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.

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

Primary Crystallization:

This is the initial phase of crystallization where spherulites (spherical crystalline structures)
nucleate and grow within the polymer melt or amorphous matrix.

Characteristics of primary Crystallization :

• Nucleation and Growth:

Primary crystallization begins with the formation of nuclei, which are small, stable
crystalline embryos within the amorphous or liquid phase. These nuclei then grow into
larger crystalline structures, typically spherulites, which expand radially until they impinge
on each other.
• Factors Influencing Kinetics:
The rate of primary crystallization is influenced by several factors, including:
• Temperature: Lowering the temperature below the melting point increases the
driving force for crystallization.
• Cooling Rate: A slower cooling rate allows for more time for nucleation and
growth, leading to larger spherulites.
• Pressure: Higher pressure can increase the density of the material, potentially
accelerating nucleation.
• Presence of Additives: Additives can act as nucleating agents, promoting the
formation of nuclei.
• Mathematical Modeling:
Primary crystallization kinetics can be modeled using the Avrami equation, which describes
the relationship between the degree of crystallinity and time.

Secondary Crystallization:
This phase occurs after the spherulites have impinged and space for growth is limited. It involves
perfection or further ordering within the crystalline regions and possible thickening of lamellae.

Characteristics of Secondary crystallization :

Further Development:

After the primary crystallization stage, secondary crystallization involves the further
organization and development of the existing crystalline structure. This can include:
• Thickening of Crystalline Lamellae: The individual crystalline lamellae within the
spherulites may thicken further, increasing the overall crystallinity.
• Infilling: Amorphous regions between spherulites can undergo crystallization,
filling in the gaps and further increasing the crystallinity.
• Kinetics:
Secondary crystallization is generally slower than primary crystallization and often involves
a square root dependence of fractional crystallinity.
• Factors:
Factors that influence secondary crystallization include:
• Time: Secondary crystallization is a time-dependent process, with the extent of the
process increasing over time.
• Temperature: Annealing (heating and then slowly cooling) can promote secondary
crystallization.
• Modeling:
Secondary crystallization kinetics can be modeled using equations that account for the
diffusion-controlled nature of the process, such as a square root dependence of crystallinity
with time.

5.(a)What are homogeneous and heterogeneous polymerization? Cite examples.

Homogenous Polymerization : Polymerization where the monomer, initiator, and growing polymer
chains are all in the same phase, usually liquid or gas.

Example : Polyvinyl acetate (PVAc) in solution polymerization using benzoyl peroxide as an

initiator in ethyl acetate.

Heterogeneous Polymerization : Polymerization where more than one phase exists—such as a

solid, liquid, or gas—during the reaction.
 Example : Polystyrene via suspension polymerization in water.

2020

3.(a)Define crystalline melting and equilibrium melting temperature with examples

Ans:Crystalline melting temperature : Crystalline melting temperature is the temperature at

which a pure crystalline substance transitions from a solid state to a liquid state, where both
phases coexist in equilibrium.

Example : The melting point of water (ice) is 0°C at standard pressure. At this temperature, ice and
liquid water can exist in equilibrium.

Equilibrium temperature : The idealized melting temperature of an infinitely large and perfect
crystal, where the solid and liquid phases have the same free energy.
Example:
For polymers, Tm represents the melting temperature of a perfectly ordered, infinite crystal.

(b)Briefly discuss the glass transition temperature (Tg) of polymers. List the factors that increase
the Tg.
Ans:
The glass transition temperature (Tg) is the temperature at which an amorphous polymer (or the
amorphous regions of a semi-crystalline polymer) transitions from a hard, glassy material to a
soft, rubbery state.
Below Tg, the polymer chains have limited mobility and the material is rigid. Above Tg, the
chains gain mobility, resulting in increased flexibility and elasticity.

Factors that increase the Tg are

1. Rigid Backbone Structure – Polymers with stiff chains (e.g., aromatic rings) have higher Tg.

2. Strong Intermolecular Forces – Hydrogen bonding or dipole interactions raise Tg.

3. High Crosslinking Density – Crosslinks restrict chain movement, increasing Tg.

4. Bulky Side Groups – Large or bulky side groups hinder rotation, raising Tg.

5. Low Chain Flexibility – Reduced flexibility (e.g., due to polar groups or double bonds)
increases Tg.

6. Crystallinity – Though Tg relates to amorphous regions, higher crystallinity can limit chain
mobility, indirectly affecting Tg.

(C)Discuss the reasons for the differences in Tg for the following pairs of polymer with similar
chemical structures

(i)Polyethylene (~-120°C) and Polypropylene (~-20°C)

(ii)Poly(alpha- methylstyrene) (192°C),Poly(Ortho-methylstyrene)(119°C) and Poly(meta-

methylstyrene)(72°C)

(iii)Poly(methyl acrylate)(10°C) and Poly (vinyl acetate)(32°C)

(iv)Poly(but-1-ene)(-24°C) and Poly(but-2-ene)(-73°C)
(v)Poly(ethyl acrylate) (-24°C) and Poly(methyl methacrylate)(105°C)

Ans: (i) Polyethylene vs Polypropylene:

• Polyethylene (PE) has a lower Tg (~ -120°C) because it has simple, flexible chains (–
CH2–CH2–), allowing easy chain mobility.
• Polypropylene (PP) has a higher Tg (~ -20°C) due to the presence of a bulky –CH3
(methyl) group on every other carbon, which restricts chain mobility and increases Tg.

(ii) Polymethylstyrenes:

• Poly(α-methylstyrene) (192°C): Highest Tg due to the methyl group on the α-carbon,

causing strong steric hindrance and restricting rotation near the backbone.
• Poly(ortho-methylstyrene) (119°C): Methyl group on the ortho position of the phenyl
ring causes steric hindrance with the backbone, moderately increasing Tg.
• Poly(meta-methylstyrene) (72°C): Meta substitution causes less steric hindrance, so
chain mobility is less restricted, resulting in a lower Tg.

(iii) Poly(methyl acrylate) (10°C) vs Poly(vinyl acetate) (32°C):

Reason: Vinyl acetate has a bulkier, more polar acetate group, which limits chain mobility more
than the smaller ester group in methyl acrylate → higher Tg.

(iv) Poly(but-1-ene) (-24°C) vs Poly(but-2-ene) (-73°C):

Reason: Poly(but-1-ene) has a more regular structure, allowing better packing and higher Tg.
Poly(but-2-ene)’s double bond position introduces irregularity and flexibility → lower Tg.

(v) Poly(ethyl acrylate) (-24°C) vs Poly(methyl methacrylate) (105°C):

Reason: PMMA has a bulky side group (–CH3 on α-carbon) and strong dipole interactions due to
ester group, restricting chain motion → much higher Tg than the more flexible poly(ethyl
acrylate).

4.(a)Briefly describe the crystallization and nucleation of polymer processing. list the factors that
affect the crystallization process of polymers.

Ans: Crystallization in polymers refers to the formation of highly ordered regions within a
polymer matrix when the polymer chains fold and pack into a regular arrangement. These
regions coexist with amorphous (disordered) regions, giving many polymers a semi-crystalline
nature. It occurs during cooling from the melt, solution, or through stretching.It doesn't happen
like in small molecules because polymer chains are long and entangled.Crystallites typically
form lamellae structures, where polymer chains fold back and forth.
Crystallization Process Steps:

1. Nucleation – Initiation of crystal formation.

2. Crystal Growth – Chains fold and organize around the nucleus.

3. Lamella Formation – Chain folds result in thin, plate-like structures.

4. Spherulite Growth – Lamellae radiate outward forming spherical crystallinestructures

(spherulites), visible under polarized light.

Nucleation:Nucleation is the first step in crystallization, where small regions of the polymer
begin to organize into a crystalline structure.

Types:

1. Homogeneous Nucleation:

Nuclei form spontaneously without any impurities or surfaces.Requires greater undercooling

(temperature drop below melting point).

2. Heterogeneous Nucleation:

Nucleation occurs at interfaces, impurities, fillers, or additives.Easier to initiate and more

common in industrial processing.

Factors Affecting Polymer Crystallization:

1. Polymer structure (regularity, symmetry, tacticity)

2. Cooling rate (slower cooling allows more crystallization)

3. Molecular weight (higher MW can hinder crystallization)

4. Presence of plasticizers or additives

5. Pressure and temperature conditions

6. Chain branching (more branching = less crystallinity)

7. Nucleating agents (promote crystallization)

(b)How the growth rate at a particular temperature depends upon the molar mass of polymers?

Ans: The growth rate of polymers at a specific temperature is affected by molar mass, with a
relationship often expressed as G∝Mα, where G is the growth rate and α is an
exponent. Generally, at a given temperature, higher molar mass polymers have a lower growth
rate due to increased viscosity and entanglement of the larger chains, hindering their movement
and crystallization.

1. Molecular Weight and Viscosity:

• As the molecular weight of a polymer increases, its viscosity also tends to increase. This
is because larger molecules have more interchain interactions, leading to greater
resistance to flow.
• The increased viscosity makes it more difficult for the polymer chains to move and
arrange themselves into a crystalline structure, thus slowing down the crystallization
process.

2. Entanglements and Mobility:

• Higher molecular weight polymers have a greater number of entanglements between their
chains. These entanglements hinder the movement and diffusion of polymer chains,
further reducing the growth rate.
• The reduced mobility of larger chains also makes it more difficult for them to find and
attach to the growing crystal, thus slowing down the crystallization process.

3. Bell-Shaped Temperature Dependence:

• The growth rate of polymers typically exhibits a bell-shaped temperature dependence,

meaning that it increases with increasing supercooling (temperature difference below the
melting point) up to a maximum rate, and then decreases with further increases in
supercooling.
• The maximum growth rate (Gmax) is a characteristic value for the crystal growth
behavior and is related to the intrinsic properties of the polymer.
• The molecular weight dependence of Gmax can be scaled as a -0.5 power to molecular
weight for all crystalline polymers.

4. Other Factors:
• Factors like the degree of supercooling (ΔT) and the specific type of polymer also
influence the growth rate.
• The effect of these factors on the exponent α in the growth rate equation (G∝Mα) can
vary.
(C)Derive the Avrami Equation of crystallization process of polymer in terms of specimen
volume. Write the significance of avrami exponent.

Ans: Avrami Equation:

Significance of Avrami exponent

i)Reflects the dimension of crystal growth (1D, 2D, or 3D)

ii)Indicates nucleation type: instantaneous or continuous

iii)Higher n → more complex growth/nucleation process

5.(a)What is entropy in polymer? what happens to entropy when monomers form into polymers?

Ans: Entropy is a measure of disorder or randomness in a system. In polymers, it refers to the

number of ways polymer chains (or segments) can arrange themselves.

When monomers form polymers entropy decreases because free monomers have more freedom
(higher randomness).When they link into a chain, the system becomes more order.

(b)How does molecular weight affect of polymer crystallinity?

Ans:

1. Low Molecular Weight

Higher Crystallinity: Shorter polymer chains can more easily align and pack into an ordered,
crystalline structure.

Less Chain Entanglement: With fewer entanglements, the chains have more freedom to organize
into crystals.

2. High Molecular Weight

Lower Crystallinity: Long polymer chains tend to become entangled, which disrupts their ability
to align neatly into a crystalline arrangement.

Increased Amorphous Regions: The more entangled and bulky the chains, the more disordered
regions form.
2019.

4.(a)Define crystalline and amorphous polymer. list the factors that affect the glass transition
temperature (Tg) of polymer.

Ans : A crystalline polymer has regions where the polymer chains are arranged in a highly
ordered, repeating pattern.

Example :Polyethylene

An amorphous polymer has chains that are arranged in a random, disordered fashion, with no
long-range repeating order.
Example :Polystyrene

list of factors that affect the glass transition temperature (Tg) of a polymer:
1. Chain Flexibility

2. Molecular Weight

3. Side Groups

4. Crosslinking

5. Crystallinity
6. Plasticizers

7. Intermolecular Forces

8. Tacticity

(b)Briefly describe the factors that affecting the degree of crystallinity of a polymer ?what are the
effects of crystallinity on the polymer properties?

Ans: Factors Affecting Degree of Crystallinity in Polymers:

1. Chain Structure:
o Regular, symmetrical structures (e.g., linear chains) favor crystallinity.
o Irregular or branched chains hinder packing and reduce crystallinity.
2. Tacticity:
o Isotactic and syndiotactic polymers crystallize more easily than atactic ones.
3. Intermolecular Forces:
o Strong forces (e.g., hydrogen bonding) promote closer packing and higher
crystallinity.
4. Molecular Weight:
o Moderate molecular weight favors crystallinity; very high weight causes
entanglements and reduces it.
5. Cooling Rate:
o Slow cooling allows chains to align and crystallize; fast cooling traps them in an
amorphous state.
6. Plasticizers or Additives:
o These can disrupt chain packing and reduce crystallinity.

Effects of Crystallinity on Polymer Properties:

• Higher Crystallinity:
o Increases tensile strength, stiffness, and chemical resistance.
o Increases density and opacity.
o Improves dimensional stability.
o Decreases permeability to gases and liquids.
• Lower Crystallinity:
o Increases flexibility and impact resistance.
o Usually results in better optical clarity.
o Enhances processability.
5.(c)Briefly discuss the effect of intermolecular bonding and entropy on the crystalline melting
point (Tm).

Ans: Effect of Intermolecular Bonding and Entropy on Crystalline Melting Point (Tm):

1.Intermolecular Bonding:

Stronger intermolecular forces (e.g., hydrogen bonding, dipole-dipole interactions, van der Waals
forces) increase Tm.

These forces hold the polymer chains tightly in the crystalline regions, requiring more thermal
energy to break them and transition to the molten state.

Example:Nylon has a high Tm due to strong hydrogen bonding between chains.

2. Entropy:

Crystallization reduces entropy (more ordered state).To melt a crystalline polymer, the system
must overcome the entropy loss that occurred during crystallization.Higher entropy difference
(ΔS) between crystalline and molten states generally lowers Tm, as less energy is needed to
achieve disorder.

(d)Explain the role of abrami equations to describe the crystal rate of a polymer sample.

Ans:

The Avrami equation (often mistakenly referred to as "Abrami") is used to describe the
crystallization kinetics of polymers — specifically, how the crystalline fraction of a polymer
increases over time during isothermal crystallization.

Avrami Equation:

X(t) = 1 - e^{-k t^n}

Where:

• : Relative degree of crystallinity at time

• : Crystallization rate constant (depends on temperature and material)
• : Avrami exponent (related to nucleation and growth mechanism)
• : Time
Role of Avrami Equation in Polymer Crystallization:

1. Describes Crystallization Rate:

It quantifies how fast a polymer crystallizes under specific conditions.
2. Gives Insight into Mechanisms:
The Avrami exponent indicates:
o Type of nucleation (instantaneous or sporadic)
o Growth geometry (1D, 2D, or 3D)
3. Useful in Processing:
Helps in optimizing cooling rates and molding conditions in polymer manufacturing.

Example Use:

If n=3,it suggests 3D spherulitic growth with either instantaneous or sporadic nucleation.

2018

2(b)Discuss the temperature molecular weight diagrams for amorphous polymers and crystalline
polymers.

Ans:
(d)Write the mechanism for degradation of Poly vinyl(PVC) chloride to produce HCl at 200°C.
what types of polymers are generally stable at high temperature?

Ans:

3.(b) Illustrate the Lauritzen-Hoffman theory of crystal growth for polymers.

Ans:

The Lauritzen-Hoffman theory of crystal growth in polymers explains how polymer chains fold
and stack to form lamellar crystals. It's based on the idea that crystal growth occurs by the
addition of polymer stems (sections of chain) to a growing surface, driven by nucleation and
secondary nucleation events. The theory considers the temperature dependence of the growth
rate, supercooling, and transport of polymer chains, all of which influence the final crystal
structure.

1. Nucleation:

• Primary Nucleation:
The initial step where a small, stable seed (the nucleus) forms from random fluctuations in
the polymer melt or solution.
• Secondary Nucleation:
Further polymer chains deposit on the existing nucleus, extending the crystal.

2. Crystal Growth:

• Stem Growth:
The polymer chain extends into a stem, which is a section of the chain folded and stacked
on the crystal surface.
• Lamellar Growth:
These stems are laid down side by side, forming a lamellar structure (a thin, flat sheet).
• Chain Folding:
The Lauritzen-Hoffman theory accounts for chain folding, where sections of the polymer
chain fold back on themselves, allowing them to fit into the lamellar structure.

3. Temperature Dependence:

• The growth rate is temperature-dependent, with faster growth at higher supercooling (the
difference between the melting point and crystallization temperature).
• The theory considers the transport of polymer chains to the growing crystal face, which is
influenced by temperature and viscosity.
• The glass transition temperature (Tg) and melting temperature (Tm) of the polymer play a
role in crystal growth kinetics.