Text Books

• Engineering Chemistry, Jain P.C.; Jain M., Dhanpat Rai and Sons, Delhi, 17th
Edn. 2015.
• Engineering chemistry, Wiley India Pvt. Ltd., 2nd Edn. 2014.

Reference Books

• Chemistry in Engineering and Technology, Kuriacose J.C.; Raja R. J., Vol. I/II
McGraw Hill Education, 2001.
• Materials Science for Engineering Students, Fischer T., Academic Press,
London, 2009.
• Fuel Science &Technology, James G Speight; Marcel Dekker, New York, 1990
Syllabus
Module: Advanced materials and polymers: Advanced materials and polymers: Introduction, Definition,
classification of polymers – based on origin, thermal behaviour, Polymerization reactions and applications,
Tacticity. Functionality, Degree of polymerization, Co-polymerization – alternating, random, block and graft
polymers. Mechanism of free radical polymerization and ionic polymerization. Mechanism of coordination
polymerization, Condensation polymerization reactions, Glass transition temperature & factors affecting it.
Molecular weight of polymers, Number average and weight average molecular weights, Numerical problems.
Preparation, properties and applications of Polythene (LDPE and HDPE), Nylon(6:6, 6, 6:10, 11), PF resins and
Polyester. Natural rubber, Processing of Natural Rubber, Vulcanization, Compounding of rubber; Synthetic
Rubber: Buna-N, Buna-S. Composites, biomaterials, their properties and applications..

Module – Advanced Materials and Polymers

Module 1: Advanced materials and polymers: Introduction, Definition, classification of polymers – based on origin, thermal behaviour,
Polymerization reactions and applications, Tacticity. Functionality, Degree of polymerization, Co-polymerization – alternating, random, block
and graft polymers
Mechanism of free radical polymerization and ionic polymerization. Mechanism of coordination polymerization, Glass transition
temperature & factors affecting it.
Molecular weight of polymers, Number average and weight average molecular weights, Numerical problems.

Preparation, properties and applications of Polythene (LDPE and HDPE), Nylon (6:6, 6, 6:10, 11), PF resins and Polyester. Natural rubber,
Processing of Natural Rubber, Vulcanization, Compounding of rubber; Synthetic Rubber: Buna-N, Buna-S.

Composites and biomaterials: properties and applications

 Development of civilization

Stone age → Bronze age → Iron age → Polymer age

A world of polymer
 What are polymers?
A polymer is a high molar mass molecular compound made up of many repeating chemical units (Monomers).

The word ‘polymer’ comes from the Greek words poly (meaning ‘many’) and meros
(meaning ‘parts’).

The number of repeating units in chain formed in a polymer, is known as the degree of
polymerization. It may be hundreds/thousands/ or many more

The process by which monomers are transformed into polymers is called polymerization.
 Few Queries???

• What are some of the polymers that you encounter every day?
Sandwich bags, carpets, nylon stockings, stackable chains, milk
cartons, etc.
• Why do different polymers have different properties?
They have different chemical compositions (different monomer units),
different structures, different ways of being fabricated, etc.
• Imagine samples of LDPE (sandwich bag, squeeze bottle) and HDPE
(milk jug, grocery bag). What are some of the differences in the physical
properties of these substances?
LDPE – more transparent, flexible, waxy
HDPE – more opaque, rigid, non-waxy
 DEFINITION:
The word polymer is derived from the two greek words
poly and mers

many parts or units

e.g.
mer mer mer
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH 3 H CH 3 H CH 3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Polymers are macro molecules formed by linking smaller

molecules repeatedly, called monomers.
Examples:
Polyethylene is formed by linking a large number of
ethylene molecules
H H
H H
n C C Polymerisation
C C
H H n
H H
Ethylene polyethylene

polystyrene is formed by linking styrene molecules

H H H
H
n C C Polymerisation
C C
H n
H
styrene polystyrene
Drawing polymers – shorthand formulae
Polymers contain thousands of molecules, so how can their structures be easily drawn?

Part of the polymer molecule can be drawn:

A better way is to show a shorthand formula:

The ‘n’ means that the polymer contains a very large number of
the repeating unit shown in the brackets.
Degree of Polymerization
The main characteristic of polymer which determines the
physical properties of polymer materials is defined as the
degree of polymerization. A large molecule is made up of
rings or chains of linked repeating subunits referred to as
monomers called a polymer. The number of monomeric
units present in a polymer is known as the degree of
polymerization. They generally have high boiling and
melting points.
Degree of polymerization = Mw/Mo
where Mw is the average molecular weight of the polymer
and Mo is the molecular weight of the repeating unit
or monomer.
How to calculate the degree of polymerization?
1.Write the chemical formula of the polymer.
For example, let us consider tetrafluoroethylene. Its chemical formula is written as -
(CF2-CF2)n.
2. Evaluate the molecular weight.
To calculate the molecular weight follow the sequence below:
 Multiply the atomic mass of carbon element by the number of carbon atoms in the
monomer
 Multiply the atomic mass of fluorine element by the number of fluorine atoms in
the monomer
 Therefore, the molecular weight of tetrafluoroethylene is 12 x 2 + 19 x 4 = 100.
3. Divide the molecular mass of the polymer by the molecular weight of the monomer.
For example, if the molecular mass of a polymer of tetrafluoroethylene is 1,20,000,
then its degree of polymerization is calculated as
DP = Mw/Mo = 1,20,000 / 100 = 1,200.
Therefore, the degree of polymerization is 1,200.
Homopolymer is a polymer made up of only one
type of monomer
( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n
Teflon Polyethylene Cl
PVC

Copolymer is a polymer made up of two or more

monomers

( CH CH2 CH2 CH CH CH2 )n

Styrene-butadiene rubber
Copolymers

two or more monomers polymerized together

A B

Alternating A and B alternate in polymer

chain

Block large blocks of A units alternate

with large blocks of B units

Random A and B randomly positioned

along chain

Graft chains of B units grafted onto

A backbone
Classification of Polymers:
1. Based on origin:

A. Natural Polymers

These occur in nature in plants and animals and are very essential for life. For e.g., proteins, nucleic acids,
Starch, cellulose, protein, silk, wool and natural rubber are some natural polymers.

B. Synthetic Polymers

Synthetic polymers are man-made polymers which include fibers like teflon and dacron, synthetic rubbers,
Polyethylene, Polystyrene, polyvinylchloride, nylone, polyester
2. based on polymerization reactions:

Based on the mode of polymerization, polymers are

classified as:

1. Addition polymers
2. condensation polymers
Addition polymers
Addition polymers are formed when monomer units are separately added to form long chains without
elimination of any by-product molecules. These polymers are formed by reactions between monomer
molecules possessing multiple bonds.
Example: Ethylene undergoes polymerization to form polythene.

The empirical formula of the monomer and polymer are the same. Other examples:
Polypropylene is an addition polymer of propylene.

Styrene-butadiene rubber is an addition polymer formed by addition reactions between butadiene and
styrene.
Condensation polymers
Condensation polymers are formed when the monomers containing active functional groups (generally
two), which react together with the elimination of a small molecule like water, ammonia, alcohol etc.

Examples: Nylon-66, polyester, Bakelite etc.Nylon-66 is formed by condensation between

hexamethylene diamine and adipic acid as shown below:
3. Based on thermal behavior
The response of a polymer to mechanical forces at elevated temperature is
related to its dominant molecular structure.
Thermoplastics and Thermosets are the 2 categories.

1. A thermoplastic is a polymer that turns to a liquid when heated and

freezes to a very glassy state when cooled sufficiently. Thus thermoplastics
can be moulded on heating. Most thermoplastics are high-molecular-weight
polymers whose chains associate through weak Van der Waals forces
(polyethylene); stronger dipole-dipole interactions and hydrogen bonding
(nylon).
These polymers have no cross-linking between chains. Examples:
Polyethylene, polystyrene etc.
2. Thermosetting polymers
Thermosetting polymers made from relatively low molecular mass semi-fluid
polymers which when heated in a mould forms an insoluble hard mass which
is infusible. This is due to extensive crosslinks between the different polymer
chains forming three dimensional network of bonds.
Example: Bakelite and melamine
18
 weak intermolecular forces
–
these let the chains slide past
each other

Plastics made of these polymers are stretchy and have a

low melting point. They are called thermoplastic polymer.
 strong intermolecular
forces
(cross-links) –
these hold the chains firmly in
place

Plastics made of these polymers cannot be stretched, are rigid and have a high melting point. They are
called thermosetting plastics (or ‘thermosets’).
4. Classification of polymers based on applications:

1. Elastomers: a natural or synthetic polymer having

elastic properties, e.g. rubber.

2. Resins: Resin is a natural or synthetic compound that

begins in a highly viscous state and hardens with
treatment. Eg. PF resins , epoxy resins

3. Fibers: a thread or filament from which a vegetable

tissue, mineral substance, or textile is formed. Eg. Nylon

4. Plastics : Organic materials of high molecular weight,

which can be moulded into any desired form, when
subjected to heat and pressure in the presence of a
catalyst eg. Bakelite, pvc.
Elastomers are viscoelastic polymers with long chains of molecules
that are held together by weak forces. They can stretch to at least
twice their length under low stress and return to their original shape
when the stress is released.
Uses
Elastomers are used in many applications, including rubber bands
and industrial seals.
Following are examples of elastomers with their applications:
Natural rubber: These are used in the automotive industry and in the
manufacture of medical tubes, balloons, adhesives.
Polyurethanes: These are used in the textile industry for
manufacturing elastic clothing like lycra.
Polybutadiene: These are used for providing wear resistance in
wheels of vehicles.
Silicone: These are used in the manufacture of medical prostheses
and lubricants as they have excellent chemical and thermal
resistance.
Neoprene: These are used in the manufacture of wet-suits and in
industrial belts.
Resins: Resin is a natural or synthetic compound that
begins in a highly viscous state and hardens with treatment.
Eg. PF resins , epoxy resins
Structure
Polymers are large molecules made up of repeating
structural units connected by covalent chemical bonds.
Resins are viscous substances that are a subset of
polymers.
Sources
Resins can be derived from both natural and synthetic
sources. Synthetic resins are man-made polymers.
Uses
Epoxy: A coating material made from polymer resins and
hardening chemicals that creates a rigid plastic-like surface.
Fibers: a thread or filament from which a vegetable tissue,
mineral substance, or textile is formed. Eg. Nylon
Fiber polymers have many properties, including:
•High strength-to-weight ratio
•Stiffness
•Resistance to corrosion, wear, impact, and fire

Plastics : Organic materials of high molecular weight,

which can be moulded into any desired form, when
subjected to heat and pressure in the presence of a
catalyst eg. PVC.
 Tacticity- Plane representation of polypropylene
polymer
1. Isotactic polymers
H H H H H
CH2 C CH2 C CH2 C CH2 C CH2 C
Functional groups on the
CH3 CH3 CH3 CH3 CH3 same side of the main carbon
skeleton

2. Syndiotactic polymers

H CH3 H CH3 H
Functional groups arranged in
CH2 C CH2 C CH2 C CH2 C CH2 C the alternate fashion of the
main carbon skeleton
CH3 H CH3 H CH3

3.Atactic polymers

H CH3 CH3 H H
Functional groups arranged in
CH2 C CH2 C CH2 C CH2 C CH2 C a random manner around the
main carbon skeleton
CH3 H H CH3 CH3
Tacticity : the orientation of monomeric units in a polymer molecule
It affects the physical properties of polymers.

R groups on same
side of chain
Isotactic

R groups alternate
from side to side
Syndiotactic

R groups disposed
at random
Atactic
Tacticity is a property of polymers that refers to the
arrangement of pendant groups along a polymer's
hydrocarbon chain.
Importance of tacticity
The practical importance of tacticity lies in its impact on the
physical properties of a polymer. The regularity of the
polymer's macromolecular structure determines whether it
exhibits rigid, crystalline long-range order or flexible,
amorphous long-range disorder. A clear understanding of a
polymer's tacticity also aids in predicting its melting
temperature, solubility in solvents, and mechanical
properties.
 Functionality
The number of reactive sites present in a monomer is called functionality

1.

O
Linear chain polymer is formed if the functionality of the
HO C CH2 NH2
monomer is only two (Bifunctional)

2. Ex. Glycine

O
O
HO C CH2 NH2
OH CH2 CH C OH
NH2
Glycine
Ex. Serine
O
OH CH2 CH C OH Cross linked chain polymer is
formed if the functionality of the
NH2 monomer is more than two
(multifunctional)
Functionality

The number of bonding sites in a monomer is referred

as its functionality

Bifunctional: eg. alkene

Trifunctional: eg. Monomethylsilicon trichloride (MeSiCl3)

Polyfunctional: eg. Silicon tetrachloride (SiCl4)

 Functionality

the number of reactive sites or bonding sites

Some mono functional hydrocarbons

Alcohols Methyl alcohol

Ethers Dimethyl Ether

Aromatic
hydrocarbons Phenol
Some bi functional hydrocarbons

Terephthalic acid

adipic acid (hexanedioic acid)

ethylene glycol

1,6-hexanediamine
Ethylene is considered to be bifunctional

H H H H

C C C C

H H H H

H H

C O C O

H H
General method of polymerization
Two major methods generally used for preparing polymers:

1. Addition polymerization

2. Condensation polymerization

Addition Polymerization
It is a reaction that yields a product, which is an exact multiple of the original monomeric molecule. Such a
monomeric molecule usually contains one or more double bonds, which by intermolecular rearrangement
may make the molecule bifunctional. The addition polymerization reaction must be instigated by the
application of heat, light, pressure or a catalyst for breaking down the double covalent bonds of monomers.

Condensation polymerization
May be defined as a reaction occurring between simple polar-group-containing monomers with the formation
of polymer and elimination of small molecules like water, HCl etc.

Examples: Nylon-66, polyester, Bakelite etc.Nylon-66 is formed by condensation between hexamethylene

diamine and adipic acid as shown below:
Mechanism of addition polymerization:

1. Free radical polymerization

2. Cationic polymerization

3. Anionic polymerization

4. Coordination polymerization or Ziegler-Natta

polymerization
1. Free redical polymerization mechanism:
(i) Initiation step is considered to involve two reactions. The first step is
the production of free radicals by homolytic dissociation of an initiator
to yield pair of radicals.(benzoylperoxide, tert-butylperoxide, AIBN)

I 2R
(Initiator) Free radicals
Azobisisobutyronitrile

The second part of the initiation steps involves the reaction of this radical
with first monomer unit (M) to produce chain initiating species

O
O
O
R + M M1 O
monomer
(ii) Propagation step consists of the growth of M1 free radical by successive reaction of
large numbers of monomers molecules

M1 + M M2
monomer

M2 + M M3
monomer

M3 + M M4
monomer

In general
Mn + M Mn+1
monomer
Termination steps
a)Termination by coupling
b) Termination by disproportionation

Termination by coupling

Termination by disproportionation
Free redical polymerization mechanism:
 IONIC CHAIN POLYMERIZATION
Ionic polymerization is more complex than free-radical polymerization

Whereas free radical polymerization is non-specific, the type of ionic

polymerization procedure and catalysts depend on the nature of the substituent
(R) on the vinyl (ethenyl) monomer.

Cationic initiation is therefore usually limited to the polymerization of monomers

where the R group is electron-donating This helps stabilize the delocalization of
the positive charge through the p orbitals of the double bond

Anionic initiation, requires the R group to be electron withdrawing in order to

promote the formation of a stable carbanion

Using catalyst, not initiator

Highest reaction rate

Termination step is just disproportionation

Environment must be pure

Ionic Polymerization
 2. Cationic Polymerization
• Involves the polymerization of monomers that have
strong electron-donating groups, eg, propylene etc.

• typical initiators (catalysts) are compounds with electron

acceptor properties eg. AlCl3, SnCl4, TiCl4, and BF3

• Steps of polymerization
i) Initiation : AlCl3 initiates the reaction and carbocation is
formed

ii) Propagation

iii) Termination
3. Anionic Polymerization
Involves the polymerization of monomers that have strong electron-withdrawing
groups, eg, acrylonitrile, vinyl chloride, methyl methacrylate, etc.

typical catalyst include KNH2, n-BuLi, and Grignard reagents such as alkyl
magnesium bromides

If the monomer has only a weak electron-withdrawing group then a strong base
initiator is required, eg, butyllithium; for strong electron-withdrawing groups only a
weak base initiator is required, eg, a Grignard reagent.

Steps of polymerization
i) Initiation: KNH2 initiates the reaction and carbanion is formed
ii) Propagation
iii) Termination