Natural rubber/Polyaniline nanofiber composites

Chapter 3
NATURAL RUBBER/POLYANILINE
NANOFIBER COMPOSITES
Part A
Synthesis and characterization of polyaniline nanofibers
Contents

Part B
Preparation and characterization of Natural rubber/
polyaniline nanofiber composites

Part A

Synthesis and characterization of polyaniline nanofibers

3A.1 Introduction
Conducting polymers are unique as substitutes for conductors and
semiconductors. Several research groups have been pursuing the goal of
preparing a tailor made conducting polymer with respect to its electrical,
mechanical, optical and thermal properties. The main drawback of intrinsic
conducting polymers is their low processability since they are insoluble in
most of the organic solvents and even the solvents capable of dissolving
them cannot make a coherent film. Improving processability is an essential
requirement for developing practical applications for conducting polymers.
For this reason, significant research efforts in the past several years have

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been directed towards the synthesis of processable forms of conducting

polymers and their nanocomposites [1]. Among conducting polymers,
polyaniline is considered to be the oldest, unique and most useful, because
of its simple synthesis methods and peculiar acid/base doping/dedoping
characteristics. Aniline is comparatively cheap and polyaniline can be
prepared economically with good environmental stability, redox reversibility,
and electrical conductivity. It has the potential to be used for a wide
variety of applications which include antistatic coatings, anticorrosion
coatings, separation membranes, batteries and sensors [2].

Nanostructured polyaniline (with dimension smaller than 100 nm) has

been of great interest during the past few years because of its novel
properties and enhanced performance. Conventional synthesis of polyaniline is
known to produce large particulates with irregular shapes. Eventhough in
conventional polymerization at the initial stages of preparation nanofibers
are formed, they undergo secondary growth to form irregularly shaped
particles leading to the formation of granular agglomerates. Therefore
modifications of conventional polymerization technique have been developed
to make nanostructures of polyaniline (PAni).

One of such methods is to introduce “structural directing agents” in

the reaction mixture during the polymerization. Structural directing agents
used for the purpose of preparing nanostructures of PAni include,
surfactants [3-4], liquid crystals [5], polyelectrolytes [6], nanowire seeds
[7], aniline oligmers [8], and bulky organic dopants [9-10]. These groups
of chemicals act as either hard templates (e.g., polyelectrolytes) or
promote the formation of “soft templates” (e.g. micelles, emulsions)
capable of producing PAni nanostructures [11]. Another method is
chemical oxidization via interfacial polymerization which utilizes an
immiscible interface formed in water and organic solvent.

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Zhang et al. prepared PAni nanoparticles having enhanced microwave

absorption properties by a reverse dropping method with the assistance of
polyvinylpyrrolidone (PVP) and found that PVP and the dropping rate play
critical roles in determining the morphology of prepared PAni particles
[12]. Kim et al. prepared nano PAni in amphiphilic copolymer micelles. In
the synthesis, hydrophobically end capped polyurethane resins aggregating
in flower type micelles at low concentration, were used as nano reactors.
The prepared nanoparticles were in "donut-like" shape [13]. Li et al. prepared
PAni nanoparticles by an in-situ electro deposition. The morphologies of PAni
nanoparticles could be controlled by the growth time in the electrodeposition
process [14].

Of late, preparation of one-dimensional (1D) nanostructures of PAni

such as nanofibers, nanotubes and nanobelts has attracted a great deal of
interest because of the combined advantages of nano dimensional systems
and organic conductors. They possess high potential to be used in applications
such as gas-separation membranes [15], conducting molecular wires [16], light
emitting and electronic devices [17], chemical sensors [18], biosensors [19]
and neuron devices [20].

Huang et al. were the first to report that PAni nanofibers can be
prepared by an interfacial polymerization without the use of any templates.
The prepared nanofibers were of diameter from 30 nm to 50 nm and length
from 500 nm to several micrometers [21]. In interfacial polymerization PAni
nanofibers formed at the interface migrate to the aqueous phase and get
separated from the monomers and oxidants sealing off the possibility for
further polymerization thus preventing the nanoparticles formed initially
from growing into irregular shaped granular particles. This results in the
continued formation of primary nanofibers without any secondary growth
[22]. Jing et al. demonstrated that ultrasonic synthesis is an effective

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method for preparing PAni nanofibers with higher yield and solubility
[23]. Chiou et al. also synthesized PAni nanofibers without using any
templates. They adopted dilute polymerization with reduced concentrations
of both monomer and oxidant and a constant molar ratio. Diameters of
PAni nanofibers obtained were tunable by appropriate selection of
dopant acids. A dispersion of PAni nanofibers could be cast to form
highly porous nanofibrous films without deformation of the nanofiber
morphology [24].

Huang et al. were able to prepare PAni nanofibers by a simple

method of rapidly mixed reactions. In the method initiator and monomer
solutions in 1 M HCl are rapidly mixed together all at once. Therefore the
initiator molecules are depleted during the formation of nanofibers,
disabling further polymerization which leads to overgrowth [25]. All of
the aniline and oxidant are consumed during the formation of the primary
nanofibers itself, thus suppressing any secondary growth from the surface
of the primary nanofibers.

In this part of the work, we studied the effect of preparation methodology

on the morphology and properties of PAni. The first method of preparation
followed the conventional procedure for making PAni. In the second
method, rapid mixing was utilised to prepare nano fibers of PAni. In both
cases ammonium persulphate was used as initiator, keeping aniline/initiator
molar ratio as 1:1.25. PAni prepared by the two methods were characterized
and compared.

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3A.2 Experimental
3A.2.1 Materials
Aniline, ammonium peroxydisulphate and hydrochloric acid (HCl).
3A.2.2 Preparation of PAni
3A.2.2.a Preparation of PAni by conventional method
1g of aniline monomer was dissolved in 100 ml 1 M HCl. Ammonium
peroxydisulphate (5g), dissolved in 100 ml 1 M HCl, was added dropwise
to the monomer-acid mixture with constant stirring. After the complete
addition of ammonium peroxydisulphate, stirring was continued for 12 hours.
The precipitate formed was filtered, washed with 0.2 M HCl and then with
acetone till the filtrate became colorless. The filtrate was then dried in an air
oven at 60 °C. The powder obtained was pelletized by using KBR PRESS
MODEL M-15 of Technosearch Instruments.

3A.2.2.b Preparation of PAni nanofibers

Aniline monomer was taken in a beaker. 1M HCl was added. Ammonium
peroxydisulphate was dissolved in 1M HCl and added to monomer-acid
mixture rapidly in a stretch without stirring. Aniline to ammonium persulphate
ratio was kept 1:1.25 and left undisturbed for 12 hours. The precipitate formed
was filtered, washed with three 100 ml portions of 0.2 M HCl and then with
acetone till the filtrate became colorless. The filtrate was then dried in an air
oven at 60 °C. The powder obtained was pelletized by using KBR PRESS
MODEL M-15 of Technosearch instruments.

3A.2.3 Characterization
Scanning electron microscopy (SEM), X- ray diffraction (XRD), thermo
gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR)
and conductivity measurements were used to characterize PAni.

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3A.3 Results and discussion

3A.3.1 Scanning electron microscopy

a b

Fig. 3.1 (a & b): SEM images of PAni prepared in conventional method

a b

Fig. 3.2 (a & b): SEM images of PAni nanofibers

Figs. 3.1 and 3.2 show the morphology of the PAni prepared by
conventional and rapid mixing methods respectively. a and b denote lower
and higher magnifications as seen through the scanning electron microscope.
Conventional preparation method produces PAni particles agglomerated to
large irregular shapes with some of them in fiber form. At the same time,
PAni prepared by rapid mixing method consists exclusively of nanofibers
with a uniform size of 40-50 nm. This indicates the effectiveness of the
rapid mixing method.

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3A.3.2 X- ray diffraction studies

Varying patterns of X-ray diffraction are shown by PAni due to the
irregular arrangement of polymeric chains. It varies depending on the
synthesis route, solvent used and ionization state. The XRD patterns of
PAni prepared by different methods have been reported to show
various percentages of crystallinity [26]. XRD pattern of PAni synthesized
through conventional stirring method is shown in Fig. 3.3. Peaks observed
are with 2θ values of around 14º, 18º and 25º along with other prominent
peaks. This is similar to the results reported by Shukla et al. [27] in the
preparation of highly crystalline PAni. So it can be inferred from the XRD
spectum that conventionally synthesized PAni has a highly crystalline
nature.

Fig. 3.3: XRD patten of PAni prepared in conventional method

XRD pattern of the synthesized PAni nanofibers is shown in Fig. 3.4.

The figure shows broad peaks at 2θ of around 20° and 27°. Similar pattern
has been reported by Kavitha et al [28]. The absence of sharp peaks in the

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diffraction pattern is typical of large molecular weight PAni [26]. Thus the
XRD spectrum reveals amorphous nature and high molecular weight of the
synthesized PAni nanofibers. The high molecular weight of the PAni
nanofibers may be the reason for its higher conductivity over conventionally
prepared PAni.

Fig. 3.4: XRD patten of PAni nanofibers

3A.3.3 Thermo gravimetric analysis

Figs. 3.5 and 3.6 show TG and DTG (derivative thermogravimetry)
curves of PAni prepared by conventional stirring method and rapid mixing
method respectively. PAni prepared by both methods show a four step
decomposition process. The initial stage of weight loss is due to the
volatilization of water. Second stage is the elimination of oligomers and
unreacted monomers. At higher temperatures the protonic acid component
of the polymer is lost and finally at more extreme temperatures the polymer
chain break can lead to production of gases such as acetylene and ammonia

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[29]. The degradation behavior can be better understood by DTG curves in

Fig. 3.6. The first peak around 100 C corresponds to the loss of moisture.
The second degradation corresponds to monomer as well as oligomer
elimination. Next stage of degradation around 270 C is due to dopant
evolution and the final continuous decrease in weight occurs due to
degradation of PAni chain. The considerable residue due to the formation
of stable carbonaceous char is typical of the aromatic polymer backbone. In
the case of conventional method, the continuous stirring results in almost
complete conversion of monomers and oligomers, to long polymer chains. As a
result the second peak corresponding to the elimination of unreacted
monomers and oligomers is much shortened compared to the similar peak
in rapid mixing method in which the conversion percentage of monomers
and oligomers to long polymer molecules is less. In the case of PAni
nanofibers formed by the rapid mixing method, the dopant molecules are
more strongly bonded due to higher surface area. So the peak corresponding
to dopant elimination shifts to a higher temperature.

Fig. 3.5: TG curves of PAni

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Fig. 3.6: DTG curves of PAni

3A.3.4 FTIR studies

Fig 3.7: FTIR spectrum of PAni

The FTIR spectrum of PAni shows C=N in the quinoid units appearing
at 1565 cm-1. Stretching of benzoid ring is observed at 1410 cm-1 and N-H
stretching at 3217 cm-1 [30].

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3A.3.5 Conductivity measurements

The conductivities of PAni prepared by different methods are given in
Table 3.1 It can be seen that conductivity of PAni prepared by rapid mixing
method is one order of magnitude higher than PAni prepared by
conventional method. The high molecular weight, uniform size and fiber
nature of PAni prepared by rapid mixing method makes the conduction of
charge through the polymer easier than that through the non-uniformly
shaped and sized PAni prepared by conventional method.

Table 3.1: Conductivities of PAni

Conductivity (S/cm)
Conventional method Rapid mixing method
-1
4.61 X 10 1.234

3A.4 Conclusions
PAni prepared via the rapid mixing method was found to be in nano
dimensions with fiber morphology, while conventional method produced
agglomerated particulates with irregular structure. The PAni nanofibers
have diameters below 100 nano meter and length more than 500 nano
meters. XRD pattern of the PAni nanofibers contains broad peaks as a result
of the nano scale structure and high molecular weight. The prepared PAni
nanofibers follow the typical thermal degradation pattern of PAni, but with
higher thermal stability. Conductivity of the PAni nanofibers is in the order
of 1.2 S/cm, one order of magnitude higher than that of PAni prepared by
conventional stirring method.

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Chapter 3

Part B

Preparation and characterization of Natural rubber/polyaniline nanofiber

composites

3B.1 Introduction
Considerable effort has been focused on applied research in the field of
conducting polymers to turn them into useful products. Conducting
polymers possess interesting inherent electrical and optical properties which
can be utilized in applications such as organic solar cells, printing electronic
circuits, organic light-emitting diodes, actuators, super capacitors, chemical
sensors, flexible transparent displays, electromagnetic shielding etc. Ever
since the discovery of its conducting forms, polyaniline (PAni) has been
one of the most studied conducting polymers. A fundamental problem
hindering the extensive use of PAni in intended applications is the
limitations on processability. One way of overcoming these problems is to
prepare blends and composites of conducting PAni with non-conducting
polymers. Such composites possess mechanical properties of the insulating
host and electrical properties of the conducting guest [31]. Electrical
properties of these composites depend on concentration, size and shape of
conductive particles [32]. Extend and anisotropy of the dispersion of
conducting particles in the host matrix also plays a major role in determining
the mechanical and electrical properties.

The potential applications of the conducting composite materials have

lead to the formation of several methods for the preparation of these
materials and each processing method has significant influence in
determining its properties. The methods include simple grinding [33], zone
casting [34], two- step reticulate doping [35], electrochemical method [36],

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blending method [37-38], grafting reaction [39-41], two phase synthesis

[42-43] and in-situ polymerization method. Srivastava et al. used nucleate
doping method to prepare a three component composite when the conducting
polymer was difficult to dissolve in any solvent [44]. Among the different
methods proposed for the preparation of conducting composites, blending
method seems to be technologically more desirable for large-scale production,
particularly with melt processing techniques. Blending methods can probably
become more practical when techniques to produce inexpensive, nano-sized
PAni are well developed [45].

Flexible composites consisting of conductive filler particles dispersed

in a non conducting matrix can be used in applications such as strain
sensors [46], electronic eyeball cameras [47], flexible LED display devices
[48-49], stretchable electrodes [50], die attach [51], thermistors [52] and
pressure-sensing elements [53]. Other uses of such composites include
electromagnetic shielding, antistatic devices [54] and chemical sensors [55].
An ideal flexible matrix for the composites would be an elastomer which
can offer high extensibility and elasticity.

In this part of the work, we used natural rubber (NR) as the matrix
material for the composites. Natural rubber is a unique biopolymer of
strategic importance such that it cannot be replaced by synthetic alternatives
in many of its most significant applications. The uniqueness of NR lies in
its remarkable extensibility and toughness, as evidenced by its ability to be
stretched repeatedly to seven or eight times its original length. The conducting
ingredient, PAni nanofibers, was incorporated into NR by mixing in a two
roll mill along with other compounding ingredients. The compound obtained
was vulcanized in a compression mould using hydraulic press. The vulcanized
sheets were evaluated for mechanical, thermal, electrical and shielding
properties.

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3B.2 Experimental
3B.2.1 Materials
Natural rubber (ISNR-5), zinc oxide, stearic acid, TQ (1,2-dihydro-
2,2,4-trimethylquinoline) ZDBC (zinc dibutyldithiocarbamate) sulphur and
polyanilne nanofibers.

3B.2.2 Preparation of NR/PAni nanofiber composites

PAni nanofibers were prepared by the chemical oxidative polymerization
of aniline using ammonium peroxydisulphate as oxidant and HCl as dopant
according to the method explained in section 3A.2.2.b of this chapter. The
formulation for the preparation of the composites is given in Table 3.2. A
low temperature vulcanization system using zinc dibutyldithiocarbamate
was employed with filler content varying between 0 and 90 phr.

Table 3.2: Formulation of the mixes

Ingredients Phr
NR 100
PAni nanfibers 0, 30, 50, 70, 90
ZnO 4
Stearic acid 2
TQ 1
ZDBC 1.5
Sulphur 2

A series of NR/PAni nanofiber composites were prepared, with

varying amounts of the PAni nanofibers as per the processing method
described in section 2.2 of Chapter 2.

3B.2.3 Characterization
Cure characteristics, mechanical properties, Thermo gravimetric analysis
(TGA), Dynamic mechanical analysis (DMA), Morphology studies, DC

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electrical conductivity, Dielectric properties, Microwave properties and EMI

shielding measurements were used to characterize NR/PAni composites.

3B.3 Result and discussion

3B.3.1 Cure characteristics
Figures 3.8 and 3.9 show the variation of cure time and scorch time, with
PAni loading of the composites. Cure time and scorch time increase with PAni
loading. This is because of the acidic nature of HCl doped PAni. An acidic
ingredient added to the rubber matrix generally retards sulphur vulcanization.

Differential torque is the difference between maximum and minimum

torque experienced in Rubber Process Analyzer during the curing process at
90 °C. Figure 3.10 shows the variation of differential torque with PAni
loading. Differential torque increases almost linearly with PAni loading.
This shows that with increase in the amount of PAni, matrix is being
increasingly restrained.

Fig. 3.8: Variation of cure time with PAni content

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Chapter 3

Fig 3.9: Variation of scorch time with PAni content

Fig 3.10: Variation of differential torque with PAni content

3B.3.2 Mechanical properties

Tensile strength of the PAni rubber composites as a function of PAni
content is given in Fig.3.11. Tensile strength gradually decreases with
increasing PAni content. Natural rubber being nonpolar is incompatible with

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the polar PAni and the interaction between the two would be minimum,
especially in the absence of any compatibilizer. So PAni, instead of
contributing to the reinforcement will act as an idle constituent in the
matrix. At high strains PAni will be debonded from the matrix. The voids
formed act as stress concentrators leading to the early failure of the
composites and lowering the tensile strength with increasing PAni
content.

Fig. 3.12 shows the variation of tear strength with PAni loading. Tear
strength increases at lower loading of PAni. This may be due to the fiber
nature of PAni, which is oriented in a direction perpendicular to the
propagation of crack front. This orientation will be effective in deviating or
arresting the crack propagation. At higher loadings ineffective dispersion of
nano PAni leads to the formation of agglomerates. These agglomerates act
as weak points causing the reduction of tear strength.

Fig. 3.11: Variation of tensile strength with PAni content

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Chapter 3

Fig. 3.12: Variation of tear strength with PAni content

Fig. 3.13 shows the variation of modulus with PAni content. The modulus
goes on increasing with PAni content unlike in the case of tensile strength
where the property decreases.

Fig. 3.13: Variation of modulus with PAni content

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The modulus is measured at low strains. These strains are not high enough
to initiate cracks by stress concentration at agglomerates of PAni at higher
PAni loadings, whereas high strains involved in the case of tensile strength
measurements leads to failure by stress concentration and resultant crack
initiation at PAni agglomerates.

Fig. 3.14 shows the variation of elongation at break of the composites

with respect to PAni content. Elongation at break decreases steadily with
PAni content. The incompatibility of NR and PAni cause micro voids to form
at higher elongations. These voids will act as points of stress concentration
resulting in premature failure of the composites and thus reducing the
elongation at break.

Fig. 3.14: Variation of elongation at break with PAni content

3B.3.3 Thermogravimetric analysis

The TG curves of the composites are shown in Fig. 3.15. NR/PAni
composites are represented as NR/P x where „x‟ denotes the amount of PAni in
the composites. The pure NR samples show a single degradation step while the

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NR/PAni composites show additional degradation steps in their thermograms.

The degradation behavior can be better understood by differential
thermogravimetry curves given in Fig. 3.16. Pure NR shows degradation
between 350 to 500 C. For NR/PAni composites the first stage of degradation
starts at 125 C due to oligomer elimination and second stage, which
corresponds to dopant elimination, begins at 270 °C. The peak due to the
dopant evolution overlaps with the degradation peak of NR which begins at
350 °C. The entire NR/PAni composites show lower degradation rate than the
GUM (sample without PAni) due to the lower rate of degradation of PAni
compared to NR. With increase in PAni loading rate of degradation
decreases, with 90 phr composites showing the least rate of degradation.
NR/PAni composites show more residue than pure NR and it increases with
increase in PAni loading. This may be due to the formation of stable
carbonaceous char which is greater in the case of aromatic compounds.

Fig. 3.15: TG curves of the NR/PAni composites

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 Natural rubber/Polyaniline nanofiber composites

Fig. 3.16: DTG curves of the NR/PAni composites

3B.3.4 Dynamic mechanical analysis

Variation of storage modulus with frequency in dynamic mechanical
testing of the PAni composites is shown in Fig. 3.17. Theoretically, increasing
the frequency has the same effect of decreasing the temperature on the
composites. At low temperature, storage modulus will be high. When the
temperature is gradually raised to the glass transition of the sample there will
be a large decrease in storage modulus. When the temperature is above glass
transition, that is when the sample is at the rubbery plateau, the modulus
remains constant. Accordingly, with increase in frequency, storage modulus
increases. There is a marked increase in the storage modulus beyond a
frequency of 21.25 Hz. This could be equated to the transition region of the
composites. A corroborating trend is observed in the case of loss modulus
(Fig. 3.18) also. Loss modulus shows a maximum at frequencies beyond
21.25 Hz and then decreases. This can be considered similar to the loss
modulus behavior at the transition region. Storage modulus increases with
PAni content. The composites follow the same trend as in the case of tensile
modulus. Even though the tensile strength decreases with PAni content, at low

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strains as that encountered in frequency sweep tests, the modulus goes on

increasing with PAni content. The loss modulus also increases with PAni
content. With increase in PAni content the loss at filler-filler and filler matrix
interface increases especially when there is low interaction between the non
polar matrix and the polar filler.

Fig. 3.17: Variation of storage modulus with frequency of NR/PAni composites

Fig. 3.18: Variation of loss modulus with frequency of NR/PAni composites

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3B.3.5 Scanning electron microscopy

a b

Fig. 3.19 (a & b): Morphology of fracture surface of NR/PAni composite with
70 phr PAni content

Figs. 3.19 (a & b) show the fracture surface of NR/PAni composite with
70 phr PAni content. The PAni phase can be seen distributed throughout the
matrix which makes it possible to form a continuous network of conducting
nano particles. This is cofirmed by the percolation threshold reached at a PAni
content of 70 phr as revealed from conductivity measurements.

3B.3.6 Conductivity measurements

Fig. 3.20: DC electrical conductivity of NR/PAni composites

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Chapter 3

The DC electrical conductivity of NR/PAni composites is presented in

Fig 3.20. With increase in PAni content, the conductivity of the composites
increases. But the increase is nominal up to a PAni content of 50 phr.
Beyond this filler loading, at 70 phr, a sharp increase in conductivity is
observed. This indicates that the percolation threshold of NR/PAni composites
is at 70 phr loading. Thereafter, the rate of increase of conductivity is lower
showing a tendency to reach a plateau.

3B.3.7 Dielectric properties

(i) Frequency dependence of dielectric properties
The dielectric properties of NR/PAni composites were evaluated at
room temperature. The effect of frequency on the dielectric constant (real
part of complex permittivity) of NR/PAni composites is shown in
Fig. 3.21. At low frequencies dielectric permittivity is high and it
decreases exponentially with increasing frequency. At low frequencies,
the dipoles can rotate and charge carriers can move following the direction
of the external electric field and change the polarization. The time lag
between the change in polarization and applied electric field is called
relaxation time. At higher frequencies, that is, when the time period of
oscillation of electric field is lower than the relaxation time, the dipoles
and charge carriers may not be able to remain aligned with the external field
and cannot contribute to the polarization of the material thus decreasing the
dielectric constant.

As the composites are heterogeneous, there will be interfaces between

the individual constituents [56]. The buildup of space charges at these
interfaces causes polarization called Maxwell-Wagner-Sillars interfacial
polarization. As the frequency increases the phase lag between polarization
and the external electric field results in reduced dielectric permittivity. As
the PAni content increases in the NR/PAni composites rubber/filler interfaces

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increase resulting in improved interfacial polarization and increased

dielectric constant.

Fig. 3.21: Variation of dielectric constant with frequency of NR/PAni

composites

The variation of dielectric loss, the imaginary part of complex

permittivity, with frequency is shown in Fig. 3.22. It decreases with
increase in frequency as in the case of dielectric constant. Dielectric loss
is the dissipation of energy in a dielectric material through the movement
of charged particles under an alternating field. PAni in the doped state
contains polaron/bipolaron system as free charges and dipoles as bound
charges [56]. Polaron/bipolaron system is free to move through the
conducting polymer under the influence of an external filed, while the
mobility of dipoles is restricted and cause polarization in the system under
the electric field.

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Chapter 3

Fig. 3.22: Variation of dielectric loss with frequency of NR/PAni composites

The orientation of the dipoles and bound ions faces resistance from the
surrounding matrix and lags behind the electric field by a definite time period
called relaxation time. Due to this, there is a phase difference between the
electric field and the polarization which appears as the dielectric loss. When the
frequency is high, that is, when the period of oscillation is much lower than the
relaxation time, the orientation of dipoles and bound ions or may not be able to
keep up with the alternating field. This reduces the dielectric loss. With the
increase in PAni content the space charge accumulation at the interface
increases, which increases the interfacial polarization which in turn increases
both dielectric constant and dielectric loss [57].

Variation of AC conductivity of NR/PAni composites with frequency

is plotted in Fig. 3.24. It shows an increase in conductivity with increase in
frequency. The total AC conductivity is given by the equation

AC = DC + As ....................................................................... (3.1)

where DC is the DC electrical conductivity, A is a constant depending on

temperature,  is the angular frequency (2f) and s is a fractional exponent

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 Natural rubber/Polyaniline nanofiber composites

whose value depends on both frequency and temperature and lies between
0 and 1.

At low frequencies DC conductivity is the prominent mechanism

which will mask the contribution from AC conductivity. DC conduction in
conducting polymers and composites is carried out via the hopping
mechanism of charge carriers, that is, polarons and bipolarons. With increase in
frequency the hopping of these charged species multiplies thereby increasing
the conductivity. At higher frequencies conductivity shows power law
behaviour according to equation (3.1). In NR/PAni composites an appreciable
rise in AC conductivity with frequency is noticed for 70 phr PAni content
where the composite exhibits percolation threshold. This confirms that the
prominent contributor of conductivity is the DC counterpart which increases
with increase in PAni content. The migration of polaron/bipolaron system and
ions is carried out through the formation of a conducting network. At a still
higher PAni content (90 phr) the conductivity increases by manifolds due to the
better inter particle contact of the conducting components.

Fig. 3.23: Variation of AC conductivity with frequency of NR/PAni

composites

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Chapter 3

(ii) Loading dependence of dielectric properties

Variation of dielectric permittivity with the loading of PAni is shown
in Fig. 3.24. The dielectric permittivity is found to increase with increase
in PAni content at all frequencies. The increase is more pronounced at
lower frequencies where dipoles and space charges at the interfaces orient
in the alternating field producing strong polarization. When PAni content in
the composites increases there will be more bound charges (dipoles) and
more conducing-non conducting interfaces enhancing the polarization and
hence the dielectric constant. At higher frequencies where the period of
oscillation is lower than the relaxation time, the polarization will not be able
to keep up with the frequency resulting in low dielectric constant. Since the
dielectric constant varies with the PAni content, it is possible to tune the
material for desired dielectric constant.

Fig. 3.24: Variation of dielectric constant with PAni content of NR/PAni

composites

The variation of dielectric loss with PAni loading at different frequencies

is shown in Fig. 3.25. Dielectric loss increases with increase in filler

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 Natural rubber/Polyaniline nanofiber composites

loading. Dielectric loss arises due to localized motion of charge carriers

(ions and polaron/bipolaron system). The increase in dielectric loss with
increase in loading is due to increased number of mobile charges. Apart
from the mobile charges the bound charges (dipoles) and the space charges
in the interfaces also contribute to dielectric loss by the phase difference
between the applied electric field and resulting polarization. With increase
in PAni content dipoles and interfaces also increase giving higher dielectric
loss. As in the case of dielectric constant, dielectric loss also gives higher
values at lower frequencies.

Fig. 3.25: Variation of dielectric loss with PAni content of NR/PAni

composites

The effect of loading of PAni on AC conductivity of NR composites is

depicted in Fig. 3.26. The conductivity increases with PAni content, as
expected. In conducting composites conducting polymers are dispersed in a
non-conducting polymer matrix and the formation of the conducting path is
through a network formation of conducting filler particles. For this type of
conducting path formation a critical amount of conducting fillers is needed.

97
Chapter 3

And this critical concentration depends upon filler properties such as

structure, size and surface area and the matrix properties such as polarity
[58]. The increase in AC conductivity with increase in conducting filler is
due to increase in charge carriers, that is, in this case increase in concentration
of polarons and bipolarons. An increased filler concentration results in the
reduction of inter particle distance and increases conductivity. Even when
there is a few nanometers gap between conducting particles the hopping
mechanism of charge conduction facilitates a continuous path through the
matrix.

For the same PAni loading, the conductivity is considerably higher for
higher frequency measurements. In conducting polymers and its
composites, conductivity is mainly through the hopping mechanism of
charge carriers- polarons and bipolarons. At high frequencies the hopping
of charged species multiplies thereby increasing the conductivity.

Fig. 3.26: Variation of AC conductivity with PAni content of NR/PAni

composites

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 Natural rubber/Polyaniline nanofiber composites

3B.3.8 Microwave studies

The variation of the real part of permittivity (ɛ) with PAni content of
NR/PAni composites in X and S bands, respectively is shown in Figs. 3.27
(a & b). In both bands, ɛ increases with PAni content. According to
Koops [59], the dielectric permittivity is inversely proportional to the
square root of resistivity. Conductivity of the composites increases with
PAni content especially beyond the percolation threshold. In a conducting
composite, the conducting polymer is separated by an insulating matrix
causing space charges to accumulate at the interfaces on application of an
electric field. The alternating electric field induces interfacial polarization
along with intrinsic dipole polarization [60] arising from the permanent
electric dipoles of doped PAni. Both these polarizations contribute to the
dielectric permittivity. Variation in ɛ with respect to frequency is
insignificant especially in higher frequency X band.

Fig. 3.27.a: Variation of real part of permittivity with PAni content of

NR/PAni composites in X band

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Chapter 3

Fig. 3.27.b: Variation of real part of permittivity with PAni content of

NR/PAni composites in S band

The variation of imaginary part of permittivity (ɛ) with PAni loading

in X and S band frequencies is shown in Figs. 3.28 (a & b). In both bands
ɛ increases with increase in PAni loading as in the case of ɛ. Dielectric
loss (ɛ) is a measure of energy dissipated in the form of heat in a
dielectric material. It is caused by the movement of polarons, bipolarons
and ions through the material under the influence of an alternating electric
field. The phase difference between the electric field and the polarization
in the material also appears as dielectric loss. In conducting composites
where a conducting polymer is dispersed in a nonconducting matrix,
dipolar and interfacial polarization are mainly responsible for the
dielectric loss. With increase in PAni content, the number of dipoles in the
bulk of the material and space charges in the interface increase enhancing
the ɛ in the material. In both bands increase in frequency does not have a
significant effect on ɛ.

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 Natural rubber/Polyaniline nanofiber composites

Fig. 3.28.a: Variation of imaginary part of permittivity with PAni content

of NR/PAni composites in X band

Fig. 3.28.b: Variation of imaginary part of permittivity with PAni content

of NR/PAni composites in S band

Loss angle, δ of a dielectric is the angle between the vectors for

capacitance current and total current. Tangent of the loss angle is equal
to the ratio of the imaginary to the real part of dielectric permittivity and
is called loss tangent or dissipation factor [61]. It is a measure of the

101
Chapter 3

energy lost in the form of heat in a dielectric placed in an oscillating field.

Figs. 3.29.a and 3.29.b show the variation of tan δ of NR-PAni composites
in X and S band frequencies, respectively. Loss tangent of all the
composites shows an increase with PAni content in both X and S bands.
The movement of polarons/bipolarons system through the matrix together
with, out of phase oscillations of dipoles and interfacial polarizations are
responsible for the dissipation of energy in NR-PAni composites. With
increase in PAni loading, the amount of charge carriers and extent of
polarization increase in the composites giving higher values for the loss
tangent. The increase is more pronounced beyond the percolation
threshold. The effect of frequency on tan δ shows a similar pattern as in ɛ
in both bands.

Fig. 3.29.a: Variation of tan δ with PAni content of NR/PAni composites in X

band

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 Natural rubber/Polyaniline nanofiber composites

Fig. 3.29.b: Variation of tan δ with PAni content of NR/PAni composites in S

band

3B.3.9 Electromagnetic interference shielding

The EMI shielding effectiveness of the composites at X and S bands
are shown in Figs. 3.30.a and 3.30.b. With increasing PAni loading the
shielding efficiency (SE) of the composites was found to be increasing.
EMI shielding may be due to reflection loss, absorption loss or through
multiple reflection at interfaces in the composites. For reflection to take
place the presence of charge carriers in the material is necessary [62]. The
polaron/ bipolaron system and bound ions present in PAni can contribute to
the shielding through reflection. The electric dipoles in PAni may aid in the
absorption assisted shielding. In the case of a non magnetic material where
relative magnetic permeability (r) is considered to be 1, both reflection loss
and absorption loss are related to conductivity and dielectric loss of the
material [63]. With PAni loading, both conductivity and dielectric loss
increases which in turn improves the shielding effectiveness. Considerable
improvement in SE after the percolation threshold can be due to the
increased conductivity.

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Chapter 3

Fig. 3.30.a: EMI shielding efficiency of NR/PAni composites in X band

Fig. 3.30.b: EMI shielding efficiency of NR/PAni composites in S band

The interfaces between the PAni and the matrix can play their part in SE
through multiple reflections. They also cause interfacial polarization and
corresponding dielectric loss thereby improving SE [64]. When PAni
loading increases interfacial polarization also increases [65]. SE through
absorption can also be related to skin depth through the equation

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 Natural rubber/Polyaniline nanofiber composites

SEA = 20 (t/δ) log e = 8.68 (t/δ),

where t is the sample thickness and δ is the skin depth.

With PAni content, skin depth decreases increasing absorption loss

[66].

From the figures it can be inferred that the composites exhibit higher
shielding efficiency at X band frequencies. So they can be used as effective
shielding materials for X band applications. In S band where the shielding
effectiveness is lower the composites can be utilized for static charge
dissipation [67-68].

3B.4 Application of NR/PAni composites

Pressure and temperature sensing

Sensors convert any form of energy to electrical or optical signals

while actuators convert electrical signal to mechanical signals. Sensors and
actuators are essential elements in industrial, automobile, aeronautic,
medicine and laboratory equipment. A main disadvantage of elements in
conventional sensors such as pressure gauges or temperature probes is their
lack of flexibility and incompatibility with large deformations [69]. Flexible
sensors adaptable to textile structures have been developed by integrating
metallic yarns or optical fibers [70]. An alternate way to develop flexible
sensors would be to use electro sensitive flexible conductive materials based
on conducting rubber composites [71-73]. These composites have advantages
of low weight, cost, flexibility, elasticity, easy processibility and mouldability
to large surface area products over conventional semiconductor materials. If
the conducting phase of the composite is a conducting polymer, they produce
observable electrical conductivity variations over changes in stress,
temperature, UV radiation and humidity [74-75].

105
Chapter 3

Electrical properties of conducting composites are dependent on

concentration, size and shape of the conductive particles [32]. Conducting
composites of PAni in different thermoplastic polymers have been prepared
where conductivity varies a few orders of magnitude with composition [76].
If the insulating matrix in the PAni composite is a rubber, its high
compressibility can be utilized for pressure sensing applications. In the
normal state the conduction mechanism in the composite is inter particle
hopping. On application of pressure the inter particle distance decreases
changing the conduction mechanism to that of a percolated network. There
has been earlier attempts to fabricate pressure and temperature sensors from
synthetic polyisoprene/PAni composites [77]. But the composites were in
the unvulcanised state which severely affected the elasticity and recovery
from deformation of the composites after the removal of pressure. This will
render the pressure sensor not usable after the initial use. If the composites
have been vulcanized (crosslinked) pressure sensing can be done repeatedly.

Here we have prepared a vulcanized conducting composite of natural

rubber and PAni and used it for pressure and temperature sensing
applications. The sheet of conducting composite was cut into required
dimensions and placed in a lab made setup for applying pressure while
measuring conductivity as shown in Fig. 3.31. The composite was placed
between two copper plates of the same dimensions and weights were placed
on the upper plate in increasing order which were converted to pressure
terms. Conductivity was measured for each pressure and plotted against
pressure. Then the weights were removed one by one measuring conductivity
again. Conductivity Vs pressure plot was prepared as shown in Fig. 3.32.

106
 Natural rubber/Polyaniline nanofiber composites

Fig. 3.31: Schematic diagram of setup for studying the effect of pressure on
conductivity

Fig. 3.32: Variation of conductivity with pressure in NR/PAni composites

To prepare the composite for temperature sensing applications the sheets

were heated on a hot plate to different temperatures from 25 C and the
surface conductivity was measured using a two probe method. A schematic
diagram of the set up is shown in Fig. 3.33. The variation of conductivity
with temperature is plotted in Fig. 3.34. Conductivity of the composite
decreases with increase in temperature. This may be due to the thermal
expansion of rubber upon being heated. In the expanded state inter particle
distance between the PAni domains increases disrupting the conducting
network and thereby reducing the conductivity. On lowering the temperature

107
Chapter 3

the trend is reversed but conductivity could not reach the level before the start
of the experiment. This shows the irreversible lose of conductivity at higher
temperatures. At 290 C the sheet becomes an insulator as shown in
Table 3.3. This change from semiconductor to insulator behavior of these
composites can be utilized in fuses which will blow up when the temperature
of the system goes beyond the danger level.

Fig. 3.33: Schematic diagram of setup for studying the effect of temperature
on conductivity

Fig. 3.34: Variation of conductivity with pressure in NR/PAni composites

Table 3.3: Effect of temperature on conductivity

Temperature State of conduction
Room Temperature Semi conductor
Above 290 C Non conductor

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 Natural rubber/Polyaniline nanofiber composites

3B.5 Conclusions
Flexible conducting composites of polyaniline nanofibers and natural
rubber were prepared through mill mixing. Cure time and scorch time of the
composites increased by the addition of polyaniline. The conductivity of the
composites increased with polyaniline content and showed a percolation
threshold at 70 phr. Continuous phase formation of polyaniline at 70 phr is
confirmed by SEM images. Static and dynamic modulus and tear strength
of the composites were found to be increased while tensile strength and
elongation at break were decreased. Thermal stability of polyaniline
composites reduced compared to GUM. Dielectric properties, microwave
absorption and shielding efficiency of the composites improved with
polyaniline content. Conductivity of the composites varies with pressure
and temperature, which can be used for pressure and temperature sensing
applications.

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