Structure–Properties Relationship of Polymers
1. Crystallinity in Polymers
Crystallinity refers to the degree of ordered, regular arrangement of polymer chains in a
polymer material.
Polymers may be:
Amorphous (random chain arrangement)
Semi-crystalline (both crystalline and amorphous regions)
Structural Factors Affecting Crystallinity
Linear chains → higher crystallinity
Regular structure (isotactic, syndiotactic) → higher crystallinity
Small side groups → closer packing
Strong intermolecular forces → increased order
Effect of Crystallinity on Properties
↑ Density
↑ Melting temperature
↑ Mechanical strength
↓ Transparency
↓ Permeability
Polymer Nature
HDPE Highly crystalline
LDPE Low crystallinity
Nylon Semi-crystalline
Polystyrene Amorphous
2. Strength of Polymers
Strength is the ability of a polymer to resist deformation or fracture under applied stress.
Structural Factors Influencing Strength
(a) Molecular Weight
Higher molecular weight → longer chains → greater entanglement
Leads to higher tensile strength
(b) Crystallinity
More crystalline regions → better load transfer
↑ Tensile and yield strength
(c) Intermolecular Forces
Hydrogen bonding and dipole interactions increase strength
Example: Nylon > Polyethylene
(d) Cross-linking
Light cross-linking → improved strength
Heavy cross-linking → rigid and brittle polymers
Examples
Nylon → high strength due to H-bonding
Epoxy resins → strong due to cross-linking
3. Elasticity of Polymers
Elasticity is the ability of a polymer to return to its original shape after removal of applied
stress.
Structural Requirements for Elasticity
Long flexible chains
Low crystallinity
Weak intermolecular forces
Light cross-linking (prevents chain slippage)
Mechanism of Elasticity
Stretching uncoils polymer chains
On release, chains recoil due to entropy effects
Role of Structure
Structure Effect
Linear flexible chains High elasticity
Heavy cross-linking Low elasticity
High crystallinity Reduced elasticity
Examples
Natural rubber → highly elastic
Silicone rubber → excellent elasticity over wide temperature range
4. Chemical Resistivity of Polymers
Chemical resistivity is the ability of a polymer to resist attack by chemicals such as acids,
bases, solvents, and oils.
Structural Factors Affecting Chemical Resistivity
(a) Polarity
Non-polar polymers resist most chemicals
Polar polymers are attacked by polar solvents
(b) Crystallinity
Crystalline regions act as barriers to chemical penetration
Higher crystallinity → better chemical resistance
(c) Cross-linking
Cross-linked polymers swell less and resist solvents
(d) Functional Groups
Reactive groups (–OH, –COOH) reduce chemical resistance
Polymer Chemical Resistance
PTFE (Teflon) Excellent
PVC Good
Nylon Moderate
Polyesters Poor in alkalis
Structure–Property Relationship
Structural Feature Effect on Properties
High crystallinity ↑ strength, ↓ elasticity
High molecular weight ↑ strength
Flexible chains ↑ elasticity
Cross-linking ↑ strength, ↓ solubility
Non-polar structure ↑ chemical resistance
The mechanical and chemical properties of polymers are directly related to their
molecular structure. By controlling crystallinity, molecular weight, and cross-linking,
polymers can be designed for specific engineering applications such as elastomers, fibers,
plastics, and chemically resistant materials.