SAI VIDYA INSTITUTE OF TECHNOLOGY – Dept.

of Chemistry

Module-3
Engineering Materials
(“Better thing for better living – through polymers”)

Engineering Materials
Polymers: Introduction, Synthesis and applications of Polyurethanes.
Polymer composites Introduction, synthesis, properties & applications of Kevlar Fibre,
Conducting Polymers: Introduction, Synthesis & Mechanism of conduction in polyaniline and
factors influencing conductivity of organic polymers.
Biodegradable polymers: Introduction and their requirements. Synthesis, properties and
applications of Poly lactic acid.
Nanomaterials: Introduction, size dependent properties (Surface area, Electrical, Optical and
Catalytic properties). Synthesis of nanomaterials: Top down and bottom-up approaches,
Synthesis by Sol-gel, and precipitation method, Nanoscale materials: Fullerenes, Carbon
nanotubes and graphenes –brief Explanation, properties and applications.

Definition: “Polymers are macro sized molecules of high molecular mass formed by the
combination of a large number of simple molecules by covalent bonds”.
Ex: Polyethylene, polyacetylene, polystyrene, polyvinyl chloride, natural and synthetic rubbers
etc.

Polymerization: “The process by which the monomers are converted into polymers is called
Polymerization”.

1) Polyurethanes:

Synthesis: It can be synthesized by the polymerization of di-isocyanate with glycol.

Properties:

1. It is a spongy, transparent, polymer.

2. It has high degree of flexibility.
3. It is resistance to water, oil and corrosive chemicals.

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Applications:

1. It is used for tyre retreading and industrial wheels.

2. It is used for making lightweight garments, swim suits, etc.
3. It is used as cushions for furniture & automobiles.

POLYMER COMPOSITES
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. When one of the components
is a polymer, resulting composite called as polymer composite.

Kevlar: Kevlar is synthesized in solution of N-methyl-pyrrolidone & calcium chloride from the
monomers 1, 4-phenylene-diamine (para-phenylenediamine) & terephthaloyl chloride

through a condensation reaction with liberation of HCl as a byproduct.

Properties:

1. It has very light weight.

2. It has high tensile strength and stiffness.
3. It has very good corrosion resistance.

Applications of Kevlar:

1. It is used to make light weight boat hulls

2. aircraft fuselage panels, pressure vassals, high performance race car, bullet proof vests,
3. Used in puncture resistance bicycle tyres etc.

CONDUCTING POLYMERS
Definition: “An organic polymer with highly delocalized pi-electron system having electrical
conductance is called conducting polymer”.
Ex: Polyacetylene, polypyrrole, polythiophene, polyphenylene, polyaniline, etc.

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Synthesis of Polyaniline

PANI is synthesized by oxidative polymerization using 0.1 M aniline hydrochloride in 1 M

HCl and ammonium peroxydisulfate (NH4)2S2O8 (APS) as oxidizing dopant (equimolar to
aniline). The polymerization reaction was carried at a temperature of 0-3°C.
Polyaniline is a redox active material and in conducting state it is green in colour. It changes
its color and conductivity when exposed to different media. For example, under reducing
condition, it is yellow in colour and under oxidizing or basic condition it is blue in colour.

Structure of electrically conducting Emeraldine (green form, partially oxidized and partially
reduced)
General structure of polyaniline is

It exhibits in three forms depending on n and m forms.

1. Leucoemeraldine -colourless and it is in the reduced form.

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2. Pernigraniline- Violet colour and it is in the oxidised form.

3.Emeraldine - Green or blue colour and it is either fully oxidised or fully reduced.

Each form of the polyaniline can be reversibly interconverted through electron transfer. Out of
these three forms, emeraldine salt is conducting (103S/cm).

Mechanism of conduction in polyaniline:

Mechanism follows protonic acid doping. In this type current carrying charged species are
created by the protonation of imine N2. The mechanism steps are as follows.

1. Polyaniline is first partially oxidized using suitable oxidizing agent into base form of
polyaniline.
2. This base form of polyaniline when treated with aqueous 1 M HCl, undergo protonation of
imineN2 creating current carrying positive charges in polyaniline.
3. The positive charges are compensated by anions of doping agent, resulting in corresponding
salt.

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Factors influencing conductivity of organic polymers

Dopant: The electrical conductivity of an organic polymer increases when it was doped with
an electron donor such as alkali-metal ion or an acceptor such as AsF5 or Iodine. Doping is
reversible, removal of dopant or de-doping produces the original low conducting, semi
conducting or insulating polymer without degradation of the polymer backbone.
Temperature: Conductance of conducting polymer increase with increase in temperature
because of higher thermal excitation of electrons give rise to increase in electronic conduction
Band gap: Conductivity increases with decreasing in band gap which is the amount of energy
needed to promote an electron from the highest occupied energy level (valence band) to the
empty band (conduction band) immediately above it.

Applications of Conducting Polyaniline

1. It is used as an electrode material in rechargeable batteries.
2. Used as Sensors; Gas sensors; Biosensors.
3. In electro chromic display windows.
4. In information storage device.
5. In light emitting diodes.
6. In fuel cells as the electro catalytic materials.

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7. Used as a membrane for gas separation.

8. It is used as conductive track on PCB’s.
Biodegradable polymers:
These are termed as “biopolymers” as these polymers are derived from various natural
sources. They are defined as “materials whose chemical and physical characteristics undergo
deterioration and completely degrade when exposed to microorganisms, aerobic and
anaerobic processes”.

Requirements and Characteristics of biodegradable polymers

1. They should be hygroscopic in nature.
2. The biodegradable polymer should have hydrolysable linkages such as esters, amide and
ethers.
3. The product obtained after degradation should act as compost.
4. It reduces the volume of waste in packaging materials.
5. It should reduce environmental pollution i.e., it is eco-friendly.
6. It should economical i.e., it should available at a low cost.
7. Promote sustainable development.
8. Reduces carbon emission.

Synthesis of Polylactic acid

It was synthesized by condensation polymerization of lactic acid.

Properties
1 It is a linear and thermoplastic polymer.
2 It has around 37% crystalline in nature
3 Its glass transition temperature in the range of 50-80°C.
4 Melting point temperature in the range of 170-180 °C.

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5 It can be processed in to fibres.

6 Soluble in chlorinated solvents, dioxane, benzene.

Applications
1 It is used in biomedical implants in the form of plates, pins, rods, screws etc.
2 Also used in sutures in surgery, dialysis medium, drug delivery devices etc…
3 Disposable food packaging, compost bags, tableware etc…
4 Used in disposable garments, feminine hygiene and diapers.

NANO MATERIALS
The word “Nano” is derived from a Greek word “Nanos” meaning Dwarf or Small. “The
materials having at least one dimension in the nano scale range of 1-100 nm are called as
nanomaterials”
Materials reduced to the nanoscale can suddenly show different properties compared to what
they exhibit on a macroscale, enabling unique applications.
Size dependent properties of Nanomaterials
Nanomaterials exhibits several size dependent properties like;
Surface area and catalytic activity:
Due to their small dimensions, nanomaterials have thelarge surface area to volume ratio, which
makes a large to be the surface or interfacial atoms, resulting in more surface dependent
material properties. As surface area per mass of a material increases, a greater amount of the
material can come in contact with surrounding materials, thus affecting reactivity. Hence higher
the surface area, the higher will be the catalytic activity of the nanomaterials.
Electrical properties:
In the bulk materials, because of the presence of more atoms, there is an overlapping of orbital
takes place. As the size decreases, orbital becomes separated and there is a gap between the
bands (valence and conduction bands). This decides the nature of the nanomaterial. The same
metals which are good conductors in bulk, becomes semiconductor or insulators as their size
decreases in nano scale.

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Optical properties:
The reduction of material dimensions has a prominent effect on the optical properties of
nanomaterials. Decreasing the size of a nanostructured material increases the energy difference,
∆E between the higher energy level and lower energy level. When an electron drops from

higher energy state to lower energy state, light is emitted with wavelength i.e . Larger

∆E implies shorter wavelength and the color of the nanomaterial different from that of bulk
materials.
SYNTHESIS OF NANOMATERIALS
There are two methods of preparing nanomaterials. One is top-down approach & the other is
bottom-up approach.

 In top-down approach, the material is reduced from bulk size to nano scale.
Examples for top-down approach are ball milling method & nanolithography.
 In bottom-up approach, matter in atomic or molecular level gets assembled to form tiny
clusters which grow to reach nano-size.
Examples for bottom-up approach are arc discharge method, chemical vapor deposition,
physical vapor deposition & sol gel method.
SOL – GEL PROCESSES
Sol gel processes principle is conversion of precursor solution into gel via hydrolysis and
condensation reactions.
Sol gel processes allow to synthesis of nano materials of high purity.
This process involves five steps

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1. Preparation of sol: sol is prepared by suspended particles in water during suspension

hydrolysis reaction takes place.

2. Conversion of sol into gel: sol is converted into gel by condensation reaction forming
network between oxides. When networking takes place, the viscosity of the solution increases.

3. Aging of gel: during which poly condensation reaction continue until the gel is
transformed into solid mass.
4. Removal of solvent: Further the solid mass is isolated from the solvent by thermal
evaporation. The product formed is xerogel.
Heat treatment: solid mass (xerogel) obtained is dried at nearly to 800C to get fine nano particle
powder.
Advantages:
Nano materials of high purity with good homogeneity can be obtained.
Samples can be prepared at low temperature.
Easy to control the synthesis parameters like shape and size of resulting material

PRECIPITATION METHOD
Principle: The principle involved in the precipitation of precursor materials at constant pH via
condensation.
Processes: In this method inorganic metal salt such as chloride, sulphate, nitrate ions etc.., are
used as precursor. Precursor materials is dissolved in water and undergo hydrolysis where metal
ions exist in metal hydrates form. On adding base like NaOH/NH4OH, pH of the solution
changes and reaches super saturation level leading to condensation of precursor to form metal
hydroxide precipitate. The precipitate is washed with water, filtered and finally calcinated at
higher temperature to convert metal hydroxide into metal oxide by dehydrogenation takes
place.

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Advantages:
 The process is relatively economical.
 The wide range of single and multi-components to oxide nano powders can be
synthesized.
NANO SCALE MATERIAL
Nano scale materials are defined as a set of substances where atleast one dimension is less than
approximately 100nm. A nanometer is one millionth of a millimeter. Nano materials are of
interest because of this scale unique optical, magnetic, electrical and other properties emerge.
These emergent properties have the potential for great impacts in electronics,
medicine and other fields.

FULLERENES: Fullerenes are class of molecules made of only carbon atoms

having closed cage like structure. Many numbers of fullerene molecules with
different carbon atoms like C60, C70, C74, C76 etc.., have been prepared but C60 is more stable.
The C60 molecule had spherical shape resembling a soccer ball (football). It is also commonly
called as Bucky ball. The C60 molecule consist of 12 pentagons and 20 hexagons and each
pentagon is surrounded by five hexagons and each hexagon is surrounded by three hexagons
and three pentagons placed next to each other alternately fold in the form of ball. Each carbon
atom on the cage surface is bonded to three carbon neighbors therefore is sp2 hybridized. The
chemical formula for fullerene is C20+2n.
In fullerenes, 12 pentagonal rings are necessary and sufficient to form the cage closure. It is
quite stable, breaking the balls requires temperature of about 1000C. Fullerene has high tensile
strength and high packing density.

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Applications:
It is used in electrographic imaging, solar cells, nonlinear optical thin films etc..,
Used to make carbon films, diodes, double layer capacitor and storage devices.
Used for the conversion of diamond
Used as gas sensors, temperature sensors, particle sensors and detection of organic
vapors.
CARBON NANO TUBES: Carbon nanotubes are allotropes of carbon with a cylindrical
nanostructure having diameter of 1nm and longer than a micrometer. It is one dimensional
material like nano wires. CNT is made up of graphite sheet. When the graphite sheet is rolled
up hexagonally, it forms a tube-like structure is called as CNT.

Types of CNT:
1. Single walled nanotubes (SWCNT): These are formed by rolling up of single graphite layer.
Diameter is 1.4nm and length upto few micrometers.

2. Multi walled nanotubes (MWCNT): These are formed by rolling up of two or more graphite
layers. Diameter is from 30 to 50nm and length upto few micrometers.
Properties:
CNTs have High Electrical Conductivity, Tensile Strength, Thermal Conductivity,
flexibility and elasticity.
Applications: It can be used in
Conductive plastics, Structural composite materials, Flat-panel displays, Gas storage
Micro- and nano-electronics, Radar-absorbing coating, Batteries with improved lifetime,
Biosensors for harmful gases.

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Graphenes
It is a substance composed of pure carbon, with atoms arranged in a regular hexagonal pattern
similar to graphite, but in a one atom thick sheet. It is chemically the most reactive form of
carbon. graphene is an allotrope of carbon in the form of a plane of sp2-bonded atoms with a
molecular bond length of 0.142 nanometres. Layers of graphene stacked on top of each other
form graphite, with an interplanar spacing of 0.335 nanometres. The separate layers of graphene
in graphite are held together by van der Waals forces. It is strongest, lightest, and best conductor
of electricity. It is the basic structural element of many other allotropes of carbon, such as
graphite, diamond, charcoal, carbon nanotubes and fullerenes.
Graphene is a crystalline allotrope of carbon with 2-dimensional properties. Its carbon atoms
are packed densely in a regular hexagonal pattern. Each atom has four bonds: one σ bond with
each of its three neighbors and one π-bond that is oriented out of plane. The atoms are about
1.42 Å apart.

Properties:

1. Very high electrical conductivity when exposed to an electric field.

2. The strongest material ever measured. Up to 150 times stronger than the equivalent
weight of steel.
3 Graphene oxide reportedly has the ability to attract radioactive material.
4. Graphene has the ability to transmit up to 98% of light.
5. Its absorption of light across the visible and near-infrared parts of the spectrum

Applications: It is used in touch screens, transistors, super capacitors, sensors, batteries,

computer chips, water filters, solar cells etc.,

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