‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘
‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘

 
 
‘
Polymers are long chain giant organic molecules assembled from many smaller molecules called
monomers. Polymers consist of many repeating monomer units in long chains. The interlinking
of many units has given the polymer its name, 
meaning µmany¶ and meaning µpart¶ (in
Greek) (Gowariker 
, 1987). A polymer is analogous to a necklace made from many small
beads (monomers). These monomers react together chemically to give a variety of molecular
architectures ranging from linear structures to a three dimensional network of polymer chains.
Another common name for many synthetic polymers is plastic which comes from the Greek
word "plastikos", suitable for molding or shaping. Many objects in daily use from packing,
wrapping, and building materials include half of all polymers synthesized. Plastics are polymers,
molecules that form long chains, repeating themselves like pearls in a necklace.

‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘ ‘
‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘ ‘‘
In becoming electrically conductive, a polymer has to imitate a metal, that is, its electrons need
to be free to move and not bound to the atoms. The first condition for this is that the polymer
consists of alternating single and double bonds, called conjugated double bonds. Conducting
polymer are polymers which can exhibit significant level of electrical conductivity. The
electrical conductivity exhibited by conducting polymers is attributed to the presence of ³free
electrons´ within the body of the specimen. Conducting polymers are usually polyconjugated
structures which are insulators in the pure state but when treated with an oxidizing or a reducing
agent can be converted into polymer salts with electrical conductivities comparable to metals.
Conducting polymeric materials posses great design flexibility together with a number of
characteristics that are desirable for a number of specific applications in the fields of catalysis,
conversion and storage of energy, chemical and biochemical sensing, microelectronics and
optoelectronics .Supercapacitors are attracting great attention because of their high capacitance

c
and potential applications in electronic devices. There has been more interest in two types of
supercapacitors, the double layer supercapacitors and the redox supercapacitors with different
charge storage modes. The redox supercapacitor involves faradic process due to redox reaction.
Due to versatility of structure and low cost compared to noble metal oxides, electronically
conducting polymers represents a promising class of active materials for electrodes of the redox
supercapacitors . For most of the history of polymer technology, one of the most valued
properties of synthetic polymers has been their ability to act as excellent electrical insulators both
at high voltages and at high frequencies. In spite of this there has been an interest for many years
in the possibility of producing electrically conducting polymers. The obvious attraction is to
combine in one material the electrical properties and the high added value applications of a
semiconductor or a metal with the advantages of a polymer. Approximately two decades ago, it
has been discovered that polyacetylene, which is a type of polymer containing conjugated single
and double bonds in its structure, could become highly conductive after carrying out a structural
modification process called ³doping´. During the doping process, an organic polymer, either an
insulator or a semiconductor having a small conductivity typically in the range of 10-10 to 10-5
S/cm, is converted to a polymer, which is in the metallic conducting regime (1-10-4 S/cm). The
polymer is called a µconjugated polymer¶ because of the alternating single and double bonds in
the polymer chain. Due to the special conjugation in their chains, it enables the electrons to de-
localize throughout the whole system and thus many atoms may share them. The de-localized
electrons may move around the whole system and become the charge carriers to make them
conductive. This polymer can be transformed into a conducting form when electrons are
removed from the backbone resulting in cations or added to the backbone resulting in anions.
Anions and cations act as charge carriers, hopping from one site to another under the influence of
an electrical field, thus increasing conductivity.
However, the conjugated polymers are not conductive, since they are covalently bonded and do
not contain valence band like pure metal does. It is universally agreed that the doping process is
an effective method to produce conducting polymers.Doping allows electrons to flow due to the
formation of conduction bands. As doping occurs, the electrons in the conjugated system, which
are loosely bound, are able to jump around the polymer chain. Electric current will be produced
when the electrons are moving along the polymer chains. In future, conducting polymers or
organic metals may replace inorganic metal in several critical areas.

D
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‘‘


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 ‘

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Conductivity can be defined simply by Ohms Law.

V= IR

Where R is the resistance, I the current and V the voltage present in the material. Thus from this
relationship conductivity is found . The conductivity depends on the number of charge carriers
(number of electrons) in the material and their mobility. For example in a metal it is assumed
that all the outer electrons are free to carry charge and the impedance to flow of charge is mainly
due to the electrons "bumping" in to each other. Thus for metals as temperature is increased the
resistance in the material increases as the electrons bump in to each other more as they are
moving faster.

‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘ ‘

‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘ ‘

Insulators however have tightly bound electrons so that nearly no electron flow occurs so they
offer high resistance to charge flow. So for conductance free electrons are needed. The diagram
below shows how the conductivity of conjugated polymers like polyactelyene can vary from
being a insulator to a conductor.

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Conducting polymer research dates back to the 1960s, when Pohl, Katon, and their coworkers,
first synthesized and characterized semiconducting polymers [3]. The discovery of the high
conductivity of polysulfurnitride (SN)x, a polymeric material containing interesting electrical
properties, was a step forward for research in conducting polymers. The beginning of conducting
polymer research began nearly a quarter of a century ago, when films of polyacetylene were
found to exhibit profound increases in electrical conductivity when exposed to halogen vapor.

)‘ *+ and ,(" produced conjugated conducting polyacetylene when
monomer of acetylene was doped with bromine and iodine vapor; the resulting electrical
conductivity was 10 times higher than the undoped monomers¶.

-‘$‘!‘ (‘& '$(‘ !"%

It is well known that graphite is a good conductor, previously it was thought that polymers which
substitute a carbon (e.g. adding hydrogen's to make hydrocarbons) for another atom could not
conduct, however our greater knowledge of conjugated systems has enabled the discovery of

Î
conducting polymers. As in a conjugated system the electrons are only loosely bound, electron
flow may be possible. However as the polymers are covalently bonded the material needs to be
doped for electron flow to occur. Doping is either the addition of electrons (reduction reaction)
or the removal of electrons (oxidation reaction) from the polymer. Once doping has occurred,
the electrons in the pi-bonds are able to "jump" around the polymer chain. As the electrons are
moving along the molecule a electric current occurs. However the conductivity of the material
is limited as the electrons have to "jump" across molecules so for better conductivity the
molecules must be well ordered and closely packed to limit the distance "jumped" by the
electrons. This occurs better in trans undoped polyactelyene. By doping, the conductivity of
the polymer increases from 10-3 S m-1 to 3000 S m-1. An oxidation doping (removal of
electrons) can be done using iodine. The iodine attracts an electron from the polymer from one
of the pi bonds. Thus the remaining electron can move along the chain.

.‘,!(‘ /‘ !"#$‘

In general there are two fundamental mechanisms of charge transport in condensed matter:
hopping and band transport. In band transport mechanism due to extended states, known as
bands, the charge carriers (electrons) behave as ³free particles´. The electrons are moving freely
accelerated by the applied electric field losing their momentum through scattering by impurities
(defects) and phonons. In a band transport phonons are a source of resistance and the
conductivity decreases with an increase of temperature as an effect of more intense phonon
scattering. The electron motion may be described as quantum diffusion. This conductivity
behavior occurs in bulk metals with small and moderate disorder. Band transport mechanism of
conductivity leads to non-zero conductivity at 0 K, which is determined by the scattering on the
impurities and lattice defects. In the hopping mechanism the electrons are hopping between
localized states by absorbing or emitting phonons. Since the charge carriers are localized the
external energy of phonons is necessary to initiate the electron jumps. The electronic transport is
realized as a random walk of successively hopping electrons. This process may be described as
classical incoherent diffusion and is inelastic. In contrast to band transport, in hopping
mechanism phonons are the source of electrical conductivity. The hopping conductivity increases
with temperature and vanishes at 0 K. Hopping transport is a general mechanism for the
electrical conductivity of disordered materials with localized electronic states such as doped

 
semiconductors and glassy materials. The probability of a hopping event depends on the physical
distance to another site chain and the difference in energy between the sites. Hence, the extent of
the hopping and the hopping range are limited by the available energy of phonons. As the
temperature increases more phonons of higher energy becomes available and the electrons can
hop to states further and further away or higher in energy. Obviously, the localization length L of
the electronic states loc strongly influences the hopping rates. The degree of charge carrier
localization depends on the amount of structural disorder in the material, and well ordered
film are thus expected to have better charge transport properties.

‘ -‘ ‘ (&‘ "&!"!‘ /‘ ''‘  !"#$‘ / ‘ "//!‘ !& ‘
(!(‘

The nature of electrical conductivity of conducting polymers cannot be completely accounted for
by considering only one of the mechanisms described above, because of their complex structure.
The interplay of strongly disordered (amorphous) parts and the relatively well ordered crystalline
regions play the crucial role for the global electronic properties of the system. The nature of local
electronic transport in crystalline and amorphous regions is also strongly determined by the
molecular anisotropy of polymeric chains, its flexibility and possible conformations. Some
conducting polymers exhibits the electrical conductivity temperature dependence characteristic
for semiconductors, others show metal-insulator like transitions. The unique mixture of band and
hopping mechanisms of electrical conductivity resulting in the difficulty of development of the
one complete (describing all feature) model of electrical transport in conducting polymers. As a
consequence many models of electronic transport have been proposed and the electrical
phenomena of conducting polymers are still strongly debated.

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‘-‘‘

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All materials can be divided into three main groups: conductors or metals, insulators and
semiconductors. They are differentiated by their ability to conduct or the ability to allow the flow
of current. Generally, conducting polymers are classified as semiconductors although some
highly conducting polymers, such as polyacetylene, fall into metal range. Table 1 compares some
of the physical properties of insulators, semiconductors and conductors.

2'‘1‘ (& !‘ /‘&$'‘& &‘ /‘(')‘!' ‘!"‘ !"!‘& '$(‘

‘
PROPERTY CONDUCTING METALS INSULATORS
POLYMERS
Electrical 10-11-103 10-4-106 10-20-10-12
conductivity
(S/cm)
Carriers Electrons of Valence electrons
conjugated of half filled -
double bonds band
Concentration of 1012-1019 1022-1023 ‘‘‘‘‘‘‘‘‘‘‘‘3‘
3
carriers per cm ‘
Effect of impurity Impurities of Effect ‘
0.1-1% change comparatively Strong effect
conductivity by slight
2 to 3 orders of
magnitude
Magnetic Paramagnets Ferro and Diamagnets
properties diamagnets

Conducting polymers have some similarities to conventional polymers, but the extensive main-
chain p-conjugation, which radically increases the chain stiffness, strongly determines its
physical properties . They are usually insoluble and difficult to processing. As a consequence
conducting polymers form less ordered structures with many defects and distortion. It is
convenient to describe the conducting polymers by considering several groups exhibiting
different structural characteristics which depend on the internal chain architecture . The first
basic group consists of linear unsubstituted conducting polymers with a stiff (rigid-rod) chains
like poly(acetylene) or poly(thiophene) or semiflexible (rods) chains like polyaniline. The

G
investigations carried out to develop new materials with better properties for new applications
result in next group with a range of structural form. This group of compounds called hairy-rod is
based on flexible side group substitution to the conducting polymer backbone.

-‘4(&'‘ /‘ !"!‘ '$(‘

Polyacetylene, in view of possessing the simplest molecular framework, has attracted the most
attention, especially of physicists, with an emphasis on understanding the mechanism of
conduction . However, its insolubility, infusibility and poor environmental stability has rendered
it rather unattractive for technological applications. The technologically relevant
front runners belong to essentially four families: polyaniline (PAn), polypyrroles (PPy),
polythiophenes (PT) and polyphenylene vinylenes (PPV).

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A number of synthetic routes have been developed for the preparation of conjugated
polymers.The diversity has been driven by the desire to examine many different types of
conjugated polymers and attempts to improve material properties.Material property enhancement
has centered on the synthesis of polymers that are processible in various forms. In some cases
high molecular weight precursor polymers are prepared that can be converted in to the
conjugated form after processing. The conjugated polymer itself can also be soluble or fusible
and is processed prior to doping. Five primary classes of conjugated polymers have been shown
to exhibit high levels of electrical conductivity in the doped state. This include polyacetylenes,
polyarylenes, and polyheterocycles , poly(arylene vinylenes), and polyanilenes.

.‘ '$!'!‘
Polyaniline is one of the oldest conductive polymers known. It was first prepared by Letheby in
1862 by anodic oxidation of aniline in sulphuric acid. It has been known as an electrically
conductive polymer (ECP) for the past thirty years. ECPs are able to conduct electricity because
of their conjugated p -bond system, which is formed by the overlapping of carbon  orbitals and
alternating carbon-carbon bond lengths. In some systems, such as polyaniline, nitrogen 

orbitals and C<SUB< SUB itxtvisited="1"> rings are also part of the conjugation system
(Figure 4.1). The conjugated double bonds permit easy electron mobility throughout the
molecule because the electrons are delocalized. Delocalization is the condition in which p -
bonding electrons are spread over a number of atoms rather than localized between two atoms.
This condition allows electrons to move more easily, thus making the polymer electrically
conductive. ‘

‘.‘'‘/ ('‘ /‘!" &"‘ ‘

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Polyaniline (PANi) exists in a variety of forms that differ in chemical and physical properties .
The most common green protonated emeraldine has conductivity on a semiconductor level of the
order of 100 S cm±1, many orders of magnitude higher than that of common polymers (<10±9 S
cm±1) but lower than that of typical metals (>104 S cm±1). Protonated PANI, (e.g., PANi
hydrochloride) converts to a nonconducting blue emeraldine base when treated with ammonium
hydroxide .
‘
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The synthesis was based on mixing aqueous solutions of aniline hydrochloride and ammonium
peroxydisulfate (Fig.4.2) at room temperature, followed by the separation of PANI hydrochloride
precipitate by filtration and drying. The goal of this study was to prepare PANI with a defined
conductivity, not necessarily the highest possible. The efficient polymerization of aniline is
achieved only in an acidic medium, where aniline exists as an anilinium cation. A variety of
inorganic and organic acids of different concentration have been used in the syntheses of PANI;
the resulting PANI, protonated with various acids, differs in solubility, conductivity, and
stability. For the present study, we have selected hydrochloric acid in equimolar proportion to
aniline, i.e., aniline hydrochloride was used as a monomer. The handling of solid aniline salt is
preferred to liquid aniline from the point of view of toxic hazards.

‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘‘ ‘.‘‘&& !‘ /‘ ‘& +"‘

Peroxydisulfate is the most commonly used oxidant, and its ammonium salt was preferred to the
potassium counterpart because of its better solubility in water. The concentration of aniline

cc
hydrochloride was set to 0.2M. Various oxidant/ monomer ratios have been used in the literature.
To minimize the presence of residual aniline and to obtain the best yield of PANI, the
stoichiometric peroxydisulfate/aniline ratio 1.25 is recommended (Fig.4.3). The polymerization
is completed within 10 min at room temperature and within 1 h at 0±2 °C . The oxidation of
aniline is exothermic so the temperature of the reaction mixture can be used to monitor the
progress of reaction [16±18]. Temperature profile is well reproducible.
Figure4.4 shows a typical course of polymerization recorded at the Institute of Macromolecular.

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Project participants followed the same instructions to oxidize 0.2 M aniline hydrochloride with
0.25 M ammonium peroxydisulfate in aqueous medium. Aniline hydrochloride (purum; 2.59 g,
20 mmol) was dissolved in distilled water in a volumetric flask to 50 mL of solution.
Ammonium peroxydisulfate (purum; 5.71 g, 25 mmol) was dissolved in water also to 50 mL of
solution. Both solutions were kept for 1 h at room temperature (~18±24 °C), then mixed in a
beaker, briefly stirred, and left at rest to polymerize. Next day, the PANI precipitate was
collected on a filter, washed with three 100-mL portions of 0.2 M HCl, and similarly with
acetone. Polyaniline (emeraldine) hydrochloride powder was dried in air and then in vacuo at
60°C. Polyanilines prepared under these reaction and processing conditions are further referred
to as ³standard´ samples. Additional polymerizations were carried out in an ice bath at 0±2 °C.
The acidity of the reaction mixture was increased by replacing 10 mL of water with 10 mL of
10 M HCl in several experiments.

‘ ; !‘ /‘& '$!'!‘

Conductivity of all samples was measured at room temperature by a four-probe method on
pellets compressed at 700 MPa, 13 mm in diameter and 1±1.5 mm thick, using a high-voltage
current source and 2010 low-noise multimeter . The Archimedes method was used to determine
the polymer density by weighing the pellets in air .

‘ '‘!"‘ !‘
•‘ & !‘ !" !‘
Polyaniline of higher molar mass is produced at lower reaction temperatures , but the electrical
properties of the polymer are not greatly influenced by molar mass. We have selected ambient
temperature for the present study while being aware of the ambiguous definition of such
conditions. As temperature increases during the reaction, this increase being dependent on the
surface-to-volume ratio of the experimental set-up (Fig. 4.4), the precise control of temperature
was not attempted. The effect of reaction temperature on the conductivity of PANI was assessed
and is discussed. Polymerization in the presence of excess 1 M HCl, i.e., at higher acidity,
proceeds faster than in its absence and yields a product of enhanced conductivity. A still higher
concentration of HCl above 2 M concentration leads to the reduction of conductivity . The rate of

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aniline oxidation depends on the presence of various impurities and additives that may promote
the progress of oxidation . Distilled water was used; the potential presence of iron ions in tap
water may accelerate the aniline oxidation. Washing the PANI precipitate with 0.2 M HCl
removes residual monomer, oxidant, and its decomposition products. The treatment with
hydrochloric acid solution provides a more uniform protonation of PANI with chloride
counterions, although some of the sulfate or hydrogensulfate anions from the decomposition of
peroxydisulfate also participate as counterions. A final washing with acetone removes low-
molecular-weight organic intermediates and oligomers. It also prevents the aggregation of PANI
precipitate during drying, and the product is obtained as a fine powder. The greenish PANI
(emeraldine) hydrochloride was stored in polyethylene containers.
‘
‘
‘
‘8‘ 

, ‘
0,6
‘
The second method is via electrochemicalpolymerization, which involves placing both counter
and reference electrodes (such as platinum,gold), into the solution containing diluted monomer
and electrolyte (the dopant) in a solvent. After applying a suitable voltage, the polymer film
immediately starts to form on the working electrolyte.
‘0.02 M aniline in 0.5 M H2SO4 solution was polymerised by potential cycling between -0.2 and
0.9 V at a scan rate of 20 mV/s. The solution was thoroughly degassed in advance by pure N2.
After polymerisation, the PANI film was thoroughly rinsed with 0.5 M H2SO4.
The real and imaginary parts of the dielectric constants of the PANI thin films at several doping
levels was determined quantitatively by taking into consideration the thickness values obtained
from the EQCM measurement.
‘ ' & '$( !‘ /‘!'!‘
Electrochemical polymerization of aniline on the gold surface was achieved by applying
potential cycling between í0.2 and 0.9 V at a scan rate of 20 mV/s . The cyclic voltammograms
(CV) obtained during the electropolymerization are shown in Figure 4.5 (A) up to the seventh
cycle. Similar conditions in aqueous H2SO4 in the potential range described, has been used by
many groups. As reported previously, the first redox process (ca. 0.22 V in the positive scan and
0.05 V in the negative scan) corresponds to the electron transfer from/to the electrodeposited

cÎ
PANI film. In order to compensate the charge of the PANI film, anion transport from/to the
electrolyte solution, i.e., anion doping and dedoping, should occur.

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This phenomenon is responsible for the dramatic change in the conductivity of the PANI film.
The electrodeposition of PANI on the Au electrode proceeds via a radical cation mechanism. The
second redox process (ca. 0.5 and 0.45 V, for the oxidation and reduction, respectively) probably
corresponds to side reactions such as decomposition of the polymer. The large currents observed
at the positive end of the CV are due to the superposition of two distinct processes: one is the
electron transfer from the PANI film corresponding to the oxidation of the PANI film and the
other is the electron transfer from the aniline monomer to the electrode corresponding to the
oxidation of the aniline monomer to produce a precursor for the PANI film. A series of angular
SPR curves taken after each potential cycle are shown in Figure 4.5 (B). These scans were
measured in the solution at open circuit potential (OCP § 0.15 V). Shifts of the minimum
resonance angles in the SPR curves were observed, indicating that PANI was deposited onto the
gold film electrode during each potential cycle. Besides, as can also be seen, the deposited PANI
in each following cycle increased almost exponentially. The in situ formation of the PANI film
on the gold electrode surface was monitored simultaneously by the measurement of the charge
transferred, by QCM and by SPR.
‘
‘

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 ‘ ,(!‘!"‘!(! !‘
The main detection method in the present study is the combination of electrochemistry with
surface plasmon based optical techniques (ESPR, Fig.4.6). Besides, electrochemistry was also
combined with the quartz crystal microbalance (EQCM) in order to gain more information of the
studied systems. Other techniques used include transmission electron microscopy (TEM), atomic
force microscope (AFM), low potential scanning electron microscope (LPSEM), UV-vis
spectroscopy, etc.
•‘ ' ($3/‘'( !‘&  &$‘9:
Since conducting polymers are electroactive materials, their properties depend heavily on the
degree of oxidation (p-doping) or reduction (n-doping) of the conjugated polymer backbone.
Therefore, electrochemistry plays an important role in the synthesis, characterization and
applications of conducting polymers. Besides, due to the low cost, fast response, high sensitivity
and easy compatibility with different technologies, electrochemistry is gaining much more
popularity than any other techniques in studying conducting polymers.

Surface plasmon optical techniques have been shown to be an effective optical tool for the
characterization of interfaces and thin films, as well as for the sensitive detection of kinetic
processes, e.g. for monitoring. interfacialbinding reactions or the swelling or shrinking processes
of a conducting polymer.

In recent years, the combination of electrochemistry with surface Plasmon spectroscopy (ESPR)
has emerged to be a powerful tool for probing extremely small changes of various films at the
metal/solution interface. In our study, we use ESPR not only to monitor the film deposition in
real-time, but also to examine the film conformation and properties in its different oxidation
states (i.e. different doping levels). Besides, we demonstrated here that the bioelectrocatalytic
processes can also be monitored in situ by ESPR.

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processes, e.g. for monitoring. interfacialbinding reactions or the swelling or shrinking processes
of a conducting polymer.
In recent years, the combination of electrochemistry with surface Plasmon spectroscopy (ESPR)
has emerged to be a powerful tool for probing extremely small changes of various films at the
metal/solution interface. In our study, we use ESPR not only to monitor the film deposition in
real-time, but also to examine the film conformation and properties in its different oxidation
states (i.e. different doping levels). Besides, we demonstrated here that the bioelectrocatalytic
processes can also be monitored in situ by ESPR.
Shown in Figure 4.6(A) are the schematic drawing of the ESPR setup we used and its various
extensions, based on the Kretschmann geometry. The laser beam passes first a chopper (for lock-
in detection) and two polarizers (for attenuation and polarization, respectively), and then is
reflected off the base of the coupling prism. Coupled to the prism is an Au substrate (both for
coupling surface plasmons and as the working electrode), index matched by an immersion oil
(n=1.725) with the prism. The reflected light is focused by a lens onto a photodiode which is
connected to the lock-in amplifier. Both the prism/sample and the photodiode are mounted on
two co-axial goniometers, respectively, allowing different operation modes such as an angular
scan in a ș-2ș reflection geometry or a kinetic mode at a fixed incident angle, but as a function of
time.
The enlarged image of the electrochemical flow cell is shown in Figure 4.6(B). This Teflon
cuvette has two holes for reference and counter electrodes for the electrochemical measurements,
as well as an inlet and outlet for sample exchange and rinsing. The whole cell is attached to the
Au substrate, and sealed by O-rings and a BK7 glass slide. The effective area of the Au substrate
exposed to the solution is 0.65cm2. The electrochemical measurements were performed with an
EG&G 263A potentiostat or an AutoLab (Eco Chemie B.V., The Netherlands), with a coiled
platinum wire being used as the counter electrode, and an Ag/AgCl(3M NaCl) electrode as the
reference electrode. All potentials reported here are with respect to this reference electrode.
For fluorescence measurements, a photomultiplier (PMT) is attached to the SPR setup from the
backside of the cell to monitor the photons emitted from the metal/dielectric interface. The
emitted light is focused by a lens and passes through an interference filter before it is collected
by the PMT, which is connected to a photoncounter unit. The whole module is mounted to the
sample goniometer so that it rotates with the sample cell, thus always collecting the emitted light

c0
at a constant angle relative to the metal surface. To minimize photo-bleaching effects of the
fluorescent dyes, a programmable shutter is also installed to constantly block the laser unless
during the data recording. In this case, the SPR setup is transformed into a surface plasmon
resonance enhanced fluorescence spectroscopy (SPFS) setup.

•‘ ' ('‘7;‘ $'‘, 2'!‘97 ,:

In some parts of this study, EQCM was also used in order to get more information of the
investigated systems or to confirm the results from the ESPR experiments.
QCM is very sensitive for probing small changes (especially mass changes) in thin surface films.
This technique relies on the fact that the resonant frequency of a quartz crystal oscillator changes
linearly with the amount of rigidlyattached mass.
In the early 1980s, several groups reported the combination of electrochemistry with QCM
(EQCM) by using one of the oscillator electrodes also as the working electrode of an
electrochemical cell (Fig.4.7). In this way, the mass changes and various other processes (such as
viscoelasticity change) involving thin films on electrode surface could be monitored in real-time.
Since then, EQCM has matured into a powerful tool that has found broad applications in studies
of adsorption, electrodeposition, corrosion, oxide formation and reactivity, chemo- and bio-
sensors, polymer and material sciences, ect., as have been reviewed by several groups.
The schematic diagram of the EQCM setup we used is shown in Figure 4.6, similar to that
reported previously. The quartz crystal (Fig.4.7B) is clamped in a Teflon flow cell sealed by
appropriate O-rings to expose only one of the Au electrodes to the solution. This Au electrode is
also the working electrode for electrochemistry and is thus part of both the electrochemical
instrument and the oscillator circuits. The crystal is driven by a broadband oscillator circuit that
tracks the resonant frequency change of the crystal caused by the electrochemically-induced
changes on the electrode surface. The frequency is measured with a frequency counter. Both the
oscillator/frequency counter and the electrochemical instrument are directly interfaced to a
computer. The computer not only generates the electrochemical excitation waveforms, but also
measures the current passing through the EQCM working electrode as well as the frequency of
oscillation of the quartz disk.
In EQCM measurements, the electrode surface area was determined to be 1.33 cm2. The crystals
were plasma cleaned before every experiment.

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Transmission electron microscopy (TEM, operated at 120kV) was used to characterize the
prepared Au nanoparticles. The specimen was prepared by first dispersing the particles in an
aqueous ethanol solution, placing a few drops of particle solution onto the amorphous carbon-
coated copper microgrids and then let it dry for the measurements. Image J software was used to
analyse the obtained images to get the size distribution of the Au nanoparticles.
Atomic force microscope(AFM, Dimension 3100 or Mutimode) was used to examine the quality
of the prepared PANI gratings operated in a tapping mode. A silicon cantilever was used, which
has a spring constant of 42 N/s and a resonant frequency of 300 kHz. A Low potential scanning
electron microscope(LPSEM, operated at 1 kV) was used to check the obtained PANI inverse
opals.
UV-vis spectroscopy was carried out on a Lambda UV/VIS/NIR spectrophotometer (Perkin-
Elmer) to characterize the prepared Au nanoparticles.
‘  '$( !‘(!(
‘No matter whether PANI is synthesized electrochemically or chemically, it is generally assumed
that there is a close similarity in their polymerisation mechanism. In both case, the
polymerisation process proceeds via the following mechanism:
The first step is the formation of the radical cation by an electron transfer from the 2s energy
level of the aniline nitrogen atom, as shown in Figure 4.8. The formed aniline radical cation has
several resonant forms, in which (c) is the more reactive one due to its important substituant
inductive effect and its absence of steric hindrance.

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A major advantage of chemical polymerization concerns the possibility of mass-production at a
reasonable cost .This is often difficult with electrochemical methods. On the other hand, an
important feature of the electropolymerization technique is the direct formation of conducting
polymer films that are highly conductive, simple, and suitable for use especially in electronic
devices.
‘& !‘ /‘ ‘,''$‘ '(‘
Most of the studied PANI composite films were prepared on Au substrate using the layer-by-
layer (LBL) method, as pioneered by G. Decher et al. The preparationprocedure is sketched in
Figure 4.9.

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!‘ ‘)‘''‘‘2 #‘& ‘+‘"‘ ‘!‘‘/' +‘''‘
First, the freshly prepared Au substrate was functionalised with a layer of 3- mercapto-1-
propanesulfonic acid (MPS) by immersing it into a 1mM MPS ethanol solution for 2h, then
rinsing first with ethanol, followed by rinsing with Milli-Q water, and then dried under a stream
of nitrogen (steps 1 and 2). The functionalised Au substrates were negatively charged, and then
immersed alternately in the solutions of PANI and the corresponding poly(anion)s for 15min
each, with rinsing steps in between (steps 3-6). Repeating steps 3-6 allows one to get a multilayer

DD
film with a desired thickness. It should be noted that, in our case, all the above processes were
carried out in a flow cell (Fig.4.6 and Fig.4.7) in order to monitor the film selfassembly process
in real-time.‘
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In 1958, polyacetylene was first synthesized by Natta et al. as a black powder. This was found to
be a semi- conductor with a conductivity between 7 x 10-11 to 7 x 10-3 Sm-1, depending upon how
the polymer was processed and manipulated. This compound remained a scientific curiosity
until 1967, when a postgraduate student of Hideki Shirakawa at the Tokyo Institute of
Technology was attempting to synthesise polyacetylene, and a silvery thin film was produced
as a result of a mistake. It was found that 1000 times too much of the Ziegler-Natta catalyst, had
been used. When this film was investigated it was found to be semiconducting, with a similar
level of conductivity to the best of the conducting black powders. Further investigations,
initially aimed to produce thin films of graphite, showed that exposure of this form of
polyacetylene to halogens increased its conductivity a billion fold.

‘ *+‘!>‘
This process is known as Shirakawa technique,involves polymerization of acetylene on a thin
film coating of a heterogeneous Ziegler Natta initiator system in a glass reactor,as shown in
eqation below,

Al (C2H5)3
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:4
TiO(C4H9)4

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The resulting porous, fibriller polyacetylene film is highly crystalline, so it is therefore insoluble,
infusible, and otherewise nonprocessible. It is also unstable in air in both the conducting and
insulating form.
Much effort has been expended toward the improvement of the properties of polyacetylenes
made by the direct polymerization of acetylene. Variation of the type of the initiator system,
annealing or aging of the catalyst, and stretch orientation of the film has resulted in increase in
conductivity and improvement in the oxidative stability of the material. The improvement in
properties is likely the results of a polymer with fewer defects.

‘  &!‘ /‘& '$$'!‘

P-doping: [CH]n+ 3x/2 I2 [CH]nx++ xI3-(oxidation with halogen)
N-doping: [CH]n+ xNa [CH]nx-+ xNa+ (reduction with alkali metal)

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Polypyrrole is an intrinsic conducting polymer which can be made to have conductivites up to
1000 Sicm±1 rendering its versatile applications in batteries, electronic devices, functional
electrodes, electrochromic devices, optical switching devices, sensors and so on. In recent years,
polypyrrole is popular in research and has been the focus of many studies over other conducting
polymers because of its high chemical and air stability and ease of preparation. Oxidizing pyrrole
to polypyrrole can be achieved either by electrochemical method or chemical method.

One advantage of polypyrrole concerns the low oxidation potential of pyrrole. The typical
polypyrrole, which is insoluble and infusible, exhibits poor processability and lacks essential
mechanical properties. Efforts to overcome these drawbacks have led to numerous researches on
the synthesis of polypyrrole by both electrochemical and chemical routes. Among them, a
significant strategy to approach both high electrical conductivity and desirable mechanical
properties is preparing blends or composites of polypyrrole polymer with other insulating
polymers having desirable mechanical properties. Nanodimensional composites of polypyrrole

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with colloidal silica, tin oxide and zirconium oxide have been studied extensively. Clay minerals
have been adapted to the field of nanocomposites because of their small particle size and
intercalation property, especially in the application of reinforcement materials with polymers.
In this present communication, we report the synthesis of polypyrrole-montmorillonite clay
composite by chemical method in aqueous medium and their structural, thermal and
morphological characterizations.
‘ 4&(!'
In this study, the monomer pyrrole was distilled prior to use. FeCl3 . 6 H2O was used as the
oxidant while montmorillonite clay was used as the clay material. Distilled water was used as
the solvent. For the synthesis of polypyrrole/montmorillonite clay nano-composites in aqueous
medium, the montmorillonite clay dispersion in aqueous medium was first prepared by adding
known weight of nanodimensional montmorillonite clay into known volume of distilled water
under constant stirring. After 1 hour, FeCl3 . 6 H2O was added to the dispersion in such a way
that it would attain the required concentration. Pyrrole (known volume) was then added into the
dispersion under constant stirring at room temperature (25 ºC). The relative proportions of
FeCl3/pyrrole were varied with mole ratio ranging from 0.5 to 4.0. The total volume of the
reaction mixture was kept at 50 ml. The gradual change of colour from light black to deep
greenish-black indicated the formation of polypyrrole. The reaction mixture was then kept under
room temperature for 24 hours. The resulting deep greenish-black mass was filtered and then it
was thoroughly washed with distilled water until it was completely free from FeCl3. This process
was repeated several times to remove all adhering substances. Finally, the product was washed
with water again and then it was dried at 90 °C for 24 h to yield a very fine deep greenish-black
powder. A Hand Press instrument for pellets preparation was used. The powder obtained was
made pellets by using stainless steel mold applying 10 ton/cm2 pressures under vacuum for 10
minutes.
The electrical conductivity was measured at room temperature using a standard Four Point Probe
technique. The probes were placed on surface of the pellet. The thickness of the pellets was
measured by using a micrometer.
The electrochemical polymerization of pyrrole in a template produced by lithography-
electroforming technology allows the production of micro structured polymer films as shown in
the figure below.

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In dependence on the polymerization parameters films with one or two dimensional structure can
be obtained. Despite these films are very thin they have a high mechanical stability.
Copolymerizartion or the embedment of additives provides modified polymerfilms for
electrochemical sensor application.
The ESR-spectrum of polypyrrole shows in vacuum a symmetrical and very narrow one line
spectrum with a g-factor of 2.0026. In air the line width reversibly increases tenfold. This allows
the quantitative mesurement of oxygen concentration by ESR-spectroscopy.

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There are two distinct types of stability. Extrinsic stability is related to vulnerability to external
environmental agent such as oxygen, water, peroxides. This is determined by the polymers
susceptibility of charged sites to attack by nucleophiles, electrophiles and free radicals. If a
conducting polymer is Extrinsic unstable then it must be protected by a stable coating.
Many conducting polymers, however, degrade over time even in dry, oxygen free environment.
This intrinsic instability is thermodynamic in origin. It is likely to be cause by irreversible
chemical reaction between charged sites of polymer and either the dopant counter ion or the p-

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system of an adjacent neutral chain, which produces an sp3 carbon, breaking the conjugation.
Intrinsic instability can also come from a thermally driven mechanism which causes the polymer
to lose its dopant. This happens when the charge sites become unstable due to conformational
changes in the polymer backbone. This has been observed in alkyl substituted polythiophenes.

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Conjugated polymers may be made by a variety of techniques, including cationic, anionic,
radical chain growth, co-ordination polymerization, step growth polymerization or
electrochemical polymerization. Electrochemical polymerization occurs by suitable monomers
which are electrochemically oxidized to create an active monomeric and dimeric species which
DG
react to form a conjugated polymer backbone. The main problem with electrically conductive
plastics stems from the very property that gives it its conductivity, namely the conjugated
backbone. This causes many such polymers to be intractable, insoluble films or powders that
cannot melt. There are two main strategies to overcoming these problems. There are to either
modify the polymer so that it may be more easily processed, or to manufacture the polymer in its
desired shape and form.

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Although several conducting polymers have been prepared, it was soon realized that they cannot
compete with metals in traditional electrical applications, like wiring, transmission cables etc.
Researchers have, therefore, focussed on other applications that exploit the existence of extended
conjugation in these polymers. A few interesting possibilities are mentioned below for a novel
biomedical application.

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One of the first applications of conducting polymers that was the focus of attention world-wide
was that of light-weight batteries. While a lot of the conjugated polymers were tried most of
them failed to exhibit the desired properties, specifically with respect to stability. However,
batteries made using either polypyrrole or polyaniline as the positive electrode (cathode) and

D
lithium± aluminium alloy as the negative electrode (anode) exhibited much more respectable
properties. The electrolyte in these cases were either LiClO4 or LiBF4 in propylene carbonate
(a highly polar aprotic solvent, which is also fairly resistant to oxidation). During the battery
discharge, electrons move from the lithium alloy (which gets oxidized) to the polyaniline cathode
(which gets reduced), as Li+ from the anode and BF4 ± from the cathode enter the electrolyte.
One major drawback of this battery is that the energy density or energy storage capacity is low
and its recyclability (charging±discharging cycles) is relatively poor. More recently, however,
some composites of an alkali metal alloy and polyphenylene have been very effectively used as
anode materials in batteries that exhibit much higher energy densities, of around 65mWH/g
(compare with standard nickel±cadmium batteries which have about 39mWH/g). In these cases,
the conducting polymer serves as a binder for the alkali metal alloy, forming a multiply
connected electronically and ionically conductive network within which the alloy particles are
held. The mixed ionic and electronic conductivity of the conducting polymer binder allows the
alloy particles to continue the electronic and ionic processes associated with the charge-discharge
cycles, consequently extending the battery cycle life. Thus, the prospect of a polymeric battery is
still alive and is awaiting further technological refinement.

=‘'  (‘&'$‘

Electrochromic display is another interesting application which utilizes the electrochemical
doping and undoping of conducting polymers. The basic idea, in such devices, is to effect a

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significant change in the colour (both the wavelength of absorption and its intensity) upon
application of an electric potential. Depending on the conducting polymer chosen, either the
doped or undoped state can be essentially colourless or intensely coloured. In general, the
absorption of the doped state is dramatically red-shifted (moves to longer wavelength) from that
of the undoped state. Because of their very high absorption coefficients (ca. 105 cm±1) in the
visible range of the electromagnetic spectrum, only very thin films are required to provide
display devices with high contrast and a very broad viewing angle. Polyaniline, polypyrrole,
polythiophene and their derivatives have been successfully used to prepare prototypes of such
display devices. However, for successful commercial utilization of these materials in display
devices, one important aspect is again the cycle life, which should be > 10 7. A maximum of
about 106 cycles has been achieved using 50nm thick polyaniline films, wherein the switching
occurs between transparent yellow and green in less than 100ms. Thus, while these materials are
yet to achieve the set target (in terms of their life cycle) for use as electrochromic displays, other
interesting and innovative applications, such as electrochromic windows and other applications
in the automotive industry are being actively pursued. Electrochromic windows, for instance, are
windows in buildings automobiles which can be made to go from low transmitting (during the
day) to high transmitting (during the night); the switching in such systems occurs upon
application of an electric potential.
‘
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Other exciting phenomena, that have caught the imagination of both scientists and technologists
alike, are the phenomena of photoluminescence and electroluminescence in conjugated

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polymers. Emission of light upon irradiation is termed as photoluminescence, while the emission
on application of a voltage is termed electroluminescence. Light emitting diode is an example of
utilization of the latter phenomenon. It was recently demonstrated that PPV films can be used as
the emissive layer in electroluminescent devices. Structures for electroluminescent devices are
fabricated with the polymer film formed on a bottom electrode, which is deposited on a suitable
substrate (such as glass), and the top electrode is deposited on the fully converted PPV film (i.e.
after thermal elimination of the precursor). Electrode materials are chosen with a low work
function for use as negative, electron-injecting contact, and with a high work function as the
positive holeinjecting contact. At least one of these layers must be semitransparent for light
emission normal to the plane of the device. Both indium-tin oxide and thin aluminium films (7
15 nm) have been used as the transparent electrode. For polymer films, of about 100 nm, the
forward voltages were as low as 10 V. Further improvements, using soluble PPV derivatives
such as 2,5-dialkoxy PPV¶s and lower work function metals, particularly calcium, as the
electron-injecting contact layer, have resulted in a further drop in forward voltage to about 5 V,
and an increase in the efficiency to about 1% (photons per electron injected). These devices are
believed to operate by double charge injection of electrons and holes from the negative and
positive electrodes, respectively. These singly charged excitations combine to form excitons
which can then decay by photoemission. Changing the band-gap of these conjugated polymers,
by appropriate chemical modification, can result in a change in the wavelength of the
photoemission: red-shifted upon reduction of band-gap and blue-shifted upon increasing the
band-gap. Enhancement of the photoemission efficiency and further lowering of forward
operating voltage are two of the primary areas of current activity that is expected to lead to
improved devices of greater technological relevance.
‘
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In recent years the interest in analytical methods for determining the virus concentration in
surface, sewage and drinking water has been growing, mainly due to the concern about viral

åD
disease. Contrary to the quantification of chemicals, few satisfactory methods are available for
the quantitative determination of viruses, due to the time-consuming and not always reliable
methods of concentrating materials from large sample water volumes and the frequent
unsatisfactory recovery of biological materials from filters, a procedure which has to be
performed before inoculating in cell cultures and quantitatively estimating the viral charge.
Recently, the use of microporous filters appears to be the most promising technique, for
detecting viruses; also, "charge modified" filters have been introduced on the market, where the
modification of the charge is performed by surface treatments; "positive" and "negative" filters
have been tested, the best performances being attributed to "positive" filters.
•‘ It was thought that conducting polymers in their "doped" state (polypyrrole, polyaniline
and similar water stable materials) could find useful application in virus filtration, i.e. a
purpose very different from the universal attention to their possible uses in electrical or
electronic devices suggested by their electrical conductivity. In fact, most "doped" conducting
polymers have the unique property of carrying a number of positive charges well spread over
their polyconjugated backbone, while negative charges are typically localized on low basicity
anions.
•‘ The formation of a membrane having suitable mechanical strength, flexibility and
porosity did not appear easily feasible, when made of pure polymer; therefore, we took
advantage Of our previous experience in preparing polypyrrole composites by chemical
oxidation of pyrrole monomer adsorbed on many different types of substrate, in water and/or
other solvents.
‘ '‘!"‘" !‘
•‘ After a preliminary screening of various supporting materials, we focused our attention
on disc filters, made out of filter paper or glass fibres. Such porous membranes were treated with
a pyrrole solution in ethyl acetate (1:1) in order to obtain a uniform distribution into the pores of
the filters and to make the procedure well reproducible as far as final composite material is
concerned.
•‘ Wet filters charged with the monomer were then dipped in an aqueous solution of
iron(III) chloride (1 M), which caused pyrrole to be oxidatively polymerized to the
corresponding conducting polymer; well spread all over the fibres and inside the pores. The

åå
polymerization reaction was allowed to proceed at 5-20 ~ for 3 h; filters were then thoroughly
washed with dilute hydrochloric acid, water, and finally dried in air.
•‘ Membranes prepared with this procedure were tested for weight increase upon
polypyrrole deposition: 25%. of the final weight was due to polypyrrole on the filter paper
(Whatman, 0.15 mm thickness) and 60% on fibreglass supporting materials (0.25 mm thickness).
Also, electrical conductivity was usually measured, in order to evaluate the efficiency and
reproducibility of the procedure (approximately 50 S cm- 1 for paper filters and 10 S cm- 1 for
fiberglass ones were obtained).
•‘ Further control was made using SEM (see figures), which showed different morphologies
for polypyrrole deposition according to the supporting materials used. The supposed utility of
such materials for the concentration of enteric viruses from water was tested against Polio 1,
Coxackie B3 and Echo 7 viruses.
‘ Further ascertained "#! for the proposed application of conducting polymers in
this field are:
(i) the efficiency of virus filtration is practically constant over the pH range from 4-8;
(ii) there is no need to modify the pH of the water samples, nor to add chemicals of any kind
before filtration, in order to improve the efficiency of virus retention;
(iii) the easy removal of trapped viruses from polymer membranes (90%-100%) by elution with
beef extract;
(iv) the easy preparation of membranes and the possibility of scaling up to cartridge filters or
Largearea filters; we tested cartridge filters (5 cm diameter and 12 cm height) with excellent
results in filtration of large samples of artificially contaminated waters ( ~> 200 litre);
(v) short filtration time, being virus removal due more to electrostatic interactions between viral
Particles and the polymer than to the pore size.

‘ We are presently testing the efficiency of our materials in field studies, still using
cartridges on large water volumes, eventually prefiltered in order to remove larger particles of
solids. Sampling of large volumes is, in fact, necessary when a very low, but positive, virus
contamination of water has to be detected. Finally, preliminary experiments show that
conducting polymer composite membranes could be recycled more than once by a suitable

åÎ
chemical treatment of used filters, a feature which should be very important in the case of the
foreseeable future widespread application of these materials in environmental control studies.

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The recent methods of corrosion protection are not very lasting and are coming under increased
scrutiny by the Environmental Protection Agency (EPA). As an example, the use of chromium
and cadmium for anti-corrosion will soon be banned.
•‘ A mechanism for corrosion protection involves the use of a sacrificial electrode, such as
zinc coating, which will corrode (oxidize) in safekeeping the substrate. Unfortunately, the
coatings do not last very long. The oxidized zinc metal is dissolved by water or moisture. For
this reason, there are extreme environmental concerns, since toxic metals are being released into
the ecosystem.
•‘ Barrier coatings, such as epoxy, are employed extensively but are not very durable once a

å 
pit or hole in the coating has been formed. The corrosive species then attacks the underlying
metal and thereby increases the exposed surface, accelerating the corrosion process.
•‘ MacDiarmid first suggested the corrosion inhibiting-property of conducting polymers in

‘‘‘‘‘‘‘‘‘‘‘‘‘‘ ‘==‘(‘''!‘‘   !‘!2 ‘'9 :‘(!(‘

‘
1985. Initial studies on the protection of metal surfaces against corrosion by conducting
polymers were reported in the literature that same year. A major type of corrosion occurs by
oxidation of a metallic surface by a water medium to produce oxides and hydroxides. As these
are formed, soluble species are produced, the surface pits increase their surface area, and the rate
of decomposition accelerates. One way to provide corrosion protection is to coat the metal with a
barrier to prevent the reactive species from reaching the surface. Galvanization with zinc (or
other metals with low oxidation potential) prevents corrosion via the creation of an interfacial
potential at the metal-zinc interface. The zinc will corrode preferentially. While the reactive
species may encounter the metal, the increased oxidation causes the metal to be insensitive.
Corrosion is therefore inhibited.

=@‘
‘ !'‘ ‘&&' !‘
Conducing polymer can also be used in RADAR Application, as a Bio sensors, as a
PESTICIDES sensor, in preparation of liquid crystal, in DNA Hybridisation ,
‘
‘

å]


‘
Conducting polymers have, thus, come a long way from purely laboratory curiosity to a class of
materials that can find end use in a wide variety of commercial products, ranging from batteries
to biosensors. Such a development is a classic example that serves to illustrate the wide range of
expertise, starting from chemists, physicists, biologists and technologists, that is required to take
some invention in the laboratory to the market place.

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  ‘1‘
‘
‘  *‘1‘
1. Encyclopedia of chemical technology by Kerk Othmer
2. Polemer Science by Govariker, 1987
3.Polymer Science by Bahadur
4. Handbook of conducting polymer, 3rd edition
‘ š !'‘1‘
1. Corrosion science, volume 45
2. Material and deaign, volume 26
3. Material and science, volume 26
4. journal of coating technologies, volume 69

‘ 2‘!*‘1‘
1. http://www.ese.iitb.ac.in/hydrogen_energy_fuel_cells/SS.pdf
2. www.!/resonance/Nov1997/&"//Nov1997p48-58.&"/
3. www.mpip-mainz.mpg.de/knoll/publications/thesis/tian_2005.pdf
4.  ©
©


 

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