Open Elective Course for B. Tech. /M. Tech. /Ph. D.

Course Title- Polymer Chemistry

Course Code- CYOE 402
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Scheme & Credit – L-3, T-0, P-0, C-3

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-Dr. Sanjeeb Sutradhar

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 Distribution of Marks
Theory
Subject Code- CYOE 402
Total Marks- 100
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Attendance- <75.0% - can’t appear final exam (Will be detained)
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Continuous Assessment – 20anje
Quiz-I: 5 D r. S 75.1%-79.9% = 1
80.0%-84.9% = 2
Objective test-I : 5 85.0%-89.9% = 3
Objective test-II : 5 90.0%-94.9% = 4
95.0%-100.0%= 5
Group Assignment: 5
Class Participation/Interaction: 5
Mid Semester Term: 30
End Semester Term: 50 2
 Grading Procedure

Grade Points Description of performance Recommended Cut off marks*

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S 10 Outstanding
tr a 90-100
A 09 Excellent
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B 08 Very Good 70-79

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C 07 Good 60-69
D 06 Average 50-59
E* 05* Marginal 40-49
I - Incomplete -
U - Unsuccessful -
W - Withheld due to shortage of attendance or withdrawal -
NP - AuditPass -
NF - Audit Fail -
 SGPA and CGPA Calculations

Semester Grade Point Average (SGPA)

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∑ tr
(𝑪𝒓𝒆𝒅𝒊𝒕 𝑷𝒐𝒊𝒏𝒕𝒔 × 𝑮𝒓𝒂𝒅𝒆 𝑷𝒐𝒊𝒏𝒕
u a)(𝑫𝒖𝒓𝒊𝒏𝒈 𝒂𝑺𝒆𝒎𝒆𝒔𝒕𝒆𝒓 )
𝑺𝑮𝑷𝑨=
e
∑ 𝑪𝒐𝒖𝒓𝒔𝒆 𝑪𝒓𝒆𝒅𝒊𝒕𝒔 S
b (𝑫𝒖𝒓𝒊𝒏𝒈 𝒂 𝒔𝒆𝒎𝒆𝒔𝒕𝒆𝒓 )
a nj e
S
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Cumulative Grade Point Average (CGPA)

𝑪𝑮𝑷𝑨=
∑ (𝑪𝒓𝒆𝒅𝒊𝒕 𝑷𝒐𝒊𝒏𝒕𝒔 × 𝑮𝒓𝒂𝒅𝒆 𝑷𝒐𝒊𝒏𝒕)(𝑼𝒑𝒕𝒐 𝒂 𝑺𝒆𝒎𝒆𝒔𝒕𝒆𝒓 )
∑ 𝑪𝒐𝒖𝒓𝒔𝒆 𝑪𝒓𝒆𝒅𝒊𝒕𝒔 (𝑼𝒑𝒕𝒐 𝒂 𝒔𝒆𝒎𝒆𝒔𝒕𝒆𝒓 )
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 Conducting Polymers (Lectures-5)
Introduction, classification, different types of doping, synthesis, applications in
different fields.

References
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Online Sources: https://chem.libretexts.org/
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 Conducting Polymers
Introduction
Solids show a wide range of electrical conductivities from 10-20 to 107 S/m. On

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the basis of electrical conductivity, the solid can be broadly classified into three
types-
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Conductors: Solids which have conductivities in the order of 104 to 107 S/m.
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Metals are good conductors of electricity.

Insulators Dr.
Solids which have very low conductivity in the range 10-20 to 10-10 S/m.
e.g. wood, rubber, sulfur, phosphorus etc.

Semiconductors
It has conductivity in between conductor and insulator up to the order of 10-6 to
104 S/m.
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 Conducting Polymers

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 Conducting Polymers

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n semiconductor (1eV)
Conductor
e.g.DCu,
S
r. Pb e.g. Si, Ge Insulator (6eV)
e.g. Plastic, Paper

Acceptor Donor

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 Conducting Polymers
Interest in organic semiconductors originated from the transfer of electrons
from molecule to molecule may play an important role in fundamental physical
processes of living organisms.
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In 1906, a measurable electrical conductionSwas reported for anthracene.
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 Conducting Polymers
Conducting polymers:
Those polymers which conduct electricity are called conducting

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polymers. The conduction of polymer may be due to unsaturation or due to the
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presence of externally added ingredients in them.
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Ordinary polymers obtained by usual methods are nearly insulators. However,

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some specific polymers may act as conductors.

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.
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 Conducting Polymers
But, like insulating polymers, they are organic materials. They can offer high
electrical conductivity but do not show similar mechanical properties to other
commercially available polymers.
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The electrical properties can be fine-tuned using the methods of organic
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synthesis and by advanced dispersion
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e.g.
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Polypyrrole
Polyaniline 12
 Conducting Polymers
In 1977, Alan J. Heeger, Alan MacDiarmid and Hideki Shirakawa reported
similar high conductivity in oxidized iodine-doped polyacetylene. For this
research, they were awarded the 2000 Nobel Prize in Chemistry "for the
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discovery and development of conductive polymers." ar
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 Conducting Polymers
Classification
The conducting polymers can be classified in following ways.

Conducting polymers
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Intrinsic conducting S Extrinsic conducting
polymers D polymers

Intrinsic Doped Conductivit Blended

polymer with conducting y element conducting
conjugation polymers polymer
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 Conducting Polymers
Intrinsic conducting polymers:
These polymers are characterised by intensive of double bonds in
their structure i.e. backbone of the polymer.
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Again, intrinsic conducting polymers are of two types-
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Intrinsic polymers with conjugation
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Doped conducting polymers

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 Conducting Polymers
Intrinsic polymers with conjugation
Such polymers having conjugated double bonds in the backbone possess their
conductivity due to π electrons.
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In π bonding the overlapping of the orbitals is lateral over the entire backbone
b valence bands and higher energy
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resulting in the formation of lower
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n by a significant fermi energy gap.
energy
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conducting bands which were separated

The electrical conductivity takes place only after thermal or photolytic activation
of the electrons, which give them sufficient energy to jump the gap and reach
into conduction band.

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 Conducting Polymers
e.g.

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− 𝐶𝐻=𝐶𝐻 − 𝐶𝐻=𝐶𝐻 −𝐶𝐻=𝐶𝐻 −
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Polyacetylene
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Dr. Delocalisation of π
electrons

¿𝐶𝐻 − 𝐶𝐻=𝐶𝐻 − 𝐶𝐻=𝐶𝐻 − 𝐶𝐻=¿

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 Conducting Polymers
Doped conducting polymers
The conducting polymers having π electrons in the backbone can easily be

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oxidised or reduced because they possess low ionisation potential and high
electron affinities.
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Hence their conductance can be increased by introducing a positive charge or

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negative charge on polymer backbone by oxidation or reduction.

This process is similar to semiconductor technology and is called Doping.

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 Conducting Polymers
Doping is the process of disturbing polymer molecule either by adding electrons
(reduction) or removing electrons (oxidation) through treating it with Lewis base
or Lewis acid called doping agent or dopant.
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Doping is of two types:
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Creating a positive site on polymer backbone called p–doping

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Creating a negative site on polymer backbone called n–doping

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 Conducting Polymers
p–doping
p–doping is done by oxidation of a conducting polymer like polyacetylene with a
Lewis acid or iodine vapour. This is called Oxidative doping.
r+ -
FeCl4 FeCl2
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jee b 3

a n
S radical called ion called polaron having a hole
During oxidation process the removal of π electrons from polymer backbone lead
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to the formation of a delocalised
in between valence band and conducting band as shown below-

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 Conducting Polymers
The second oxidation of the polaron results in two positive charge carriers in
each chain called bipolaron, which are mobile because of delocalisation. These
delocalised charge carriers are responsible for conductance when placed in
electric field.
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Soliton
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 Conducting Polymers
n–doping
This is done by reduction process. For this conductance, polymers having
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conjugation is treated with Lewis base like sodium naphthalide.
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 Conducting Polymers

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 Conducting Polymers
Extrinsically conducting polymers:
These polymers possess their conductivity due to the presence of
externally added ingredients in them. These are of two types:
Conductive element filled polymers:
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The polymer acts as the binder to hold the conducting element (such as carbon
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black, metallic fibres, metallic oxides, etc.) together in the solid entity.
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Minimum concentration of conductive filler, which should be added so that
polymer starts conducting, is known as percolation threshold. Because at this
concentration of filler or conducting element, a conducting path is formed in
polymeric material. Such compounds have been important.

e.g. In hospital operating theatres where it was essential that static charges did
not build up, leading to explosion involving anaesthetics.
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 Conducting Polymers
Blended conducting polymers:
These polymers can be obtained by blending processes. They possess better

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physical, chemical, electrical and mechanical properties and they can be easily
processed.
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e.g. Up to 40% of polypyrrole will have little effect on tensile strength and give

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much higher impact strength- Such compounds are of interest in
electromagnetic shielding.

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 Conducting Polymers
Difference:
Conductive element filled polymers Blended conducting polymers

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Insulative polymer matrix + discrete Physical/chemical mixture of insulating
tr a
metal particles, CNTs)
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conductive fillers (e.g. carbon black, polymer + intrinsically conductive
b polymer (e.g. PEDOT:PSS, PANI)
a je
n Continuous conductive phases
Dependent on percolation Sthreshold
(random filler contact) Dr.
or
molecular-level charge transfer
Requires precise dispersion to avoid Needs compatibility optimization (often
agglomeration requires surfactants)
Higher maximum conductivity possible More uniform conductivity and better
and better mechanical robustness processability at low loadings
Electromagnetic interference shielding, Flexible electronics, bioelectrodes
antistatic coatings
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 Conducting Polymers
Approaches for Making Conducting Polymers
A practical and more obvious approach involves incorporation of metallic

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powders, flakes or whiskers or other conductive fillers such as graphite powder
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or conducting carbon blacks into common plastics or rubbers.
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However, such filled conducting compositions have their own limitations.

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Despite infusion of conductivity due to the incorporation of the conducting
filler particles, the prominent insulation or resistance character of the matrix
polymer generates heat during passage of electricity.

Accumulation of heat and consequent rise in temperature and thermal

expansion cause the conducting filler particles in such filled polymer systems
move further apart, thereby leading to a dropping trend in conductivity with
time of passage of electricity.
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 Conducting Polymers
First approach:
Electron delocalization favourably occurs as a molecular system becomes more
conjugated.
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Second approach:
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Likewise, in charge-transfer (CT) complexes, a partial electron transfer occurs
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from the donor site to the acceptor site of the molecule.

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e.g. Crystalline complex of quinoline with tetracyanoquinodimethane (TCNQ),
having a room temperature conductivity of the order of only 1 S/cm.

Donor Acceptor
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 Conducting Polymers

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J. Mater. Chem. C, 2014,2, 3065-3076
 Temperature Effect on Solids
 Conductor is heated its resistance increases: Atoms vibrate more and the electrons
find it more difficult to move through the conductor with increase in temperature.

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a n je
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 Semiconductor is heated its S
. resistance decreases: Electrons can be excited up to the
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conduction band with increase in temperature and conductivity increases.

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 Conducting Polymers
Conducting Polymers
1. Polyacetylene (PA)

2. Polyaniline (PANI)
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3. Polypyrrole (PPy)
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Polyparaphenylene (PPP)

5. Polythiophene (PT)

6. Polyphenylene vinylene (PPV)

7. Poly(3,4-ethylenedioxythiophene) (PEDOT)
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 Conducting Polymers
Synthesis approach
1. Electrochemical polymerization: Based on the deposition of the polymer
onto the surface of a solid electrode material.
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d in presence of oxidant
2.
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Oxidative chemical polymerization: Polymerization
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3
a n je
(oxidizing agent). e.g. FeCl , NaBH
4 .
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3. Dr. Polymerization due to addition of simple
Chemical polymerization:
chemical substance and may loss small group of molecules like H 2O,
CH3OH.

4. Plasma polymerization method: Polymerization due to use of plasma

(fourth state of matter).
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 Conducting Polymers
Synthesis and Applications of
Polyacetylene (PA)
Removing one H-atom from each
carbon atom in the chain molecules
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of polyethylene, leaving one spare tr a
electron on each carbon atom
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forming the chain backbone; the
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electrons can be made to flow
through the polymer mass so that nn
the hypothetical polymer
intermediate can be called a
“metallic polymer”.

Polymerization process:
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 Conducting Polymers

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n
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It is a first electro-conductive polymer synthesized by Shirakawa et al. in
1970.

Its invention attracted attention of researcher toward the discovery of new

conductive polymers due to their wide applications in electronics.
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 Conducting Polymers
Electrical conductivity of PA with different dopants

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Conductivity increases

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 Conducting Polymers
It can also be efficiently prepared by metathesis polymerization, electro-
chemical polymerization, high pressure polymerization methods.

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Using electron acceptor or electron donor species for doping the polymer to

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gain electrical conductivity. Bare and doped PA has been explored for the
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construction of

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electrical conductors,
semiconducting devices,
rechargeable batteries,
solar cells
sensors
battery electrodes

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 Conducting Polymers

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 Conducting Polymers
Synthesis and Applications of Polyaniline (PANI)

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n

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In 19th century Henry Lethe was discovered PANI for the first time and studied
electrochemical and chemical oxidation product of aniline in acidic medium.
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 Conducting Polymers
Electro-chemical synthesis method for preparation of PANI is known for the
generation of purest product. Electro polymerization of aniline was carried out

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in single compartment electrochemical cell containing aniline and hydrochloric
acid in distilled water.
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 Conducting Polymers
Electrical conductivity of PANI with different dopants

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 Conducting Polymers
PANI is the most studied and promising conductive polymer because of its
inexpensive monomer, controllable electrical properties, good environmental
stability, and potential applications.
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It can be synthesized from monomericSaniline tr a unit by electro chemical
e b
polymerization, oxidative chemicaljepolymerization,
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and plasma polymerizationr.method.
chemical polymerization,

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Bare PANI is employed as transparent antistatic coatings, corrosion protection,
and doped PANI is used as a conducting material, electromagnetic shielding
material in electronics, to construct electrochromic glass, supercapacitors,
flexible electrodes, light emitting devices, sensors, and conductive fibres.

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 Conducting Polymers
Synthesis and Applications of Polypyrrole (PPy)
PPy is prepared by electrochemical and chemical oxidative polymerization
methods.
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n ( ) n

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 Conducting Polymers
Electrical conductivity of PPy with different dopants

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 Conducting Polymers
PPy compounds has been used for sensors for estimation of various gases and
volatile organic compounds, microwave shielding, batteries, super capacitors
and corrosion protection.
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Polypyrrole sensors are highly sensitive forS u t
polar
r a
gas than non-polar gas.
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 Conducting Polymers
Synthesis and Applications of Polyparaphenylene (PPP)
PPP is the rigid-rod polymer made up of repeating p-phenylene units and
converted to conductive form using dopant. Chemical polymerization is an
efficient method for its preparation.
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n

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 Conducting Polymers
Electrical conductivity of PPP with different dopants

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Due to its environmentally stable and electroluminescence behavior, it is used

for the fabrication of Light emitting devices.
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 Conducting Polymers
Synthesis and Applications of Polythiophene (PT)
Polythiophene (PT) is synthesized by polymerization of thiophene monomer
unit.
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n
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n
n

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 Conducting Polymers
Electrical conductivity of PT with different dopants

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 Conducting Polymers
Due to the properties of thermally and environmental stability, it is useful as
electrical super capacitor, antistatic coating, electromagnetic shielding
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materials, imaging materials, memory devices, batteries, solar cells, and LEDs.
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Iodine doped PT has electrical conductiveSproperties,
a
je e b it is used to fabricate
a n
polymer based electrode for a battery.
S
D r.
It is useful for fabricating electro optical display devices. It has electrochromic
properties i.e. changes color from red to blue on applying voltage.

It has been explored as humidity sensors, radiation detectors, and gas sensors.
Nanosized PT have high surface area with uniform porosity provides better
supercapacitor performance.
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 Conducting Polymers
Synthesis and Applications of Polyphenylene vinylene (PPV)
Polyphenylene vinylene is the combination of PA & Polyphenylene. High

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molecular weight PPV can be synthesized with good purity. It is relatively
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stable and quite insoluble. It has extremely low electrical conductivity of the
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order of 10-13 S/cm which can be increased upon doping in the range of 10-3 to
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102 S/cm with I2, FeCl3, alkali metals, or acids but with less stability.

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 Conducting Polymers
Electrical conductivity of PPV with different dopants

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 Conducting Polymers
Its unique electrical, optical, physical property, process ability and
environmental stability led to be investigated for its utilization in variety of
applications.
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Substituted PPV can also achieve appreciable
e b S conductivity on doping.

a j e
n for electroluminescence property. It can be
r. S
These materials were investigated
D
used in the construction of LEDs, transistors, etc.

PPV and its derivatives are studied for their photoconductive property which
has direct application in photodiodes, photovoltaic cell and electro
photography.

Substituted PPV i.e. poly 2,5 dimethoxy-p-phenylene vinylene is found to have

52
appreciable tensile strength on doping.
 Conducting Polymers
Synthesis and Applications of Poly(3,4-ethylenedioxythiophene) (PEDOT)
In late 1980s Jonas and Heywang decided to extend thiophene molecules to
bicyclic ring systems.
d h ar
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e S
In 1988 they finally got success with 3,4-ethylene
b polymer. dioxythiophene (EDOT) in

a n e
order to achieve stable heterocyclic jconductive
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 Conducting Polymers

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 Conducting Polymers
Electrical conductivity of PEDOT with different dopants

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 Conducting Polymers
PEDOT based materials are used as electro-chemical sensors like for the
detection of inorganic species such as Cd, Pb, Zn, Cu, and metalloids.

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PEDOT film with hollow-microflower was used to develop nitrite sensor as nitrite
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content in food, water and environmental samples as over intake would cause
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serious health issues (nitrosamine, carcinogenic)
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Hybrid PEDOT nanosensors incorporated with ionic liquid, polymer, graphene,
CNT, and metal oxide has been used for sensing gas like TNT (trinitrotoluene),
ammonia, CO2, NO2, and volatile organic compounds.

PEDOT:PSS based complex is introduced as antistatic layers coating for

industrial photographic films. Also, PEDOT:PSS has been employed in organic
solar cells as transparent conductive layer, buffer layer, and transparent anode.
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 Conducting Polymers

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 Conducting Polymers
Q: Which one is better efficient for doped conjugate polymer matrix and why?
Answer:

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Q: What is doping and what is the purpose of adding dopant to the less conductive
tr a
Su
polymer?

Q: Draw the density of state (DOS) n je e b

r. S a for the following redox, ionic, or pristine species
with PEDOT?
D

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 dh ar
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