Chapter 3: Polymer Properties

EGCH 3260
Mr. Mohammed Al Adawi | Welding workshop
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Learning Outcomes
1. Study introduction to polymers, polymerization, Classification of polymers, Definition of polymer terms, Polymer chain
length, Degree of polymerization, Mn, Mw, PDI, calculations related to this

2. Understand types of polymerization: Addition, Step-growth, and Copolymerization; Ring opening polymerization,
Mechanism related to these; Isomerism: classification and examples

3. Understand chemical bonding in polymers: Primary and Secondary bonds; Thermodynamics of polymers,
Polymerization techniques, their advantages and disadvantages; polymer properties, glass transition temperature,
crystalline temperature, melting temperature, Mechanical properties of polymers, structure-property relationship

4. Polymer processing, compounding of plastics: resins, plasticizers, Fillers and extenders, Polymer Extrusion, Extruder
classification, key steps in extrusion process, Reactive extrusion, application of extrusion; Injection molding, process
cycle of injection molding, injection molding application

5. Perform laboratory experiments either individual or in a group

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Chapters

Chapter 1: Introduction to polymer science & technology

Chapter 2: Polymerization mechanisms

Chapter 3: Polymer properties

Chapter 4: Polymer processing

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Chapter 3: Polymer Properties

Chemical Bonding in Polymers

Thermodynamics of Polymers

Polymerization techniques

Properties of Polymers

• Glass Transition Temperature

• Crystallization Temperature
• Melting Temperature
• Mechanical Properties

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Chemical Bonding in Polymers

Atom: smallest particle of a substance that can exhibit all the properties of that substance

Electrically neutral: Equal number of Electron

negatively charged electrons and positively
charged protons Neutron
Nucleus
Proton

Protons (+) = Electrons (-)

Atom

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Chemical Bonding in Polymers

Ions: atoms that have gained or lost one or more electrons.

Loss of electrons Gain of electrons

Electro-Positive (positive ion) Electro-Negative (negative ion)

K + , Ca2+ O2−, Cl−

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Chemical Bonding in Polymers

❑ Primary Bonds ❑ Secondary Bonds

Valence electrons are involved in bonding Valence electrons are NOT involved in bonding

▪ Ionic Bonding ▪ Dipole Forces

▪ Covalent Bonding ▪ Hydrogen Bonding

▪ Metallic Bonding ▪ Induction Forces

▪ Van Der Waals (Dispersion) Forces

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Primary Bonding

❑ Ionic Bonding
Valence electron is lost from one atom and gained by another.
Electrostatic
attraction

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Primary Bonding

❑ Ionic Bonding
Ionic bonds are not common in polymeric materials. However, some metallic ions can act as
cross-links between carboxyl groups in natural resins.

Surlyn
Na+ or Zn+

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Primary Bonding

❑ Covalent Bonding
Each atom shares at least one electron to the bond

Methane

Note: Atoms with a single bond are free to rotate (Flexible), While atoms with double or triple
bond are fixed (Rigid)

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Primary Bonding

❑ Metallic Bonding

Valence electrons are free to move

throughout the entire metal (”sea of
electrons”) and not bound to any
particular atom.

Metallic bonds do NOT exist in Polymers,

they only exist in Metals

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Secondary Bonding

❑ Dipole Forces
Chlorine is more electronegative than
Attractive intermolecular forces between hydrogen, pulling the shared electrons closer
the oppositely charged ends of two polar to itself
molecules.

Dipole forces play a crucial role in defining Partial

the tertiary structure and, hence, properties negative
of some polymers. Partial charge
positive
charge

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Secondary Bonding

❑ Hydrogen Bonding
A strong intermolecular attraction between a hydrogen atom covalently bonded to a
highly electronegative atom (like O, N, or F) and a lone pair of electrons

Kevlar

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Secondary Bonding

❑ Van der Waals forces

Weak intermolecular attractions that arise

from fluctuating electron distributions in
molecules

In thermoplastic polymers, van der Waals

forces are weak enough to be broken by
heating

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Interaction Energy

Chemical Bond Interaction Energy (kJ/mol)

Induction Forces ≤2
van der Waals Forces 0.08–4.0
Dipole Forces ≤20
Hydrogen Bonds ≤50
Covalent Bonds 60–600
Ionic Bonds 560–1000

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Secondary Structure

➢ Size of polymer: discussed in terms of molecular weight (Mn, Mw).

➢ Shape of polymer: influenced by the nature of the repeating unit and the manner in
which the repeating units are together

• Configuration: Arrangement fixed by primary valence bonds

• Conformation: Arrangement established by rotation about primary valence bonds

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Configuration
Arrangement fixed by primary valence bonds

▪ Head-to-Tail Configuration

▪ Head-to-Head Configuration ▪ Tail-to-Tail Configuration

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Conformation
Arrangement established by rotation about primary valence bonds

Example:

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Thermodynamics of Polymers
Polymerization is a reversible reaction between monomers and a polymer

The equilibrium between these two forms depends on the Gibbs free energy change (ΔG):

ΔG = ΔH − TΔS

• ΔG: Change in Gibbs free energy • ΔS: Change in entropy (measure of disorder)
• ΔH: Change in enthalpy (heat absorbed or released) • T: Temperature (in Kelvin)

❑ If ΔG < 0, the reaction is spontaneous — polymerization is favored.

❑ If ΔG > 0, the reaction is non-spontaneous — depolymerization is favored.

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Thermodynamics of Polymers

ΔG = ΔH − TΔS

❑ If ΔG < 0, the reaction is spontaneous — polymerization is favored.

❑ If ΔG > 0, the reaction is non-spontaneous — depolymerization is favored.

When a polymer forms from a monomer:

o ΔH (enthalpy) is usually negative (exothermic) → Bonds form between monomer units, releasing energy.
o ΔS (entropy) is usually negative → The system becomes more ordered: small monomers → one large chain.
o T (Temperature) is usually small → TΔS is small → ΔG can be negative

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Polymerisation Techniques
Polymerization techniques are methods for combining monomers into polymers
Reactants:
• Monomer
Polymerisation Techniques • Catalyst
• Solvent
• Initiator

Homogenous System Heterogenous System

Reactants are all mutually soluble and Reactants and the polymer product
compatible with the resulting polymer are mutually insoluble
❑ Bulk polymerisation ❑ Suspension polymerisation
❑ Solution polymerisation ❑ Emulsion polymerisation

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Bulk Polymerisation
Also called mass polymerisation is the simplest and purest form of polymerisation

• Adding pure monomer to a soluble initiator Stirrer

in a liquid state.
• The reaction is initiated by heating or Insulation
Jacket
exposing to radiation. Monomer
+ initiator
• As the reaction proceeds the mixture
becomes more viscous.
• The reaction is exothermic.

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Bulk Polymerisation
Advantages
▪ The polymer obtained is pure.
Application
▪ Simple system setup
▪ Polymer mixture can be cast for final product form ▪ PMMA
Disadvantages ▪ PE

▪ Highly exothermic reaction. ▪ PS

▪ Heat transfer and mixing becomes difficult as the

viscosity increases.
▪ Difficulty in controlling the temperature can result in
a non-uniform molecular weight distribution.

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Solution Polymerisation
A method for creating polymers by dissolving monomers and an initiator in a suitable solvent

• Monomers and an initiator are dissolved

in a solvent.
• The reaction proceeds, creating a polymer
that is also soluble in the solvent.
• After the polymerisation is complete, the
solvent must be removed from the final
Waste
polymer product.

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Solution Polymerisation
Advantages
▪ Good control over reaction conditions, including
Application
temperature and viscosity. (Presence of solvent)
▪ Result in narrower molecular weight distribution ▪ Adhesives
Disadvantages ▪ Surface coating
▪ The solvent must be removed from the final polymer,
which is a complex and costly
▪ Some solvents can participate in unwanted chain-
transfer reactions, which can complicate the process
▪ It is not suitable for dry polymers

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Suspension Polymerisation
A heterogeneous radical polymerization process that uses mechanical agitation to mix a monomer or
mixture of monomers in a liquid phase

• A functional monomer and initiator are dissolved in

an organic solvent as an organic phase
• The dispersant is dissolved in water as an water phase
• Water phase and organic phase are mixed by stirring
to form a suspension.
• Finally, polymerization reaction occurs in the single
and very tiny polymerizable droplets, producing large
uniform particles.

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Suspension Polymerisation
Advantages
▪ Better control of heat due to the presence of water
Application
▪ Low viscosity
▪ Cost-effective process ▪ PVC
▪ PMMA

Disadvantages ▪ PVA
▪ PS
▪ Monomers must be insoluble in the continuous phase
▪ Particle size is difficult to precisely control

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Emulsion Polymerisation
A type of free radical polymerization where an insoluble monomer is dispersed in water with the help of
a surfactant, forming an emulsion.

Key components:
▪ Monomer
▪ Water
▪ Initiator
▪ Surfactant (Emulsifier)
Hydrophilic head

Hydrophobic tail

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Emulsion Polymerisation
A type of free radical polymerization where an insoluble monomer is dispersed in water with the help of
a surfactant, forming an emulsion.
Stages:
1. Micelle formation: Surfactant molecules
aggregate in water to form micelles
2. Monomer swelling: The monomer dissolves into
the micelles, causing them to swell.
3. Initiation and propagation: A free radical from the
initiator enters a micelle and reacts with a
monomer, creating a growing polymer chain
4. Termination: Two growing chains combine

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Emulsion Polymerisation
Advantages
▪ High polymerisation rate
Application
▪ Temperature control
▪ Produces stable latexes ▪ Adhesives
▪ Latex paints

Disadvantages ▪ Synthetic rubbers

▪ Limited Polymer Types (only insoluble monomers)

▪ Complicated Process Control

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Properties of Polymers

▪ Glass Transition Temperature (Tg)

▪ Crystallization Temperature (Tc)

▪ Melting Temperature (Tm)

▪ Mechanical Properties

Differential Scanning Calorimetry (DSC) is a thermal analysis

technique used to measure how much heat a material absorbs or
releases as it is heated, cooled, or held at constant temperature.

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Glass Transition Temperature
The Glass Transition Temperature (Tg) is one of the most important properties of polymers & it is
the temperature region where the polymer transitions from a hard, glassy material to a soft, rubbery material.

➢ Hard plastics like PS and PMMA are used below their

glass transition temperatures; that is in their glassy state.
Their Tg's are well above room temperature, both at
around 100 °C

➢ Elastomers like polyisoprene and polyisobutylene, are

used above their Tg's, that is, in the rubbery state, where
they are soft and flexible.

➢ Endothermic process

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Glass Transition Temperature
▪ Amorphous polymers
Polymers whose chains are NOT arranged in ordered crystals
Tg exists
Hard, glassy state to a soft, rubbery state
▪ Crystalline polymers
Polymers whose chains are arranged in ordered crystals
Tm exists
Crystalline regions melt into a disordered liquid

▪ Crystalline and amorphous polymers Tm

This is when the same sample of a polymer can have both a glass
transition temperature and a melting temperature.
Amorphous portion undergoes the glass transition only, and the crystalline portion undergoes melting only.

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Glass Transition Temperature

▪ Amorphous polymers ▪ Crystalline polymers

Specific Volume

Specific Volume
Tg Tm

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Crystallisation Temperature
Above the glass transition, the polymers have a lot of mobility. When they reach the right temperature, they will
have gained enough energy to move into very ordered arrangements (crystalline domains) & give off heat.

➢ Crystallization is an exothermic process

Polymer gives off heat when it crystallizes

➢ Exists only in Semi-crystalline polymer

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Melting Temperature
The temperature at which the crystalline regions of a semi-crystalline polymer break down and become
a disordered (liquid-like) phase.

➢ Melting is an endothermic process

Involves the breaking of inter-chain bonds.

➢ Exists only in Semi-crystalline polymer

➢ Note: If the process were reversed so that

the sample were being cooled from the
melt Tm does not exist in cooling

The broader the melting peak, the less perfect the crystalline structure
Defects and irregularities weaken local intermolecular forces, so some
regions melt early.

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Heating Cycle

1. During heating, the polymer changes from a hard, glassy

material to a soft, rubbery one at the glass transition
temperature (Tg). This is an endothermic transition, as the
polymer absorbs heat and its molecular motion increases.

2. Above Tg, the polymer chains gain more mobility and may
begin to rearrange into crystalline regions. This crystallization
process releases heat, making it an exothermic transition.

3. As the temperature continues to rise, these crystals eventually

melt. At the melting temperature (Tm), the polymer exists in
equilibrium between solid and liquid states. Beyond Tm, the
crystalline regions are completely destroyed, and the polymer
becomes a viscous liquid.

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Cooling Cycle

1. When a polymer is cooled from the melt, it transitions from a

high-energy liquid to a low-energy solid, releasing heat — an
exothermic process. As cooling continues, crystallization occurs,
where polymer chains arrange into ordered structures; this is
also exothermic, as energy is released during crystal formation.

2. At still lower temperatures, the polymer eventually becomes

glassy and rigid as it passes through the glass transition
temperature (Tg), marking another exothermic change from the
soft, rubbery to hard, glassy state.

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Factors affecting Tm and Tc

➢ Chain stiffness (e.g. single vs double bonds)- rigid

chains have higher melting temperatures

➢ Size/weight of molecule- Increasing molecular

weight increases Tm

➢ Size, shape of side groups, side branches,

crosslinking, defects etc.

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Mechanical Properties
Compared with those of metals and ceramics, polymer properties show a much stronger dependence
on temperature and time due to the viscoelastic nature of polymers.

Viscous + Elastic = Viscoelastic

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Mechanical Properties
Compared with those of metals and ceramics, polymer properties show a much stronger dependence
on temperature and time due to the viscoelastic nature of polymers.

Viscous Elastic Viscoelastic

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Mechanical Properties
Stiffness = Young’s Modulus
High stiffness means the material does NOT
bend or deform easily

▪ Polymers bend and stretch easily because of

their low stiffness
▪ Polymers are not suitable for structural and
load-bearing applications

𝑆𝑡𝑟𝑒𝑠𝑠
𝒀𝒐𝒖𝒏𝒈′ 𝒔 𝑴𝒐𝒅𝒖𝒍𝒖𝒔 = 𝐸 =
𝑆𝑡𝑟𝑎𝑖𝑛

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Mechanical Properties
• Tensile Strength Engineering Stress/ Strain Curve
The maximum amount of pulling or stretching
stress a material can withstand before it breaks.

o Engineering Stress
Force F
Stress, σ = =
Cross−Sectional Area 𝐴Ο

o Engineering Strain
Elongation 𝐿𝑖− 𝐿0 Δ𝐿
Strain, ε = = =
Original Length 𝐿0 𝐿0

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Mechanical Properties
• Tensile Strength Polymers compared to other materials
The maximum amount of pulling or stretching
stress a material can withstand before it breaks.

o Engineering Stress
Force F
Stress, σ = =
Cross−Sectional Area 𝐴Ο

o Engineering Strain
Elongation 𝐿𝑖− 𝐿0 Δ𝐿
Strain, ε = = =
Original Length 𝐿0 𝐿0

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Mechanical Properties
True curve
❑ True Stress/Strain Curve
This curve is more accurate because it accounts for
the change in area as the material deforms.

o True Stress

σ 𝑇𝑟𝑢𝑒 = 𝜎𝐸 1 + 𝜀𝐸

o True Strain

ε 𝑇𝑟𝑢𝑒 = ln(1 + 𝜀𝐸 )
Engineering Stress/ Strain Curve

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Mechanical Properties
• Compressive Strength Tensile and compressive tests do not give the same results
The material's ability to withstand loads that Strength and yield stress are generally higher in
tend to reduce its size compression than in tension.

(Ductile)

(Brittle)

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Mechanical Properties
• Flexural Strength • Shear Modulus (Modulus of Rigidity)
A measure of a material's ability to withstand A measure of a material's stiffness and its
deformation under bending. resistance to shear deformation.

3FL Shear Stress τ

Flexural Strength = 𝜎 = 𝐺= =
2b𝑑 2 Shear Strain γ
Δ𝑥
γ=
τ ℎ

d
b

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Mechanical Properties
• Elongation at Break • Toughness
Elongation at break indicates how much a The ability of a polymer to absorb energy
polymer can stretch before breaking, before fracturing
expressed as a percentage
Impact-modified plastics (like ABS) are designed
for high toughness.

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Mechanical Properties
• Poisson’s Ratio
A material property that measures the tendency of a material to deform in directions perpendicular to
the direction of applied stress

E = 2G (1 + 𝑣)

∆𝑉 = 1 − 2𝑣 ε𝑉0
V: volume of material
𝜀

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Mechanical Properties
❖ Problem 1
In a tension test, a brittle polymer experienced an elastic engineering strain of 2% at a stress
level of 35 MPa. Calculate:
a. The true stress
b. The true strain

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Mechanical Properties
❖ Problem 2
Polypropylene has an elastic modulus of 2 × 10^5 Pa and Poisson’s ratio of 0.32. For a
strain of 0.05, calculate the shear stress and the percentage change in volume.

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Mechanical Properties
Stress/Strain Curves
Mechanical Properties of selected polymers

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