Beruflich Dokumente
Kultur Dokumente
DOI 10.1007/s10965-012-0049-5
ORIGINAL PAPER
Received: 25 June 2012 / Accepted: 7 December 2012 / Published online: 19 December 2012
# Springer Science+Business Media Dordrecht 2012
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
Experimental
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
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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
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Fig. 6 TGA thermogram of pure PAni (0 wt.%) and PAni/Ag nanocomposites (0.252 wt.%)
Fig. 5 UV-visible spectra of pure PAni (0 wt.%) and PAni/Ag nanocomposites (0.252 wt.%)
Fig. 7 DSC thermogram of pure PAni (0 wt.%) and PAni/Ag nanocomposites (0.252 wt.%)
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
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
Fig. 9 Mechanism of intramolecular charge transfer and intermolecular charge hopping in PAni/Ag nanocomposites
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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
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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