GLOBAL ACADEMY OF TECHNOLOGY

Module -4
Material Chemistry: Polymers and Nanomaterials
Polymer Chemistry: Introduction, Polymerization. Synthesis, properties
and applications of PMMA and Polyurethane. Polymer composites –
Kevlar Fibre and carbon fibre-synthesis & applications. Conducting
Polymers: Mechanism of conduction in conducting polyaniline.
Nanomaterials: Introduction to nanomaterials, Synthesis: top-down and
bottom-up approaches. Synthesis of nano materials-solution combustion,
hydrothermal methods. Carbon based nanomaterials - Carbon nanotubes,
graphene and Fullerenes. Applications of nanomaterials.
Polymer Chemistry
Introduction:
Polymers: Polymers are the macromolecules with high molecular weight formed by
repeated linking of small molecules called monomers.
Monomers: Monomers are the small molecules which combine with each other to
form a polymer.
Polymerization: It is the process by which monomers combine chemically to form a
polymer chain.
Example: Polymerization of ethylene

Synthesis, Properties and Applications of PMMA (poly methyl meth acrylate)or

Plexi glass:
PMMA are the high polymeric material with repeated linkage of –COOCH3 groups.
Synthesis: When methyl meth acrylate is heated to about 60-70oC in presence of
H2O2 catalyst, it undergoes Bulk polymerisation to form PMMA.
Chemical Reaction:

Properties:
PMMA are
1. Amorphous and Transparent.
2. Good Optical clarity (RI=1.4), poor stretch resistant.
3. Good mechanical properties.
4. Tougher than Polystyrene.

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5. Resistance to water, alkalies, inorganic salts, but dissolves in Organic solvents.

Applications:
It is used in the manufacture of
1. Artificial teeth, contact lenses.
2. Paints and adhesives.
3. Laser discs & DVD’s.
4. Transparent bath tub & basins.
5. Automobile lamp housing, street light housing TV screen housing, signal light
etc.,

Synthesis, Properties and Applications of Polyurethane:

Polyurethane is high polymeric material with repeated linkage of –NHCOO- groups
Synthesis: When an alkyl isocyanate is heated with diols/triols/polyols in presence of
tertiary amine catalyst, it undergoes addition polymerisation to form Polyurethane.
Chemical reaction:

Properties:
Polyurethanes are
1 . Excellent abrasive resistance.
2. Good stretching property.
3. Translucent OR opaque
4. High tensile strength. Resistance to water, organic solvents, oil and corrosive
chemicals.
Applications:
Polyurethane is used in the manufacture of
1. Gymnasium dance floors.
2. Soles for shoes & Chappals.
3. Swim suits, Foundation garments
4. Gaskets, seals, tyres, Industrial wheels.
5. Cushions for furniture and automobiles.

Polymer Composites:
Polymer composites are the combination of two or more distinct components to form
a new class of material suitable for structural applications is referred to as Composite
materials.
Polymer composites are made up of two components:
Matrix: made up of thermoplastics or thermosetting polymers.
Reinforcement:

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Fiber reinforcement: made up of fibres like glass fibre, carbon fibre or Kevlar fibre.
Filler reinforcement: made up of particles.

Synthesis and applications of Kevlar fibre:

It is an aromatic polyamide (IUPAC name–Poly (para-phenylene terephthalamide).
Synthesis: When terephthaloylchloride is heated with para-phenylenediamine
undergoes condensation polymerization to form Kevlar fibre.

Kevlar Fiber
Applications:
Kevlar fibre is used for
1.Puncture resistant bicycle tyres.
2. Bridge structures and bullet proof vests.
3. Light weight boat hulls, aircrafts panels and race cars.

Synthesis and applications of Carbon fibre:

The carbon fibres are also called as graphite fibres, which are strong, stiff, light
weight and corrosion resistant.
Synthesis: The carbon fibres are prepared by using polyacrylonitrile (PAN).
The PAN is synthesized by the polymerization of acrylonitrile in presence of FeSO4
and H2O2.

As prepared PAN is subjected to spinning at 200oC to 300oC, which forms PAN fibres.
The PAN fibres undergo cyclization by heating to 600oC to 700oC, followed by
heating at 60oC which expels hydrogen to form polycyclic PAN. The polycyclic PAN
undergoes carbonization by heating slowly to 2000oC, which forms ribbon like carbon
fibre.

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Applications:
Carbon fibres are used in
1 . Industrial products.
2. Textile.
3. Aerospace parts
4. Automobile parts
5. Sports items.
6. House hold items.
7. Electronic and electrical products.

Conducting Polymers:
Conducting polymers are organic polymers which conduct electricity; such
compounds may have metallic conductivity or can be semiconductors.
Conducting polymers are prepared by doping technique with an oxidizing or a
reducing agent into organic polymers consisting of alternative double and single
carbon – carbon bonds.
Doping:
1. Oxidative doping (p-type doping):
Polymer is treated with an oxidizing agent like iodine, aluminium chloride, perchloric
acid. Oxidizing agents take away the electrons from the polymer chain creating holes.
Thus, polymer become p-type conductor as it conducts electricity by the movement of
holes (+ve charge carriers).

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2. Reductive doping (n-type doping):

Polymer is treated with a reducing agent like sodium, lithium, naphthalides, etc.
Reducing agents supplies electrons to the polymer chain. Thus, polymer become n-
type conductor as it conducts electricity by the movement of free mobile electrons (-
ve charge carriers).

Mechanism of conduction in conducting polyaniline:

 Polyaniline exists in several different oxidation states of which only emaraldine
salt is conductive.
 Polyaniline is partially oxidized using a ammonium persulphate to form base
form of polyaniline.
 Base form of polyaniline is treated with aqueous HCl. During this, it undergoes
protonation creating positive charges on the polymer chain. These charges are
compensated by the anions Cl- of the doping agent giving corresponding salt.

Applications of conducting Polyaniline:

Conducting polyaniline is used
 as electrode material for batteries.
 as conductive tracks on PCB.
 as sensors like humidity sensors, gas sensors, glucose sensors.
 in electrochromic display windows.
 in light emitting diodes.

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Nanomaterials
Nanomaterials are commonly defined as materials with an average grain size less than
10-9m. Nanomaterials have extremely small size which having at least one dimension
100 nm.
Size:
 A meter is about the distance from the tip of your nose to the end of your hand
(1 meter = 3.28 feet).
 Millimeter- One thousandth of meter (10-3m).
 Micron: a micron is a millionth of a meter (or) one thousandth of millimeter
(10-6m).
 Nanometer: A nanometer is one thousandth of a micron (10-9m) (or) a billionth
of a meter i.e., one billion nanometers in a meter.

Synthesis of Nanomaterials:
Two approaches:
1. Bottom-up
2. Top-down

Bottom-up Approaches:
 Bottom-up approach refers to the build up of a materials from the bottom:
atom by atom, molecule by molecule.
 Atom by atom deposition leads to the formation of self-assembly of
atoms/molecule and clusters.
 This clusters come together to form self-assembled monolayer on the surface
of substrate.
 In the bottom-up technique, the starting material is either gaseous state or
liquid state of matter.

Top-down Approaches:
 The top-down approach refers to slicing or successive cutting of a bulk
materials to get nano-sized particles.
 In top-down method or technique, the starting materials is solid state.
 Nano-materials are synthesized by breaking down bulk solid into nano-sized
and provides desired shape and order.

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Chemical methods of synthesis:

1. Solution Combustion method.
2. Hydrothermal method.
3. Sol-gel method
4. Chemical Vapour Deposition (CVD)
Solution Combustion method:
Solution Combustion Synthesis is a versatile, simple and rapid process, which
allows effective synthesis of a variety of nano- size materials. This process involves
a self-sustained reaction in homogeneous solution of different oxidizers (e.g., metal
nitrates) and fuels (e.g., urea, glycine, hydrazides).
Synthesis
 Dissolve the oxidizer (metal nitrate) into distilled water and mix up with
magnetic stirrer.
 Add fuel (Urea, Glycerine), again stirrer it.
 Put the container on electrical heater.
 Following steps will takes place – Boiling & frothing – Smoldering – Flaming –
Fumes.

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 After cooling the container, collected metal oxide nano material obtained is
sent for the calcination.
Calcination
Calcination involves thermal decomposition, phase transition or removal of a
volatile fraction.
 The calcination process normally takes place at temperatures below the
melting point of the product materials.
Advantages:
1.20-50 nm size nanoparticles can be synthesized.
2. Low cost and less time are required
3. No need of vacuum and no inert gas in required.

Hydrothermal method:
Hydrothermal synthesis is normally conducted in steel pressure vessels called
autoclaves with or without Teflon liners under controlled temperature or pressure with
the reaction in aqueous solution. The temperature can be elevated above the boiling
point of water, reaching the pressure of vapour saturation. (critical point of water:
374ºC, 218 atm).
Procedure:
In the synthesis of nanoparticles,
 Mixing a known mass of precursor solution (metal salt) in deionized water.
 Solution stirred vigoursly for 30- 45mins to get clear solution and aging period
for 24hours.
 Then the solution transferred to stainless steel vessel (autoclave) and placed
into oven at 180ºC to 12hours.
 Autoclave cooled down to room temperature. Solution is filtered and washed
with distilled water.
 Solution dried at 100ºC to get nanocrystals.
 Finally crushed into fine powder.
Carbon based Nanomaterials:
1. Carbon Nanotubes (CNT’s):
 CNTs are allotropic forms of carbon
 It is tubular made of SP2 hybridized C-atoms having diameter of nanometer
order
 There are two types:
1. Single-walled carbon nanotubes (SWCNT)
2. Multi-walled carbon nanotubes (MWCNT)

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Sl. SWCNT MWCNT

No.
1 Formed by rolling up of single Consists of two or more concentric
graphite layer. graphite layers with vanderwaal’s force
between them.
2 Difficult to synthesize pure and Bulk synthesis is easy with high purity.
defect-free form of SWCNT.
3 It accumulates less in the body and It accumulates more in the body.
hence can be used for biomedical
applications.
4 Diameter ranging from 1-2nm. Diameter ranging from 2-25nm.
Synthesis:
It is synthesized by solution combustion method.
Properties:
1. It has cylindrical carbon molecules which exhibits physical and chemical
properties.
2. CNT exhibits high electrical conductivity and high thermal conductivity.
3. CNT have low density and very high mechanical strength
4. CNT emits electrons when subjected to high electric field.
Applications:
1. Used as electrode material for Li-ion rechargeable batteries.
2. Used in field emission X-ray tubes.
3. CNTs are used to obtain composite materials with enhanced mechanical strength.
4. SWCNTs are used in cancer thermotherapy to kill cancer cells without affecting
healthycells.
5. SWCNTs are used to store H2 as a fuel source.
6. SWCNTs used in solar panels.

2. Graphene:
 Graphene is allotropic form of carbon.

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 It is consisting of single layer of SP2 hybridized C-atoms arranged in a hexagonal

lattice.
 It is unique transparent material and has planar network of one layer of C-atoms.

Synthesis:
It is synthesized by solution combustion method.
Properties:
1. It is the lightest material and the strongest compound.
2. Graphene is a good conductor of heat and electricity at room temperature.
3. It has high thermal conductivity and excellent mechanical properties.
4. Graphene has extreme chemical stability and unique optical behaviour.
Applications:
Graphenes are used in
1. Touchscreen
2. Transistor
3. Computer chips
4. Batteries
5. Supercapacitors
6. Solar cells etc.

3. Fullerenes:
 Fullerenes are clusters made of only carbon atoms having closed cage like
structure.
 Fullerenes with different carbon atoms like C60, C70, C74, C78 and C84 has
prepared and investigated.
 Fullerenes have closed structure with hexagonal and pentagonal rings. The
pentagons provide curvature of closed structure.
 C60 molecules has spherical resembling soccer ball(football) called bucky
ball.
 Solutions of pure buckminsterfullerene have a deep purple color.
Solutions of C70 are a reddish brown in color.

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Synthesis:
It is synthesized by solution combustion method.
Properties:
1. Fullerenes are stable and can withstand high pressures and temperatures.
2. Fullerenes are highly reactive.
3. Fullerenes are insoluble in water, sparingly
soluble in many other solvents. 4.Fullerenes are
non-toxic but some of their derivatives are toxic.
5.Fullerenes have unique electronic properties, including semiconducting behavior.
Applications:
1. Fullerenes are promising components of future micro electrical.
2. Fullerenes can be act as supercapacitors and used in fibre optics.
3. Fullerenes are used in medical applications and used in cosmetics
4. It is used as lubricants, adhesives, catalyst and as charge transfer complexes etc.
5. It is used as electrode material in secondary batteries and as hydrogen
storage material for fuel cell electrodes.

Applications of nanomaterials:
1. Energy storage and conversion.
2. Environmental Remediation.
3. Biomedical applications.
4. Advanced materials.
5. Electronics and optoelectronics.
6. Catalysis
7. Structural applications.
8. Defense and aerospace.
9. Sensors and Actuators.
10. Agriculture.

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1. Energy Storage and Conversion

 Batteries: Nanostructured materials like carbon nanotubes, graphene, and
nanoscale metal oxides are used in lithium-ion batteries for increased energy
density and faster charging.
 Fuel Cells: Nanocatalysts improve the efficiency of hydrogen fuel cells.
 Solar Cells: Quantum dots and perovskite nanomaterials are revolutionizing
solar energy by increasing efficiency and lowering costs.
2. Environmental Remediation
 Water Purification: Nanomaterials like titanium dioxide (TiO₂) nanoparticles
are used for photocatalytic degradation of pollutants.
 Air Filtration: Nano-sized filters capture fine particulate matter (PM2.5) and
harmful gases.
 Soil Remediation: Iron oxide nanoparticles remove heavy metals from
contaminated soil.
3. Biomedical Applications
 Drug Delivery: Nanoparticles like liposomes and dendrimers enable targeted
drug delivery, reducing side effects.
 Diagnostics: Quantum dots and gold nanoparticles improve imaging
techniques in detecting diseases like cancer.
 Antimicrobial Coatings: Silver nanoparticles are used in coatings to prevent
bacterial growth.
4. Advanced Materials
 Lightweight Composites: Nanomaterials enhance the strength-to-weight ratio
of materials used in aerospace and automotive industries.
 Smart Materials: Shape-memory alloys and piezoelectric materials integrated
with nanostructures offer applications in robotics and medical devices.
 Self-Cleaning Surfaces: Nanostructured coatings (e.g., hydrophobic coatings)
mimic lotus leaves to create self-cleaning surfaces.
5. Electronics and Optoelectronics
 Flexible Electronics: Graphene and conductive polymers enable the
development of wearable devices.
 Quantum Computing: Quantum dots are being used to create next-generation
computing systems.
 Displays: Nanophosphors and OLEDs (organic light-emitting diodes) offer
better resolution and energy efficiency.
6. Catalysis
 Industrial Catalysis: Nanoparticles provide higher surface area-to-volume
ratios, improving the efficiency of catalysts in chemical reactions (e.g.,
ammonia production, oil refining).
 Green Chemistry: Nanocatalysts reduce energy consumption and enable eco-
friendly processes.
7. Structural Applications
 Concrete and Construction Materials: Nanomaterials like silica
nanoparticles improve the durability and strength of concrete.
 Coatings and Paints: Nanoparticles enhance corrosion resistance, thermal
insulation, and UV protection.
8. Defense and Aerospace
 EMI Shielding: Nanomaterials like carbon-based fillers (graphene, carbon
nanotubes) provide lightweight and effective electromagnetic shielding,
crucial for aircraft and military applications.

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 Thermal Protection: Nanostructured ceramics are used in heat shields for

spacecraft.
9. Sensors and Actuators
 Chemical Sensors: Nanostructured sensors detect gases, toxins, and
biomolecules with high sensitivity.
 Mechanical Sensors: Nano-enabled devices monitor stress and strain in
engineering structures.
10. Agriculture
 Nano-Fertilizers: Controlled release of nutrients improves crop yields.
 Pesticides: Nano-encapsulation ensures targeted delivery, reducing
environmental impact.

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