2022.

3.(a)What is the crystalline state of the polymer? Write the properties of the polymer
influenced by crystallinity?

Ans: The crystalline state of a polymer is characterized by a regular arrangement of

conformationally regular polymer chains.

Properties of the Polymer Influenced by Crystallinity:

1. Density:Higher crystallinity increases density due to tighter packing of chains.
2. Melting Point and Thermal Stability:
More crystalline polymers have higher melting points and better thermal resistance.
3. Mechanical Strength and Hardness:

Crystallinity improves tensile strength, stiffness, and hardness.

4. Barrier Properties:
Crystalline regions reduce permeability to gases and liquids.
5. Transparency:
Increased crystallinity often reduces transparency, making the polymer more opaque.
6. Solubility and Chemical Resistance:

Crystalline polymers are less soluble and more chemically resistant.

7. Elasticity and Flexibility:
More crystalline polymers are typically less flexible and more brittle.

(b)Give a few characteristics of the amorphous state of the polymer.

Ans: The amorphous state of a polymer refers to a disordered arrangement of polymer

chains, lacking the regular crystalline structure. Here are a few key characteristics:

1. Random Chain Arrangement: Polymer chains are arranged in a disordered, non-

crystalline manner.

2. Transparency: Amorphous polymers are often transparent due to the lack of crystalline
domains that scatter light.

3. Lower Density: They have lower density compared to crystalline polymers because of
inefficient packing of chains.
4. Glass Transition Temperature (Tg): Amorphous polymers exhibit a glass transition
temperature instead of a melting point.

5. Flexibility and Softness: They tend to be more flexible and softer at room temperature.

6. Isotropic Properties: Mechanical and thermal properties are generally the same in all
directions.

(c)Explain how Tg and Tm are strongly influenced by the chemical structure of repeating
units.

The chemical structure of repeating units in a polymer significantly influences both the
glass transition temperature (Tg) and the melting temperature (Tm). Specifically, the
presence of bulky side groups, aromatic rings, or rigid structures in the repeat unit
generally leads to higher Tg and Tm values. Conversely, flexible or symmetric repeat
units tend to lower these temperatures.

• Tg and Chain Mobility:

The glass transition temperature (Tg) represents the temperature at which a
polymer transitions from a rigid, glassy state to a more flexible, rubbery state. Tg is
heavily influenced by the mobility and flexibility of the polymer chains. Factors like
bulky side groups or rigid structures in the repeat unit restrict chain movement,
leading to a higher Tg.
• Tm and Crystallinity:
The melting temperature (Tm) is the temperature at which a crystalline polymer
melts, transitioning from a solid to a liquid state. Crystallinity, which refers to the
degree of order in the polymer structure, plays a major role in Tm. Symmetrical and
regularly shaped repeat units facilitate the formation of crystalline structures,
leading to higher Tm values.
• Influence of Repeat Unit Structure:
• Bulky side groups: Large or inflexible side groups attached to the backbone
can hinder chain flexibility and mobility, increasing Tg and Tm.
• Aromatic rings: Aromatic rings within the repeat unit can impart rigidity and
increase the strength of intermolecular forces, resulting in higher Tg and
Tm.
 • Flexibility: Flexible repeat units, like those with longer alkyl chains or those
that allow for free rotation, generally lead to lower Tg and Tm values as the
chains are more mobile.
• Symmetry: Symmetrical repeat units promote the formation of ordered
crystalline structures, leading to higher Tm values.
• Cross-linking: The presence of cross-links between polymer chains can also
affect Tg and Tm. Increased cross-linking reduces chain mobility and
increases Tg, while it can also inhibit crystallization and lower Tm.
• Example:
Consider the difference between polyethylene (PE) and polyethylene terephthalate
(PET). PE has a simple repeat unit (-CH2-) and a relatively low Tg and Tm. PET has a
more complex repeat unit (with an ester linkage and aromatic ring) and exhibits
significantly higher Tg and Tm due to its greater rigidity and stronger intermolecular
forces.

(d)Discuss the thermodynamics of thermal transition

Ans:Upon heating and cooling, polymers experience distinct phase transition when passing
through specific temperature. This process is called thermal transition in polymer. When
temperature is raised,they physically transition from solid to glassy to robbery and in the case of
thermoplastics from robbery to liquid like flow with additional heating.

Fundamental difference between the thermal behavior of polymers and simple molecules :
Molecular motion in a polymer sample is promoted by by its thermal energy which is
opposed by the cohesive forces between structural segments along the chain and between
neighbouring chains. These cohesive forces and consequently thermal transitions in
polymers depend on the structure of the polymer.

Two important temperatures at which certain physical properties of polymers undergo

drastic changes have been identified –

(1)Crystalline melting point, Tm

(2)Glass transition temperature, Tg

Importance of thermal transition in polymers

a) knowledge of thermal transition in polymers is important improper processing

fabrication conditions
b) the characteristics of physical and mechanical properties of a material
c) determination of appropriate and uses.

2021

4)(a)What is the crystalline melting temperature?narrate the factors influencing crystalline

melting temperature?

Ans: The crystalline melting temperature (Tm) is the temperature at which a

substance transitions from a crystalline solid to a liquid state.

Factors affecting crystalline melting temperature are

• Intermolecular Bonding:
Stronger intermolecular forces, like hydrogen bonds, generally lead to higher
melting points. Conversely, weaker forces, like van der Waals interactions, result in
lower melting points.
• Chain Structure:
• Regularity: More regular, crystalline structures tend to have higher melting
points. Conversely, irregular structures or amorphous regions lower the
melting point.
• Branching: Chain branching creates defects in the crystalline structure,
reducing the melting point.
 • Side Chains: Bulky or large side chains can restrict chain flexibility and
increase the melting point.
• Presence of Specific Groups:
• Polar Groups: Polar groups (Cl, OH, CN) in the main chain or side chains can
enhance hydrogen bonding and increase the melting point.
• Aromatic Groups: Aromatic groups increase rigidity and thus raise the
melting point.
• Double Bonds: Double bonds also increase rigidity and elevate the melting
temperature.
• Crystallinity:
A higher degree of crystallinity (more ordered crystalline regions) generally leads to
a higher melting point.
• Crosslinking:
Crosslinking, or the formation of bonds between polymer chains, increases rigidity
and thus the melting temperature.

(b)Describe the batch reactor of polymerization

Ans: A batch reactor used for polymerization is a closed system where all reactants are
loaded at the beginning of the reaction, and the process proceeds without additional input
or removal of materials until the desired level of polymerization is reached. Here's a
breakdown of its key features:

1.Structure and Operation:

It typically consists of a jacketed vessel with stirrers for proper mixing and temperature
control systems.Monomers, initiators, catalysts, and solvents are added at the start.The
reactor is sealed, and the polymerization reaction is carried out under controlled
temperature and pressure.

2. Types of Polymerization:

Suitable for step-growth and chain-growth polymerizations.Can handle bulk, solution,

suspension, or emulsion polymerization processes.

3. Advantages:

Flexibility: Easy to switch between different polymer products.

High conversion: Reactions can run for longer to achieve higher molecular weights.

Simple design and operation.

4. Disadvantages:

Batch-to-batch variability: May lead to inconsistency in product quality.

Difficult heat removal: Especially in highly exothermic reactions like polymerization.

Not continuous: Lower productivity compared to continuous reactors.

5. Applications:

Commonly used in R&D, pilot plants, and small-scale production.

Suitable for specialty polymers or where precise control of molecular weight and
composition is needed.

Fig: Batch reactor of polymerization

(C)Discuss the kinetics of primary and secondary crystallization.