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Materials Today: Proceedings 14 (2019) 288–295 www.materialstoday.com/proceedings

ICRAMC_2018

AC conductivity studies of PVA/Al2O3 composites

S. Devikala*, P. Kamaraj and M. Arthanareeswari
Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur 603 203, India

Abstract

Polymeric materials have special interest because they are useful for the development of advanced high energy
electrochemical devices and photo electro-chemical cells. The importance of polymers is mainly because polymers are still
regarded as a cheap alternative material. Recently polymer matrix-ceramic composites receive increased attention due to their
electrical and electronic properties. Polyvinyl alcohol (PVA) has especially been given a great deal of attention due to the
characteristics of easy preparation, good biodegradability, excellent chemical resistance and good mechanical properties.
Alumina is one of the most widely used engineering ceramic material due to its high elastic modulus, high wear resistance and
chemical corrosion resistance, high-temperature stability and the retention of strength at high temperatures. In this work, PVA/
Al2O3 composites were prepared by using sol gel method. The composite samples were characterized by XRD, FTIR, DSC and
SEM. The incorporation of Al2O3 improved the structural, morphological, and conductivity properties of the composite. The
dielectric and a.c. conductivity of the samples were found to increase with increase in the concentration of Al2O3 and
temperature. The synthesized polymer composites were suitable for different technological applications.
© 2019 Elsevier Ltd. All rights reserved.
Selection and/or Peer-review under responsibility of 2nd International Conference On Recent Advances In Material Chemistry.

Keywords: PVA, Al2O3, Conductivity, dielectric constant;

1. Introduction

Polyvinyl alcohol (PVA) has especially been given a great deal of attention due to the characteristics of easy
preparation, good biodegradability, excellent chemical resistance and good mechanical properties. PVA has been
used on many biomedical applications [1]. It is a biologically friendly polymer since it is water soluble and has
extremely low cytotoxicity, which allows the application of PVA based composites in the biomedical field. The
binding characteristics of PVA offer excellent adhesion to porous and water-absorbent surfaces. It is well
established that crystalline and amorphous phases in variable amount co-exist in most of the polymeric materials.
PVA is one of the partially crystalline polymers exhibiting both the glass transition temperature, Tg (characteristic of
amorphous phase) and melting isotherm, Tm (characteristic of crystalline phase). Electrical conduction in polymers
has been extensively studied in recent years to understand the nature of charge transport in these materials [2].

* Corresponding author. Tel.: +91 9444844369;

E-mail address: sdevikala@gmail.com

2214-7853 © 2019 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of 2nd International Conference On Recent Advances In Material Chemistry.
 S. Devikala et al. / Materials Today: Proceedings 14 (2019) 288–295 289

Various conduction mechanisms such as Schottky effect, the Pool-Frenkel effect, space charge limited conduction
and hopping conduction [3] have been suggested for the charge transport. It is a good insulating material with low
conductivity and hence is of importance to microelectronic industry. Its electrical conductivity depends on the
thermally generated carriers and also on the addition of suitable dopants. Although charge transport in polymers is a
problem with great technological implication, the current understanding of the elemental processes involved is still
unsatisfactory [4]. It has excellent emulsifying, film forming, and adhesive properties. It is also resistant to grease,
oil, and solvent. However these characteristics are dependent on humidity, in other words, with higher humidity
more water is absorbed. It is also a quick dissolver and fully degradable [5-8]. It is considered among the best
polymers as host matrix for silver nanoparticles, and it is frequently used as a stabilizer due to its optical clarity,
which enables investigation of the nanoparticle formation [9-10]. The dielectric properties of polymeric films doped
with filler have attracted considerable attention. Extensive observations have been made by several workers on the
molecular motion and the charge carrier migration in a variety of polar/nonpolar polymers containing one or more
fillers [11-12]. Although the dielectric properties of a number of polymers have been investigated, the molecular
orientation behavior and the associated relaxation mechanisms of the polymers are not fully understood [13]. The
study of dielectric loss as a function of temperature and frequency is one of the most convenient and sensitive
methods of investigating the polymer structure of a polymeric film. The polarization of a dielectric is contributed by
the electronic, ionic, and dipolar polarization. Metal oxides play a versatile and important role in heterogeneous
catalysis, electrochemistry, gas sensors, and corrosion/wear protection, etc. Alumina is one of the most widely used
engineering ceramic material due to its high elastic modulus, high wear resistance and chemical corrosion resistance,
high-temperature stability and the retention of strength at high temperatures [14]. It is an electrical insulator but has
a relatively high thermal conductivity. In its most commonly occurring crystalline form, called corundum or α-
aluminium oxide, its hardness makes it suitable for use as an abrasive and as a component in cutting tools. An
original combined method for electrical conductivity measurement of polymer composites under extensional
deformation has been reported [15-16].

2. Experimental

2.1 Materials used

All chemicals used were of Analar grade and were used as received from the supplier without further
purification. The following chemicals were used in this study: Polyvinyl alcohol (PVA) (Alfa Aesar) and
Aluminium Titanium trioxide (Al2O3) (Fischer Scientific, India).

2.2 Preparation of PVAl composites

A definite quantity of PVA was dissolved in water at 60 o C followed by the addition of a known quantity of Al2O3
and then it was made into a paste in an agate mortar and was subjected to heat at 80 ° C for 30 minutes in a hot air
oven and made into a powder. PVAl composites were prepared in the following proportions of PVA and Al2O3:
PVAl 1 – 9:1, PVAl 2 – 8:2, PVAl 3 - 7:3, PVAl 4 -6:4, PVAl 5 – 5:5 and PVAl 6 – 4:6.

2.3 AC conductivity

Composite samples for conductivity measurements were disc shaped and studied over the temperature range
from 30°C to 60°C using Hioki 3522-50 LCR Meter.
The measured conductance G, from 50 Hz to 5 MHz is used to calculate ac conductivity, σ(ac) using the
following expression:
σ(ac) = G d/A (1)
where d is the thickness of the sample and A is the cross sectional area of the electrode.
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3. Results and Discussion

3.1. XRD

The XRD pattern of pure PVA Figure 1 shows a characteristic peak for an orthorhombic lattice centered at 19.40
and 40.0o, indicating the presence of semicrystalline phase [17]. The average grain size is found to be 0.1486µm.

Fig. 1 XRD pattern of PVA

The peak positions (2θ =37.53( 3 1 1), 39.27 (2 2 2), 45.66(4 0 0), 66.60 (4 4 0) and 84.46o (4 4 4 ) and relative
intensities obtained for Al2O3 match with the JCPDS Card no. 50-0741 file, identifying it as Al2O3 with γ phase
Figure 2. The average crystallite size is found to be 0.1654 µm.

Fig.2 XRD pattern of Al2O3

Upon addition of Al2O3 to PVA, the peak broadens and shifts toward higher 2θ values. This feature ascertains
improvement in system morphology with complete absorption of Al2O3 particles in the PVA matrix. At higher
concentrations of Al2O3 , the characteristic reflections of Al2O3 start reappearing. (Figure 3(i) – (iii)). Peak at around
68° is due to Al2O3 with plane value (4 4 0). The average crystallite size is found to be 0.1424 µm. From the XRD
study, it is concluded that Al2O3 particles are homogenously dispersed throughout the polymer matrix with
maximum uptake of Al2O3. The XRD pattern reveals that the intensity of peaks decreases as the oxide content
increases. The strong and sharp diffraction peaks in Al2O3 and PVA indicate higher crystallinity, which disappear in
case of polymer composites which in turn contributes to higher conductivity.
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Fig.3 (i) XRD patterns of PVAl 1 and 2

Figure 3 (ii) XRD patterns of PVAl 3 and 4

Figure 3 (ii) XRD patterns of PVAl 5 and 6

3.2. FTIR

The absorption band in the region 3528-3115 cm-1 is due to the intermolecular hydrogen bonded O-H stretching
frequency of PVA [18]. It shows chemical bond positions such as O-H stretching at 3324 cm-1, C-H stretching at
2945 cm-1 , CH-OH bending at 1435 and 1337 cm-1 , C-O stretching at 1085 cm-1 and C-C stretching at 813 cm-1
(Figure 4).

Fig. 4 FTIR spectrum of PVA

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An absorption band at 1620 cm-1 is observed which is in accordance with reported literature [19]. The band at 1040
cm-1 corresponds to the Al-O stretching vibration [20]. Absorption bands at 649, 657, 474, 490 cm-1 are due to Al-O
stretching (Figure 5) vibrations [21].

Fig.5 FTIR spectrum of Al2O3

The spectrum of PVAl composites show the main characteristic band of PVA at 3710 cm-1 is due to O-H stetching.
A broad and strong peak at 3222 cm-1 is shifted to 3388 cm-1 is due to the stretching vibrations of O –H group in the
composite. The peaks due to –CH and –CH2 asymmetric stretching, -CH2 bending, C-O-C stretching, C-H-OH
bending, CH rocking is also shifted when compared to PVA. The presence of band at 1714 cm-1 confirms the
presence of free carboxylic acid group in the composite [22]. The characteristic Al2O3 bands are shifted to 2358,
2338, 2220, 2177, 2169, 2150, 2075, 2083, 2041, 2007, 1971, 1955, 1944, 1922 cm-1 respectively. Upon the
addition of Al2O3 to PVA, the intensity of peaks decreases which in turn decreases the crystallinity of host polymer
and favours ionic conduction (Figure 6(i) – (iii)).

Figure 6 (i) FTIR spectra of PVAl 1 and 2

Figure 6 (ii) FTIR spectra of PVAl 3 and 4

 S. Devikala et al. / Materials Today: Proceedings 14 (2019) 288–295 293

Figure 6 (iii) FTIR spectra of PVAl 5 and 6

3.3. SEM

The SEM images of PVA and PVAl 6 is shown in the figure 7. SEM image reveals the spherical shape and porous
nature of polymer composites. The surface of the composites is mostly homogenous, although several rounded
lumps projected from the surface. The morphology indicated that the beads have rough surfaces. The presence of
beads proved that ceramic oxides are scattered inside the PVA matrix. Incorporation of Al2O3 into the PVA matrix,
reduces the crystallinity and alters the original polymer structure and thus the conductivity of polymer composites
increases. When the concentration of ceramic oxides are increased, the ceramic oxides are well dispersed and
micropores distributed in part in the entire region of surface. It shows that the crystallinity of the composites
decreases as the concentration of oxide is increased and it resembles the XRD pattern and also responsible for higher
conductivity. From the micrograph of composites, it can be seen that the addition of ceramic oxides increases the
pore size, as a result of higher ionic conductivity [23]. It could be concluded that the presence of homogenous pore
structure, which leads to ion mobility, hence higher conductivity.

Fig. 7 SEM images of (a) PVA (b) PVAl 6

3.4. DSC

The Tg of pure PVA is found to be 88 °C whereas for PVAl 1 and PVAl 6 the values are found to be and 87 and
85 °C respectively. The Tg of polymer composites is decreased as compared to pure PVA as shown in the figure.
The thermal stability is decreased probably due to the additive effect of Al2O3 and the chemical reaction between
PVA and Al2O3. The polymer phase is identified as a medium of transport and reservoir for conducting ions. The
ceramic oxides also improves the transport of charge carriers trough the localized influence on the polymer chain
conformation (Figure 8). It is also observed that composite with higher Al2O3 content, possess low Tg value. This
may be attributed to highest conductivity of PVAl 6. It can be concluded that the ceramic not only facilitates for
ionic conductivity but also interacts with the polymer phase.
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Fig.8 DSC plots of (a) PVA (b) PVAl1 and (c) PVAl 6

3.5. AC Conductivity

The room temperature AC conductivity and the temperature dependence of PVA and PVAl composites are shown in
Table 1. The conductivity is found to increase with the temperature as well as with Al2O3 concentration. The
increase in conductivity with temperature is interpreted as a hoppping mechanism between coordinate site, local
structural relaxations, and segmental motion of the polymer. The observed continuous increase in conductivity of
composites system with increasing Al2O3 concentration is attributed to a decrease in degree of crystallinity and
increase in amorphisity and was confirmed by XRD studies. As amorphous region progressively increases, however
the polymer chain acquires faster internal modes in which bond rotations produce segmental motion. This is turn
favours hopping interchain and intrachain ion movements, and conductivity of polymer composites thus becomes
high. The high AC conductivity at high temperature could be attributed to small polaron hopping [24]. The increase
in conductivity with temperature may be explained based on the assumption that within the bulk, the oxygen
vacancies due to the loss of oxygen, are usually created during increase in temperature and the charge
compensation, which would leave behind free electrons. In metal oxides, electrical conduction occurs through strong
coupling between phonons and electrons with the creation of polarons . The increase in electrical conductivity with
Al2O3 concentration is due to an increase in the number of mobile charge carriers and a decrease in the crystallinity
of the host polymer [25-27].

Table 1 AC conductivity of PVA and PVAl composites at different temperatures

Conductivity (S/cm)
System studied 303K 313K 323K 333K

PVA 4.45X10-9 5.74X10-9 7.62X10-9 3.56X10-8

PVAl 1 1.11 X10-8 1.34X10-7 1.50X10-6 1.16X10-5
PVAl 2 2.35 X10-8 2.90X10-7 2.59 X106 2.97X10-5
PVAl 3 3.56 X10-8 3.73X10-7 3.68 X106 3.73X10-5
PVAl 4 4.98 X10-8 4.74X10-7 4.05X10-6 4.49X10-5
PVAl 5 5.14 X10-8 5.33X10-7 5.86X10-6 5.42X10-5
PVAl 6 6.32 X10-8 6.75X10-7 6.92X106 6.52X10-5

Conclusion

PVA/Al2O3 composites were prepared by using sol gel method. The composite samples were characterized by
XRD, FTIR, DSC and SEM. As the temperature increases, the charge carries are thermally activated and the free
volume increases and more vacant sites are created for the motion of ions, which in turn enhances the conductivity.
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