UNIVERSITY INSTITUTE OF CHEMICAL TECHNOLOGY

JALGAON

Topic Seminar

On

“CONDUCTING POLYMER”

Submitted by

Mr. Mayur Bhausaheb Bhoite

Guided By

Prof. Dr. R. G. Puri

University Institute of Chemical Technology

KBC, NMU, Jalgaon

2018-2019
 UNIVERSITY INSTITUTE OF CHEMICAL
TECHNOLOGY

KAVAYITRI BAHINABAI CHAUDHARI, NORTH

MAHARASHTRA UNIVERSITY
P.B. NO.80, UMAVI NAGAR, JALGAON-425001. (MS)

CERTIFICATE

This is to certify that Mr. BHOITE MAYUR BHAUSAHEB

has successfully completed the Topic seminar on “CONDUCTING
POLYMER ”. The Topic seminar is approved as the fulfillment of
the award of Bachelor of Technology in Paint Technology during
the academic year.

2018-2019

Prof. Dr. R. G. Puri Prof.Dr. J. B. NAIK

Head of Paint division, Director of University Instituteof
University Institute of Chemical Chemical Technology,
Technology, KBC,North Maharashtra University,
KBC,North Maharashtra University, Jalgaon (MS)
Jalgaon (MS)
 INDEX

CONTENT
SR.NO
Page No

1 ACKNOWLEDGEMENT
4

2 INTRODUCTION
5

3 LITERATURE REVIEW
6

4 CONDUCTING POLYMER
7

5 POLYANILINE
12

6 POLYPYRROLE
15

7 BASIC OF CORROSION
18
CONDUCTING POLYMER FOR
8
CORROSION PROTACTION 21

9 CONCLUSION
25

10 REFERENCE
25
 ACKNOWLEDGEMENT

I take opportunity to express my gratitude to all those who have rendered co-operation
and guidance that supported me while developing this Technical Report.

I would like to express my deepest gratitude to wards Prof. Dr. R. G. Puri (Paint
Division HOD, UICT, KBC, NMU, Jalgaon) for giving me such an opportunity.

I also present my respective gratitude to all the teaching and non-teaching staff and all
my friends who were very keen to me during report.

With sincere gratitude,

Mr. Mayur B Bhoite

Fourth Year B. Tech. (Paint Tech.)

 1. INTRODUCTION

1.1 BACKGROUND

Polymers, by virtue of their light weight and greater ease of fabrication, have
replaced and are continuing to replace metals in several areas of applications; as often
remarked - ‘from buckets to rockets’. Polymers have traditionally been considered good
electrical insulators and a variety of their applications have relied on this insulating property.
However, for more than a decade now, researchers have shown that certain class of polymers
which are conjugated (those that possess an extended π-conjugation along the polymer
backbone), exhibit semiconducting behavior. This special class is called Conducting
Polymers. Conducting polymers are relatively new materials that have been under extensive
research for the past two decades. Conducting polymers are composed of conjugated chains
containing π delocalized electrons along the polymer backbone of C, H and heteroatom’s
such as N and S. Their unique π conjugation properties impart electrical conductivity at room
temperature. EAPs are semi conductive polymers that can be doped and converted into
electrically conductive forms. Their unique properties such as mechanical strength, electrical
conductivity, corrosion resistance and feasibility of their synthesis by chemical as well as
electrochemical methods, make them useful for various applications Recently, conducting
polymer nanostructures became a new field of research and development, due to their
potential applications in the fields of rechargeable batteries, electro chromic displays,
electrochemical sensors and capacitors, and recently used in preparation of active corrosion
protection coatings and electromagnetic interference(EMI) Shielding.

Why Conducting Polymers?

1. Environmental stability, easy processing, and economical efficiency
2. A high conductivity combined with very light weight, flexibility, reasonably facile
processibility and simple conductivity control
3. High conductivity/weight ratio
4. Very promising properties because of the chemical nature of the macromolecular chains in
which electronic conduction occurs at long range.
5. The polymer's conductive nature provides an electroactive interaction with the metal
surface and forms a passivation layer between the metal surface and the polymer coating.
Therefore, it functions as a barrier coating as well as surface conversion agent, similar to the
chromate coatings.

There is increasing interest in the use of electroactive conducting polymers (ECPs) as

components of corrosion resistant coating systems, either directly as a prime coating or
surface treatment, or as a component blended with conventional coatings. The insertion of
conductivity into various materials (insulating polymer matrix, reinforcing fabrics,
honeycomb structure) is now possible which leads to complex structures. They absorb radar
waves and can match new environmental constraints (mechanical properties for example).
The driving idea is based on the growing process at molecular scale of the conducting entity
leading to a uniform macroscopic network in the material. Thus it is useful for EMI shielding.

2. Literature Review

2.1 History

A polymer (material containing a long chain of molecular structures) is first and

foremost an insulator. The idea that polymers or plastics could conduct electricity is
considered absurd. Their wide application as an insulating material is the reason they are
studied and developed in the first place. In fact, these materials are commonly used for
surrounding copper wires and manufacturing the outer structures of electrical appliances that
prevent humans from coming in direct contact with electricity.
In 1958, polyacetylene was first synthesized by Natta et al. as a black powder. This
was found to be a semi-conductor with 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 Hideki Shirakawa at the Tokyo
Institute of Technology was attempting to synthesize 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, Ti(O-n-But)4 - Et3Al, 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. Undoped, the polymer was silvery, insoluble and intractable, with conductivity
similar to that of semiconductors. When it was weakly oxidized by compounds such as iodine
it turned a golden color and its conductivity increased to about 104 Sm-1.In the 1980's
polyheterocycles were first developed. Polyheterocycles were found to be much more air
stable than polyacetylene, although their conductivities were not so high, typically about 103
Sm. By adding various side groups to the polymer backbone, derivatives which were soluble
in various solvents were prepared. The ability to control the level of conductivity in polymers
has given researchers the tools to tailor properties to specific needs and devices. EAPs have
potential applications in many diverse areas as actuators, supercapacitors/batteries, molecular
electronics, electrochromic windows/displays, transistors, photovoltaic’s, bio/chemical
sensors, corrosion protection and electromagnetic interference (EMI) Shielding. Corrosion
protection using electroactive polymers was first suggested by MacDiarmid in 1985. EAPs
undergo insulating to the conducting state through several doping techniques.

2.2 Conducting Polymer

Conducting polymers are composed of conjugated chains containing π delocalized

electrons along the polymer backbone of C, H and heteroatoms such as N and S. Their unique
π conjugation properties impart electrical conductivity at room temperature. ICPs conduct
electricity due to their property of conjugation. The term used for the presence of alternate
single (sigma) and double (sigma and π) bonds in polymer molecules. The carbon atoms
2 2
along the ICP backbone have sp hybridizations (three sp orbitals in the plane and pz orbital
2
out of plane). In sp hybridization, the Pz orbital of the adjacent carbon atoms overlap each
2
other and form additional π bonds, and the sp orbitals form the sigma bonds. The energy
difference between the highest occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO) is smaller in the case of π bonds compared to the
sigma bonds that provide the semiconducting behaviour, and the optical absorption properties
are in or near the visible spectral range. This π-π overlap causes the delocalization of
electrons that provide the pathway for the free electron charge carriers to move along the
polymer chain. EAPs are semiconductive polymers that can be doped and converted into
electrically conductive forms. The Intrinsic conductivity of conducting polymers is very less
 -3
typically in the range of 10 S/cm. Conductivity of conducting polymer is increased by
doping i.e. by simple chemical or electrochemical oxidation or reduction by appropriate
reagent. These reagents are called as dopants.

A Logarithmic conductivity ladder of some of these polymers are shown below.

Logarithmic conductivity

Conductivity of conducting polymer is increased by doping i.e. by simple chemical or

electrochemical oxidation or reduction by appropriate reagent. These reagents are called as
dopants. The concept of doping is the unique, central, underlying, and unifying theme which
distinguishes conducting polymers from all other types of polymers] During the doping
process, an organic polymer, either an insulator or semiconductor having a small
conductivity, typically in the range 1010 to 105 Scm-1, is converted into a polymer which is in
the metallic conducting regime (ca. 1 to 104 Scm-1). Doping is reversible to produce the
original polymer with little or no degradation of the polymer backbone. Both doping and
undoping processes, involving dopant counterions which stabilize the doped state, may be
carried out chemically or electrochemically. By controllably adjusting the doping level, a
conductivity anywhere between that of the non-doped (insulating or semiconducting) and that
of the fully doped (highly conducting) form of the polymer can be easily obtained.

Figure 2.1 conductivity chart representing conductivity of undoped and doped

conducting polymer

The oxidative doping of polypyrrole proceeds in the following way. An electron is

removed from the p system of the backbone producing free radical and a spinless positive
charge. The radical and cation are coupled to each other via local resonance of the charge and
the radical. In this case, a sequence of quinoid-like rings is used. The distortion produced by
this is of higher energy than the remaining portion of the chain. The creation and separation
of these defects costs a considerable amount of energy. This limits the number of quinoid-like
rings that can link these two bound species together. In the case of polypyrrole it is believed
that the lattice distortion extends over four pyrrole rings. This combination of a charge site
and a radical is called a polaron. This could be either a radical cation or radical anion. This
creates new localized electronic states in the gap, with the lower energy states being occupied
by single unpaired electrons. The polaron state of polypryyole is symmetrically located about
0.5 eV from the band edges.
 Upon further oxidation the free radical of the polaron is removed, creating a new
spinless defect called a bipolaron. The bipolarons are located symmetrically with a band gap
of 0.75 eV for polypryyole

Figure 2.2 Polypyrrole systems in Polaron and bipolaron form

 Conjugated polymers with a degenerate ground state have a slightly different
mechanism. As with polypryyole, polarons and bipolarons are produced upon oxidation.
However, because the ground state structure of such polymers are twofold degenerate, the
charged cation are not bound to each other by a higher energy bonding configuration and can
freely separate along the chain. The effect of this is that the charged defects are independent
of one another and can form domain walls that separate two phases of opposite orientation
and identical energy. These are called solitons and can sometimes be neutral. Solitons
produced in polyacetylene are believed to be delocalized over about 12 CH units with the
maximum charge density next to the dopant counter ion. The bonds closer to the defect show
less amount of bond alternation than the bonds away from the centre. Soliton formation
results in the creation of new localized electronic states that appear in the middle of the
energy gap. At high doping levels, the charged solitons interact with each other to form a
soliton band which can eventually merge with the band edges to create true metallic
conductivity. This is shown below.

Figure 2.3 Bands in polaron and solitons

There are two main groups of applications for these polymers. The first group utilizes
their conductivity as its main property. The second group utilizes the electroactivity. They are
shown below
 TABLE 2.1 Classification based upon applications utilizing Conductivity and
Electroactivity

Group 1 Group 2
Electrostatic materials Molecular electronics
Conducting adhesives Electrical displays
Electromagnetic shielding Chemical biochemical and thermal sensors
Printed circuit boards Rechargeable batteries and solid electrolytes
Artificial nerves Drug release systems
Antistatic clothing Optical computers
Piezoceramics Ion exchange membranes
Active electronics (diodes transistors) Electromechanical actuators
Aircraft structures ‘Smart’ structures
Switches

2.3 Polyaniline

PANI is a quite old material, prepared in the 19th Century by H. Letheby. At that time
the polymeric nature of PANI was not understood; the material was called "aniline black" and
was used in textiles as dyes and in printing . Polyaniline is one of the conductive polymers
used for coating that has been intensively investigated.

Figure2.4: Polyaniline structure

 Oxidation of aniline is the most widel employed synthetic route to polyaniline and can
be performed either electrochemically or chemically. The reaction is usually carried out in
acidic medium with chemical oxidizing agents such as ammoniumpersulfate, sodium
persulfate.Branching or even crosslinking during polymerization occurs through the
formation of radicals at the 2 and 6 position.

Figure 2.5 : Mechanism of Polyaniline formation

PANI has several advantages over most current CPs. The advantages are:

(a) Easy chemical and electrochemical polymerization,

(b) Easy doping and re-doping by treatment with standard aqueous acid and base and

(c) High resistance to environmental degradation.

 Figure 2.6: Polyaniline in the range of semiconductor

PANI is a difficult material to process under normal conditions. Several methods used
for improving the processability and solubility of PANI. These methods include modification
of the polymer backbone by introducing various functional groups such as alkoxy, amino,
alkyl, aryl and sulfonyl, or by using novel acids such as camphor sulfonic acid, dodecyl
benzensulfonic acid to obtain a conducting soluble form of PANI.
 Figure 2.7: Soluble form of PANI

The protonic acid doping is done by the following way

Figure 2.8: Protonic acid doping

PANI can be produced from both chemical and electrochemical process can exist in
four different oxidation states: leucoemeraldine, pernigraniline, emeraldinebase(intermediate
form)and emeraldine salt (conductive form)
 Figure 2.9: Oxidation states of PANI

These different forms of PANI find different uses like leucoemeraldine— the
completely reduced form find applications in electrochromic devices and in Li–PANI
batteries; perningraniline is used for non-linear optics while emeraldine base consisting of
50% reduced and 50% oxidised moieties is used in HCl sensors and for making thin films.
While conducting PANI have the applications in electrostatic charge dissipation,
electromagnetic interference, anticorrosion coating, light emitting diodes and batteries.
2.4 Polypyrrole

Other example of conducting polymer is the heterocyclic monomers (figure 2.10) that
can be polymerized to form fully conjugated polymers. Electrochemical deposition technique
is often used to form polypyrrole coatings. Pyrrole monomer is a non-carcinogenic
compound. It is usually higher in conductivity and lower in reduction potential compared to
polyaniline. Polypyrrole (PPy) was first reported in 1916. They have been polymerized using
both chemical and electrochemical methods. Polypyrrole was prepared by the chemical
oxidation of pyrrole using hydrogen peroxide and called "pyrrole black". Chemical
polymerization remains the simplest route, but electrochemical polymerization is the most
important and versatile method, producing high quality films and high conductivities (102
S/cm). Polypyrrole (PPy) can be doped to give moderate to high conductivities. The resulting
polymers are electron-rich materials that are easily oxidized and stable in the oxidized form.
Of all known intrinsically conducting polymers, polypyrrole is most frequently used in
commercial applications, mainly due to the long-term stability of its conductivity, improved
processability and due to the possibility of forming homopolymers or composites with
optimal mechanical properties

Figure 2.10: Heterocyclic structure

Figure 2.11: Mechanism of formation of Polypyrrole

In the generally accepted mechanism for the electro-initiated polymerization of

pyrrole, the first step is the electro oxidation of pyrrole to form a radical cation, which then
couples with another radical cation. The point of attachment is alpha position, being the side
of highest electron density. The radical coupling is followed by dimerization through
deprotonation. The dimer so formed has a lower oxidation potential and it is preferably
oxidized further. This repetitive oxidation and coupling sequence leads to a lengthening of
the polymer chain. The mechanism is illustrated in figure 2.11. The pyrrole units as shown in
figure 2.11 are coupled to one another through the 2 and 5 positions. The results of several
structural investigations indicate that pyrrole units polymerize through the 2- and 5-positions.
It has been suggested that polypyrrole predominantly consist of aromatic and quinoid
structures (figure 2.12). Between the two fundamental structures, the aromatic structure
corresponds to the undoped (neutral units) state and the quinoid structure corresponds to the
doped state (oxidized units). Polypyrrole can be doped to give moderate to high
conductivities.

Figure 2.12: Undoped aromatic form and doped form of pyrrole

PPy can found into three forms which are Neutral form (non conductive), polaron
form (partially conductive) and bipolaron (highly conductive) shown in figure.
 Figure 2.13: Polypyrrole in different forms

2.6 BASICS OF CORROSION

Corrosion can be defined as the degradation of a material due to reaction with its
environment. Materials can be metals, polymers (plastics, rubbers, etc.), ceramics (concrete,
brick, etc.) orcomposites. In general term the corrosion means electro-chemical oxidation of
metals in reaction with an oxidant such as oxygen. Rusting i.e. the formation of iron oxide is
a well-known example of electrochemical corrosion. Degradation implies deterioration of
physical properties of the material. This can be a weakening of the material due to a loss of
cross-sectional area or shattering of a metal due to hydrogen embrittlement or cracking of a
polymer due to sunlight exposure.

Common structural metals are obtained from their ores or naturally-occurring

compounds by the expenditure of large amounts of energy. These metals can therefore be
regarded as being in a metastable state and will tend to lose their energy by reverting to
compounds more or less similar to their original states

Figure 2.31: Corrosion in terms of energy

Virtually all corrosion reactions are electrochemical in nature. In electrochemical

terminology, an electrode at which an oxidation reaction occurs is called an anode and an
electrode at which a reduction reaction occurs is called a cathode. The process of oxidation
involves a loss of electrons by the reacting species, as occurs in the metal dissolution reaction
while reduction involves a gain in electron. Thus an area where dissolution of metal occurs is
an anode and an area where the reduction reaction occurs is called a cathode.

Anodic Reaction:

Cathodic Reaction:

Acidic Medium
Neutral medium

Corrosion occurs in several widely differing forms. Classification is usually based on

one of three factors:
 Nature of the corrodent:Corrosion can be classified as “wet” or “dry.” A liquid or
moisture is necessary for the former, and dry corrosion usually involves reaction with
high-temperature gases.
 Mechanism of corrosion:This involves either electrochemical or direct chemical
reactions.
 Appearance of the corroded metal:Corrosion is either uniform andthe metal
corrodes at the same rate over the entire surface, or it is localized, in which case only
small areas are affected.

Eight forms of wet (or aqueous) corrosion can be identified based on appearance of
the corroded metal.
 Uniform or general corrosion
 Pitting corrosion
 Crevice corrosion, including corrosion under tubercles or deposits,
 filiform corrosion, and poultice corrosion
 Galvanic corrosion
 Erosion-corrosion, including cavitation erosion and fretting corrosion
 Intergranular corrosion, including sensitization and exfoliation
 Dealloying, including dezincification and graphitic corrosion
 Environmentally assisted cracking, including stress-corrosion cracking,
 Corrosion fatigue and hydrogen damage
 Figure 2.32 : Schematics of the common forms of corrosion
The indirect consequential losses resulting from corrosion are less amenable for
calculations but may well outweigh the direct costs. The unpredictable failure of critical parts
of industrial equipment, aircraft or other means of transport can cause accidents costing both
lives and money.
Failures of various kinds and the need for expensive replacements may occur even
though the amount of metal destroyed is quite small
2.7 Conducting Polymers for Corrosion Prevention

The initiation and propagation of corrosion are major concerns in various

technologies. Consequently, there is an ever increasing interest in formulating new corrosion
control measures that are environmentally acceptable. Recently, it has been shown that
conducting polymers, when deposited onto corrosion susceptible materials, can inhibit
corrosion opening up the avenue for a new corrosion-control methodology. Up to now, only
little is known about how corrosion protection by conducting polymers might work. Several
hypotheses have been suggested for the mechanism of corrosion protection using conducting
polymers. The following four mechanisms are most relevant.

 The displacement of the electrochemical interface

This is quiet similar to the situation where an oxidizable metal is coated with a noble
one (Ni or Cr) in order to prevent corrosion by completely isolating the underlying metal to
escapes from the aggressive environment. When an oxidizable metal is coated by a conducting
polymer film in its oxidized state, the electrochemical interface moves from metal solution to
polymer solution interface. As long polymer remains in its oxidized conductive state it derive
that the electrical potential drop at the metal polymer interface is small. thus the driving force
for metal oxidation disappears. The underlying metal is no longer in contact with the aggressive
environment. The reduction of O2 can take place at the polymer surface is also of great
importance because this implies that the OH- species, responsible for disbondment and
delamination, has no effect on the adherence of the polymer.

 Ennobling of the metal surface.

Assumption behind ennobling is that the conducting polymer, in its oxidized state,
will set the metal at a potential within its passive range where the dissolution rate is slow. This
involves the formations of thin insulating metallic oxide layers which protects the metal from a
rapid dissolution and make it behave like a noble metal. Mechanism of iron protection against
corrosion through a PANI coating was proposed by Wessling. According to this scheme, a
redox reaction occurs between Fe and (PANI) ox leading to (PANI) red and Fe++.

 The self healing properties provided by counter ions with inhibitor properties

If there is a small scratch on a metal coated by a conducting polymer then there is a

galvanic coupling between metal and polymer. This galvanic coupling involves, on the one
hand, the reduction of the polymer associated with release of the doping anions and, on the
other hand, the oxidation of the metal. The released A- either interacts with M+n and leads to an
insoluble salt with inhibiting properties or is adsorbed onto M and provides anodic inhibition.
Due to this property conducting polymer are considered as smart coating.

Figure 2.33:Self healing mechanism for a metal (M) coated by a conducting

polymer(P+n)
 Obviously the efficiency of the self healing depends upon the mobility of the anion
and on the anion and on its aptitude to be released by the polymer.
 Barrier effect
A barrier effect is one of the main features needed for good protection against
corrosion. A strong barrier effect will indeed slow down O2 and water diffusion through the
coating and consequently reduce corrosion at the interface. But Cl- diffusion occurs through
ion exchange in polymer and could be critical in the case of doped conducting polymers.
Therefore, depending on the nature of the doping ion, this could be an important cause of
corrosion. The coating is impermeable to cations so it slowdown the anodic dissolution and
hence corrosion rate reduced.

But if we use polyaniline primer with cation exchange resin then we can get a very
good corrosion protection.

Cationic topcoat prevents aggressive anions and thus anodic dissolution inhibited and
polyaniline provides anodic protection and delays lamination. Hence it will protect
metal.Anion exchange nature of conducting polymer is responsible for anticorrosion
behavior.

Conclusion

 For conductance free electrons are needed.

 Conjugated polymers are semiconductor materials while doped polymers are
conductors.
 The conductivity of conductive polymers decreases with falling temperature in
contrast to the conductivites of typical metals, e.g., Silver which increase with falling
temperature.
 Today conductive plastics are being developed for many users.

Reference

1) Conducting polymers for corrosion protection: a review Pravin P. Deshpande, Niteen

G. Jadhav, Victoria J. Gelling, Dimitra Sazou
2) CONDUCTING POLYMERS By Colin Pratt
3) Conjugated conducting polymers: A brief Overview
4) www.google.com \wikipedia.com