4.

7 CONDUCTING POLYMERS

Polymers, due to their light weight and easy fabrication, have replaced almost all the materials
made up of either nonmetals or metals. Polymers have traditionally been considered good electrical
insulators and a variety of their applications have relied on this insulating property. However, to
replace metals polymer should exhibit conducting behavior. There is class of polymer which are
conjugated (those that possess an extended -conjugation along the polymer backbone), exhibit
semiconducting behavior. The polymeric materials, which possess electrical conductivities on par
with metallic conductors, are called conducting polymers Conductivities as high as 1.5x 10 -1 ohm-
1
m-1 have been attained in these polymeric materials.

Conducting mechanism in Polymers

4.7.1 Classification of Conducting Polymers

There are mainly two classes of Conducting polymers

(I) Intrinsically conducting polymer (ICP)

(II) Extrinsically conducting polymer
(I) Intrinsically conducting polymer (ICP)

Those polymers which possess conductivity due to their structure are called
intrinsically conducting polymers. These polymers have some unique features in their
structure which impart conductivity to the polymer backbone.
These polymers are of further classified in to
(1) Intrinsically conducting polymers having extensive conjugation.
These are those polymers whose backbones or associated groups consist of delocalized
electron – pair or residual charge. Such polymers essentially contain conjugated –
electrons backbone, which is responsible for electrical charge. In an electric field,
conjugated electrons of the polymer get excited, thereby can be transported through the
solid polymeric material. Overlapping of orbitals (of conjugated electrons) over the
entire backbone results in the formation of valence bands as well as conduction bands,
which extends over the entire polymer molecule. Presence of conjugated electrons in a
polymer increases its conductivity to a larger extent.
e.g. Polyacetylene, Polyaniline, polypyrrole etc.
Polyacetylene is the simplest polymer that shows a great value of conductivity. The
alternating double and single bond in the polymer structure is what gives the polymer
the ability of resonate. As dopants are inserted in the polymer, the chains of polymers
presents charges. The movement of these charge, by resonance when a field is applied,
gives rise to the conductivity of the material.

Polyaniline has a rather unique structure, containing an alternating arrangement of

benzene rings and nitrogen atoms. The nitrogen atoms can exist either as an imine (in
an sp2 hybridized state) or an amine (sp3 hybridized). Depending on the relative
composition of these two states of nitrogen, and further on whether they are in their
quartenized state or not, various forms of polyaniline can result. The structures of these
forms can be best represented by choosing a minimum of four repeat units, as shown
below.
The only form that is conducting, among the four, is the green protonated emeraldine
form, which has both the oxidized iminium and reduced amine nitrogens, in equal
amounts (i.e., it is half oxidized). Thus, the blue insulating emeraldine form can be
transformed into the conducting form by lowering the pH of the medium and vice-
versa. fashion, by causing the imine and amine nitrogens to exchange places along the
polymer backbone (in protonated emeraldine).
 Other polymers having extended conjugation are listed in following table.

Maximum
Conducting Polymers
Conductivity (S/cm)

100

Polythiophene

2000

Polypyrrole

1000

Polyphenylene

1000

Polyphenylene-vinylene

2. Doped Conducting Polymers

It is obtained by exposing a polymer to a charged transfer agent in either gas phase or in

solution. Intrinsically conducting polymers possess low conductivity but these possess low
ionization potential and high electron affinities, so these can be easily oxidized or reduced.
Consequently, the conductivity of ICP can be increased by creating either positive (or) negative
charges on the polymer backbone by oxidation or reduction. This technique, called doping.
Doping is classified into 2 types.

(a) p –doping: P – doping involves treating a conducting polymer having extensive

conjugation with a Lewis acid, there by oxidation process takes place and positive charges
on the polymer backbone are created. Some of the common p – dopant used are I2, Br2,
AsF5, PF6, Naphthylamine, etc, used.

+
CH A
CH CH CH CH + +
A CH CH CH

Polyacetylene Lewis acid

n –doping: It involves treating an intrinsically conducting polymer with a lewis base thereby
reduction process takes place and negative charges on the polymer backbone are created.
Some of the common N – dopant used are Li, Na, Ca, tributyl ammonium, FeCl 3 etc.

+
CH CH CH CH + B- CH CH CH CH B-

Polyacetylene Lewis acid

(II) Extrinsically Conducting Polymers

Those conducting polymers which owe their conductivity due to the presence of
externally added ingredients in them are called extrinsically conducting polymers.
They are of two types :
1. Conductive element filled polymers : In this type, polymer acts as a binder to hold
the conducting elements together in solid entity. Material which is used as filler are
carbon black, metal oxide, metal fibers etc. The minimum concentration of the
conductive filler, which is added to let the polymer start conducting is called the
percolation threshold. Important characteristics of these polymers are : (a) They possess
good bulk conductivity. (b) They are cheaper. (c) They are light in weight. (d) They are
mechanically durable and strong. (e) They are easily processable in different forms,
shapes and sizes.
2. Blended conducting polymers: These types of polymers are obtained by blending a
conventional polymer with a conducting polymer either physically or chemically. Such
polymers can be easily processed and possess better physical, chemical and mechanical
properties.

4.7.2 Applications of conducting polymers:

Some of the important applications of conducting polymers are:
(i) In rechargeable Batteries: light weight batteries based on perchlorate doped
polyacetylene – lithium system. These are about 10 times, lighter than conventional
lead storage batteries.
(ii) In optically display devices: Optically display are based on polythiophene. When the
structure is electrically based, the optical density of the film changes, i.e., color
changes. Such electrochromic systems produce colored displays with faster switching
time and better viewing than conventional liquid crystal display devices.
(iii) Light Emitting Diodes (LED): LEDs based on Polyphenylenevinylene. When
compared to inorganic or organic materials for LEDs, the main advantages of the
polymer electroluminescence devices are their fast response times, process ability, the
possibility of uniformly covering large areas, low operating voltages, and the many
methods were applied to fine-tune their optical and electrical properties.
(iv) Solar Cell: Conducting polymers are used in the design and fabrication of low cost
organic electronic devices like photovoltaic devices in solar cell. When comparing the
organic technology to the silicon-based photovoltaics (PV), the two very different
technologies are complementary in many ways. Organic photovoltaics (OPVs) offer
low cost solution processing, flexible substrates, low thermal budget and a very high
speed of processing. The widely used donor constituents are mainly the conjugated
polymers, such as polyphenylene vinylene, polythiophene, polyfluorene or their
derivatives.
(v) Field Effect Transistors (FET): Conducting polymers are widely used in the
synthesis of field effect transistors. Conducting polymers’ advantages over
conventional materials, such as silicon and germanium, include low cost and ease of
processing. Organic or polymer-based semiconductors have been applied to fabricate
 field-effect transistors (FETs) since 1983, various polymers like polypyrrole,
polythiophene and their derivatives are used for this application.
(vi) Biosensors: Biosensor is a device which has a biological sensing element either
connected to or integrated within a transducer. The purpose is to produce a digital
electronic signal, proportional to the concentration of a specific chemical or set of
chemicals. The biochemical transducer or biocomponent imparts to the biosensor,
selectivity or specificity. Conducting polymers found to be a suitable matrices of
biomolecules that can be used to enhance stability, speed, and sensitivity and thus as
being useful in medical diagnostics,
(vii) It is used in wiring in aircrafts and aerospace components
(viii) It is used in telecommunication systems
(ix) It is used in antistatic coatings for clothing.

4.8 BIODEGRADABLE POLYMERS

These are those polymers which can decompose under aerobic or anaerobic conditions, as
a result of the action of microorganism/enzymes. The materials develop it like starch,
cellulose, and polyesters. Aliphatic polyesters are the most commonly used polymers of
this type.
4.8.1 Process of Biodegradation
Biodegradable polymers contain polymer chains that are hydrolytically or enzymatically
cleaved, resulting in, soluble degradation products. Biodegradability is particularly desired
in biomedical applications, in which degradation of the polymer ensures clearance from
the body and eliminates the need for retrieval or explant. Biodegradation takes place
through the action of enzymes and/or chemical deterioration associated with living
organisms. This event occurs in two steps. The first one is the fragmentation of the
polymers into lower molecular mass species by means of either abiotic reactions, i.e.
oxidation, photodegradation or hydrolysis, or biotic reactions, i.e. degradations by
microorganisms. This is followed by bioassimilation of the polymer fragments by
microorganisms and their mineralisation.
Biodegradability depends not only on the origin of the polymer but also on its chemical
structure and the environmental degrading conditions. Mechanisms and estimation
techniques of polymer biodegradation have been reviewed. The mechanical behaviour of
biodegradable materials depends on their chemical composition, the production, the
storage and processing characteristics, the ageing and the application conditions.
Those polymers which are natural in origin or having ester linkage are easily attacked by
micro-organism.
4.8.2 Types of Biodegradable polymers
1. Natural: Naturally occurring polymers are biodegradable like starch, cellulose, protiens
etc.
2. Synthetic: Synthetic biopolymers generally includes polyesters. Following are the
important biopolymers.

(i) Poly β-hydroxybutyrate – co-β-hydroxy valerate (PHBV):- It is derived by

combining 3-hydroxy butanoic acid and 3-hydroxy pentanoic acid, in which monomers are
cross-linked by an ester linkage. It decomposes to form carbon dioxide and water. It is
brittle in nature, and it can be used in the production of drugs and manufacturing of bottles.
(ii) Nylon 2–nylon 6:- It is a polyamide copolymerization
of glycine (H2N−CH2−COOH) and aminocaproic acid (H2N−(CH2)5−COOH).
(iii) Polyhydroxy butyrate (PHB):- It is formed by the condensation of
hydroxybutyric acid (3-hydroxy butanoic acid) molecules.
(iv) Polylactic acid (PLA): formed by the condensation polymerization of lactic acid.

4.8.3 Applications of Biodegradable Polymers

(i) Polylactic acid decomposed harmlessly in the human body therefore used for
medical application incuding surgical implants which do not require operative
removal.
(ii) PHBV is used in the manufacture of bottles and containers.
(iii) Polylactic acid and cellulose are used for the packaging applications.
(iv) They are used in drug delivery