Fundamentals of Polymer Engineering

Week-1

Lec. Ayesha Raza

SCME, NUST
Plastic comes from Greek word Plastikos
 POLYMER
Polymer is a molecule made up of smaller molecules
that are joined together by chemical bonds
 Degree of Polymerization
The degree of polymerization, or DP, is usually defined
as the number of monomeric units in a polymer

Calculate the degree of polymerization for

• A low density polyethylene with a molecular weight
of 20,000 amu
Answer: 713
• A high density polyethylene with a molecular weight
of 30,000 amu
Answer: 10,700
Bonding in Polymers
Bulk properties

•Molecular properties
•Collective properties
Bulk Properties
When many molecules of same types are joined together then the
properties are measured for the large collection of molecules. Known
as Bulk properties

Bulk properties depends upon

• Molecular properties: Depends upon molecular nature of materials
such as chemical reactivity
• Collective properties: Depends upon the interaction of the
molecules such as crystal formation
Resin
Resin is a polymer that has not yet been formed
into final useful shape
 Bonding in Polymers
Bonding
Bonding occurs when two or more atoms having appropriate chemical
reactivity come into close proximity resulting in an attraction between the atoms.

In energy term, attraction is the result of a lowering of the energy of the system.
 Primary Bonding
• Ionic Bonding
Primary Bonding
 Primary Bonding
• Metallic Bonding
Primary Bonding
 Primary Bonding
• Covalent bonding
Primary Bonding
 Secondary Bonding
• Several types of atomic attraction exist that
are much weaker than the ionic, metallic and
covalent bonds. These weaker attractions are
called secondary bonds
• Exist between molecules, rather than within
molecules
• Example: Van der Waals forces, Hydrogen
bonding, Dipole dipole forces etc
 Bonding in Polymers
1) Covalent Bonding 2) van der Waals Bonding/
Secondary Bonding/Hydrogen Bonding
 Hydrocarbon Molecules
Normal Alkane Hydrocarbons

n-number of CH2 groups----

 Hydrocarbon Molecules

Ethylene Acetylene

 Combination of hydrogen and carbon

 Unsaturated and saturated bonds

 Hydrocarbon Molecules

A Polymer is made up of very large molecules, which are long chains of repeated smaller
units joined together.

These smaller units are known as monomers.

 From Smaller to Bigger Molecules

Chemical structure of Polyethylene (PE)

It is generated from the structure of ethylene monomers

Melting point of Polyethylene (PE) = 140 oC

The greatest difference between PE and WAX lie in their mechanical behavior

WAX is a brittle solid while PE is a tough plastic.

 From Smaller to Bigger Molecules
The greatest difference between PE and WAX lie in their mechanical behavior.

WAX is a brittle solid while PE is a tough plastic.

 From Smaller to Bigger Molecules
PE is a tough plastic solid because

1) Its chains are long enough to connect individual stems together by chain folding.
2) The chains also wander between lamellae, connecting several of them together.

Strong chains connection between the lamellae

as well as within the lamellae occurs

Additionally, certain portion of the PE chains are

Amorphous, imparting flexibility to the entire
material

Long chain length allows for entanglements,

which helps in holding the whole materials
together under stress
 Role of Entanglements

Entanglements are simply the mutual wrapping of polymer chains around each other.

Higher MW imply longer polymer chains and longer polymer chains imply more entanglements.

When the polymers are entangled, they resist sliding over each other due to the generation of
secondary forces among them.

Thus entanglements tend to keep the molecular chains associated together.

 Classification of Polymers
Polymers are classified on the basis of

Intermolecular forces
Molecular structure
Type of ‘mer’ in the main chain
• On the basis of inter-molecular forces, It is classified into three
main categories;
 Classification of Polymers
 On the basis of inter-molecular forces, It is classified into three main categories;

1) Thermoplastic Polymers

• Thermoplastics are solid at room temperature that are melted or softened by heating, placed into a
mold or other shaping device, and then cooled to give the desired shape.
• It can be reshaped at any time by reheating the part
• Examples: Polyamide, Polystyrene etc

2) Thermosetting Polymers

• Thermosets can be either liquids or solids at room temperature that are placed into a mold and
then heated to cure (harden), thus giving the desired shape and solids properties.
• Thermosets cannot be reshaped by heating
• Examples: Polyester etc
Elastomers
• Cross linked rubbery polymers
• Can be stretched easily to high extensions
(3x to 10x their original dimensions) and rapidly recover their
original dimensions when the applied stress is released
• Low cross linked density
Cross linking of polymer chains
Examples of thermoplastics
Examples of thermosetting plastics
 Classification of Polymers
On the basis of skeletal structure, polymers are classified into three main categories

 Linear Polymers: Monomeric units are joined in the form of long straight chains

 Branched Polymers: have side chains or branches of significant length which are bonded
to the main chain at branch points

 Network Polymers: have three dimensional structures in which each chain is connected to
other chains by covalent bonds. They are characterized by cross link density
• Non- linear polymers may be formed by polymerization, or
can be prepared by linking together pre-existing chains

• Variation in the skeletal properties give rise to major

differences in properties. For example linear polyethylene
has melting point about 20°C higher than that of branched
polyethylene
 Classification of Polymers
On the type of ‘mer’ in the main chain,

Homopolymers: Only one type of ‘mer’ units are repeating throughout for the
formation of polymers

Blending polymers: Two or more types of ‘mers’ are combined by physical bonding

Copolymers: Two or more types of ‘mers’ are combined by chemical bonding

Example: Natural Rubber

 Classification of Copolymers
Random Copolymer
• There is no pattern in the order of the monomers along the polymer chain

Alternating Copolymer
• Monomers have regular, alternating sequence that can be represented as
X-Y-X-Y-X, etc

Block Copolymer
• Long sequence of one monomer join long sequence of other monomer to
form the chain

Graft Copolymer
• A polymer chain is formed by one monomer and then a chain of other
monomer is attached as a branch to the main backbone
Classification of Copolymers
• Different types of co-polymer have different properties. On the
right, the medical vials are made of a random co-polymer of ethene
and propene which give a flexible and clear material. Covering of
the cable is a block co-polymer of the two alkenes, giving a very
tough material with rubber-like properties
 Nomenclature for Copolymer

An alternating copolymer of styrene and maleic anhydride is named as

Poly[ styrene-alt-maleic anhydride]
AABB copolymer of styrene(A) and isoprene(B) is named as
Polystyrene-block-polyisoprene
Rubber

Polybutene-block polystyrene-block polybutene

Recognition of Polymers:
1) Aliphatic Polymers: Hydrocarbons based on linear chain structures e.g. PE, PP

2) Aromatic Polymers: Hydrocarbons that contain benezene or naphthalene ring in the

backbone of the chain e.g. PET, PTT, PTN

O C O
O O

O C C O (CH2)3 (CH2)3 O C

n
n
 Quick Quiz

What is the difference between elastomer and thermoset?

What similarities do they share?

Why thermosetting polymers are always amorphous?