Module-3; Functional Materials and Deposition Techniques

Polymers: Conducting polymers, types, polyaniline

synthesis, and applications.

Dr. A. A. NAPOLEON, M. Pharm., Ph.D.

Professor Grade-2, Chemistry Dept, SAS,
VIT University, Vellore – 14.

Cabin: Technology Tower - II Floor (TT-212)

Mobile No: 9842626161
 Functional Materials-

Polymers are not just a human invention.

Nature has many examples of polymers.

Cotton fibers, Hair, wool, and other
natural fibers.

They are made by chaining one or two

substances one after another.
1953/1954 Polyethylene/polypropylene
Karl Ziegler & Giulio Natta (Nobel Prize 1963)
polypropylene was discovered by Giulio Natta.
Awarded jointly to Karl Ziegler and
Giulio Natta "for their discoveries
in the field of the chemistry and
technology of high
polymers“(Nobel Prize in Chemistry
1963)
Polypropylene uses range
from plastic packaging, plastic parts
for machinery and equipment and
even fibres and textiles.

Discovered that Polyacetylene can be

made conductive almost like a metal.-
like semiconductor/

(Nobel Prize for Chemistry in 2000).

 Module3: Polymers Introduction
Polymers : Poly + mers
Poly means many; mers means units or parts
Polymers - Many parts or many units
Definition
Polymers are macromolecules (giant molecules of higher molecular weight) formed by the
repeated linking of large number of small molecules called monomers.
The word plastic is derived from the Greek plastikos meaning "capable of being shaped
It refers to their malleability, or plasticity during manufacture, that allows them to be
cast, pressed, or extruded into a variety of shapes—such as films, fibers, plates, tubes,
bottles, boxes, and much more.

n CH2 = CH2 (CH2-CH2-CH2-CH2-)n

Ex:
ethylene (monomer) polyethylene (polymer)

MONOMERS are basic units from which MACROMOLECULES are built upon!
 Polymerization
• Polymerization is a process in which large number of small molecules
(monomers) combine to give a big molecule (polymer) with or without
elimination of small molecules like water.

Polymerisation
- CH2 - CH -
n Cl n
Cl
Vinylchloride Polyvinylchloride
• MONOMERS are basic units from which MACROMOLECULES are built upon!

n CH2 = CH2 (CH2-CH2-CH2-CH2-)n

ethylene (monomer) polyethylene (polymer)

 Classification of polymers:
• Natural polymers : Polymers isolated from natural materials.
e.g. Silk, cotton wool and Rubber

• Synthetic polymers : Polymers synthesized from low molecular weight

compounds.
e.g. Polyethylene, PVC, Nylon

• Organic polymers : Polymers whose backbone is made of carbon atom.

e.g. Bakelite

• Thermoplastic polymers : Polymers which soften on heating and stiffen on

cooling.
e.g. PVC, Nylon

Thermosetting polymers: Polymers which becomes infusible and insoluble mass on

heating. e.g. Phenol formaldehyde plastic or bakelite
 Tacticity
Tacticity describes the spatial arrangement of pendant groups along a polymer chain's
backbone, determining
if they're regular (isotactic/syndiotactic) or random (atactic),

which profoundly impacts the polymer's physical properties like crystallinity, melting
point, and mechanical strength by affecting how well chains pack together
 Applications of Polymer: For Addl. Knowledge, Not for Examn.
Polyester (PES) – Fibers, textiles

Polyethylene terephthalate (PET) – Carbonated drinks bottles, peanut butter jars,

plastic film, microwavable packaging
Polyethylene (PE) – Wide range of inexpensive uses supermarket bags, plastic
bottles
High-density polyethylene (HDPE) – Detergent bottles, milk jugs, and molded
plastic cases
Polyvinyl chloride (PVC) – Plumbing pipes and guttering, shower curtains,
window frames, flooring

Polyvinylidene chloride (PVDC) – Food packaging, such as Saran

Low-density polyethylene (LDPE) – Outdoor furniture, floor tiles, shower
curtains, clamshell packaging

Polypropylene (PP) – Bottle caps, drinking straws, yogurt containers, appliances,

car fenders (bumpers), plastic pressure pipe systems

Polystyrene (PS) – Foam peanuts, food containers, plastic tableware, disposable

cups, plates, cutlery, compact-disc (CD) and cassette boxes

High impact polystyrene (HIPS) – Refrigerator liners, food packaging, vending

cups

Polyamides (PA) (Nylons) – Fibers, toothbrush bristles, tubing, fishing line, low-
strength machine parts- engine parts or gun frames.
Applications of Polymer: For Addl. Knowledge, Not for Examn.

Most common plastic Polyethylene

is used for bottles, buckets, jugs,
containers, toys, even synthetic
lumber, and many other things.
 Conducting Polymers Conducting polymers:
Polyacetylene- mechanism of
(Nobel Prize winners for Chemistry in 2000).
conduction- Applications

Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa have changed this
view with their discovery that a polymer, polyacetylene, can be made conductive
almost like a metal like semiconductor
.

CH≡CH.
Acetylene
polyacetylene
 some Polymers do conduct electricity and are called as Conducting Polymers

The chemistry Nobel prize in 2000 was awarded for the discovery
and study of conducting polymers
 Some Examples of Conducting polymers:

PANI

Polypyrrole (Ppy) Today PPy has been used in numerous applications including
fuel cells, corrosion protection, computer displays,
microsurgical tools, biosensors, drug delivery systems,
neural tissue engineering

PANI is the best-known conducting polymer and the most well-studied material.
p-phenylenediamine was added to PANI to improve its interaction with the electrolyte at
the interface; it resulted in a high specific capacitance of 550 F g−
1
 Introduction- Polymers are insulated
Polymers are one of the most used materials in the modern world-
Uses and application ranges from containers to clothing.

Polymers (or plastics ) are known to have good insulating properties due to their
very high resistivity having covalent bonds.
They are used to coat metal wires to prevent
electric shocks.

Insulators have tightly bound electrons so that nearly no electron flow

occurs, and they offer high resistance to charge flow.
 Introduction- Conducting Polymer
Most polymer materials are poor conductor of electricity because of the absence
of large number of free electrons needed for the conduction process.
They are used to coat metal wires to prevent electric shocks.
Insulators have tightly bound electrons so that nearly no electron flow occurs,
and they offer high resistance to charge flow.

Most polymers are poor conductors due

to non-availability of large number of
free electrons.
Polyethylene
For conductance, free electrons are needed.
Conductivity in polymers can be induced by delocalizing their orbitals
with conjugated p-electron backbones.

Polyacetylene
 Band gap energy

Band gap energy

due to non-availability of large number

of free electrons.

Most polymers are poor conductors due to non-availability of large number of free
electrons.
 Band structure of a polymer and a conductive polymer

According to the Band Theory, polymers have the band structure of an insulator, because
have a big band gap.
This theory is derived from the Schrodinger's Equation in a periodic potential, representing
the lattice.
When a polymer is doped, it arises charges in the polymer.

For polymers with alternating double and single bonds, which was doped, has a
movement of charge in the chain by resonance resulting in conductivity.

Thus, the polymer which conducts electricity is called as ‘ Conducting Polymer’.

 Polyaniline Synthesis: Oxidative polymerization of aniline
The synthesis of polyaniline (PANI) from aniline using ammonium persulfate ((NH₄)₂S₂O₈ or
APS) as the oxidant.

It is a well-established oxidative polymerization method conducted in an acidic aqueous

medium, typically involving HCl, to produce the emeraldine salt form of polyaniline.
Preparation of Polyaniline :
Prepare an aniline solution by adding aniline monomer to 1 M HCl.

Oxidant Addition: Dissolve Ammonium Persulfate (APS) in 1 M HCl to create the initiator
solution.
Reaction: Add the APS solution dropwise to the aniline solution at 0–25 °C while stirring.

Completion: The mixture is stirred for several hours (e.g., 2–4 hours) to ensure complete
reaction.
Purification: Filter the green precipitate, wash it thoroughly with water and acetone to remove
unreacted monomers and impurities.
Yield: This method typically yields highly conducting polyaniline (emeraldine hydrochloride).
 Polyaniline Synthesis: Oxidative polymerization of aniline
The synthesis of polyaniline (PANI) from aniline using ammonium persulfate
((NH₄)₂S₂O₈ or APS) as the oxidant.
Well-established oxidative polymerization method conducted in an acidic aqueous
medium, typically involving HCl, to produce the emeraldine salt form of polyaniline.

Oxidant: Ammonium persulfate (APS) is a strong oxidizing agent with an oxidation potential of
+2.01 V, commonly used for this purpose.
Medium: Acidic aqueous solutions (e.g., 1 M HCl) are essential for polymerization.

Mechanism: Autocatalytic mechanism initiated by the oxidation of aniline to form aniline

radical cations, which propagate to form polymer chains.

Temperature Influence: The polymerization temperature affects the structure and properties of
PANI; decreasing temperature (e.g., -3 °C) increases molecular weight and crystallinity.

Product Transformation: The reaction typically turns light blue to green, indicating the
formation of the emeraldine salt, which is then often treated with base (e.g., ammonium
hydroxide) to obtain the emeraldine base, which is stable at room temperature.
Polyaniline Synthesis: Oxidative polymerization of aniline

Oxidant: Ammonium persulfate (APS)

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Polyaniline Synthesis: oxidative polymerization of aniline

21
 Types of Conducting Polymers

Conducting
Conducting polymers are of three types:
polymers
Intrinsically Conducting Polymer (ICP)
Doped Conducting Polymer (DCP) and
Extrinsically Conducting Polymer
(ECP).
Intrinsically
conducting Extrinsically
polymers conducting
polymers

Polymers
Conjugated Doped Polymers with with
conducting conducting conducting conducting
Polymers polymers element
blends
Different Types of Conducting Polymers:

1. Intrinsically conducting polymers (ICP)

2. Doped Conducting polymers (DCP)
3. Extrinsically conducting polymers (ECP)

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 [Link] Conducting Polymers (ICPs)
⮚ Polymer consisting of alternating single and double bonds is called
conjugated double bonds.
⮚ In conjugation, the bonds between the carbon atoms are alternately single
and double.
⮚ Every bond contains a localised “sigma” (σ) bond which forms a strong
chemical bond.
⮚ In addition, every double bond also contains a less strongly localised “pi”
(π) bond which is weaker.
⮚ Conjugation of sigma and pi-electrons over the entire backbone, forms
valence bands and conduction bands.
Eg: Poly-acetylene, poly-p-phenylene, polyaniline, polypyrrole polymers

Polyacetylene

24
 (2). Doped Conducting Polymer (DCP):
It is obtained by exposing a polymer to a charge transfer agent in gas or solution phase.
ICPs possess low conductivity (10-10 S or Mho/cm), and high electron affinity.
So they can be easily oxidised or reduced.
Conductivity of ICPs can be increased by creating
positive charges (oxidation) or
negative charges (reduction) on the polymer backbone.

This technique is called doping.

In other words, polymer structure has to be disturbed - either by removing electrons
(oxidation) from or inserting them (reduction) into the materials.

There are two types of doping:

Oxidation with halogen (p-doping) and

Reduction with alkali metal (n-doping).
2) Doped Conducting Polymer (DCP):
Conductivity Mechanism in Polyacetylene: p-type doping,
In p-type doping, The dopant
(Iodine, I2) attracts an electron
from the polyacetylene chain to Polaron
form (I3-) leaving a positive soliton
(carbenium ion) in the polymer
chain that can move along its Polyacetylene
length.
The lonely electron of the double Partial oxidation
bond, from which an electron was Combination
removed, can move easily. of radicals
Soliton
As a consequence, the double
Conducting polyacetylene
bond successively moves along
polymer
the molecule, and the polymer is
stabilized by having the charge
spread over the polymer chain.
 p-doping n-doping
Oxidation with halogen (p-doping). An Reduction with alkali metal called n-doping
electron was removed can moved easily.

Doping in trans-polyacetylene
 ICP with a Lewis base for reduction: n-type doping
It involves treating an ICP with a Lewis base which leads to reduction
process and negative charges on the polymer backbone are created.

Some of the n-dopants are

Li, Na, Ca, Naphthylamine, Tetrabutyl ammonium etc. _

…-CH=CH-CH=CH-… + C10H7NH2 …-CH=CH-CH=CH- + C10H8

I
Naphthylamine +NH
Mechanism:
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 negative solitons (anions) transfer electrons to a neutral soliton (radical) in a

neighbouring chain through an isoenergetic process (A process where the energy is kept
constant is called isoenergetic).

The charged solitons are responsible for making polyacetylene a conductor.

 3. Extrinsically Conducting Polymers
These are the polymers whose conductivity is due to the presence of
externally added ingredients in them. Two types:
(1) Conductive element filled polymer:
▪ It is a resin / polymer filled with carbon black, metallic fibres, metal oxides
etc. Polymer acts as a binder to those elements.

▪ These have good bulk conductivity and are low in cost, light weight,
strong and durable.
▪ They can be in different forms, shapes and sizes.

(2) Blended Conducting Polymers:

▪ It is the product obtained by blending a conventional polymer with a
conducting polymer either by physical or chemical change.

▪ Such polymers can be processed and possess better physical, chemical

and mechanical strength.

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 3. Extrinsically Conducting Polymers
The conductivity of these polymers is due to the addition of external ingredients
added to them.
When carbon black or some metal oxides or metallic fibres (metal alloys, ) are added,
the polymer becomes conductive.

The minimum concentration of the element required for the conductivity is called
percolation threshold.
The filler (ingredients) that percolate have more surface area, more porosity and
filamentous nature due to which they can enhance the conducting properties.

Polyphenylenevinylene, polyacetylene, polythiophene (X = S)

and polypyrrole (X = NH), polyaniline (X = N, NH) and polyphenylene sulfide (X=S).
Conductivity Comparison between Conductive Polymers and Other Materials

34
Conductivity Comparison between Conductive Polymers and Other Materials

The order of conductivity of polymers

The conductivity of conductive polymers decreases with falling temperature in
contrast to the conductivities of typical metals, e.g. silver, which increase with
falling temperature.
 Factors that affect the conductivity:
Factors affecting conductivity include
Material type, temperature, concentration of charge carriers (ions/electrons), impurities, and solvent
properties (like viscosity for solutions), with c

Conductivity generally decreasing in metals as temperature rises but often increasing in semiconductors
and electrolytes due to more charge carriers becoming available.

1. Density of charge carriers

2. Their mobility

3. The direction
4. Presenceof doping materials (additives that facilitate the polymer
conductivity in a better way)
5. Temperature
 Polyphenylene vinylene may soon be
used in mobile phone displays.

Polydialkylfluorenes are used in

the development of new colour
screens for video and TV.

Polyaniline (PANI) is a versatile conducting

polymer used in sensors, flexible displays,
LEDs, transistors, Touch screen
 Applications of conducting polymers
1. Useful in discharging large quantities of static electricity in computer industries and in
chemical industries.
This can be accomplished by coating the conducting polymer over an isulating surface.
Hence conducting polymers are used as antistatics.

2. Absorb harmful electromagnetic radiation. So these can be used to coat on the cases of
computer monitors and cell phones.

3. Printed circuit boards are used in electrical and electronic instruments.

They contain copper coated epoxy resins which are expensive and have less adhesive
nature. But
polymer sheets coated with conducting polymers are inexpensive and have better
adhesive properties.

4. Useful in the preparation of artificial nerves i.e., biocompatible conductive polymers can
be used for transmitting electrical signals in the body.

5. Artificial intelligent materials: also called as smart materials; These materials can remember
configuration and can confirm when exactly same stimulus is given.
This property can be utilized in generating pass words where high security is required.
.
6. It is also used on computer screens, protecting the user from electromagnetic radiation,
and as a corrosion inhibitor.
 Applications of conducting polymers- Contd
7. Conducting polymers can undergo oxidation and reduction depending upon the reagent
with which they react.

This property can be utilized in detecting the gases. For e.g,

The resistance of poly pyrrole increases on contact with NH3 (reducing gas)
while the resistance decreases in presence of NO2 (oxidizing gas).

8. Polymer rechargeable batteries:

Repeated oxidation and reduction of polymeric back bone constitutes the
principle of polymer rechargeable batteries. For e.g,

In poly-pyrrole lithium cell is useful rechargeable battery compared to

conventional Ni-Cd cell. So, these are environmentally safe and non toxic.

8. Polyphenylene vinylene may soon be used in mobile phone displays.

Polydialkylfluorenes are used in the development of new colour screens for video
and TV.
[Link] can applied in Flat Panel Displays (less than 2 mm thick) which are thinner
than liquid crystals displays or plasma displays and useful as Flexible Display
Devices for mobile phones.
 Applications of conductive polymers
Polythiophene derivates, that are of great commercial use in antistatic treatment
of photographic film.
 They can also be used in devices in supermarkets for marking products.
 The checkouts will then automatically register what the customer has in the
trolley.

Doped polyaniline in antistatic material, e.g. in plastic carpets for offices and
operating theatres, where it is important to avoid static electricity.

It is also used on computer screens, protecting the user from electromagnetic

radiation, and as a corrosion inhibitor.

Materials such as polyphenylenevinylene may soon be used in mobile

phone displays.

Polydialkylfluorenes are used in the development of new colour screens for video
and TV.
Electronic components based on polymers, and polymer-based integrated
circuits, will soon find their place in consumer products where low processing
costs will be more important than high speed.
 Smart" windows
Shield for computer screen
against electromagnetic "smart"
windows radiation

Photographic Film Solar cell

Light-emitting
diodes