as compared to the values for other samples containing IL. It refers to a more conducting
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325 medium in which the dielectric loss is expected to be higher. The same behavior is obvious
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326 in Fig. 5(c) for conductivity. It concludes that IL makes the medium more conducting as

327 compared to CNF. Furthermore, every sample exhibits the usual behavior of decrease in
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328 dielectric loss value with increasing frequency (up to 1 MHz) only an exception in sample

329 P-C-I (4) where a sudden increase in dielectric constant (Fig. 5(a)), dielectric loss (Fig.
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330 5(b)) and conductivity (Fig. 5(c)) value is exhibited at frequency near to 16.90 kHz.
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331 5. Conclusions

332 In summary, a series of CPNC membranes comprising of CNF and IL as conducting fillers

333 were fabricated using a solvent casting technique. The microstructure analysis by SEM

334 revealed porous structures developed due to the presence of IL and the heating rate.

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335 Further, the XRD and FTIR confirmed the change of PVDF from α to β phase which

336 ensured good mechanical and electrical behavior of PVDF. The thermal behavior by DSC

337 and TGA concluded that IL in composite (CPNC) bring no major change in the

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338 crystallization points of PVDF but only a slight change in enthalpy of the system. Whereas

339 in a tensile test a maximum elongation of 5.8309 ± 2 mm and a highest gauge factor (4.08)

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340 for a sample P-C-I (2) containing IL is also observed. In a tensile test, a high modulus and

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341 tensile strength at a small elongation of a P-C sample were observed as compared to

342 samples containing the IL. The AC analysis revealed the usual behavior of decrease in

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343 dielectric loss value with increasing frequency (up to 1 MHz) except for a sample
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344 composition of P-C-I (4) which exhibited a sudden increase in dielectric constant at a

345 frequency near to ~ 16.90 kHz.

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346 Conclusively, the introduction of IL in PVDF/CNF membrane helps in changing the phase

347 of PVDF and provides an electrolyte mixture of CNF and IL for the facile flow of ions
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348 through it. Hence, a combined, conduction in the composite membrane takes place due to
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349 the connected CNF’s present in the shrink lattice of composite (developed due to the
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350 presence of IL) and due to a facile flow of ions through electrolyte mixture of CNFs and IL.

351
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352 Acknowledgment
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353 The authors acknowledge the financial support from the Science and Engineering Research

354 Board (SERB) [ECR/2016/001113] Government of India.

355 Figure captions

356 Figure 1. Pictorial interaction of PVDF/CNF/IL: formation of a conductive nanocomposite.

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357 Figure 2. Fig. 2 SEM micrographs (a, b, c) showing the pure PVDF membrane and

358 PVDF/CNF membrane. (d, e, f) represents the thickness and porosity across the

359 fractured end with the CNF fibers.

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360 Figure 3. (a) Represents the XRD patterns (b) shows the presence of functional groups (c)

361 shows the DSC micrographs and (d) represents the thermal behavior by TGA.

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362 Figure 4. Illustration of elongation scenario in a membrane at the micro-level and the

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363 stress-strain curve obtained on tensile test.

364 Figure 5. Represents the (a) dielectric constant, (b) dielectric loss and (c) conductivity with

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365 respect to frequency.
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366

367 Table captions

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368 Table 1. Determination of mechanical properties by the stress-strain curve.

369 Table 2. Determination of electrical properties of conductive nanocomposite membrane.

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370
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