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Manuscript Number: MATPR-D-19-02927

Title: Impedance characteristics analysis of rGO/polymers (PVDF, PMMA,

PTFE) nanocomposite membranes

Article Type: 10 ICMPC 2020

Keywords: rGO; PMMA, PVDF; PTFE; nanocomposites, impedance, membranes

Corresponding Author: Dr. Dr. fateh Gill,

Corresponding Author's Institution: Graphic Era University

First Author: Divya Uniyal, M.Sc.

Order of Authors: Divya Uniyal, M.Sc.; Brijesh Prasad, M.Tech; Nithin

Kumar K C, M.Tech; Sarita Chandra, Ph.D.; Varij Panwar, Ph.D.; pradeep
Juneja, Ph.D.; Vivechna Agarwal, Ph.D.; Dr. fateh Gill

Abstract: In this work, the electrical impedance characteristic of

different combinations of rGO/polymers (PVDF, PMMA, and PTFE)
nanocomposites is presented. The nanocomposites membranes were prepared
by solution casting method and characterized by SEM (EDAX) which revealed
the distribution of rGO in membrane. The low wt% of rGO (i.e.0.5 wt%)
showed capacitive behaviour whereas 1, 2, and 4 wt% (Higher
concentration) of rGO membranes exhibited conductive behaviour
(independent of frequency). The conduction in higher concentration
nanocomposite membrane was due to interconnectivity of rGO sheets and
tunnelling between close rGO sheets (< 10 angstrom). Conduction in higher
concentration membranes indicated percolation threshold. The Nyquist
plots also indicated polarisation of membranes. The polarization at
higher wt% might be due to capacitance of rGO. The applicability of
conductive membranes can be explored for EMI shielding or as a biosensor
due to its reactive property.
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[10th international conference on material processing and characterization (ICMPC-2020)]

Impedance characteristics analysis of rGO/polymers (PVDF,

PMMA, PTFE) nanocomposite membranes

Divya Uniyala, Brijesh Prasadb, Nithin Kumar K Cc, Sarita Chandrad, Varij

Panware, Pradeep Junejaf, Vivechna Agarwalg, Fateh Singh Gillh*

a,b,c,d,e,f,h
Graphic Era Deemed to Be University, Dehradun, India
g
Center for Research in Engineering and Applied Sciences, UAEM, Av. Universidad, Col. Chamilpa, Cuernavaca, Morelos, Mexico

Abstract

In this work, the electrical impedance characteristic of different combinations of rGO/polymers (PVDF, PMMA, and PTFE)
nanocomposites is presented. The nanocomposites membranes were prepared by solution casting method and characterized by
SEM/EDX which revealed the distribution of rGO in membrane. The increasing loading of rGO reduced the real impedance
values. The low wt% of rGO (i.e.0.5 wt%) showed capacitive behaviour with frequency whereas 1, 2, and 4 wt% (Higher
concentration) of rGO membranes exhibited conductive behaviour (almost independent of frequency). The conduction in higher
concentration nanocomposite membrane was due to interconnectivity of rGO sheets and tunnelling between close rGO sheets (<
10 angstrom). Conduction in higher concentration membranes indicated percolation threshold. The Nyquist plots also indicated
polarisation of membranes. The polarization at higher wt% might be due to capacitance of rGO. The applicability of conductive
membranes can be explored for EMI shielding or as a biosensor due to its reactive property.

[copyright information to be updated in production process]

Keywords: rGO; PMMA, PVDF; PTFE; nanocomposites, impedance, membranes

1. Introduction

Composites are the engineered materials which fulfills the requirement in various fields and shaping our present
scenario. The development in nanotechnology has also opened the production of many materials in nano form like
carbon, gold, copper and many more [1]. Therefore, in electronic field the search of light weight conducting
composites is advancing. Hence, researchers are using light weight conducting nano materials instead of heavy nano
conducting ones such as carbon’s conducting nano derivatives like carbon-nano-fibers (CNFs), graphene and
reduced-graphene-oxide (rGO) for electromagnetic interference shielding (EMI), sensing, capacitive and
electrostatic painting applications [2]. Among these the graphene is single layer graphite sheet or 2D material
whereas CNFs are few µm long fibers having ~50-150nm diameter and both are conducting in nature due to π-π
bonding in carbon [3]. The CNFs provide good conductivity in a polymer matrix due to interconnectivity of its long
fibers [4,5] whereas graphene provides large surface area for interaction with other atoms or molecules having
already oxidized sites, Moreover, the rGO has reduced no of oxidized sites therefore the layer of a rGO is shredded
in fact therefore more reactive than graphene but still conducting [6]. Hence, graphene and rGO membranes
(composites) provide better possibilities of a sensor because of their enhanced reactive property due to large surface
area as compared to CNFs [7-9]. The single layer graphene has also a theoretical capacitive of 21 µF/cm2.
 In this work, PVDF, PMMA and PTFE membranes were prepared by the incorporation of reduced rGO as the
conductive filler. The electrical impedance characteristic analysis of 0.5, 1.2 and 4wt% of rGO with blend of PVDF,
PMMA, PTFE polymers (nanocomposite) have been presented. The variation of real and imaginary impedance with
frequency has been studied as well as the capacitive behavior of the membranes with Nyquist plots has also been
discussed.

1. Experimental (Membrane preparation)

Solution mixing and casting technique was used to fabricate composite membrane. For this the ingredient as rGO,
PVDF, PMMA and PTFE were taken in powdered form. To dissolve the polymer and rGO a solvent called N-N,
Dimethylformamide (DMF) of 99.5% purity was used. For developing the composite membrane firstly, DMF was
poured into the beaker containing powdered PVDF in the weight ratio 10/90 and then allowed for stirring about 3-4
hours to get homogeneously dissolved PVDF/DMF transparent solution. Further, PTFE, PMMA and rGO were
added to the solution and allowed to mix using magnetic stirrer for 4-5 hours at 550 rpm at 85oC. The PTFE is
hydrophobic in nature and rGO does not dissolve in non polar polymer i.e. PMMA therefore the PTFE and rGO got
entrapped in the heterogeneous mixture of PMMA and PVDF/DMF solution. The obtained heterogeneous mixture
was then poured on glass petridish. The petridish was allowed to heat for the evaporation of the solvent, thus formed
a dry flexible membrane.

2.1 Characterization

The dispersion of rGO in blend of PVDF, PMMA and PTFE polymer were investigated by SEM technique. Further
the electrical behavior of the developed composite was studied using the E4900A impedance analyzer in the
frequency range of 20 Hz to 1MHz. Real and imaginary values of impedance have been obtained from the
impedance analyzer.

Fig. 1 SEM image of rGO/PVDF (PV*)/PMMA (PM*)/PTFE (PT*) nanocomposites and its elemental analysis
(EDX). *(abbreviation used is mentioned)

Fig. 1 shows the surface SEM image of rGO/PV/PM/PT nanocomposites as well as its elemental analysis (EDX)
(adjacent) which confirms distribution of rGO in blend of PMMA, PVDF and PTFE polymers. Sine rGO has
reduced no. of oxidized sites therefore here the oxygen content in EDX image refers to expected sites of rGO.
2. Result and discussion

Fig. 2 real part of impedance (Z’) (a) and (b) imaginary part of impedance (Z’’) of rGO/PV/PM/PT nanocomposites as function of rGO
concentration (i.e. r0.5 = 0.5wt%, r1 = 1wt%, r2 = 2wt% and r4 = 4wt %) and ac frequency.

Impedance (Z) is a complex number a real part (Z’) which represents the resistance or power dissipation and an
imaginary part (Z”) which gives information about the loss factor or energy storage; i.e. Z = Z’ (real) + jZ”
(imaginary) where j = √-1. The insulating materials are characterized by a remarkable decrease in Z’ with the
increase in frequency such behavior is expected for the unfilled PVDF/PMMA/PTFE membranes or with low
concentration of rGO in such membranes (below the electrical percolation threshold).

Fig. 2 (a) shows the real part of impedance of rGO/PV/PM/PT nanocomposite membranes of 0.5, 1, 2, and 4
wt% of rGO as a function of frequency. In Fig. 2 for the lowest wt% of rGO (0.5 wt%) the dissipation of power (i.e.
real part of impedance) decreased from 10 5 to 104 order with increase in frequency up to 1MHz. whereas for rGO
wt% of 1, 2 and 4 wt% membranes there is almost no significant variation in real part of impedance with frequency;
in other words, the dissipation of power is almost independent of frequency for taken 1, 2 and 4 wt% of rGO. But a
decrease in impedance (Z’) is observed with increasing wt% of rGO (refer figure 2 and in figure 3 refer the order of
values of Z’ on Y axis i.e. the order changes from 107- 101) moreover with the increase in rGO content above 0.5
wt%, it became almost independent of frequency indicating that interconnecting pathways (near percolation) has
been formed and transportation of the electrons is via direct contact between rGO sheets or with tunneling effect
between close rGO sheets. Tunneling between agglomerated rGO sheets having distance less than 10 angstrom can
be prevailed [10].

Since the imaginary impedance (Z’’) is related to capacitive behavior (Z’’=1/iωC where ω = applied frequency
and C = capacitance) i.e. charge/power storage in nanocomposite system. Further in Fig. 2 (b) the curves between
imaginary part of impedance (i.e. power storage) and frequency shows that for 0.5wt% (lowest wt %) it decreased
from 107 to almost zero whereas for membranes containing 1, 2 and 4 wt% of rGO showed almost zero power
storage means these almost exhibited a nature of pure conductor. It means no relaxation process took place at these
concentrations of rGO [11].
 Fig. 3 Nyquist plots of different wt% of rGO in PVDF /PMMA /PTFE polymers (nanocomposites membranes).

Generally, Nyquist plot (a normal scale plot of Z’’ vs. Z’) exhibit a circle form. At certain cut-off frequency,
called the characteristics frequency, there is a transition in nanocomposites behaviour from resistive type to
capacitive type but here in our case the Nyquist plots of 0.5, 1, and 4wt % of rGO are not absolute circle but have
either decreased or increased half semicircle form. Only r2/PV/PM/PT has the absolute half semicircle shape.
Generally the number of semicircle in a plot represents the relaxation processes in a composite system. Hence,
r2/PV/PM/PT confirms a single relaxation process or the presence of polarization. Since the Nyquist plot of
r1/PV/PM/PT is not continuous it may be due to non uniform distribution of rGO in the composite. It is observable
that there is a kind of decreasing half semicircle behaviour of plots in 0.5, 1, and 2 wt% but 4 wt% membrane has an
increasing half semicircle; it shows that dissipation (Z’) is increasing and capacitance is decreasing (Z’’=1/iωC) (
since Z’’ values are also increasing) at this loading of rGO [12, 13]. Conclusively, the real and imaginary
impedances are increasing in 4wt% membranes.

3. Acknowledgement

The author, Fateh Singh Gill is very grateful to Dr. (Prof.) Kamal Ghanshala (Chairman, Graphic Era Deemed to
be University, Dehradun, India) for his motivational support for this research work.
4. Conclusion

The rGO/PVDF/PMMA/PTFE nanocomposite membranes filled with 0.5, 1, 2 and 4 wt% were prepared by
the solvent casting process. SEM (EDX) revealed the distribution of rGO in the nanocomposite. The real and
imaginary impedance with frequency revealed that 0.5 wt% is frequency-dependent whereas the 1, 2 and 4 wt%
were less dependent on frequency. This concluded that 0.5wt% membrane has capacitive behavior and 1, 2 and
4wt% are conductive in nature hence these can be tested to find application in EMI shielding or as biosensor. The
values of real impedances decrease with increase in loading of rGO. The higher wt% membranes seem to achieve
percolation threshold hence the conduction is due to interconnecting rGO sheets and possibly due to tunneling
between rGO sheets (having distance < 10 angstrom). Nyquist plots also indicated the polarization behavior of the
membrane. The polarization for high wt% may be due to the capacitive behavior of rGO.

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*Declaration of Interest Statement

To,

The Editor,

Materials Today Proceedings,

Dear Sir,

we the authors (Divya Uniyala, Brijesh Prasadb, Nithin Kumar K Cc, Sarita Chandrad, Varij Panware,

Pradeep Junejaf, Vivechna Agarwalg, Fateh Singh Gillh*) of a manuscript “Impedance characteristics

analysis of rGO/polymers (PVDF, PMMA, PTFE) nanocomposite membranes” give our consent to

publish this in your reputed proceedings. This manuscript has not been submitted in other journal or

proceedings.

Thanking You,

Dr. Fateh Singh Gill

Corresponding Author
Figure

Fig. 1 SEM image of rGO/PVDF (PV*)/PMMA (PM*)/PTFE (PT*) nanocomposites and its elemental analysis
(EDX). *(abbreviation used is mentioned)
Figure

Fig. 2 real part of impedance (Z’) (a) and (b) imaginary part of impedance (Z’’) of rGO/PV/PM/PT nanocomposites as function of rGO
concentration (i.e. r0.5 = 0.5wt%, r1 = 1wt%, r2 = 2wt% and r4 = 4wt %) and ac frequency.
Figure

Fig. 3 Nyquist plots of different wt% of rGO in PV /PMMA /PTFE polymers (nanocomposites membranes).