Measurement 122 (2018) 320–324

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Measurement
journal homepage: www.elsevier.com/locate/measurement

Durometer test and impedance measurement of metal precursor reinforced T

polymer composites
⁎
Anandraj Joseph, Girish M. Joshi
Polymer Nanocomposite Laboratory, Center for Crystal Growth, VIT, Vellore 63 2014, Tamil Nadu, India

A R T I C LE I N FO A B S T R A C T

Keywords: Polymer composites were preferred for the domestic and industrial applications due to unique high performance
Impedance properties. In the present work we demonstrated the preparation of polyvinyl alcohol (PVA)/Copper bismuth
Durometer test sulphide (CuBi2S3) metal precursor composites by solution blending. The decreased softness by 45% was con-
Metal precursor firmed as a function of metal precursor loading tested by shore – A durometer. It may be due to the presence of
Composites
metal precursor in polymer system distinguished by Scanning Electron Microscope (SEM) techniques. We ob-
served the influence of metal precursor on bulk resistance and impedance as function of temperature across the
broadband frequency and wide temperature range. The dc conductivity obeys the Arrhenius relationship and
confirmed the decrease in activation energy. This investigation may be feasible for the electrical and electronic
domains.

1. Introduction nature of polymers, molecular weight co-related to specific grades, poly

The electrical properties of polymers were highly crucial for various
applications which includes low loss cables [1], battery electrodes [2],
electromagnetic shielding [3], electronic components as capacitors and
thermistor, modern civil and military devices [4,5]. The polymer con-
ductivity and dielectric properties were essential properties for the
engineering applications and implementation. In the present study
polyvinyl alcohol (PVA) was selected due to easy casting, film forming
and glossy in nature. Several reports with PVA demonstrated improved
electrical performance of PVA system as function of fillers [6–9]. The
role of metal precursor was highly important to modify the PVA systems
enable to understand the structure, morphology co-related dielectric
properties at low frequency capacitor applications [10]. Basically the
reports on metal precursor loading demonstrated. In the present study
we motivated to select the CuBi2S3 ternary precursor system due to
wide band gap, synergic effect on near infrared photoluminescence
properties, low dielectric loss, ferro and dielectric in nature, metal
semiconductor properties and non toxic in nature. Bismuth Sulphide
(Bi2S3) enable as to protective polymer coating [11].
The mechanical properties of polymers were tested and confirmed
by Instron tester. It demonstrated the properties like stress, strain,
Young’s, bulk modulus and creep [12]. The hardness property of epoxy
and polymeric system were disclosed by Shore D tester [13]. These
properties were feasible for several engineering, domestic and in-
dustrial applications. These properties were depend on the crystalline
dispersity, heterogeneous index, thermal properties, chain stiffness,
cross linking, pendant group, intermolecular forces plasticizer. It re-
flects in view of strength, ductile, highly elastic in nature, fracture,
consistent response across the load. With this motivation we selected
the objective of work to test the influence of softness shore-A testing by
durometer technique as function of metal precursor loading disclosed in
detail. The electrical properties were tested by impedance analyzer as a
function of temperature. The concept of electrical impedance gen-
eralizes the Ohm’s law to alternating current analysis and Oliver Hea-
viside was pioneer to demonstrate this technique [14].
Impedance Spectroscopy has got a lot of applications such as to
study the battery electrodes, electrochemical reaction at the surface and
interface reaction, Corrosion study, batteries and fuel cells. Research in
bioscience affecting the process in brain, predicting sudden cardiac
death, audiometric impedance technique. Based on these applications
we motivated to disclose the effect of metal precursor loading on im-
pedance properties. Furthermore, the development of engineering ap-
plications in electrical and electronics domain may be possible by using
these properties.
1.1. Effect of CuBi2S3 as a metal precursor on properties of polymer
composites
CuBi2S3 was a non-hazardous semiconductor with a direct band gap
of 1.3–1.7 eV. The thickness dependent properties of CuBi2S3 were co-

⁎
Corresponding author.
E-mail address: varadgm@gmail.com (G.M. Joshi).

https://doi.org/10.1016/j.measurement.2018.03.030
Received 21 October 2016; Received in revised form 20 November 2017; Accepted 12 March 2018
Available online 14 March 2018
0263-2241/ © 2018 Elsevier Ltd. All rights reserved.
A. Joseph, G.M. Joshi
Fig. 1. SEM micrographs of (a) virgin PVA, (b) 10, (c) 20, (d) 30 wt% composition with PVA system.
related to the decreased the optical band gap. The constituent Bismuth
sulphide (BiS) was an interesting material for a variety of applications
such as power generator, light sensitive detectors and gas sensor de-
vices. Many authors reported that the polymer coated bismuth sulphide
was synthesized by two-step protocol method to give homogeneous
preparations. With this motivation we selected the CuBi2S3 as a metal
precursor as filler with polymer system [30].
2. Materials and experimental
The polymer PVA (MW 125,000 and DH 86–89%) supplied by SD
Fine – Chem Limited, Mumbai, India. The filler CuBi2S3 was used as a
dopant ratio of 10, 20 and 30 wt%. Distilled water was used as a solvent
throughout the casting of composite films mentioned in the report [15].
2.1. Casting of PVA/CuBi2S3 metal precursor composites
PVA/ CuBi2S3 composites were prepared by solution blending with
loading of 10, 20, 30 wt% metal precursor. Initially PVA granule was
dissolved in distilled water by gently stirred (at 400 rpm at 60 °C) to get
completely soluble. CuBi2S3 was sonicated in water (4 g in 30 ml of
water for 20 min. with sonication power 80 W at 40 °C). Then the re-
quired quantity of CuBi2S3 was added to the PVA solution with con-
tinuous stirring (at 350 rpm at 32 °C for 12 h). The homogeneous so-
lution was obtained and poured in the petri dish (for 36 h) to obtain
composite films. Finally composite film was peeled off from the petri
dish and used for further characterization.
321
Measurement 122 (2018) 320–324
3. Results and discussions
3.1. Scanning electron microscopy (SEM)
The morphology of PVA/CuBi2S3 was investigated by using scan-
ning electron microscope (SEM) techniques [16,17]. The presence of
and metal precursor is shown in Fig. 1a–d). The SEM micrograph ex-
hibits the smooth surface of pure PVA is shown in Fig. 1(a). 10 wt% of
CuBi2S3. The brighter regions distinguished by the observation of SEM
micrographs throughout the lateral surface is shown in Fig. 1(b). The
volume of metal precursor loading is reported in the present micro-
scopcopic investigation. Fig. 1(c) 20% loading of CuBi2S3 foreseen the
presence of spherical shape was obtained because of the presence of
CuBi2S3 in PVA system [18]. In Fig. 1(d) shows the SEM image formed
at 30% addition of CuBi2S3 shows bubble spots was obtained
throughout the surface. It was due to particles containing aggregates
through the polymer system for higher loading of filler volume.
3.2. Electrical impedance measurement of PVA/metal precursor composite
films
Complex impedance spectroscopy was an experimental method
used to characterize the resistivity, conductivity, temperature coeffi-
cient of resistance, permittivity and thermoelectricity. The electrical
impedance was measured over a broad band of frequency from 10−2 to
107 Hz. Impedance have resistive, capacitive and inductive components
can be determined by applying an alternating voltage across a sample.
It responds a sine wave that change alternating voltage which was re-
corded as a function of frequency.
A. Joseph, G.M. Joshi Measurement 122 (2018) 320–324

2.5e+6 8e+5

400 C
2.0e+6 600 C
6e+5
800 C

Z" (Ohms)
Z" (Ohms) 1.5e+6 1000 C

4e+5
400 C
1.0e+6 600 C
800 C
2e+5
5.0e+5 1000 C

0.0 0
0 5e+5 1e+6 2e+6 2e+6 3e+6 3e+6 0 2e+5 4e+5 6e+5 8e+5 1e+6
Z' (Ohms)
Z' (Ohms)
(c)
(a)
2.5e+6 1.4e+6
400 C
1.2e+6 0
2.0e+6 60 C
800 C
1.0e+6
400 C 1000 C
Z" (Ohms)

Z" (Ohms)
1.5e+6
600 C 8.0e+5
800 C
1.0e+6 1000 C 6.0e+5

4.0e+5
5.0e+5
2.0e+5

0.0 0.0
0 5e+5 1e+6 2e+6 2e+6 3e+6 3e+6 0.0 5.0e+5 1.0e+6 1.5e+6 2.0e+6 2.5e+6 3.0e+6 3.5e+6
Z' (Ohms) Z' (Ohms)
(b) (d)

(e)
Fig. 2. Complex impedance plots (Z′ vs Z″) of (a) virgin PVA, (b) 90/10, (c) 80/20, (d) 70/30 PVA/CuBi2S3 composites, (e) an electrical equivalent circuit in complex impedance plane.

Impedance spectroscopy was used to identify the electrical property,

grain boundary and electrode-electrolyte interface across the broad-
band frequency [19]. The electrical properties of material were in-
vestigated using complex impedance spectroscopy technique to reveal
the presence of grain and grain-boundary effects in the ferroelectric
ceramics [20].
From this we motivated to test the complex impedance (Cole-Cole
plot) by using PSM 1735: N4L impedance analyzer at various tem-
peratures (40 °C, 60 °C, 80 °C, and 100 °C). We selected PVA and
CuBi2S3 metal precursor at different weight of 0, 10, 20 and 30 wt%.
Fig. 2 shows the complex impedance plot of PVA and CuBi2S3 metal
precursor composites. The semicircular arcs of the impedance spectra
were obtained as shown in Fig. 2(a–d). It was due to a parallel com-
bination of bulk resistance (Rb) and grain capacitance (Cg). An electrical
equivalent circuit was shown in Fig. 2(e).
In virgin PVA the semicircle behavior of Cole-Cole plot indicates a
Debye relaxation process was involved in PVA system [21]. It shows the
large diameter of the semicircle which represents high interfacial
charge transfer resistance and low electrical conductivity of the mate-
Fig. 3. Temperature dependent dc conductivity of (a) virgin PVA, (b) 90/10, (c) 80/20,
(d) 70/30 PVA/CuBi2S3 composites.
rials [22]. It has reported that maximum frequency semicircle can be
assigned to electrical property of the material arising due to parallel
combination of bulk resistance (Rb) and bulk capacitance (Cb) of the
material [23]. The semicircle decreases due to increase in temperature

322
A. Joseph, G.M. Joshi Measurement 122 (2018) 320–324

Table 1
Evaluated activation energy of composites.
Sample code Sample details
a Virgin PVA
b PVA/CuBi2S3 (90/10)
c PVA/CuBi2S3 (80/20)
d PVA/CuBi2S3 (70/30)
where Ea was the activation energy. By using this Arrhenius equation
we understood that all charge carriers are thermally activated because
of that conductivity changed with temperature [29]. The activation
Activation energy (kJ/mol)
energy of PVA/CuBi2S3 was shown in Table 1. The decrease in activa-
0.129 tion energy was due to segmental motion which results in an increase in
0.127 the free volume of a system [30]. The dc electrical conductivity was
0.115
increased with respect to temperature was due to transition from semi
0.089
crystalline phase to amorphous phase [31].

3.4. Softness test of PVA/metal precursor composite films

For the testing of soft polymers and rubber durometer test was
preferred. In general the Shore A durometer version was used for the
soft polymer system in which the intender forced in the test sample
demonstrates the relative analytical motion of pointer. Soft plastics
such as fluoropolymers, vinyl groups and polyolefins, foams exhibit
better result by shore A tester. In the present investigation the softness
of PVA/CuBi2S3 composites was shown in Fig. 4.
The basic reason to decrease in the softness trend as a function of
metal precursor loading exhibit the mono dispersive in nature with host
polymer system PVA. It was confirmed by the decrease in interplanar
distance by XRD spectra and topographic morphology. The modified
proposed PVA moiety with metal precursor reported by our group
[32–35]. The micro structural change directly deals with the softness
property of the polymer/metal precursor composites. The optimized
soft property of the polymer composites may be used for suitable en-
gineering applications in automobile, aerospace, defense and industrial
domains.
Fig. 4. Durometer study of PVA/CuBi2S3 Composites.

and bulk resistance also decreases [24].
The change in semicircular behavior with CuBi2S3 was shown in
Fig. 2(b–d). The trend of impedance plot shows the quarter semicircle
region gradually bend towards the real (Z′) axis. It confirms the Debye
relaxation peak was observed in the higher frequency region [25]. It
also depends on the concentration of metal precursor and varying
temperature. The smallest radius of semicircle around 80 and 100 °C
denotes low resistance and high conductivity of materials [26].
The significant decrease in radius of semicircle with increase in
CuBi2S3 with respect to selected temperature was observed. The shape
of the semicircle appears asymmetrical in temperature around 60 °C. A
tail region indicates the low DC conductivity of the composites. This
may be due to ionic conduction which increases due to increase in the
wt% content in CuBi2S3. The radius of a semicircle decreases and
confirms a non-Debye type of relaxation process [27]. It indicates the
low resistance and conductivity of the material.
3.3. The DC conductivity
The electrical conductivity with respect to temperature was studied
to know about the conduction phenomena. The logarithmic dc con-
ductivity (log σ dc) versus 1000/T of PVA/CuBi2S3 was measured within
the temperature range from (40 °C to 100 °C) was shown in Fig. 3. The
DC conductivity increases with increasing temperature at different
weight ratio of 0, 10, 20 and 30 wt%. It was explained on the basis of
increase in ionic mobility or the concentration of carrier ions [28].
The dc conductivity of the samples was investigated by using the
following equation
l Mater. Electron. 27 (7) (2016) 7685–7692.
σ dc =
RB A
The dc conductivity also obeys the Arrhenius model and the acti-
vation energies were evaluated by using the following equation
E
σ dc = σ0exp ⎛− a ⎞
⎝ KT ⎠
4. Conclusion
PVA/CuBi2S3 composites were successfully prepared by solution
casting and their performance was evaluated as function of metal pre-
cursor loading. SEM analysis confirms the presence of metal precursor
shows the spherical shape and tiny aggregates present on the surface.
Electrical Impedance confirms the non-Debye relaxation process and
ionic conduction. The dc conductivity confirms the decrease in activa-
tion energy. Shore – A durometer test confirms the 45% decrease in
softness test. Furthermore, these composites may be developed as
softness optimized membranes for various domestic and industrial ap-
plications.
Acknowledgements
The authors would like to thank Naval Research Board, Defense
Research and Development Organization (NRB-DRDO), New Delhi
Project No. 259/Mat./11-12, for providing the instrumentation facility
for electrical characterization. Authors also thanks to VIT University for
providing the facilities of SEM under DST-FIST project.
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