Module-3

Quantum Materials and Polymers

Quantum Dots: Introduction, size-dependent properties-quantum confinement effect, surface-

to volume ratio & band gap. Synthesis of Cd-Se Quantum dots by wet chemical method and its
applications. Construction, working principle and applications of quantum dot sensitized solar
cells (QDSSCs).

Polymer: Introduction, number average and weight average molecular weight of the polymers
and numerical problems. Structure-properties relationship of polymers (Crystallinity, Strength,
Elasticity and chemical resistivity]. Synthesis and properties of nylon-6,6 and its advantages in
3D printing applications. Synthesis and properties of chlorinated polyvinyl chloride (CPVC),
and polymethyl methacrylate (PMMA) and their uses in device applications. Conducting
polymers- Introduction, synthesis of polyaniline, conduction mechanism and its engineering
applications.

Introduction

Quantum dots (QDs): Quantum dots (QDs) are nanoscale semiconductor particles typically
ranging from 2 to 10 nanometres in size. Due to their quantum confinement effects, QDs exhibit
unique optical and electronic properties, such as size-dependent light emission. These
properties make them highly valuable in various applications including display technology,
solar cells, biomedical imaging, and quantum computing. Their ability to emit specific
wavelengths of light by simply changing their size makes them a versatile tool in
nanotechnology and materials science.
 ➢ A small quantum dot has a longer bandgap, and hence it requires more energy to excite
its electron.

➢ As the frequency of emitted light is proportional to the energy, smaller quantum dots
emit radiation of higher energy or frequency, that is, shorter wavelengths.

➢ A larger quantum dots have closely spaced energy levels and emit photons of lower
energy or frequency, that is, longer wavelengths.

➢ It means that as the size of quantum dots increases, the quantum dot will emit photons
with lower energy or frequency and higher wavelength and vice versa.

TYPES OF QD’S BY MATERIAL

1. Inorganic quantum dots (IQDS): These are traditional semiconductor quantum dots,
with common examples being Cadmium Selenide (CdSe) and Cadmium Sulfide (CdS).
They offer excellent optical properties but can be toxic.
2. Carbon-based quantum dots (CQDs): Made from carbon derivatives, they are water-
soluble and are considered less toxic than some inorganic dots. A subtype of carbon-
based dots made from graphene.
Graphene quantum dots (GQDs):
Carbon nanodots (CNDs): Another subtype of carbon-based dots, often spherical in
shape.
3. Perovskite quantum dots: These have a perovskite crystal structure and are known for
their strong light-emitting properties.
Electrical Properties of quantum dots

• Surface-to-Volume Ratio: As quantum dots decrease in size, their surface-to-volume

ratio increases significantly. A greater proportion of atoms are located on the surface,
which can influence chemical reactivity, electronic states, and optical behaviour.

➢ For a spherical quantum dot with diameter D, the surface-to-volume

ratio is (6/D). As the diameter decreases (e.g., from a bulk material size
to the nanoscale range of 2–10 nm), this ratio increases dramatically.
➢ As ratio increases, quantum dot size decreases.

Band Gap Variation: The band gap in quantum dots is not fixed, unlike in bulk
semiconductors. Due to quantum confinement, reducing the size of the QD increases its band
gap energy. This size-dependent tunability of the band gap allows precise control over the
colour of light absorbed or emitted by the QD, making them highly useful in applications such
as LEDs, lasers, and biomedical imaging.
Quantum Confinement Effect: quantum confinement effect when they are very small-around
the size of a few nanometres. At this tiny scale, the movement of electrons and holes inside the
QD is limited in all directions. This causes the energy levels to become separate, like steps,
instead of being continuous. As the size of the QD gets smaller, the gap between energy levels
(called the band gap) becomes larger. Because of this, small QDs give off blue light, while
bigger ones give off red light. So, the colour of light from a QD depends on its size.

Size-Dependent Properties of Quantum Dots (QDs)

Quantum dots (QDs) are semiconductor nanoparticles typically 2–10 nm in diameter. Their
properties depend strongly on particle size due to the quantum confinement effect.

1. Bandgap Energy Increases as Size Decreases Smaller QDs have larger bandgap energy.
Larger QDs have smaller energy. “Electrons and holes are confined in a very small volume →
energy levels become quantized → increasing or decreasing the bandgap depending on size.”

Effect:

Small QDs → absorb & emit blue / high-energy light.

Large QDs → absorb & emit red / low-energy light.
2. Tuneable Optical Properties (Color Change)
• Changing QD size changes the color of light emitted.
• Small QDs → blue, green
• Medium QDs → yellow
This tunability is widely used in QD-LEDs, QD-LCD displays, and optical sensors.
3. Size Affects Exciton Bohr Radius
• When particle size < exciton Bohr radius → strong quantum confinement.
• Leads to discrete electronic states, similar to atoms.
4. Electrical Conductivity Changes with Size
• Smaller QDs → lower conductivity due to wide bandgap.
• Larger QDs → higher conductivity.
Used in solar cells (QDSSCs), photodetectors, and field-effect transistors (FETs).
5. Enhanced Photoluminescence in Smaller QDs
• Smaller QDs show brighter photoluminescence. • Emission wavelength depends on size.
Useful in bioimaging, displays, and quantum dot
lasers.
6. Thermal Properties Are Size Dependent
• Smaller QDs have lower melting point.
• Surface atoms dominate → influence heat capacity and stability.
7. Size Controls Magnetic Properties
• Quantum dots made from magnetic materials show super paramagnetism at small sizes.
• Important for spintronic devices.
8. Chemical Reactivity Increases as Size Decreases
• Smaller QDs have higher surface area-to-volume ratio.
• More reactive; useful in catalysis and sensing.

Synthesis of Cd-Se Quantum Dots by Wet Chemical Method

➢ Principle: Cd-Se quantum dots (QDs) are semiconductor nanocrystals whose optical
properties depend on particle size. They are synthesized by controlled wet chemical
routes using cadmium and selenium precursors in the presence of stabilizers/capping
agents.
1. Selection of Precursors
Cadmium source: CdCl₂, Cd(CH₃COO)₂, or Cd(NO₃)₂.
CdCl₂ → Cd²⁺ + 2Cl⁻
Selenium source: Na₂Se, or Na₂SeO₃
Na₂SeO₃ + 4NaBH₄ + 7H₂O → Na₂Se + 4B(OH)₃ + 14H₂↑
2. Preparation of Reaction Medium: Dissolve cadmium precursor in aqueous or
organic solvent. Adjust pH to mildly alkaline if needed.
 3. Addition of Stabilizer / Capping Agent: Agents like mercaptoethanol,
thioglycolic acid (TGA), or trioctylphosphine oxide (TOPO) are added. These
prevent aggregation and control nanoparticle growth.
CdSe + R-SH → CdSe-(SR)surface
4. Nucleation and Growth: Controlled heating (50-100 °C) with constant
stirring. Selenium precursor is slowly introduced into the cadmium solution.
Reaction is often carried out under inert atmosphere (nitrogen/argon) to prevent
oxidation. Particle size (2–8 nm) is tuned by varying temperature, precursor
ratio, and reaction time.
Cd²⁺ + Se²⁻ → CdSe (Quantum Dots)
5. Separation and Purification: The quantum dots are precipitated, centrifuged,
and washed with solvents. Excess unreacted species and surfactants are
removed.
6. Final Product: Stable colloidal Cd-Se quantum dots with size-dependent
photoluminescence (emission colours ranging from blue to red).

Applications:

1. Optoelectronics: Used in light-emitting diodes (QLED displays), lasers, and

photovoltaic cells.
2. Biological Imaging: Serve as fluorescent probes due to tuneable emission and
high photostability.
3. Solar Cells: Improve efficiency of quantum dot-sensitized solar cells
(QDSSCs).
4. Sensors: Employed in chemical and biosensors for detecting heavy metals,
biomolecules, and pH changes.
5. Photocatalysis: Useful in degradation of pollutants and water splitting for
hydrogen production.
6. Medical Applications: Potential use in targeted drug delivery and cancer
therapy (though toxicity issues exist due to Cd).
7. Quantum Computing: Investigated for qubit development due to discrete
energy levels.

Quantum Dot Sensitized Solar Cells (QDSSC):

Introduction:

• Quantum dots (QDs) are often referred to as artificial atoms.

• They are semiconductor nanocrystals, only a few nanometres in size, with unique
optical and electronic properties distinct from bulk materials.
• A Quantum Dot Solar Cell (QDSC) is a photovoltaic device that uses QDs as the
primary light-absorbing material.
• QDs can replace conventional bulky materials such as silicon or copper indium gallium
selenide.
• Their band gap can be tuned by simply altering the size of the dots, making them highly
adaptable across a wide range of energy levels.

Construction

1. Photoanode: A conducting glass substrate is coated with a semiconductor

layer (commonly TiO₂). The outer surface is then sensitized with QDs.
2. Electrolyte: A redox electrolyte, usually polysulfide, acts as a hole
conductor and facilitates charge transfer.
3. Cathode electrode: It helps regenerate the electrolyte and completes the
circuit.

Working Principle

1. QDs absorb sunlight and electrons are excited from the valence band to the conduction band.

2. The excited electrons are transferred to the semiconductor layer, leaving holes behind on the
QD surface.

3. The electrolyte captures these holes and undergoes reduction reactions:

S2− +S2ℎ+ → 𝑆

𝑆+𝑆𝑥2− → 𝑆𝑥+1 2− (𝑥 =2)

4. Electrons move from the photoanode to the cathode through the external circuit, producing
current.

5. At the cathode, the electrolyte is regenerated by gaining electrons:

S𝑥2− → 𝑆 +𝑆𝑥−1 2− ; 𝑆+2𝑒− →𝑆2−

Advantages:

➢ High power-to-weight ratio with excellent efficiency.

➢ Low power consumption during operation.
➢ Cost-effective with improved electrical performance.
➢ Flexible in use, enabling applications not limited to rooftops but also windows and other
transparent surfaces.

Disadvantages:

➢ Cadmium selenide (CdSe)-based QDs are highly toxic and require a stable polymer
shell for safe use.
➢ Cadmium and selenium ions are cytotoxic, raising environmental and health concerns.

Applications:

➢ Biological labelling and imaging.

➢ Detection systems and fluorescence resonance energy transfer donors.
➢ Used in LEDs, photodetectors, photoconductors, and photovoltaic devices.
➢ Biomedical and environmental applications.
➢ Catalysis and chemical reactions.

POLYMERS

Polymers are macromolecules that have high molecular mass built up by linkage together of a
large number of small molecules called monomers. In Greek Poly means many, mers means
units or parts. The molecular mass of polymers is high and ranges from 10,000 to 1,00,000.
Example: Polythene is a polymer formed by linkage of large numbers of ethylene.
Important commercial polymers are:

❖ Resins: These are the base materials used in the manufacturing of plastics by mixing
with fillers, plasticizers, lubricants, coloring agents and stabilizers.

❖ Plastics: The materials which soften at certain temperature and harden at characteristic
temperature are known as plastics.

❖ Elastomers: These consist of zigzag or helical chain of molecules, undergo elastic

changes when subjected to external source, but regain their original shape when the
force is withdrawn.

❖ Fibers: Fibers are long thin thread like polymer chain, which do not stretch or undergo
deformation like elastomers. The molecular chains are arranged in parallel, spiral,
helical pattern.

❖ Basic definitions: Polymer: A polymer is a large molecule formed by the repeated

covalent linkage of small units called monomers". Ex: Starch, Polyvinyl chloride,
Polyethylene, Nylon 6, 6 and etc.

❖ Monomer: Monomer is defined as a simple molecule or single unit representing in a

polymer with two or more binding sites either unsaturation or having two or more
than two functional groups through which it forms covalent linkages with other
monomeric units to form the macromolecule".

❖ Polymerization: “Polymerization is the process of formation of a polymer by the

repeated covalent linkage of monomeric units” or The chemical process in which the
monomers are converted into polymers is called Polymerization.

❖ Homo polymers: If all the monomeric units are same in a polymer called homo
polymer Ex: Polyethylene.

❖ Hetero polymer: If the monomeric units are different in a polymer chain called
hetero polymer. Ex: Nylon 6, 6
Polymerization: The chemical process in which the monomers are converted into polymers is
called Polymerization.

Degree of Polymerization: The number of times the unit is repeated in a homopolymer chain
is referred to as the degree of polymerization. High polymers have high degree of
polymerization.

Addition polymerization: It is a process in which unsaturated monomers, typically containing

double or triple carbon-carbon bonds, repeatedly join together to form long polymer chains
without the elimination of any byproducts.

o Polyethylene (from ethene)

o Polypropylene (from propene)

o PVC (polyvinyl chloride, from vinyl chloride)

Condensation polymerization: The polymerization process involves the reaction of
bifunctional or multifunctional monomers, each containing two or more reactive groups such
as –OH, –COOH, or –NH₂. During the formation of the polymer, small molecules like water,
hydrochloric acid, or methanol are eliminated as byproducts.

• Nylon (e.g., Nylon-6,6 from hexamethylenediamine and adipic acid)

• Terylene / PET (from ethylene glycol and terephthalic acid)

• Bakelite (from phenol and formaldehyde)

Molecular weight of polymers: The two main types of molecular mass are

a) Number average molecular Weight

b) Weight average molecular weight

Number average molecular Weight: It is defined as the total mass (Mn) of all the molecules
in a polymer sample divided by total number of molecules present.

Where n and M represent the number and molecular mass of each species respectively present
in the polymer.

The number average molecular weight M is calculated as

n

∑𝑖 𝑁𝑖 𝑀𝑖
𝑀𝑛 =
∑𝑖 𝑁𝑖

where M is the molecular weight of a chain, N is the number of chains of that

i i
molecular weight, and i is the number of polymer molecules
Weight average molecular weight: It is various molecular species in proportion to their
weights in the given material.

Polydispersity index:

➢ In order to have an idea about the homogeneity of a polymer, the term polydispersity
index is used.

➢ It is the ratio of mass average molecular mass to the number average molecular mass.

̅̅̅̅̅̅
𝑀𝑊
PDI = ̅̅̅̅̅
𝑀𝑛

➢ For natural polymers, PDI is usually equal to one, which means that they are
monodisperse. Such polymers are more homogeneous.

➢ Synthetic polymers on the contrary generally have PDI > l which means that they are
less.

Numerical: 1. A polymer sample contains 1, 2, 3 and 4 molecules having molecular weight

1×105, 2×105, 3×105 and 4×105 respectively calculate the number average and weight average
molecular weight of the polymer.

Solution: Number of molecules n1=1 n2=2 n3=3 n4=4 Molecular weight of the polymer:

m1 =1×105 m2 =2 ×105 m3 =3×105 m4=4×105

Molecular weight of the polymer:
a) m1 = (3×12+6 ×1) ×400=16800
b) m2 =(3×12+6 ×1) ×500=21000
c) m3 =(3×12+6 ×1) ×600=25200
Assignment numerical:

1. A polymer has following composition 100 molecules of molecular mass 1000 g/mol, 2000
molecules of molecular mass 2000g/mol and 500 molecules of molecular mass 5000 g/mol.
Calculate the number average and weight average molecular weight of the polymer. (June
2016)
2. In a polymer sample, 20% molecules have molecular mass 15000 g/mol, 45% molecules
have molecular mass 25000 g/mol remaining molecules have molecular mass 27000 g/mol.
Calculate the number average and weight average molecular weight of the polymer. (Dec
2015)
3. In a polymer sample, 20% of molecules have molecular mass 15000g/mol, 35% molecules
have molecular mass 25000 g/mol and remaining molecules have molecular mass 20000
g/mol. Calculate the number and weight average molecular weights of the polymer.
4. A polymer sample contains 100,200,300 and 400 molecules having molecular mass 1000,
2000, 3000 and 4000 respectively. Calculate the number and weight average molecular
weights of the polymer.
5. A polymer sample containing 50, 100 and 150 molecules having molar mass 1000, 2000
and 3000 respectively. Calculate the number and weight average molecular weights of
polymer. [Dec.2015/ Jan 2016]
6. In a polymer sample, 20% of molecules have molecular mass 15000g/mol, 45% molecules
have molecular mass 25000 g/mol and remaining molecules have molecular mass 27000
g/mol. Calculate the number and weight average molecular weights of the polymer.
[Dec.2015/ Jan 2016]
7. A polymer sample contains 200 molecules of molecular mass 2000, and 200 molecules of
molecular mass 40,000 g/mol. Calculate the number and weight average molecular weights
of polymer.
8. A polymer sample contains 100 molecules of molecular mass 20,000 g/mol , 300 molecules
of molecular mass 3000 and 500 molecules of molecular mass 5000. Calculate the number
and weight average molecular weights of polymer. [June/July- 2016].

Nylon-12
Nylon-12 (Polyamide-12 or PA-12) is a synthetic polyamide composed of repeating units
derived from 12-amino dodecanoic acid (H₂N–(CH₂)₁₁–COOH). It is a high-performance
engineering thermoplastic known for its excellent flexibility, toughness, and chemical
resistance. In recent years, Nylon-12 has become a key material for 3D printing and additive
manufacturing applications.

Synthesis of Nylon-12
Nylon-12 can be synthesized by ring-opening polymerization of laurolactam (ω-laurolactam),
which is derived from 12-aminododecanoic acid.
[Link] Preparation: Laurolactam (C₁₂H₂₃NO) is obtained from ω-amino dodecanoic
acid by cyclization.

[Link] (Ring-Opening Polymerization): The laurolactam undergoes ring-opening

polymerization under heat (~250°C) and pressure in the presence of a catalyst (e.g., water or
acid). This forms Nylon-12 polymer chains through amide bond formation (-CO–NH-).

Advantages of Nylon-12 in 3D Printing Applications

Excellent Dimensional Stability
1. Absorbs less moisture compared to other nylons, ensuring accurate printing and
minimal warping.
High Strength and Flexibility
1. Combines toughness and impact resistance, ideal for functional prototypes and
mechanical [Link] and Durable.
2. Provides metal-like performance at much lower density, useful for automotive and
aerospace parts.
Chemical and Abrasion Resistance
1. Can withstand fuel, oil, and chemical exposure, suitable for industrial
components.
Low Shrinkage and Smooth Finish.
1. Ensures precise layer bonding and a clean surface finish in Selective Laser Sintering
(SLS) 3D printing.
Temperature Resistance
1. Retains mechanical integrity even at elevated temperatures, enabling engineering grade
applications.
Recyclable and Reusable Powder
1. In SLS printing, unused Nylon-12 powder can be reused, minimizing waste.

Applications of Nylon-12 in 3D Printing

• Automotive: Air ducts, fuel lines, clips, and lightweight brackets.
• Aerospace: Structural parts, housings, and functional prototypes.
• Medical: Customized prosthetics, surgical tools (biocompatible grades available).
• Consumer Products: Wearable devices, phone cases, and durable housings.
• Industrial: Gears, fittings, and chemical-resistant components.

Polyvinyl Chloride (PVC)

Polyvinyl chloride (PVC) is a synthetic thermoplastic polymer produced from vinyl chloride
monomer (CH₂=CHCl). It is one of the most widely used plastics in the world due to its
chemical resistance, electrical insulation, and mechanical stability.

PVC is used in electronic, medical, and smart device applications because of its
excellent dielectric and structural properties.

Monomer Preparation

Vinyl chloride monomer (VCM) is produced by chlorination of ethylene:

Preparation of PVC
Vinyl chloride monomers (VCM) undergo free-radical addition polymerization in the presence
of a peroxide initiator under controlled heat and pressure to form polyvinyl chloride (PVC).

Chlorination of PVC

The obtained PVC is exposed to chlorine gas under UV irradiation, during hydrogen atoms
in the PVC chain are replaced by chlorine atoms, leading to the formation of chlorinated
polyvinyl chloride (CPVC).

Properties of PVC

1. PVC is a rigid and strong thermoplastic polymer.

2. It has good chemical resistance to acids, alkalis, and salts.
3. PVC is a good electrical insulator and has high dielectric strength.
 4. It is self-extinguishing and flame-retardant due to chlorine content.
5. PVC shows good weathering and corrosion resistance.
6. It can be made flexible or rigid by adding suitable plasticizers.

Properties of CPVC

1. CPVC is stronger and tougher than normal PVC.

2. It has higher chlorine content, which makes it more rigid.
3. CPVC can withstand higher temperatures (up to about 90–110 °C).
4. It has good resistance to corrosion and many chemicals.
5. CPVC is fire-retardant due to its high chlorine content.

Properties of PVC for Device Applications:

1. PVC is a good electrical insulator, making it ideal for wire coatings, cables, and
electronic devices.
2. It has high chemical and corrosion resistance, suitable for sensor housings and
biomedical devices.
3. PVC is mechanically strong and durable, providing structural stability for device
components.
4. It is self-extinguishing and flame-retardant because of its chlorine content, enhancing
device safety.
5. PVC offers good dimensional stability and weather resistance, ensuring long service
life in various environments.
6. It can be easily molded, extruded, and fabricated, enabling cost-effective
manufacturing of device parts.

Polymethyl methacrylate (PMMA) or Plexiglass

PMMA is synthesized by the free-radical bulk polymerization under an inert atmosphere using
methyl methacrylate (MMA) monomers using initiators such as benzoyl peroxide or potassium
persulfate and heat by addition polymerization.

Properties of PMMA:

1. High Transparency: Up to 92-93% light transmission, better than glass for some uses.
2. UV Resistance: Resists yellowing and degradation from sunlight, ensuring longevity.

3. Refractive Index: Around 1.49, useful for lenses.

3. Lightweight: Lighter than glass, easier to handle.

4. Strength: Good tensile (30-50 MPa) and compressive strength (85-110 MPa).

5. Impact Resistance: Better than glass, though can be scratched.

6. Dimensional Stability: Low moisture absorption, reliable in varying conditions.

[Link] Sealing: Can be bonded with heat for sealed microfluidic devices.

8. Electrical Insulator: Low dielectric constant, suitable for electronic components.

9. Biocompatible: Safe for implants, intraocular lenses, dental prosthetics.

10. Chemical Resistance: Resistant to water, alcohols, and many solvents, but susceptible to
strong acids/bases.

PMMA in Device Applications

• Optical devices: Used in lenses, optical fibers, and light guides due to high
transparency.
• Display panels: Utilized in LCD and LED screens for light transmission.
• Medical devices: Applied in intraocular lenses, bone cement, and dentures.
• Solar cells: As a transparent protective layer and encapsulant.
• Microfluidic devices: Due to easy machining and chemical resistance.
• Automobile parts: Headlight covers and indicator lamps because of clarity and
weather resistance.
• Protective shields: Used as a glass substitute in safety windows and aquariums.

Structure property relationship of polymer

Crystallinity:

• Linear polymers have straight chains without side branches or large groups sticking out. This
lets the chains pack closely and neatly, making them crystalline.

For example, polyethylene has a repeating unit:

 −𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻2 −

so the chain is straight, allowing the sections to line up easily.

• Polymers like polyvinyl acetate have branches:

These branches keep the chains from fitting closely, making them less crystalline.

• Factors increasing crystallinity:

1. Linear and regular chains, especially with polar groups, boost crystallinity.
2. Isotactic polymers, where all side groups are on the same side, are more crystalline
than atactic polymers (random side groups).

How Crystallinity Affects Properties

• High crystallinity makes polymers stronger, stiffer, opaquer, and less soluble in solvents.
• As crystalline increases, solubility decreases.

Tensile strength

Tensile strength is the maximum stress that the material can withstand. Tensile strength of a
polymer depends on the molecular weight. Tensile strength increases with molecular weight up
to 2,000 and thereafter increase is negligible.

Low molecular weight polymers are soft and gummy, but high molecular mass
polymers are tough and heat resistant. Cross-linked polymers are stronger than linear polymers
and less than branched polymer.
Elasticity:

Elasticity is the ability of a polymer to stretch when a force is applied and to return to its original
shape when the force is removed. This behavior occurs because the molecular chains uncoil
during stretching and recoil when the force is released. Polymers exhibit elasticity as long as
the chains do not separate from each other, preventing breakage during extended stretching.
Elasticity can be enhanced by:

• Introducing cross-links at appropriate molecular positions to connect the chains,

• Avoiding bulky groups such as aromatic and cyclic structures in the repeating units,
which hinder chain movement,
• Incorporating more non-polar groups in the chain to increase cohesion between chains,
thereby reducing chain separation during stretching.

Chemical Resistivity:

• Chemical resistivity of a polymer refers to its ability to resist swelling, softening, dissolving,
and loss of strength when exposed to solvents or chemicals.

• Polymers containing polar groups such as –OH or –COOH are typically dissolved by polar
solvents like water or alcohols.

• Polymers with non-polar groups such as –CH₃ and C₆H₅ are not easily dissolved by polar
solvents but dissolve readily in non-polar solvents like petrol, benzene, and carbon
tetrachloride.

• Polymers with a higher degree of crystallinity exhibit greater chemical resistance than their
amorphous counterparts.
• Chemical resistivity increases as the degree of cross-linking in the polymer structure
increases.

Plastic deformation (Rheology)

Some polymers on the application of heat and pressure become soft, flexible, rubbery matter
and undergo deformation. On further heating beyond Tm they melt and flow. Such property of
the polymer is called plasticity. On cooling they turn to original state.

CONDUCTING POLYMERS

"An organic polymer with highly delocalized 𝝅-electron system, having electrical conductance
of the order of a conductor is called a conducting polymer". The conducting polymers are
synthesized by doping, in which charged species are introduced in organic polymers having
𝜋-back bone. The important doping reactions, are;

1. Oxidative doping (p-doping),

2. Reductive doping (n-doping) and
3. Protonic acid doping (P-doping)

Oxidative doping (p-doping):

In this process, 𝜋 -back bone of a polymer is partially oxidized using a suitable oxidizing agent.
This creates positively charged sites on polymer back bone, which are current carriers for
conduction. The oxidizing agents used for this process are iodine vapour, I2 in CCl4, perchloric
acid and benzoquinone.
Ex: Synthesis of conducting polyacetylene.

Reductive doping (n-doping):

In n-doping, 𝜋 -back bone of a polymer is partially reduced by a suitable reducing agent. This
creates negatively charged sites on polymer back bone. These sites are responsible for
conduction. The most common reducing agent used for n-doping is a solution of sodium
naphthalidein tetrahydrofuran.
Ex: Synthesis of conducting polyacetylene.

Protonic acid doping (p-doping):

In this technique, current carrying charged species (-ve/+ve) are created by the protonation of
imine nitrogen.
Ex: synthesis of polyaniline.
synthesis of polyaniline, conductions mechanism and its engineering applications.
Synthesis of polyaniline
When n number of aniline molecules undergo oxidative polymerization in presence of dil HCl
and ammonium persulfate to form polyaniline.

Conductions Mechanism of Polyaniline

The synthesis of conducting polyaniline is an example of doping technique. In this technique

current carrying species ( -ve / +ve ) are created by the protonation of imine nitrogen.

NH NH NH NH
n

(NH 4)2S2O 8/1MHCl

partial oxidation

N N NH NH

n
base form of Polyaniline
protonation
Aq 1M HCl

H H
+ +
N N NH NH
- -
Cl Cl
n

Polyaniline exists in several different oxidation states of which only emaraldine salt (Reduced
form aniline) conducting. Polyaniline is partially oxidized using a suitable oxidizing agent, into
a base form of aniline which contains alternating reduced and oxidized forms of aniline
polymer back [Link] form of aniline treated with aqueous HCl (1M), undergoes protonation
of imine nitrogen atom, creating current carrying species (+ve) in the polymer backbone. These
charges are compensated by the anions (Cl-) of the doping agent giving the corresponding salt.

Applications
• Conductive coatings for electronics and textiles (antistatic applications).
• Corrosion protection on metals through protective coatings.
• Chemical and biosensors for detecting gases, humidity, and biomolecules.
• Electrode material in batteries, super capacitors, and rechargeable devices.
• Flexible electronics such as OLEDs, wearable sensors, and smart textiles.
• Electromagnetic interference (EMI) shielding in electronic devices.
• Environmental and biomedical applications, including water purification and drug
delivery.