Module 11 Conducting polymers: Polyacetylene and Polyaniline -

Mechanism of Conduction, doping; applications of

Conducting polymers.
Degradable Polymers- modes of degradation -
Biodegradation; Conditions for biodegradation,
Good method
 Biodegradable polymers
• Biodegradation polymers proceeds by
hydrolysis and oxidation
• Factors
• Hydrolysable and oxidisable linkages
• Suitable substitutents
• Balance of hydrophilicity and
hydrophobicity
• Conformational flexibility
 Classification
• Natural-cellulose,starch,lignin, protein
• Biosynthetic polymers- produced from
fermentation process by microorganism
• Ex- Poly(hydroxy alkanoates)
• Synthetic polymer-possessing the
biodegradable ptroperty
• Ex. Polycaprolactone and polylactic acid
 Natural polymer
• Cellulose:
• High molecular weight (> 5,70,000)
• Stereoregular and linear polymer
• Repeating units of Beta-glucose units
• Major constitutents of tree and plants
• Emprical formula: (C6H10O5)
• Polysaccharide
• Cellulose is the most abundant organic polymer on
Earth
• Cellulose is mainly used to produce paperboard and
paper
 Bio-Synthetic polymer
• Poly(hydroxy alkonates)
• High molecular weight
• Produced from bacterial fermentation of sugar and lipids
• Biocompatible thermoplastics can be melted and
moulded easily
• Use in medical and industrial applications
 Advantages of biodegradable
polymers
• Biodegradable polymers
• Less time to break down
• Renewable
• Good for the environment
• Require less energy to produce
• Easier to recycle
• Non toxic
 Conducting Polymers
Introduction
Polymers are typically insulators due to their very high resistivity. Insulators
have tightly bound electrons so that nearly no electron flow occurs, and
they offer high resistance to charge flow.
For conductance free electrons are needed. Conductivity in polymers can
be induced by delocalizing their orbitals with conjugated p-electron
backbones.

Alan J. Heeger, Alan

G. MacDiarmid and
Hideki Shirakawa
discovered that
Polyacetylene can be
made conductive
almost like a metal
(Nobel Prize for

Chemistry in 2000).
 Conducting Polymers
A conducting polymer is an organic based polymer
that can act as a semiconductor or a conductor.
The most widely studied organic polymers are
polyaniline (PANI), polypyrroles, polythiophenes, and
polyphenylene vinylenes.
Factors that affect the conductivity
1-Denesity of charge carriers.
2- Their mobility.
3-The direction.
4-presence of doping materials (additives
that facilitate the polymer conductivity)
5-Temperature.
 Conducting Polymers
The polymeric material which possess electrical
conductivity are called conducting polymer
Ex. Polyaniline, polypyrrole,polyacetylene

Types
Intrinsically conducting polymer(ICP)
Doped conducting polymer
Extrinsically conducting polymer
 . Intrinsically conducting polymer(ICP)

The polymer should consist of alternating single and double bonds, called
conjugated double bonds.
In conjugation, the bonds between the carbon atoms are alternately single and double.
Every bond contains a localized “sigma” (σ) bond which forms a strong chemical bond.
In addition, every double bond also contains a less strongly localized “pi” (π) bond which
is weaker.

Polyacetylene

The polymer structure has to be disturbed - either by removing electrons from

(oxidation), or inserting them into (reduction), the material. The process is known
as Doping.

Doping process:
Polyacetylene upon doping with halogens exhibit conductivity upto 105 S/cm.
When doped with Iodine, polyacetylene undergoes oxidation causing electrons to
be removed from the polymer, leaving "holes" in the form of positive charges that
can move along the polymer chain.
Doped conducting polymer

• The polymer has to be disturbed - either by

removing electrons from (oxidation), or inserting
them into (reduction), the material. The process is
known as Doping.
• There are two types of doping:
1. oxidation with halogen (or p-doping).

CHn   3x I  CHn   I 3
2
P-dopants: I2, Br2,AsF5, PF6

2. Reduction with alkali metal (called n-doping).

CH n   xNa  CH n x  xNa 

N-dopants: Li, Na, Ca
• The game offers a simple model of a doped polymer. The pieces
cannot move unless there is at least one empty "hole". In the
polymer each piece is an electron that jumps to a hole vacated by
another one. This creates a movement along the molecule - an
electric current.
 . Intrinsically conducting polymer(ICP)
Conductivity Mechanism in
Polyacetylene
• p-type doping process
• The halogen doping transforms polyacetylene to be a good conductor.

Oxidation with iodine causes the electrons to be jerked out of

the polymer, leaving "holes" in the form of positive charges that
can move along the chain.
 . Intrinsically conducting polymer(ICP)

• The iodine molecule attracts an electron from the

polyacetylene chain and becomes I3ֿ. The polyacetylene
molecule, now positively charged, is termed a radical cation,
or polaron.

• The lonely electron of the double bond, from which an electron

was removed, can move easily. As a consequence, the double
bond successively moves along the molecule.

• The positive charge, on the other hand, is fixed by electrostatic

attraction to the iodide ion, which does not move so readily.
 . Intrinsically conducting polymer(ICP)
Conductivity Mechanism in Polyacetylene
n-type doping process
The mechanism followed by polyacetylene for the transfer of charge from one chain
to another is called intersoliton hopping.

What is a soliton? The soliton is a charged or a neutral defect in the polyacetylene

chain that propagates down the chain, thereby reducing the barrier for
interconversion.
 . Intrinsically conducting polymer(ICP)

In n-type doping (This can be done by dipping the film in THF

solution of an alkali metal) soliton is a resonance-stabilized
polyenyl anion of approximately 29-31 CH units in length,
with highest amplitude at the centre of the defect.
The solitons (anions) transfer electrons to a neutral soliton
(radical) in a neighboring chain through an isoenergetic
process.
The charged solitons are responsible for making
polyacetylene a conductor.
 . Intrinsically conducting polymer(ICP)
DOPING - FOR BETTER
MOLECULE PERFORMANCE
• Doped polyacetylene is, e.g., comparable to good conductors
such as copper and silver, whereas in its original form it is a
semiconductor.

Conductivity of conductive polymers compared to those of other

materials, from quartz (insulator) to copper (conductor). Polymers
may also have conductivities corresponding to those of
semiconductors.
 Extrinsically conducting polymer
• Polymers whose conductivity is due to the
presence of externally added ingredient in
them.
• Two types
• Conductive element-filled polymer
• Blended conducting polymer
 Structure of Polyaniline (PANI)
Polyaniline exists as a mixed oxidation state polymer consisting of
benzoid and oxidized quinoid units.
PANI’s average oxidation state is denoted as 1-y whereby the value of
y determines the existence of each of the three distinct PANI oxidation
states as shown.
Thus PANI exists in three forms:
1. Fully reduced leucoemeraldine (LE) where 1-y = 0,
2. Half oxidized emeraldine base (EB) where 1-y = 0.5 and
3. Fully oxidized pernigraniline (PE) where 1-y = 1.

The EB is regarded as the most useful form of polyaniline due to its

high stability at room temperature, it is composed of two benzoid units
and one quinoid unit that alternate and it is known to be a
semiconductor .
 The resulting emeraldine salt has conductivity on a semiconductor
level which is many orders of magnitude higher than that of common
polymers but lower than that of typical metals .
Only 1% of the charge carriers which are available in the ES salt
actually contribute to its observed conductivity.
If all the available charge carriers were to contribute, the resulting
conductivity at room temperature would be comparable to that of
copper.
Applications of conducting polymers:

1.As sensors into clothing.

2.Conducting polymer textiles as a camouflage for defense
machinery. Since the textiles has no sharp edges they absorb
more than 50% of the incident microwave radiation.
3.In LEDs.
4.In controlled drug release applications, etc.
Doping of Polyaniline (PANI):

• Polyaniline in the undoped state is a poor semiconductor with a conductivity

of about 10-8 ohm-1/cm.

• Once it is doped with p-hydroxybenzene sulphonic acid (PHBSA), its

conductivity increases by a factor 10 ohm-1/cm or more depending on the
dopant and forms of polaron/bipolaron structure that will increase
conductivity due to the increased delocalisation.

• Among the various oxidation states that PANI can exist in, the one that can
be doped to a highly conductive state is the moderately oxidized emeraldine
base. This form of PANI has a structure which consists of equal proportions
of amines (–NH–) and imine (=N–) sites.

• Through protonic acid doping, imine sites are protonated by acids HA to the
bipolaron (dication salt) form. The bipolaron then undergoes a further
rearrangement to form the delocalized polaron lattice which is a
polysemiquinone radical-cation salt or emeraldine salt (ES).
The doping of EB with protons to form the conducting emeraldine salt
(PANI/HA) form of polyaniline (a polaron lattice)
 Conductive element-filled polymer

• Resin or polymer filled with conductive elements such as

carbon black, metallic fibres, metal oxides etc
• Polymer acts as binder to hold the conducting elements
together in the solid entity.
• These polymers possess resonably good bulk
conductivity
• Advantages: 1. Low cost
2. Light in weight, mechanically durable and
strong
3. Easily processable in different forms,
shapes and sizes
APPLICATIONS OF CONDUCTING POLYMERS

S= siemen = mho
Shield for computer screen
against electromagnetic smart" windows
"smart" windows
radiation

Solar cell
Photographic Film Light-emitting diodes
 APPLICATIONS OF CONDUCTING POLYMERS
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 and Switches

The first group utilizes their conductivity as its main property.

The second group utilizes their electroactivity
Conducting Polymers for Artificial muscles