UNIT I: POLYMER TECHNOLOGY

Polymerization:- Introduction, methods of polymerization (emulsion

and suspension), mechanical properties.

Plastics: Compounding, fabrication (compression, injection, blown film

and extrusion), preparation, properties and applications (PVC,
polycarbonates and Bakelite), mention some examples of plastic
materials used in electronic gadgets, recycling of e-plastic waste (waste
to wealth).

Elastomers: - Introduction, preparation, properties and applications

(Buna S, Thiokol and polyurethanes).

Composite materials: Fiber reinforced plastics, conducting polymers,

biodegradable polymers, biopolymers, biomedical polymers.

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INTRODUCTION:

The word polymer is derived from two Greek words,

Poly = many and meros = parts and units.

DEFINITION:

“A polymer is a large molecule which is formed by respected linking of small simple

chemical units called monomers”

Polymer often called as macromolecule.

EX: Polythene is a polymer made up of inters linking of a number of ethylene monomer.

nCH2 = CH2 [CH2 CH2] n

Ethylene polythene

TYPES OF POLYMERS:
There are several ways of classification of polymers based on some special considerations. The
following are some of the
common classifications of polymers: (1) by Source (2) by Backbone of the chain (3) by Structure
(4) by Mode of Polymerization (5) by Molecular force (6) by tacticity

(I)Classification Based on Source:

(1) Natural Polymers: These polymers are found in plants and animals. Examples are
proteins, cellulose, starch, resins and rubber.
(2) Semi-synthetic Polymers: They are the chemically modified natural polymers E.g.
Cellulose derivatives as cellulose acetate (rayon) and cellulose nitrate, etc.
(3) Synthetic Polymers:- The polymer which has been synthesized in the laboratory is
known as synthetic polymer. These are also known as manmade polymers. E.g. polyvinyl
alcohol, polyethylene, polystyrene, polysulfone, plastic (polythene), synthetic fibers
(nylon 6.6) and synthetic rubbers (Buna - S) are examples of man-made polymers.

(II)Classification Based on Backbone of the polymer chain:

Organic and Inorganic Polymers:

Organic Polymers: A polymer whose backbone chain is essentially made of carbon atoms is
termed as organic polymer.

Inorganic Polymers:
The atoms attached to the side valencies of the backbone carbon atoms are, however,
usually those of hydrogen, oxygen, nitrogen, etc. The majority of synthetic polymers are organic.
On the other hand, generally chain backbone contains no carbon atom is called inorganic
polymers. Glass and silicone rubber are examples of it.

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(III)Classification Based on Structure of Polymers:

(1)Linear Polymers:
These polymers consist of long and straight chains. Linear polymers are commonly
relatively soft, often rubbery substances, and often likely to soften (or melt) on heating and to
dissolve in certain solvent.
E.g.: high density polythene, PVC, polyvinyl, polyesters and polyamides etc.

(2) Branched Polymers:

These polymers contain linear chains having some branches, e.g. low density polythene,
glycogen etc.

(3) Cross-linked Polymers:

These are usually formed from bi-functional and tri-functional monomers and contain
strong covalent bonds between various linear polymer chains, Cross linked polymers are hard
and do not melt, soften or dissolve in most cases.
E.g. vulcanized rubber, urea-formaldehyde resins, etc.

(IV)Classification of Polymers Based on Mode of Polymerization

(1)Addition polymers:
The polymers formed by the polymerization of monomers containing double or triple
bonds (unsaturated compounds) are called addition polymers. Addition polymers have the same
empirical formula as their monomers.
Addition polymers can further be classified as follows.

(i) Homopolymers (ii) Heteropolymers

(i)Homopolymers: - The polymers which are obtained by the polymerization of a single type of
monomer are called homopolymers.

Eg

(ii)Heteropolymers: - The polymers made by addition polymerization from two different

monomers are termed as heteropolymers or copolymers.
E.g.:- Buna-S (SBR), Buna-N (NBR), etc.

(2)Condensation Polymers:
The condensation polymers are formed by repeated condensation reaction between two
different bi-functional or tri-functional monomeric units. In these polymerization reactions, the
elimination of small molecule such as water, alcohol, hydrogen chloride, etc. take place
E.g.: Terylene (Dacron), Nylon 6. 6, Nylon 6 etc.

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(V)Classification of Polymers Based on Molecular Forces

(1)Elastomers
These are rubber like solid polymers in which the polymer chains are held together by
weakest intermolecular forces.
Eg:- natural rubber, Buna-S, Buna-N etc .
The weak binding forces permit the polymers to be stretched.

(2)Fibers:-
Fibers belong to a class of polymers which are thread-like and can be woven into fabrics.
These are widely used for making clothes, nets, ropes, gauzes, etc. Fibers possess high tensile
strength.
E.g.:- Nylon-6.6, Terylene and polyacrylonitrile etc.

(3)Plastics:
A polymer is shaped into hard and tough utility articles by the application of heat and
pressure; it is used as a ‘plastic’.
Plastics are of two types (a) thermoplastic and (b) thermosetting plastic.

I. Thermoplastic:- They soften or melt on heating and harden on cooling over many cycles
of heating and cooling and retain solubility and fusibility.
E.g.: Polyethylene, polypropylene, poly-styrene, nylon polyamides, etc.
II. Thermosetting plastic:-They usually soften or melt initially on heating, but fast undergo
chemical changes to finally turn insoluble and infusible.
E.g.: Phenolic resin, amino resins, epoxy resins, diene rubbers (vulcanized) etc.,

TYPES OF POLYMERIZATION:
Low molecular weight smaller monomer units combined repeatedly to form a big
molecule with high molecular weight product, the formed product is known as polymer and the
phenomenon is known as polymerization.

Polymerization is of two types (I) Addition polymerization.

(II) Condensation polymerization.

(I) Addition polymerization or chain polymerization:-

In this type of polymerization the monomer units simply unite to form a polymer. There
is no loss of any simple molecule during the polymerization process.
Eg: polythene, poly styrene, poly acrylonitrile etc.,

Mechanism of addition polymerization:

Addition polymerization is also called chain polymerization. In addition polymerization
always an active center is formed. The active center may be free radical, cation (carbonium ion),
anion (carbanion).
Depending on the active center formed the addition polymerization takes place by three types.

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 (1)Free radical addition polymerization.
(2)Cationic addition polymerization.
(3)Anionic addition polymerization.

These three types of polymerization follow three steps.

(1) Initiation (2) Propagation (3) Termination

(1) Initiation: In this the active center attacks the monomer to form the newly formed active
center.
(2)Propagation: In this the above formed active center attacks continuously with the monomer
to form the polymer with the active center.
(3)Termination: In this the active center is removed so that the polymer is formed.

(II) Condensation polymerization.

In this type during the addition in every step simple molecules like H2O, NH3, CH3OH,
etc are lost, ultimately forming the polymer.

E.g.: Nylons, Terylene, and Bakelite etc.

Nylon 6.6

Preparation of Terylene:

Co-Polymerization:
Combination of two or more different monomers to produce a polymer. Those polymers
are called co-polymers and the process is called as Co-Polymerization. Ex: BUNA-S, BUNA-N,
etc.

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METHODS OF POLYMERIZATION (OR) TECHNIQUES OF POLYMERIZATION

There are four types of polymerization techniques.

(1) Suspension (pearl or beads) polymerization.

(2) Emulsion polymerization.
(3) Bulk or mass polymerization.
(4) Solution polymerization.

Suspension polymerization (Pearl or beads polymerization)

In this method
(1) Polymerization occurs in heterogeneous system.
(2) The water insoluble monomer is added to water, that suspends as a tiny droplets (0.1mm to
1mm) by continuous agitation.
(3) A water soluble polymer (such as poly vinyl alcohol or colloids) is added to prevent
coagulation of monomer droplets.
(4) A water soluble initiator is added to the above formed monomer droplets.
(5) After adding all the required chemicals, the mixture is continuously stirred so that reaction
starts within each droplet of the monomer to form a polymer.
(6) The formed polymer is in the form of spherical ‘pearls or beads’.
(7) These formed polymer is also water insoluble.
(8) The formed polymer is isolated by easy filtration followed by washing.

Advantages of suspension polymerization:

a) Isolation (separation) of product is easy as it needs only filtration and washing.
b) Isolated products need no further purification.

Disadvantages of suspension polymerization:

a) The method is applicable only for water insoluble monomers.
b) It is difficult to control particle size.

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Emulsion polymerization.

(1) In a large amount of water add the monomer.

(2) In this method the monomers are dispersed as a fine droplets
(10-5 to 10-6 mm).
(3) Emulsify (or stabilized) the monomer by the addition of surfactants (soap or detergents i.e.,
R-COONa, R-SO3Na).
(4) Water soluble initiator such as Persulphates and Hydrogen peroxide (H2O2) are added.
(5) After adding the initiator the system is kept agitated in the absence of Oxygen at 70oc.

Explanation:
Emulsifier (surfactant) contains a hydrophilic (water loving) polar end group (head) and a
hydrophobic (water hating) non-polar end group (tail). At low concentration (quantity) the soap
or detergent dissolves completely. If the quantity of surfactant increases the soap molecules form
aggregates called MICELLE (aggregation of 50-100 molecules).

The monomer molecules dissolve in the hydrocarbon carbon center (head) of the
micelles. The free radicals are generated in the aqueous phase.
The free radicals are diffuse into the micelles centre through the aqueous phase, penetrate into
the micelle and initiate the polymerization in each micelle. The polymerization growth inside the
polymer causes its swelling (increase in size).
The polymer growth continues until the growing chain is opposed by radical and gets
terminated. The polymer formed is in the well stabilized latex. It is isolated either by coagulation
using electrolytes or by freezing.

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Advantages of emulsion polymerization:
a) The rate of polymerization is high.
b) No viscosity builds up and hence agitation is easy.

Disadvantages of emulsion polymerization:

a) The polymer needs additional clean up and purification.
b) It is difficult to remove entrapped coagulants, emulsifiers etc.

This method is widely used to prepare polymers like PVC, Poly vinyl acetate, PMMA,
Neoprene etc.

MECHANICAL PROPERTIES OF POLYMERS

Strength: strength of the polymer depends upon the intermolecular attractive forces. Greater is
the attractive forces; higher is the strength of a polymer. Strength of a polymer increases with
increasing molecular weight of a polymer or increasing polar groups such as –OH, -COOH,
-OCH3, -COOR, & -X. So, the lower molecular weight polymers have less strength, soft and
gummy.

In crossed linked polymers the chains are strongly linked to each other by covalent
bonds, which cause higher strength, toughness, brittleness etc. strength of a polymer depends on
the shape of the molecule also. If the shape of the molecule is simple and uniform, polymer
molecule has less strength.
Ex: In PVC, large Cl atoms are present on alternative carbon atoms in the polymer.
These Cl atoms and strong attractive forces restrict the movement of the molecules in the
polymer. So, PVC is tougher and stronger polymer. In poly ethylene attractive forces are week
due to simple structure. Thus, PE is weaker than PVC.

2. Elastic character: elasticity is the property of recovering original shape after the removal of
deforming stress. Natural rubber possesses high elasticity due to the coiled helices structure of
poly isoprene.

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3. Toughness: Polymer toughness, i.e. the ability of a polymer to exhibit plastic deformation and
resistance to an impact load without failure, is a very desirable property of a material or product.
4. Plasticity: The substances which are soften on heating and harden on cooling is known as
plasticity.
5. Ductility: A ductile material undergoes large irrecoverable deformation before rupture.
6. Brittleness: A brittleness material shatters suddenly without noticeable plastic deformation
preceding failures.
7. Hardness: Refers to the ability of a material to with stand a gradually applied stress without
rupture.

PLASTICS

INTRODUCTION:
The word plastic is derived from the Greek word plastikos, which means capable of being
shaped or molded.

Definition:
“Plastics are high molecular weight organic polymers which can be moulded into desired
stable shapes by the application of heat and pressure.” All plastics are polymers but all polymers
are not plastics.

TYPES OF PLASTICS:
From Engineering point of view plastics are classified into two types
(i)Thermo plastics (ii) Thermo setting plastics

(i)Thermo plastics:
These can be softened on heating and hardened on cooling reversibly. Their hardness is a
temporary property and it changes with the raise or fall of temperature. They can be reprocessed.
These can be prepared by addition polymerization process. These are linear, long chain
polymers,

Examples: Polyethylene (PE), Polypropylene (PP), Polyvinyl chloride (PVC), polystyrene (PS),
Nylons, Poly tetra fluoro ethylene (PTFE) etc.

(ii)Thermosetting polymers

These polymers can be hardened on heating and once they are hardened, cannot be
softened i.e, they are permanently set polymers. During moulding, these polymers acquire three
dimensional cross-linked structure, with strong covalent bonds. Thermosets once moulded
cannot be reprocessed. These can be prepared by condensation polymerization.

Examples: Polyester (terylene), Bakelite, epoxy- resin (araldite), Melamine, urea- formaldehyde
resin etc.

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Differences between Thermo Plastics and Thermosetting Plastics

Thermo plastics Thermosetting plastics

1) They soften on heating and stiffen on 1) They do not soften on heating.

cooling.
2) These are the products of condensation
2) These are the products of addition polymerization mostly.
polymerization mostly.
3) These are three dimensional, cross linked
3) These are linear or branched in structure. network in structure.

4) Soluble in organic solvents. 4) Insoluble in organic solvents.

5) They are soft, weak and less brittle. 5) They are hard, strong and more brittle.

6) These can be remoulded, reshaped and 6) They cannot be remoulded, reshaped and
reused. reused.

7) These can be recycled from waste. 7) These cannot be recycled from wastes.

8) Adjacent polymer chains are held by either 8) Adjacent polymer chains are held by
Vander wall’s forces of attraction. strong Vander wall’s forces of attraction.

9) E.g.: polythene, PVC, poly styrene. 9) Eg: Nylon 6, Nylon 6.6, and Bakelite.

COMPOUNDING OF PLASTICS:
A high polymeric material is mixed with 4 to 10 ingredients during fabrication, each of
which these ingredients either discharge a useful function during moulding or impart some useful
property to the finished article. This is called a mix. Some of the main types of compounding
ingredients are:
(1) Binders (2) Fillers (3) Pigments or colorants (4) Plasticizers (5) Lubricants
(6) Stabilizers (7) catalysts or accelerators.

(1)Resin or a binder: The product of polymerization is a resin, which forms the major portion
of the body of the plastic. It also holds the different constituents together. The binders used may
be natural or synthetic resin or cellulose derivatives. Resin forms the major part of the plastic and
determines the types of treatment needed in the moulding operations.

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(2)Fillers: Fillers are added for two purposes to the plastics.
(a) To reduce the cost (b) To impart special property on the product.
Fillers impart better hardness, tensile strength, opacity, finish and workability. The percentage of
fillers is up to 50% of the total moulding mixture. In order to increase the strength certain fillers
are used they are as follows
Organic fillers: wood flour, cotton, paper pulp, graphite, carbon black, etc.

Inorganic fillers: Asbestos, powered mica, silicate clays, zinc, and lead oxides, cadmium,
barium sulphides, metals of iron, lead, copper and aluminium in powered form.
By adding carborondum or mica or quartz they impart hardness.
By adding asbestos it provides heat and corrosion resistance.

(3)Pigments or colorants: Color and appeal are very important for commercial high polymer
goods. Commonly used coloring materials are organic dye and inorganic pigments.
Organic colorants: These give bright, less dense and transparent colors.

Eg: Carbon black (black), anthra quinones (yellow), azodyes (yellow, orange, red) ,
phthalocyanins (green).

Inorganic colorants: These give opaque colors and less bright.

Eg: Zinc oxide, titanium dioxide, barium sulphate produce white color.
Zinc chromate, chromium trioxide (green), lead chromate and iron oxide (yellow).

(4)Plasticizers: These are the materials that are added to resins to increase their plasticity and
flexibility.
Most commonly used plasticizers are vegetable oils (non-drying type),camphor, esters of
Stearic, Oleic or phthalic acid.

Cyclic plasticizers used are some phosphates ( tricresyl phosphate, tributyl phosphate, tetra
butyl phosphate and triphenyl phosphate) diethyl phthalate etc.
Acyclic plasticizers used are phosphoric acid ester, Stearic acid ester, adipic acid ester etc.

(5)Lubricants: Lubricants like waxes, oils, soaps are employed to make the moulding of plastic
easier. They impart a glossy finish to the products. They also prevent the plastic material from
sticking to the fabricating equipment. They make moulding easier and impart glossy flawless
finish to the product. Commonly used lubricants are waxes, oils, stearates, oleates and soaps.
(6)Stabilizers: They improve the thermal stability during polymerization and further processing.
They protect from thermal and photo chemical degradation.
Vinyl chloride shows a tendency to undergo decomposition and discoloration at moulding
temperature. Hence, during moulding, heat stabilizers are used.
Commonly used stabilizers are salts of lead (white lead, litharge, lead chromate, red lead etc.)
stearates of lead, Cd and Ba.

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(7)Catalysts or accelerators: These are added to thermosetting plastic , during moulding
operation, to accelerate the polymerization of fusible resin, into cross-linked infusible form.
Eg: Catalysts used for compounding include H2O2, benzoyl peroxide, acetyl sulphuric
acid, metals like Ag, Cu, and Pb; metallic oxides like ZnO, NH3 and its salts.

MOULDING TECHNIQUES
The process of converting the given polymeric material into suitable designs is called moulding.
The different moulding methods used are
a. Compression moulding
b. Injection moulding
c. Extrusion moulding
d. Blow film

a. Compression Moulding:

Compression moulding method is applied to both thermoplastics and thermosetting plastics.

These are one of the oldest manufacturing technologies associated with plastics. The mould
consists of two halfes, the upper half and the lower half.

Compression moulding

The lower half contains a cavity and the Upper half has a projection. The required amount of a
compounded mixture is placed in the cavity in the lower half and the mould is closed carefully.
The gap between the projected upper half and the cavity in the lower half gives the shape of the
moulded article. The time given to polymer to set in the mould is called curing. Curing is done
either by heating as in the case of thermosetting or cooling as in the case of thermoplastics.
After curing, the moulded article is taken out by opening the mould parts. Now a day’s fully
automatic compression moulding presses are available.

Products:
Thermoset products: electric plugs, sockets, commutators for small electric motors,
automotive distributor heads.
Thermoplastic products: gramophone records.
Rubber plastics: O-ring seals, springs, anti-vibration mounting pads etc.

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2. Injection Moulding:
Injection moulding method is used for thermoplastic resins. This process is one of the
most common of all plastics manufacturing processes. The compounded mixture in the form of a
powder (or) pellet is fed into the heated cylinder of the injection moulding machine. The
softened plastic mass in the cylinder is injected at a controlled rate by a screw (or) piston under
high pressure into a cold mould. Curing of the softened plastic into rigid product occurs during
cooling in the mould. The mould is opened after sufficient curing to remove the finished product.
Thermosetting polymer can’t be moulded by this method.

Products: computer parts, radio and tv cabinets, ball bearing cages, gear wheels, car battery
cases, chair shells, shoe-soles, pipe-fittings, complete water proof shoes, mugs and buckets.

Extrusion moulding:
Extrusion moulding method is used for thermoplastic resins. This method is used to
produce continuous sheets, rods, threads, tubes, cords and cables. It is similar to injection
moulding. Dry plastic material is placed into heated injection chamber. At the end of the
chamber, the material is forced out of a small ring opening (or) a die in the shape of the desired
finished product. Extruded out plastic is placed on a moving conveyor belt for uniform cooling.

Products: films, pipes, ductings, cables, hoses, garden hose, PVC window frames, roofing,
curtain rails, wind screens, doors etc.

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3. Blow film moulding:

Blow moulding produces hollow plastic materials like bottles, tubes, tanks and drums.
Thermoplastic materials like PVC, polystyrene, polypropylene can be blow moulded.

In this process a tube is placed inside a two piece hollow mould. One end of the tube is
completely closed in heated and simultaneously air is blown to fabricate the product having the
shape of mould.

Products: Hollow spheres, bottles, dust bins, drums, oil storage containers, heater ductings,
petrol tanks for cars.

POLY VINYL CHLORIDE (PVC)

Preparation:

Vinyl chloride is obtained by treating acetylene with HCl at 60-800C in the presence of
Metal oxide catalyst.

It is a thermoplastic polymer and is obtained by the free radical addition polymerization

of vinyl chloride in the presence of benzoyl peroxide or hydrogen peroxide.
The above formed PVC is rigid PVC or unplasticized PVC. Its softening point is 148oC it is
colourless and odourless.
Plasticized PVC is obtained by adding plasticizers such as DOP (Di octyl
phthalate) and Dibutyl phthalate.

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Properties:
1. PVC is colorless, non – inflammable and chemically inert powder. It is strong but brittle.
2. It is resistant to ordinary light, atmospheric gases, moisture, inorganic acids and alkalis, but
undergoes degradation in heat or UV light.
3. It is soluble in hot chlorinated hydrocarbons like ethyl chloride
4. Pure resin possesses a high softening point.
5. It has greater stiffness and rigidity compared to polyethylene.
6. It has specific gravity 1.33

Engineering applications:
1. It is widely used as a synthetic plastic.
2. Rigid PVC is used for making sheets, light fittings, safety helmets, refrigerator components,
tyres, and cycle and motor cycle mudguards.
3. Plasticized PVC is used in making continuous sheets viz., table cloths, raincoats, curtains etc.,
4. Used in injection moulding of articles like toys, tool – handles, radio – components, chemical
containers, conveyor belts etc.
5. It is used for plastic rain wear shoes.

BAKELITE

Preparation:

It is prepared by condensing phenol with formaldehyde in presence of acidic/alkaline catalyst.

The initial reaction results in the formation of non polymeric mono, di and tri methylol phenols
depending on the reactant ratio. These compounds in the first stage react to form a linear
polymer, Novolac. Novolac in the second stage undergoes further reaction with these linear
polymers to form cross linking and Bakelite plastic resin is produced.

Properties:
(i) Phenolic resins ( like bakelite) set to rigid, hard, strong,
(ii) It is scratch-resistant, infusible, water-resistant,
(iii)It is insoluble solid, which is resistant to non-oxidizing acids, salts and many organic
solvents.
(iv) But it is attacked by alkalis, because of the presence of free hydroxyl group in their
structures.
(v) It possesses excellent electrical insulating character.
(vi) It is good anion exchange resins capable of replacing anions with –OH groups.
(vii) It is good adhesives, corrosion resistant and resistant to atmospheric gases,
moisture and UV light.

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Engineering applications:
The phenol-formaldehyde resins are extensively used
1. for making electric insulator parts like switches, plugs, switch-boards, heater handles, etc.
2. for making moulded articles like telephone accessories, cabinets for radio and television.
3. for impregnating fabrics, wood and paper.
4. as adhesives (e.g., binder) for grinding wheels.
5. in paints and varnishes.
6. as hydroxyl group exchanger resins in water softening
7. for making bearings, used in propeller shafts for paper industry and rolling mills.

Mechanism for Bakelite.

POLY CARBONATES (PC, LEXAN, MERLON)

Poly carbonates are commonly known by the trade mark name Lexan. They received
their name because of the presence of carbonate groups (-O-(C=O)-O-). The main polycarbonate
material is produced by the reaction of bisphenol –A and Phosgene (COCl2).

(OR)

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The polycarbonate material is produced by the reaction of bisphenol –A and Diphenyl carbonate.

PROPERTIES:
1. They possess high impact and tensile strength, high transparency, stiffness
2. They are soluble in organic solvents and alkalis, better corrosion and oxidation resistance
3. Maintain very good strength, even up to high temperature.

Applications
Electric insulators, sterilisable transparent containers, solar collectors etc.

Some examples of plastic materials used in electronic gadgets:

S.No. Plastic materials Uses in electronic gadgets

1 Phenol formaldehyde Fuse boxes, knobs, switches,

handles,
2 Polyamide food processor bearings, adaptors.
3 Telephones.
Polycarbonate
4 Polyethylene Cable & wire insulation.

5 Polypropylene Kettles
6 Polystyrene
Refrigerator trays/linings, TV
cabinets

7 Poly tetra fluoro ethane(TEFLON) Electrical applications

8 Cable and wire insulation,

Polyvinyl chloride Pipes, etc

9 Urea formaldehyde Fuse boxes, knobs, switches

10 Polymethyl pentane Circuit boards, microwave grills

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Recycling of e-plastic waste (Waste to wealth):

What is Electronic Waste?

Electronic Waste, also recognized as E‐Waste, is a combination of used or unwanted
electronic products that have exceeded their shelf life.
• Computer equipment, monitors/TV’s, cell phones, batteries, stereos, etc. are popular examples
of items that contain harmful toxic components that need to be recycled properly.
How is E‐Waste generated?
Manufactures need to use certain chemicals, elements, and compounds to synthesize a
final consumer product.Items that contain numerous electrical components, generate the largest
amount of e‐waste.
(i.e. Computers)
Toxins in E‐waste
• Toxins in e‐waste include polyvinyl chloride (PVC plastics), copper, lead, mercury, arsenic (in
older models), cadmium, manganese, cobalt, gold, and iron.
• Mercury, chromium, lead, and brominated flame retardants are likely to cause the most adverse
health effects in humans

How is E Waste Recycling Done?

Once e-waste is collected and transported to the recycling facilities, workers sort the e-
waste into categories according to their types and models. Then, all electronic devices will be
examined, and of which the parts that are still functional will be extracted to be reused; they can
either be sold as individual parts or be combined to form a new phone or computer. The e-waste
left behind that is not functional will be sent to recycling processing.
Here, e-waste is thrown into an enormous machine and is shredded into tiny pieces, but
before that, it must first go through a process called de-manufacturing, which refers to the action
of disassembling a product into components. This procedure is to remove all the hazardous
materials in electronic devices that will destroy the machine or contaminate the environment
once disposed into landfills.
Next, the waste is further separated with water. At this stage, almost everything leftover are
non-magnetic materials; they will go through another machine filled with water, where materials
with a low relative density, mostly plastic, will flow, while other materials, like glass, will sink.
Finally, before recycled materials are sold, is to check if there are any remaining valuable
materials stuck to the plastic.

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 ELASTOMERS

INTRODUCTION
 In 1770 PRIESTLY discovered that an exudates sample from the trees
Heaveabrasiliensis, Guayule etc, became known as Rubbers.
 In 1839, CHARLES GOOD YEAR discovered that by heating natural rubber with
Sulphur (Vulcanization) converts it into a more useful form, which is thermally stable.
 In 1888 DUNLOP’s invention of pneumatic tyre gave boost to the demand for rubber
during the world wars I and II

TYPES OF RUBBER
Rubbers can be divided into following types
1) Natural rubber.
2) Synthetic rubber.

NATURAL RUBBER
Large quantities of rubber are produced by tropical and semi tropical countries like Malaysia,
Indonesia, Thailand, Srilanka, South America and India.

Processing Of Natural Rubber:

Natural rubber consists of basic material latex which is polymerized form of Isoprene
(2-methyl-1, 3-butadiene). By making small incisions on the bark of rubber trees, like
Heaveabrasiliensis and Guayule, the rubber latex can be collected into small vessels. The rubber
latex is a milky colloidal emulsion, at regular intervals of time(about 6 months), tapping(removal
of bark) is necessary throughout the life time of the tree which is 40 years.
The latex consists of the following components approximately

Water 55%-70% Rubber30%-40% Resins1.5%-2% Proteins1.5%-3%

Sugar1%-2% Ash0.5%-1%

Latex is diluted to contain 15%-20% of rubber, after dilution it is filtrated to eliminate

any that may be present. It is then coagulated in a tank filled with 1Kg acetic acid or formic acid
per 200Kg of rubber. Sometimes ammonium or potash alum are also used as coagulants. After
washing and drying, the coagulum is subjected to any of the following methods.

(1) Crepe rubber:

It is prepared by adding little amount of Sodium bisulfate (NaHSO3) to bleach the rubber
and then it is passed through a creping machine, so that coagulum is rolled into sheets of about
1mm thickness, the sheet possess a rough surface resembling crepe paper. The sheet is then dried
at 50oC in air for 5-10 days.
(2)Smoke Rubber:
It is made by eliminating the bleaching with Sodium Sulphite (Na2SO3) and rolling the coagulum
into thicker sheets having ribbed pattern on its surface, this surface prevent them from adhering
together , the sheets are then dried in smoke houses at about 50oC in smoke from burning wood
or coconut shells. The rubber sheets thus obtained are amber in colour.

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Natural rubber can also be called as raw rubber or crude rubber.

(i) Raw or crude rubber becomes soft and sticky in hot summer, while in cold weather it becomes
hard and brittle.
(ii) It is weak, because of its low tensile strength (200Kg/cm2).
(iii) It is attacked by oxidizing agents (HNO3, CON.H2SO4 etc).
(iv)In organic solvents it undergoes swelling and gradual disintegration.
(v) It possesses tackiness.
(vi) Due to its oxidation in air it is not durable.

VULCANIZATION
In 1839, CHARLES GOOD YEAR discovered that by heating natural rubber with
Sulphur (Vulcanization) converts it into a more useful form, which is thermally stable.
Vulcanization is the transformation of rubber from plastic state into an elastic state. In
this process Sulphur is added to harden the rubber.
This process consists of introducing cross links in rubber matrix.

(i)When a mixture of 100 parts of rubber with 5to 8 parts of Sulphur is heated at 140oC for
3to 4 hours, vulcanization is completed.
(ii)When rubber is mixed with 14 to 18 parts of Sulphur and the mixture is vulcanized, a low
tensile strength is obtained.

(iii)If Sulphur content is increased 30% to 50% the rubber becomes hard with a low elongation
and high tensile strength.
The formed product is known as EBONITE.

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 The different vulcanizing agents are Sulphur, Sulphur mono chloride, antimony Penta
Sulphide etc.

Sulphur combines chemically at the double bonds of different rubber molecules.

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S.NO PROPERTY RAW RUBBER VULCANIZED
RUBBER
1 Tensile strength 200Kg/cm2 2000Kg/cm2

2 Resilience Good Very good

3 Useful temperature 10oC to 60oC -40oC to 100oC

4 Resistance to moisture, Poor Good

oxidation and abrasion.

5 Resistance to organic solvents Poor Large but limited

6 Tackiness Marked Slight

7 Elasticity Very high Low

8 Percentage elongation at break 1200 800

Applications:
1)The ordinary soft vulcanized rubber may contain 3%-5% Sulphur is used for tyres.
2)The hard rubber may contain 30% Sulphur is used for a battery case.

SYNTHETIC RUBBERS
Synthetic rubbers are also called as ELASTOMERS.

Elastomer is a synthetic rubber, which is a polymer that can stretch to at least twice in length,
but it returns to its original position as soon as stretching force is released.
The following are the synthetic rubbers.

(1)Buna-S (2) Thiokol (3) poly urethane

(1)Buna-S (or) SBR (or) Styrene -butadiene rubber (or) GR-S:

It is prepared by the co-polymerization process of 1,3-butadiene (75%) and styrene (25%)

in an emulsion system at 50oC in the presence of cumene hydro peroxide as catalyst.

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 If the emulsion polymerization is carried out at low temperatures (-18oC to 5oC) in the
presence of Redox catalyst (cumene hydro peroxide + Dextrose) in the presence of iron salt, the
resultant SBR is known as COLD RUBBER.

Since SBR contains double bonds, vulcanization can be done in the same way as natural rubber
either by Sulphur or Sulphur mono chloride.

Properties:

(i) High abrasion resistance and high load bearing capacity

(ii) Good electrical properties but not outstanding.
(iii) Low resilience than natural rubber.
(iv) Low oxidation resistance, it gets readily oxidizes.

Applications:
Motor tyres, Shoe soles, Foot wear components, Insulation wires, Cables, Carpet baking,
Gaskets, Pneumatic tyres, Chewing gum.

(3)Thiokol (or) Poly Sulphide rubber (or) GR-P:

It is prepared by the condensation polymerization of sodium poly Sulphide (Na2Sx) and

ethylene dichloride.
In these elastomers, Sulphur forms a part of high polymer chain.

S S

Cl-CH2-CH2-Cl + Na-S-S-Na + Cl-CH2-CH2-Cl

(Ethylene dichloride) (Sodium
poly Sulphide)

-NaCl Condensation polymerization

SS

(CH2-CH2-S-S-CH2-CH2) n (Thiokol)

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It can be vulcanized with metal oxides such as Zinc oxide. Vulcanization with Sulphur is not
possible because of the absence of double bonds.

Properties:
(i)Outstanding resistance to Oxygen, Ozone and Sunlight.
(ii)It has offensive mercaptan like odor which restricts its use.
(iii)It has excellent resistance to swelling and disintegration by organic solvents, gasoline,
kerosene, and lubricating oils.
(iv)It has lower tensile strength, under continuous pressure it tends to lose shape.
(v)It has poor resistance to heat and abrasion.

Applications :
Printing rollers, containers for transporting solvents, solid propellant fuels for rockets etc.,
manufacture of oil hoses, gaskets, in the preparation of balloons.

Poly Urathane:

URETHANE LINKAGE

Preparation

Poly urathanes are prepared by the re-arrangement polymerization of di or poly iso-cyanate with
di or poly hydric alcohol and they contain the characteristic urethane linkage.
The reaction of 1,4-butane diode with 1,6-hexane di iso-cyanate gives a crystalline poly urethane
know as perlon-U. Its IUPAC abbreviation is P.U.R (Poly urathane rubber).

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Properties:
I. They are highly resistant to oxidation.
II. They have good resistance to many organic solvents. But are attacked by concentrated
and hot acids.
III. In comparison with nylons poly urathane’s are less stable at elevated temperatures.
IV. Excellent abrasion resistance, good elasticity and hardness.

Applications:
I. These are used for coatings of gymnasium and dance floors.
II. These are used for making swim suits and foundation garments.
III. Flexible foamed poly urathane’s are used for making car interior and furniture cushions.
IV. They are also used for pillows and matrices.

Fiber reinforced plastics (FRP):

These are produced by reinforcing a plastic matrix with high strength fiber materials such
as glass, graphite, alumina, carbon, boron, beryllium and aromatic polyamide. The natural fibers
such as sisal, asbestos are also used for reinforcement. Depending on the desired properties of
the final reinforced composite, the nature of the fiber used is decided.

Properties:
I. High specific strength ( Tensile strength/ specific gravity)
II. High specific modulus.(modulus of elasticity)

Applications:
I. Spacecrafts.
II. Aero planes
III. Boat nulls
IV. Acid storage tanks
V. Motor cars
VI. Building materials

Types of FRP:
I. GFRP (Glass fiber reinforced plastic)
II. CFRP (Carbon fiber reinforced plastic)

Glass fiber reinforced plastic (GFRP):

These are basically made by mixing silica sand, lime stone, folic acid and minor
ingredients. The mixture is heated until it melts it about 1260ºC. The molten glass is then
allowed to flow through fine holes in a platinum plate. The glass strands are cooled, gathered and
wound. The fibers are drawn to increase the directional strength. These filaments are finer than
cotton or silk threads. The common plastic resins are used to prepare GFRP are polyesters,
apoxy, silicon, melamine, vinyl derivatives and poly amids.

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Properties:

I. Lower densities
II. Higher tensile strength
III. High Impact resistance
IV. Excellent chemical and corrosion resistance.

Applications:
I. Industrial flooring
II. Storage tanks
III. Ship building.
IV. Automotive parts

Carbon Fiber reinforced Plastic (CFRP):

Glass fibres suffer from low elastic stiffness (of course, possess excellent strength
characteristics) and limited char strength (relatively low melting point) for ablative applications.
This necessitated the use of carbon fibres in place of glass fibres for ablative and structural
applications. These are produced from certain precursors-polyacry1onitrile (PAN) fibre and
viscose rayon fibre. The work on manufacture of carbon fibre from jute and pitch which are
abundantly available in India has also been reported recently. M/s HERCULES, USA is a well
known manufacturer of carbon fibres. Carbon fibres have strength and modulus vastly superior
to glass fibres. Although, they
are at present much more costly, they will undoubtedly lead to further deveIopment of composite
materials for more exciting applications. In view of their superior heat stability, carbon fibres can
be used for reinforcing ceramics, metals, and plastics, giving engineers and technologists a
completely new range of materials.

Bullet proof plastic (kevlar) : It is also known as poly (p-phenyleneterephtalamide). It is a poly

amide. This is a type of strong but optically transparent material. It is usually constructed using poly
carbonate thermoplastic and laminated glass, upto 1.25” thick.
One-way bullet proof glass is usually made up of two layerse bullet, a brittle layer on the outside and a
flexible layer on te inside. A bullet fired from out side hits the brittle layer first, this absorbs the kinetic
energy of the bullet and slows it down, when it hits the flexible layer it is stopped.

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CONDUCTING POLYMERS:
A polymer which conducts electricity is called conducting polymer. Conducting
polymers always store and release charge through redox processes.
Eg :- Polyaniline, polyacetylene, polypyrrole, etc
They are classified into two types: Intrinsically conducting polymers & Extrinsically conducting
polymers
1. Intrinsically conducting polymers: These have extensive conjugation in the backbone which
is responsible for conductance. These polymers can be divided into…
a) Conducting polymers having conjugated π – electrons in the backbone: Conjugated
polymers are organic macromolecules that are characterized by a backbone chain of alternating
double- and single-bonds. Their overlapping p-orbitals create a system of delocalised π-
electrons, which can result in interesting and useful optical and electronic properties. But since
the valence band and the conduction band are separated by a significant band gap, conductivity
of these polymers is not very high.
eg :- polyacetylene, polyaniline, poly pyrrole, etc.

b) Doped conducting polymers: Conductivities of polymers having conjugated π – electrons in

the backbone can be increased by creating either +ve or –ve charges on the polymer backbone by
oxidation or reduction. This process is called doping. It can be done in two ways.
P – doping (Oxidative doping): It involves treating the conjugated polymer with a Lewis acid
like FeCl3 or iodine vapour, thereby oxidation takes place and +ve charges are created on the
back bone.

n – doping (Reductive doping): It involves treating the polymer with a Lewis base like RNH2
thereby reduction takes place and -ve charges are created on the polymer back bone.

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2. Extrinsically conducting polymers: Some of the polymers conduct electricity due to
externally added ingradients to them. They are of two types.
a) Conductive elements filled Polymers. b) Blended conducting polymers.

a) Conductive elements filled polymers: In these polymers, the polymer acts as a ‘binder’ and
holds the conducting element added so that the polymer becomes a conductor. Examples of
conductive elements are carbon black, metallic fibers, metallic oxides etc. Minimum
concentration of conductive filler which should be added so that polymer starts conducting , it is
known as percolation threshold.
b) these polymers posses reasonably good bulk conductivity, generally low in cost, light in
weight, mechanically durable, strong and are easily processable in different forms, shapes and
sizes.

b).Blended conducting polymers: These polymers are obtained by blending a conventional

polymer with a conducting polymer. The polymer thus obtained has good chemical, physical,
electrical properties and mechanical strength.
Ex; 40% pyrrole when blended with a conventional polymer, the combination gives conducting
polymer with good impact strength
Applications of conducting polymers:
They are used in rechargeable batteries, analytical sensors of pH, O2, NO2, SO2, NH3 etc.
Used in telecommunication systems, solar cells.
Used in making electronic display, optical fibres, ion exchangers, etc.
Used in hospital operating theaters.

Biodegradable polymers:
A polymer that can be decomposed by enzymatic action of naturally occurring micro
organisms and bacteria is called a biodegradable polymer. Biodegradation is the chemical
breakdown of materials by physiological environment. Some polymers undergo degradation
when exposed to moisture, heat, oxygen, ozone and micro organism. Generally materials
obtained from plants, animals and other living organism and synthetic materials similar to plant
and animal material undergo degradation by microorganism.
These organic materials can be degraded either aerobically or anaerobically. Like hydro
biodegradable polymers, oxo biodegradable polymers.
The biodegradable polymers are classified as..
Naturally occurring biodegradable polymers: these are devided into
(1)Polysacharides
Eg: starch and cellulose

(2)proteins
Eg: gelatin, casein, silk, wool.

(3)polyesters
Eg: polyhydroxy alkanoalis

(4) others eg: lignin, shellac, natural rubber.

It is assumed that these natural polymers are “beautiful for environmental degradation”.

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Synthetic biodegradable polymers:
There are many polymers produced from petrochemical or biological sources that are
biodegradable.
Eg: dissolving suture material used in medical field and biopolyesters.

There are many biodegradable synthetic resins produced as listed below:

(1) poly alkaline esters
(2) poly lactic acid (PLA) and its copolymers
(3) polyamide esters
(4) poly vinyl esters
(5) poly vinyl alcohol
(6) poly anhydrides.
.
Properties: These are non – toxic, PLA is high strength, PHA is thermoplastic and good
resistance to moisture, good elasticity.
Applications: Medical implants like surgical sutures, wound dressings, tissue regeneration,
screws, pins, bone plating systems, surgical mesh’s, controlled drug delivery and gene delivery,
nanotechnology, agriculture, waste management as compost bags, food industry as a packing
material, food storage, etc.

BIOPOLYMERS:
Biopolymers are natural polymers produced by the cells of living organisms.
Biopolymers consist of monomeric units that are covalently bonded to form larger molecules.
There are three main classes of biopolymers, classified according to the monomers used and the
structure of the biopolymer formed. Those are Polynucleotides, Polypeptides and
Polysaccharides.
Polynucleotides, such as RNA and DNA, are long polymers composed of 13 or more
nucleotide monomers.
Polypeptides and proteins (poly amides) are polymers of amino acids and some major
examples include collagen, actin, and fibrin.
Polysaccharides are linear or branched polymeric carbohydrates and examples include starch,
cellulose and alginate.

There are two types of biopolymers, one is obtained from living organisms and another one is
produced from renewable sources.
Applications: Biopolymers have applications in many fields including the food industry,
manufacturing, packaging, water purification and biomedical engineering.

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BIOMEDICAL POLYMERS: Biomedical polymers are a special class of materials that are
designed to work in harmony with the body, and for the basis of a growing number of artificial
organs and replacement parts intended for fitting into the human body. Biomedical polymers are
the materials that can be implanted in the body to provide special 14 functions or in diagnostic,
surgical and various therapeutic applications without causing adverse effect on blood and other
tissues. They are tailor-made or modified at will suit specific body functions.
Polymers used for medical application should be biocompatible.
Ex: Poly caprolactone, Poly glucolide, Poly lactides, PHBV
Applications of biomedical polymers:
1. PGA (Poly Glucolide) - Used to make mesh type networks. It is semi-crystalline.
2. PLLA (Poly lactides) - Used to make bio-screws, bio-anchors etc. It is crystalline polymer.
3. PCL (Poly caprolactone) – Used for long term drug delivery. It has good elongation (>700%)
4. Poly lactide-co-glycolide- Used for sutures, used to regenerate nervous tissues.
5. PHBV- Used to make capsule covers.
6. PTMC (Poly trimethylene carbonate) – Used for soft tissue regeneration.

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