CONDUCTING POLYMERS
INTRODUCTION
Conductive polymers or, more precisely, intrinsically
conducting polymers (ICPs) are organic
polymers that conduct electricity. Such compounds may
have metallic conductivity or can be semiconductors.
The biggest advantage of conductive polymers is their
processability, mainly by dispersion. Conductive
polymers are generally not thermoplastics, i.e., they are
not thermoformable. But, like insulating polymers, they
are organic materials. They can offer high electrical
conductivity but do not show similar mechanical
properties to others commercially available polymers
.
Conducting polymers have backbone of continous sp^2
hybridized carbon centers .One valence electron on each
centre resides in a pz orbital,which is orthogonal to the
other three sigma bonds.
The electron in their delocalized orbitals have high
mobility.
Classification of conducting polymers
This conduction of electricity in this type of polymer is
due to conjugation in the backbone of the polymer. The
conjugation can be due to either pi-electron or due to
doped ingredients.
Examples of conducting polymers
Polyaniline
Polyaniline is the most promising and most explored
among conducting polymers, and polyaniline has high
stability, high processability, tunable conducting and
optical properties. The conductivity of polyaniline is
dependent upon the dopant concentration, and it gives
metal-like conductivity only when the pH is less than
[Link] exists in different forms.
They are classified as leucoemeraldine, emeraldine, and
pernigraniline, by their oxidation state, i.e.,
leucoemeraldine exists in a sufficiently reduced state,
and pernigraniline exists in a fully oxidized state.
Polyaniline becomes conductive only when it is in a
moderately oxidized state and acts as an insulator in a
fully oxidized state.
Polyaniline is the most promising and most explored
among conducting polymers, and polyaniline has high
stability, high processability, tunable conducting and
optical properties. The conductivity of polyaniline is
dependent upon the dopant concentration, and it gives
metal-like conductivity only when the pH is less than 3.
Polyaniline exists in different forms. They are classified
as leucoemeraldine, emeraldine, and pernigraniline, by
their oxidation state, i.e., leucoemeraldine exists in a
sufficiently reduced state, and pernigraniline exists in a
fully oxidized state. Polyaniline becomes conductive only
when it is in a moderately oxidized state and acts as an
insulator in a fully oxidized state
Interficial polymerization is also used to synthesize
polyaniline,in which an aniline monomer is solubilized in
an organic solvent like toluene, an oxidant solution and a
dopant acid-containing aqueous solution. Polymerization
takes place in the interphase of these two immiscible
liquids when an oxidant solution is added to the
monomer solution.
A microemulsion technique is also followed for the
synthesis of polyaniline, where the polymerization also
takes place in the interface between two immiscible
liquids, but the difference is in the surfactant used. The
electropolymerization technique happens without the
effect of an oxidant, and is the same in the case of
polyacetylene.
Electrospinning is also used to synthesise fibrous
polymer morphologies of nano or micro diameters under
the influence of a strong electrical field. In this case, a
high voltage is applied to the polymer droplets, and the
charged droplets get stretched due to surface tension,
and at a critical point, the liquid erupts and starts to
weave on the counter surface.
The principles of both electrospraying and
electrospinning are the same. Electrospinning is the only
method to produce bulk polymer fibrous structure.
Conducting polymers and their composites like pure
polyaniline, polypyrrole, polyaniline/polyethylene
oxide/carbon nanotubes have been prepared by this
technique. There are lot of factors dependent on
electrospinning, such as the molecular weight of the
polymer, viscosity, distance between spinneret and
counter surface, temperature, humidity, etc.
Conduction Mechanism of Polyaniline
PANI has a structure which consist of equal proportions
of amines and imine sites. Through protonic acid
dopping ,imine sites are protonated by acids HA to the
bipolaron form .
The bipoloron then undergoes further rearrangement to
form the delocalized polaron [Link] in poloron
bands and the delocalized charges mobility is thus
responsible for the conductivity as shown in the reaction
mechanism .
The resulting emaraldine salt has conductivity of the
order of 100S/cm which is many orders of the magnitude
higher than that of common polymers.
Advantages of PANI
PANI is the second most widely used electrically
conductive polymer after PPy. Chemical and
electrochemical methods are employed in the synthesis of
PANI, although electrochemical deposition is often
preferred because it creates a high purity coating on the
surface of the distributed film .Amongst all intrinsic
conducting polymers (ICPs), PANI has attracted the
attention of many researchers due to its reversible
doping/dead doping properties, remarkable electrical
conductivity, pH change properties, low expenditure,
simple synthesis, and environmental stability . It also
has the unique ability to be doped by proton acids
(proton doping) apart from conventional redox doping.
PANI, through its molecular selfassembly, often forms
super-molecular nanofibers, lending itself to a variety of
applications due to completely different and new
properties because of the high surface-to-volume ratio.
Several PANI nanostructures such as nanofibers,
nanotubes, and nanospheres have been developed by a
set of synthesis methods. The introduction of a
secondary component, such as nanomaterials, in PANI,
further expands its performance, providing efficient
designs and advanced performance. Cooperation between
individual components enhances the properties of the
nanocomposite and expands its scope of application .
The development of PANI nanostructures and their
nanocomposites stems from the desire to discover the full
potential of these materials.
