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J Polym Res (2013) 20:49

DOI 10.1007/s10965-012-0049-5

ORIGINAL PAPER

The effect of PEG encapsulated silver nanoparticles


on the thermal and electrical property of sonochemically
synthesized polyaniline/silver nanocomposite
Satyendra Mishra & Navinchandra G. Shimpi & Tanushree Sen

Received: 25 June 2012 / Accepted: 7 December 2012 / Published online: 19 December 2012
# Springer Science+Business Media Dordrecht 2012

Abstract An investigation of microstructure of polyaniline


nanocomposite is presented. The highly stable, semiconducting polyaniline/silver nanocomposites are prepared insitu, employing the acoustic cavitation mechanism to obtain
the composite in nanophase. The materials are characterized
by UV-visible spectroscopy (UVvis), transmission electron
microscopy (TEM), thermogravimetric analyzer (TGA) and
fourier transform infrared spectroscopy (FTIR). The polyaniline nanocomposites have an extended conformation in
N-methyl-2-pyrrolidinone (NMP), as seen from UVvis
spectra. The plasmon resonances for silver nanoplates are
also seen. A high thermal stability is observed for the polyaniline/silver nanocomposites which increased with increasing silver content. The TEM studies show that the
polyaniline is formed as nanofibers, with plate-like metallic
silver nanoparticles (50 nm35 nm in dimension) embedded into them. From the electrical conductivity measurements of pure polyaniline and its nanocomposites it was
found that incorporation of polyethylene glycol stabilized
silver nanoparticles leads to increased intermolecular charge
hopping that results in enhanced electrical conductivity of
the nanocomposites. TGA and DSC results indicated greater
thermal stability for the nanocomposites along with higher
crystallinity. A study of spreading resistance of the materials, done using scanning spreading resistance microscope,
revealed localized sites of high and low conductivity within
the polyaniline. The low conducting sites were fewer in the
case of nanocomposites.
Keywords Polyaniline nanocomposite . Ultrasound . Silver
nanoparticle . Electrical conductivity . Spreading resistance
S. Mishra (*) : N. G. Shimpi : T. Sen
University Institute of Chemical Technology, North Maharashtra
University, Post Box No. 80, Jalgaon 425001, India
e-mail: profsm@rediffmail.com

Introduction
Polyaniline (PAni) has been the subject of enormous interest
due to its reversible doping/dedoping character and modifiable electrical conductivity that is found to be dependent on
its molecular weight [1, 2], type of dopant [3] and pH of the
medium [4]. These also results in microstructural changes in
PAni, which have a pronounced effect on the polymers
physical and chemical properties [5, 6]. Chen CH has studied the morphological changes in PAni by variation in
dopant [7]. Microstructural changes in PAni arising from
synthetic method have also been reported by Zuev VV [8].
Apart from changes in synthetic methods in terms of dopants and oxidants, nanocomposites of PAni with noble metals like silver, gold and platinum [9, 10] have also been
investigated in an attempt to increase the stability and conductivity of the material. Silver, in particular, has been the
choice of metal for many because of its wide range of
applications in biomedical, industrial and electronics. Such
nanocomposite systems have the potential for applications
in rechargeable batteries [11], printed circuit boards [12],
sensors [13], biological templates [14], as supercapacitors
[15] and in electromagnetic interference (EMI) shielding
[16, 17]. However, an understanding of structureproperty
correlation is crucial to application of these materials in real
devices. Mishra et al. have already reported the effect of
microstructure on the physical properties of commercial
polymers [1831]. In the present study, we investigated the
effect of incorporated silver nanoparticles on polyanilines
microstructure, and consequently on its thermal and electrical properties. Numerous methods can be found in literature
for introduction of silver nanoparticles into the polyaniline
matrix [1, 3235]. We report a facile, in-situ preparation of
polyaniline/silver nanocomposite systems assisted by ultrasound. The silver nanoparticles were stabilized by polyethylene glycol (PEG). Structural characterization was done by

49, Page 2 of 10

FTIR and UV-visible spectroscopy. TGA and DSC were


employed for the thermal analysis. TEM was used to
determine the size and morphology of the prepared
nanocomposite, which reveals the effectiveness of ultrasound in producing nanostructured materials. The electrical
conductivity of the nanocomposites was determined using
four-point probe technique and scanning spreading resistance
spectroscopy (SSRM). The SSRM provided a newer perspective for evaluating the electrical properties of PAni/Ag
nanocomposites.

Experimental

J Polym Res (2013) 20:49

2 wt.%. Pure polyaniline was also prepared which is


denoted as 0 wt.% in the text. Pure polyaniline and its
composites were all in emeraldine salt form.
Characterization
Fourier transform infrared (FTIR) spectroscopy
Fourier transform infrared (FTIR) spectra of pure PAni
and its composites were recorded on FTIR-8400 spectrophotometer (Shimadzu, Tokyo, Japan) within the
wave number range of 4004,000 cm1. The samples
were prepared in the pellet form by mixing with potassium bromide.

Materials
Transmission electron microscopy
Analytical grade aniline and ammonium persulphate
(APS) were purchased from Fisher Scientific (Mumbai,
India). Silver nitrate was procured from s. d. fine chemicals ltd. Polyethylene glycol (Mw 06,000), sodium borohydride and and N-methyl-2-pyrrolidone (NMP) were
purchased from Qualigens Fine Chemicals, Loba Chemie and
Merck (Mumbai, India), respectively. Deionized water
was used for preparation of all solutions and for washing
purposes.
Synthesis
Aqueous solution of silver nitrate (1.4 mM) with PEG
(0.05 gm wt%) was sonicated using an ultrasonic probe
(BO3 Ultrasonic Processor UP1200, Cromtech India) for
15 min. This was followed by dropwise addition of NaBH4
solution, under ultrasound at room temperature. The silver
nitrate to NaBH4 mole ratio was kept at 1. The pale grey
coloured solution obtained was centrifuged at 20,000 rpm
for 10 min, washed with water and re-dispersed in
aniline solution by sonication. Oxidative polymerization
of aniline was carried out by addition of APS with an
oxidant to aniline mole ratio of 1.25. The solutions of
both aniline and APS were prepared in 1 M HCl. The
temperature of the reaction mixture was maintained at
20 C till completion of addition, after which it was left
to stand for 13 h at room temperature (this is not the
optimum time for the reaction to complete, but the one
taken in this experiment). The dark green precipitate
was filtered using Buchner funnel and repeatedly
washed with 1 M HCl solution followed by water until
the filtrate obtained was colourless. The composite powder was first air-dried, and then dried under vacuum at
60 C for 6 h.
Eight separate batches of PAni/Ag composites were prepared in which the silver content in the composites were
varied by weight as 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75 and

A transmission electron microscope (TEM) (Philips


CM200, The Netherlands) was used to assess the morphology and size of PAni and its composites at a resolution of
2.4 A. The samples were dispersed in water and deposited
on a copper grid before viewing under the microscope.
UV-visible spectroscopy
UVvis absorption spectra of the samples dissolved in
NMP were recorded on a Double Beam UV 1800 spectrophotometer (Shimadzu, Tokyo, Japan) in the range of
2001,000 nm.
Thermogravimetric analysis
The TGA experiment was performed under nitrogen gas
purge (50 ml/min.) over a temperature range of 30600 C
at a heating rate of 10 C/min. on a TGA50 thermogravimetric analyzer (Shimadzu, Tokyo, Japan).
Differential scanning calorimetry
Phase transitions were investigated over the range of 35
300 C at 10 C/min. heating rate under nitrogen atmosphere
on a DSC60 differential scanning calorimeter (Shimadzu,
Tokyo, Japan).
Electrical conductivity measurements via four-point probe
method
The conductivity of pure PAni and composite samples
were measured by four-point probe method on pellets
compressed to a thickness of about 1 mm at 500 MPa
with a hydraulic press, using a current source (CCS-01)
and microvoltmeter (DMV-001) from Scientific Equipments, Roorkee, India. The variation in electrical

J Polym Res (2013) 20:49

conductivity with temperature was also studied. A PID


controlled oven (PID-200) was used for simultaneous heating
of the pellets.

Page 3 of 10, 49

Results and discussion


Mechanism of nanocomposite formation by ultrasound
induced cavitation

Scanning spreading resistance microscopy (SSRM)


Spreading resistance studies were done on sample films cast
from NMP on glass substrates using Solver Pro 47 atomic
force microscope (NTMDT, Moscow, Russia) and Nova
software. The AFM was operated in scanning spreading
resistance microscope (SSRM) mode by measuring the local
resistance over the sample surface using a TiN coated conducting probe.
Fig. 1 Pictorial representation
of (a) cavitation, b nuclei
growth due to bubble collapse,
c encapsulation of silver
nanoparticles by PEG and (d)
incorporation of silver
nanoparticles between
polyaniline chains

Figure 1 presents a pictorial representation of scheme of


events involved in nanocomposite formation. Ultrasound
assisted synthesis relies on cavitation mechanism to obtain
nanostructured materials. Cavitation refers to the formation,
growth and collapse of bubbles due to transmission of
acoustic waves through a medium which ruptures the molecular structure of the medium (Fig. 1a). During cavitation,
bubbles grow due to the diffusion of solute vapour into it.

49, Page 4 of 10

When non-volatile solutes are present in the liquid, as is the


present case, they get concentrated at the interface where
they react with the high energy species and nucleation
begins. On reaching its maximum size the bubble undergoes
Fig. 2 TEM micrograph of
pure PAni (0 wt.%), PAni/Ag
nanocomposites (0.252 wt.%)
and silver nanoparticles with
SAED pattern (inset)

J Polym Res (2013) 20:49

implosive collapse resulting in the solution attaining very


high temperature (up to about 24,000 K) along with very
high cooling rate [36]. At such fast kinetics the growth of
the nuclei is hindered (Fig. 1b) and consequently, nanosized

J Polym Res (2013) 20:49

Page 5 of 10, 49

silver particles are formed. These nanoparticles have a large


number of dangling bonds on their surface. For surface
stability bond formation is necessary which leads to growth
of nuclei. But when the growth is stopped prematurely, the
stabilization of the silver nanoparticles occur through
bond formation with PEG present in the solution. The
adsorbed PEG layer on the surface of nanoparticle acts
as a diffusion barrier to growth species providing surface stability, and in the process prevents aggregation, as
shown in Fig. 1c.
Further into the process, nanocomposites were prepared
by incorporation of these PEG coated silver nanoparticles
into the polyaniline matrix. When polymerization of aniline
was done it was observed that after about 20 min of sonication the solution started to turn green. This indicated the
formation of polyaniline. Due to its chain formatting ability,
polyaniline shows propensity towards directional growth
which lends it nanofibrillar morphology. When silver nanoparticles are present in the monomer solution, the nucleation
takes place on the surface of the nanoparticles as well,
followed by anisotropic growth of polyaniline, and the
nanoparticles get incorporated into the polymer (Fig. 1d).
Size and morphological study by transmission electron
microscopy
Figure 2 presents the TEM micrographs of pure PAni, PAni/
Ag (0.252 wt.%) nanocomposites and silver nanoparticles.
Plate-like, nanosized silver with dimension of about 50 nm
35 nm was formed in all the nanocomposite systems. These
non-aggregated silver nanoparticles were uniformly dispersed
and embedded into the polymer matrix. Nanofibrillar morphology of polyaniline with diameter of about 905 nm can
be seen. At times, association between PEG coated silver
nanoparticles arise due to polymer-polymer interaction. This
was, however, not seen in the nanocomposites since the presence of ultrasound leads to uniform dispersion of nanoparticles in the medium, as evident from the micrograph. The
selected area electron diffraction (SAED) pattern of silver
nanoparticles is also presented in Fig. 2. The planes (222),
(400) and (331) corresponding to the halo rings can be
indexed to that of face-centered cubic (fcc) structure of metallic silver [37]. It is thus clear that PEG encapsulation of
silver nanoparticles prevented their oxidation. From the TEM
results it is evident that ultrasound induced cavitation produced nanostructured systems, with PEG encapsulation resulting in non-aggrgated, metallic silver nanoparticles.
Functional group identification by FTIR spectroscopy
The successful formation of polyaniline in all cases is evident from fourier transform infrared spectra shown in Fig. 3.
The main peaks (framed in red) that were observed are the

Fig. 3 FTIR spectra of pure PAni (0 wt.%) and PAni/Ag nanocomposites (0.252 wt.%). The framed peaks show the aromatic structure of
polyaniline and its nanocomposites

ones at 1,552 cm1 and 1,504 cm1, which can be assigned


to quinoid and benzenoid ring stretching. The presence of
these peaks shows the aromatic structure of PAni [38]. The
absorbance peaks at 3,593 cm1 and 2,964 cm1 corresponds to N-H and C-H stretching vibrations, respectively. The band at 1,259 cm1 can be associated with bipolaron structure related to C-N bond stretching of secondary aromatic amine, while the band at 830 cm1 can be
attributed to aromatic out-of-plane C-H bending [3, 39].
Doping of PAni brings about a structural change, as can be

49, Page 6 of 10

J Polym Res (2013) 20:49

Fig. 6 TGA thermogram of pure PAni (0 wt.%) and PAni/Ag nanocomposites (0.252 wt.%)

Fig. 4 FTIR spectra of doped PAni and undoped PAni

seen from the shifting of bands towards longer wavelength


in Fig. 4 [40]. It also indicates an intimate interaction between the nano silver and the nitrogen sites of the PAni
chain. The higher intensity of peaks in the case of nanocomposite systems indicates a greater conjugation length,
which in turn is responsible for increased conductivity.
UV-visible spectroscopy studies
The UV-visible spectra of pure PAni and its nanocomposite
systems recorded in NMP are shown in Fig. 5. Characteristic

Fig. 5 UV-visible spectra of pure PAni (0 wt.%) and PAni/Ag nanocomposites (0.252 wt.%)

peaks of doped polyaniline were observed at about 304 nm


and 980 nm, arising due to -* and polaron transitions,
respectively [41]. PAni shows an extended conformation in
NMP in which the defects arising due to twisting of polymer
chain are removed. Hence a strong interaction between the
adjacent polarons takes place. This leads to the polaron band
becoming more delocalized and, as a result, appearing at a
longer wavelength with a decrease in exciton absorption
energy [42]. It has been reported by Zheng et al. that
sample with smaller localized polaron peak has higher
conductivity [43].
A peak around 370 nm indicates the presence of
silver nanoparticles. This plasmon resonance peak for
plate-like silver nanoparticles is because of the out-ofplane dipole resonance [44]. An inconclusive broad
hump around 560 nm is observed. Generally, a peak
around this wavelength is due to the in-plane dipole of
silver nanoparticles, but the absence of this peak in
some of the nanocomposite samples rule this out. The
appearance of this slight hump can thus be attributed to
the presence of some impurity.

Fig. 7 DSC thermogram of pure PAni (0 wt.%) and PAni/Ag nanocomposites (0.252 wt.%)

J Polym Res (2013) 20:49

Page 7 of 10, 49

Table 1 Weight loss and heat of fusion data for PAni and PAni/Ag nanocomposites
Ag content in PAni (wt %)

0.25

0.5

0.75

1.25

1.5

1.75

Heat of fusion, Hf (J/g)


Weight loss (%)

269.45
60.08

314.57
51.61

330.10
47.58

367.60
38.21

376.45
35.27

393.77
34.30

587.05
33.75

626.90
32.51

683.03
32.73

Thermal analysis of polyaniline and its nanocomposites


Figure 6 shows the TGA thermogram for pure PAni and
PAni/Ag nanocomposites in N2 atmosphere. Complete decomposition of material did not take place since some material was left in the pan even after 600 C. Three steps of
weight loss were seen during the heating cycle of all the
samples. Weight loss between 70 C and 100 C could be
attributed to loss of adsorbed water. The second step at 220
300 C could be due to loss of dopant molecules. The final
weight loss within 470600 C is associated with decomposition of PAni chain [45]. As can be seen from the
thermogram, for the same onset temperature of decomposition the weight loss in the samples due to degradation of
polymer backbone is significantly reduced with increasing
silver content. While pure polyaniline shows a weight loss
of about 60 %, PAni/Ag nanocomposites containing 1 wt.%
and more nano silver shows a decrease of about 25 % in
total weight loss. It can be assumed that the PEG encapsulated nano silver are able to interact with polyaniline chains.
And though weaker in nature, at nanoscale the total energy
of these interacting forces can be quite large to overcome.
This prevents complete degradation of polymer backbone.
Consequently, lower weight loss is observed for samples
with higher nano silver content. Since PEG is present in a
very small quantity, hence weight loss associated with PEG
is absent in the nanocomposites.
Phase transitions in PAni and PAni/Ag nanocomposites
were studied using DSC. From the thermogram (Fig. 7), an
increase in heat of fusion (Hf) was seen with increasing
content of nano silver which indicates a greater crystallinity
of the nanocomposites. This explains the decreased weight

Fig. 8 Variation in electrical conductivity of pure PAni (0 wt.%) and


PAni/Ag nanocomposites (0.252 wt.%) with temperature

loss in nanocomposites. Table 1 presents the Hf values and


percentage weight loss of polyaniline and its nanocomposites. Greater crystallinity of samples was observed for
higher nano silver content, which significantly improved
the thermal stability of the nanocomposite systems. Nano
silver content of 1.75 and 2 wt.% shows almost the same
weight loss though the crystallinity of the latter is somewhat
higher. This indicates that 1.75 wt.% might be the optimum
amount of silver nanoparticles that can provide maximum
interaction between PEG and polyaniline chains.
Study of electrical conductivity of PAni and PAni/Ag
nanocomposites
Four probe Van der Pauw technique [46] was employed to
measure the electrical conductivity of the sample pellet. The
following equation was used in determining the conductivity:
1=o =fG7 W=Sg:
Here, is the conductivity (S/cm), o is the resistivity, W
is the thickness of the pellets, S is the probe spacing and G7
is the correction factor. The electrical conductivity of pure
PAni and PAni/Ag nanocomposite systems, measured as a
function of temperature, is depicted in Fig. 8. All the samples have almost same electrical conductivity at room temperature; conductivity of samples with nano silver content of
1 wt.% and above is slightly higher than the rest. An
increasing trend in electrical conductivity was seen when
the samples are heated from room temperature to 150 C.
This confirms the semiconducting nature of the samples.
Nanocomposites with 0.50.75 wt.% nano silver content
shows a marginal increase in conductivity with temperature.

Fig. 9 Mechanism of intramolecular charge transfer and intermolecular charge hopping in PAni/Ag nanocomposites

49, Page 8 of 10

J Polym Res (2013) 20:49

Fig. 10 Current signal image


of (a) pure PAni (0 wt.%) and
(b) PAni/Ag nanocomposites at
2 wt.% nano silver content

A marked increase in conductivity is observed in nanocomposites containing 12 wt.% nano silver when heated above
100 C which almost levels off at 150 C. Now, although
silver has the highest electrical conductivity in bulk state, at
nanoscale it turns into a semiconductor. This is because
more energy states are lost due to the shrinking size resulting in an increase in the band gap (Eg). Moreover, surface
passivation of nano silver by PEG compromises its conductivity. Despite this, an increase in electrical conductivity is
seen with increasing content of nano silver. As stated in
Section Thermal analysis of polyaniline and its nanocom
posites, there is interaction between PEG on the surface of
silver nanoparticles and polyaniline. This decreases the intermolecular distance which promotes charge hopping. This
has been depicted in Fig. 9. It has been reported that the
increased intramolecular conductivity is a result of the more
expanded coil-like conformation of PAni chains, while the
increased intermolecular conductivity is because of the
higher crystallinity of PAni [47]. At nano silver content of
1 wt.% and more, the polyaniline chains are close enough to
enable intermolecular charge hopping. The intramolecular
charge transfer, on the other hand, takes place at the amorphous regions of the PAni chain. Hence, it can be reasonably
proposed that the increased conductivity of the PAni/Ag
nanocomposites is due to the enhanced intermolecular
Fig. 11 Current signal image
of (a) pure PAni (0 wt.%) and
(b) PAni/Ag nanocomposites at
2 wt.% showing localized
conducting and non-conducting
phases

charge hopping. The two mechanism combined contributes


towards increasing the overall conductivity of the material.
It was also observed that beyond 150 C there is virtually
no increment in conductivity. Moreover, a drop in conductivity was observed when samples were heated beyond
200 C, which is due to loss of dopant molecules.
Spreading resistance studies of localized conducting phases
in PAni and PAni/Ag nanocomposites
Scanning spreading resistance microscopy is a very efficient
mode of AFM for materials characterization in terms of local
resistance. A bias voltage is applied to a conducting probe in
contact with the sample surface, and the resulting current flow
through the sample is measured as a function of the probe with
simultaneous surface topography measurements. Assuming
that there is a constant contact between the probe and the
surface, for a given bias voltage the magnitude of the measured current flow is proportional to local resistance of the
sample under investigation. Figure 10 shows the image for
current signal of pure PAni (10a) and PAni/Ag nanocomposite
at 2 wt.% nano silver content (10b). The lighter areas in the
signal image correspond to higher conductivity. The denser
areas, as seen in Fig. 11, corresponds to sites with very low
electrical conductivity, and are fewer in 2 wt.% (Fig. 11b) than

J Polym Res (2013) 20:49

in 0 wt.% (Fig. 11a). It indicates that the ultrasound assisted


synthesis of polyaniline/silver nanocomposite leads to uniform dispersion of silver nanoparticles. This corroborates that
the interaction between PAni chains and PEG coated silver
nanoparticles increases the crystallinity of PAni and also promotes intermolecular charge hopping; the latter contributes
toward increasing the conductivity of polyaniline. Since the
region of high conductivity are localized, only a minor increase in the electrical conductivity of polyaniline is seen on
incorporation of PEG coated silver nanoparticles.

Conclusion
The acoustic cavitation mechanism is found to be effective in
producing nanostructured materials. Nanocrystalline silver
with fcc structure that are formed in presence of ultrasound
are encapsulated by polyethylene glycol which prevents their
oxidation and aggregation, and is conducive to their even
dispersion within the polyaniline matrix. The presence of
plasmon resonance band confirms the presence of silver in
the nanocomposites. Incorporation of silver nanoparticles leads
to interaction between the PEG coated nano silver and the
nitrogen in the PAni chain. This interaction renders the PAni/
Ag nanocomposites thermally more stable and increases the
electrical conductivity of polyaniline. Since the intermolecular
gap is decreased at higher nano silver content, charge hopping
between the PAni chains gets enhanced. The increment in
electrical conductivity is a result of this enhanced intermolecular charge hopping that is brought about by incorporation of
PEG coated silver nanoparticles. Spreading resistance studies
of pure PAni and PAni/Ag nanocomposites were done. It was
found that polyaniline consists of interspersed high and low
conducting phases. It is because of this that the nanocomposite
systems could not achieve very high electrical conductivity.
Overall, the incorporation of PEG encapsulated silver nanoparticles was found to impart higher thermal stability to polyaniline, along with enhanced electrical conductivity.
Acknowledgments One of the authors (T. Sen) is thankful to the
University Grants Commission, New Delhi, India for providing financial support under the RFSMS scheme. We are also thankful to the
Sophisticated Analytical Instrumentation Facility (SAIF), IIT Bombay
for transmission electron microscopy characterizations.

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