STRUCTURAL ANALYSIS OF NANOMATERIALS

Lecture 09: Basic Properties: Polymers

Dr. Kaushik Pal

Associate Professor
Dept. of Mech. & Indl. Engg.
Joint faculty: Centre of Nanotechnology
 Materials classification chart

Metals and
Ceramics Polymers Composites
their alloys

Ceramic Polymer
Ferrous = Base Nonferrous = Metal matrix
matrix matrix
Iron No Iron composites
composites composites

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Polymers:
 The word ‘polymer’ is coined from two Greek words: ‘poly’
means ‘many’ & ‘mer’ means ‘unit’ or ‘part’.
 It is defined as very large molecules having high molecular mass
(103-107 u) & referred to as macromolecules.
 These macromolecules are formed by repeated linking of small
units called monomers.
Polymerization
 Monomers are linked to each other by covalent bonds.
 A single polymer molecule may consists of hundreds to a million Process of formation of polymers
monomers and may have a linear, branched or network structure. from respective monomers

Example of polymer:
Transformation of ethene
to polythene

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 Classification of Polymer
Based on structure of Based on mode of Based on molecular Based on polymerization
Based on source mechanism
polymers polymerization forces

Natural Addition or chain

Addition
polymers Linear polymers Elastomers growth
polymers
polymerization

Semi-synthetic Branched chain Condensation Condensation

polymers Fibres
polymers polymers polymerization

Synthetic Cross linked Thermoplastic

polymers polymers polymers

Thermosetting
polymers

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Classification Based on Source:
Under this type of classification, there are three sub categories:
1. Natural polymers:
• They are derived from plants and animals.
• Examples include wood, rubber, cotton, wool, proteins, enzymes, silk etc.

2. Semi-synthetic polymers:
• Cellulose derivatives as cellulose acetate (rayon) and cellulose nitrate.

3. Synthetic polymers:
• These polymers are synthesized in the industry from chemical substances.
• They are manmade polymers extensively used in daily life and industry.
• Examples:
 Plastic (polythene)
 Synthetic rubbers (Buna-S) and synthetic fibres (nylon 6,6) .

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Classification Based on Structure of Polymers:
There are three different types based on the structure of the polymers.
1. Linear polymers:
• Consist of long and straight chains.
• Examples: High density polythene, polyvinyl chloride.

2. Branched chain polymers:

• Contain linear chains having some branches.
• Example: Low density polythene.

3. Cross linked or Network polymers:

• Formed from bi-functional and tri-functional monomers.
• Contain strong covalent bonds between various linear polymer chains.
• Example: Bakelite, melamine.

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Classification Based on Mode of Polymerization:
Polymers can also be classified on the basis of mode of polymerization into two sub groups.
1. Addition polymers:
Formed by repeated addition of monomer molecules possessing double or triple bonds.

Two types of addition polymers

Homopolymers Co-polymers
 They are made by single monomeric species  They made by addition polymerisation from
polymerization. two different monomers.
 Example: Formation of Polythene from ethane.  Example: Buna-N, Buna-S.

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2. Condensation polymers:
• Formed by repeated condensation reaction between two different bi-functional or tri-
functional monomeric units.
• In these polymerization reactions, the elimination of small molecules such as water,
alcohol, hydrogen chloride etc., takes place.

Nylon 6,6 formation by

condensation of hexamethylene
diamine with adipic acid.

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Classification Based on Molecular Forces:
On the basis of magnitude of intermolecular forces present in them, divided into four subgroups:
1. Elastomers:
• Rubber like solid with elastic properties.
• Polymer chains are held together by the weakest intermolecular forces.
• Weak binding forces causes polymer stretching.
• Example: Neoprene, Buna-S, Buna-N
Vulcanization - crosslinking process in which rubber molecules are converted into 3-D network of
interconnected polymer chains through chemical crosslinks of sulfur.

2. Fibres:
• Thread forming solids which possess high tensile strength and high modulus.
• Have strong intermolecular forces like hydrogen bonding which leads to close packing of chains
and impart crystalline nature.
• Example: polyamides (nylon 6,6), polyesters (terylene).

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3. Thermoplastic polymers:
 Linear or branched long chain molecules.
 Capable of repeatedly softening on heating and hardening on cooling.
 Possess intermolecular forces of attraction intermediate between elastomers and fibres.
 Example: polythene, polystyrene, polyvinyl etc.

4. Thermosetting polymers:
 Cross linked or branched polymer molecules, which on heating undergo extensive cross linking
in moulds and again become infusible.
 These cannot be reused.
 Examples: Bakelite, urea-formaldehyde resins etc.

Order of Strength Thermosetting > Fibres > Thermoplastics > Elastomers

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Classification Based on Growth Polymerization (Mechanism):

1. Addition polymerization
Two broad types of polymerization reactions 2. Condensation polymerization

1. Addition polymerization or chain growth polymerization:

 Polymer is formed from monomer, without loss of any material.
 Product is exact multiple of original monomeric molecule.
 Proceeds by initial formation of some reactive species like free radicals or ions
and by the addition of reactive species to other molecule, with regeneration of
reactive feature.

Free radical mechanism:

 Alkenes are polymerized in presence of free radical generating initiator (catalyst).
 Initiator (catalyst) - Benzoyl peroxide, Acetyl peroxide, Tertiary-butyl peroxide etc.

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a) Chain initiation step:
 Involves addition of phenyl free radical formed by
peroxide to ethene double bond, and forms larger radical.

b) Chain propagation step:

 Repetition of this sequence with new and bigger radicals.

c) Chain terminating step:

 Product radical thus formed reacts with another radical to
form the polymerized product.

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Preparation of Some Important Addition Polymers:
a) Polythene: It is widely used polymer and of two types:

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b) Polytetrafluoroethene (Teflon): c) Polyacrylonitrile:

 Manufactured by heating tetrafluoroethene  Addition polymerisation of acrylonitrile

with a free radical or persulphate catalyst at in presence of a peroxide catalyst leads to
high pressures. the formation of polyacrylonitrile.
Properties: Uses:
Chemically inert.  Used as a substitute for wool in making
Resistant to attack by corrosive reagents. commercial fibres as orlon or acrilan.
Uses:
In making oil seals and gaskets.
For non-stick surface coated utensils.

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2. Condensation polymerization:
• It involves a repetitive condensation reaction between two bi-functional monomers.
• Results in loss of some simple molecules as water, alcohol, etc.
• It leads to formation of high molecular mass condensation polymers.
• It is also called as step growth polymerization.
• Example:
 Formation of terylene by the
interaction of ethylene glycol
and terephthalic acid.

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Preparation of Some Important Condensation Polymers:
a) Polyamides:
 Possesses amide linkages, and an important examples of synthetic fibres as nylons.
 Product of condensation polymerisation of diamines with dicarboxylic acids and also of amino
acids and their lactams.
Preparation of nylons

i. Nylon 6,6: ii. Nylon 6:

Product of condensation polymerisation of hexamethylene Obtained by heating caprolactum
diamine with adipic acid under high pressure and temperature. with water at high temperature.

Uses: Uses:
 In making sheets.  In manufacture of tyre cords, fabrics
 In bristles for brushes and in textile industry. and ropes.

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b) Polyesters:
 Polycondensation products of dicarboxylic acids and diols.
 Manufactured by heating a mixture of ethylene glycol and terephthalic acid at 420- 460 K in
presence of zinc acetate antimony trioxide catalyst.
 Example: Dacron or terylene (crease resistant).
 Uses:
 In blending with cotton and wool fibres.
 As glass reinforcing materials in safety helmets etc.

c) Phenol - formaldehyde polymer (Bakelite):

 Condensation product of phenol with formaldehyde in presence of an acid or base catalyst.
Novolac (initial and linear product):
 It is used in paints.
 Novolac on heating with formaldehyde undergoes cross
linking to form an infusible solid mass called bakelite.
 It is used for making combs, phonograph records,
electrical switches and handles of various utensils.

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Co-polymerization:
 Polymerization reaction in which a mixture of more than one monomeric species is allowed
to polymerize and form a copolymer.
 Copolymer can be made not only by chain growth polymerization but by step growth
polymerization also.
 It contains multiple units of each monomer used in the same polymeric chain.
 Example: Mixture of 1,3-butadiene and styrene can form a copolymer.

 Copolymers have properties quite different from homopolymers.

Example:
 Butadiene - styrene copolymer - quite tough, good substitute for natural rubber.
 Used for manufacture of autotyres, floor tiles, cable insulation, etc
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Rubber:
Rubber are of two types

1. Natural rubber:
 Natural polymer and has coiled structure.
 Called as elastomer due to elastic properties.
 Linear polymer of isoprene (2-methyl-1, 3-butadiene), also called as cis - 1,4-polyisoprene.
 cis-poly-isoprene molecule consists of various chains held together by weak van der Waals
interactions.
Vulcanization of rubber:
Natural rubber becomes soft at high temperature (>335 K) and brittle at low temperatures (<283 K).
Improves

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2. Synthetic rubber:
 It is any vulcanisable rubber like polymer, capable of getting stretched to twice its length.
 It returns to its original shape and size as the external stretching force is released.
 They are either homopolymers of 1,3-butadiene derivatives or copolymers of 1,3-butadiene.

Preparation of Synthetic Rubbers

a) Neoprene b) Buna-N
 Formed by the free radical polymerisation of  Obtained by copolymerization of 1,3-
chloroprene. butadiene and acrylonitrile in presence of
peroxide catalyst.
 Resistant to the action of petrol, lubricating
oil and organic solvents.
Uses:
 For manufacturing conveyor belts, gaskets Uses:
and hoses.  In making oil seals, tank lining, etc.

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 PROPERTIES OF POLYMERS

Physical Properties Thermal Properties Mechanical Properties Chemical Properties

Melting point and Strength

Degree of
polymerization and glass transition
molecular weight temperature Percent elongation to
break

Polymer crystallinity Young’s modulus

Toughness

Viscoelasticity

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1. Physical Properties:
Physical properties of
polymers include:

Molecular weight

Degree of polymerization

Crystallinity of Polymer

Low Density

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I. Degree of Polymerization and Molecular Weight:
 Degree of polymerization: The number of repeating units in the polymer chain.
 Molecular weight of a polymer molecule: It is Product of the degree of polymerization and the
molecular weight of the repeating unit.
 Molecular Weight Averages: The polymer molecules are not identical but are a mixture of many
species with different degrees of polymerization, that is, with different molecular weights.
∞
where,
𝑷𝒊 𝑿𝒊 ⋯ ⋯ ⋯ ⋯ (𝒊) Set of values = {X1, X2,……. Xn}
𝒊=𝟎 Probability of occurrence = {P1, P2,…….Pn}
 Number-Average Molecular Weight:
 If 𝑵𝒊 is the number of polymer molecules having the molecular weight 𝑴𝒊, then the “number-
average” probability of given mass is given by:
𝑵𝒊
𝑷𝒊 = ∞ ⋯ ⋯ ⋯ ⋯ (𝑖𝑖)
𝒋=𝟎 𝑵 𝒋
∞ ∞
𝑵𝒊 𝒊=𝟎 𝑴𝒊 𝑵𝒊
𝑴𝒏 = ∞ 𝑴 𝒊 = ∞ ⋯ ⋯ ⋯ ⋯ (𝒊𝒊𝒊)
𝒊=𝟎 𝒋=𝟎 𝑵𝒋 𝒋=𝟎 𝑵𝒋

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  Physical properties (like transition temperature, viscosity, etc.) and mechanical properties (like
strength, stiffness, and toughness) depend on molecular weight of polymer.
 Lower the molecular weight, lower the transition temperature, viscosity, and mechanical properties.
 Due to increased entanglement of chains with increased molecular weight, the polymer gets higher
viscosity in molten state, which makes the processing of polymer difficult.
 Weight average molecular weight:
𝑵𝒊 𝑴𝒊
• The weight-average probability is given by: 𝑷𝒊 = ∞ ⋯ ⋯ ⋯ ⋯ ⋯ (𝒊𝒗)
𝒋=𝟎 𝑵𝒋 𝑴𝒋
∞ ∞ 𝟐
• The weight-average molecular weight 𝑵𝒊 𝑴𝒊 𝒊=𝟎 𝑵𝒊 𝑴 𝒊
𝑴𝒘 = ∞ 𝑴𝒊 = ∞ ⋯ ⋯ ⋯ ⋯ (𝒗)
is given by: 𝒋=𝟎 𝑵𝒋 𝑴𝒋 𝒋=𝟎 𝑵𝒋 𝑴𝒋
𝒊=𝟎

Degree of polymerization can be calculated using the number-average

molecular weight:
𝑵𝒖𝒎𝒃𝒆𝒓 𝒂𝒗𝒆𝒓𝒂𝒈𝒆 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒘𝒆𝒊𝒈𝒉𝒕
𝑫𝒆𝒈𝒓𝒆𝒆 𝒐𝒇 𝒑𝒐𝒍𝒚𝒎𝒆𝒓𝒊𝒛𝒂𝒕𝒊𝒐𝒏 =
𝑴𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒘𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝒕𝒉𝒆 𝒓𝒆𝒑𝒆𝒂𝒕

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II. Polymer Crystallinity: Crystalline and Amorphous Polymers:
 Polymeric chains are very large and found in the polymer in two forms as:
 Lamellar crystalline form in which chains fold and make lamellar structure arranged in the
regular manner.
 Amorphous form in which the chains are in irregular manner.
 Lamellar are embedded in amorphous part and communicate with other
lamellar via tie molecules.
 Polymers having high degree of crystallinity are rigid and have high melting
point, but their impact resistance is low.
 Amorphous polymers are soft and have lower melting points.

𝝆𝒄 𝝆𝒔 − 𝝆𝒂 where, 𝜌𝑐 = density of the completely crystalline

% 𝑪𝒓𝒚𝒔𝒕𝒂𝒍𝒍𝒊𝒏𝒊𝒕𝒚 = × 𝟏𝟎𝟎 polymer, 𝜌𝑎 = density of the completely
𝝆𝒔 𝝆𝒄 − 𝝆𝒂
amorphous polymer, 𝜌𝑠 = density of the sample.

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2. Thermal Properties:
Melting Point and Glass Transition Temperature:
• Glass transition temperature is the property of amorphous region of polymer, whereas the crystalline
region is characterized by the melting point.
• Glass transition temperature is the second order transition, where as melting point is the first order
transition.
• The value of glass transition temperature is not unique because the glassy state is not in equilibrium.
• Its value depends on several factors such as:
 Molecular weight
 Measurement method
 On the rate of heating or cooling
• Semi-crystalline polymer shows both the transitions
corresponding to their crystalline and amorphous regions so
have true melting temperatures (Tm) at which the ordered phase
turns to disordered phase, whereas the amorphous regions soften
over a temperature range known as the glass transition (Tg).

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 Continued...
• Amorphous polymers do not possess the melting
point, but all polymers possess the glass transition
Polymer Tg (°C)
temperature.
Polytetraflouroethylene -97
• The polymer melting point Tm is increased if the Polypropylene (isotactic) +100
double bonds, aromatic groups, bulky or large side
Polystyrene +100
groups are present in the polymer chain, because they
Nylon 6,6 +57
restrict the flexibility of the chain.
Polyethylene (LDPE) -120
• The branching of chains causes the reduction of Polyethylene (HDPE) -90
melting point, as defects are produced because of the Polypropylene (atactic) -18
branching.
Poly(vinyl acetate) (PVAc) +28
Polyester (PET) +69
Glass transition temperatures of some polymers Poly(vinyl alcohol) (PVA) +85
Poly(vinyl chloride) (PVC) +87

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Factors Affecting the Glass Transition Temperature:
a) Intermolecular Forces:
 Strong intermolecular forces cause higher Tg.
b) Chain Stiffness:
 The presence of stiffening groups (such as amide, sulfone, carbonyl, p-phenylene etc.) in polymer
chain reduces the flexibility of the chain, leading to higher glass transition temperature.
c) Cross-Linking:
 The cross-links between chains restrict rotational motion and raise the glass transition temperature.
 Hence, higher cross-linked molecule will show higher Tg than that with lower cross-linked
molecule.
d) Pendant groups:
 The presence of pendent group can change the glass transition temperature.
e) Plasticizers:
 Low molecular weight and non-volatile materials added to polymers to increase their chain
flexibility.
 Reduce the intermolecular cohesive forces between polymer chains, which in turn decrease Tg.

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f) Molecular weight:
 The glass transition temperature is also affected by the molecular weight of the polymer.
 Tg is increased with the molecular weight.
 The molecular weight is related to the glass transition temperature by the Fox–Flory Equation:
𝐾
𝑇𝑔 = 𝑇𝑔,∞ − 𝑀
𝑛

Where, 𝑇𝑔,∞ is glass transition temperature at the molecular

weight of infinity, 𝐾 is empirical parameter called Fox-Flory
parameter related to free volume inside the polymer.

 It is observed that Tg is increased up to the molecular weight

of approximately 20, 000, and after this limit, the Tg is not
affected.

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3. Mechanical Properties:
Mechanical Strength:
• Strength is the stress required to break the sample.

Types of Mechanical Strength

Tensile Torsional Impact Flexural Compressional
(Stretching of the (Twisting of the (Bending of the (Compressing the
(Hammering)
polymer) polymer) polymer) polymer)

Order of Increasing
Strength:

linear < branched < cross-linked < network

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Factors Affecting the Strength of Polymers:
 Molecular Weight:
 Tensile strength of polymer rises with increase in molecular weight and reaches the
saturation level at some value of molecular weight.
𝑨
𝝈 = 𝝈∞ −
𝑴
where, 𝜎∞ = tensile strength of polymer with molecular weight of infinity,
A = some constant,
M = molecular weight.

 Cross-linking:
Restricts motion of chains and increases the strength of polymer.
 Crystallinity:
It increases strength, because in crystalline phase, intermolecular bonding is more significant.
Hence, polymer deformation can result in the higher strength leading to oriented chains.

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 Percent Elongation to Break (Ultimate Elongation):
 It is the strain in the material on its breakage.
 It measures the percentage change in the length of material
before fracture.
 It is a measure of ductility.
 Ceramics have very low (< 1%), metals have moderate (1-50
%) and thermoplastic (>100%), thermosets (<5 %) value of
elongation to break.
 Young’s Modulus (Modulus of Elasticity or Tensile Modulus):
 It is the ratio of stress to the strain in the linearly elastic region.
 Elastic modulus is a measure of the stiffness of the material.
𝑻𝒆𝒏𝒔𝒊𝒍𝒆 𝑺𝒕𝒓𝒆𝒔𝒔 𝝈
𝑬=
𝑻𝒆𝒏𝒔𝒊𝒍𝒆 𝑺𝒕𝒓𝒂𝒊𝒏 𝝐

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 Toughness:
 The toughness of a material is given by the area under a stress-strain curve.
 It measures the energy absorbed by the material before it breaks.
∈𝒇

𝑻𝒐𝒖𝒈𝒉𝒏𝒆𝒔𝒔 = 𝝈 𝒅𝝐
𝟎
where, ϵf is the true strain at fracture.

 Stress–strain curve is shown which compares the stress–

strain behavior of different types of materials.
 Rigid materials possess high Young’s modulus (such as
brittle polymers), and ductile polymers also possess
similar elastic modulus, but with higher fracture
toughness.

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 Viscoelasticity:
There are two types of deformations named as:
i. Elastic deformation
ii. Viscous deformation
i. Elastic deformation:
 Strain is generated at the moment the constant load (or stress) is applied, and this strain
is maintained until the stress is not released.
 On removal of stress, the material recovers its original dimensions completely, that is
the deformation is reversible that is:
𝝈=𝑬∈
where, E = elastic modulus
𝜎 = applied stress
𝜖 = strain developed

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ii. Viscous deformation:
 Strain generated is not instantaneous and it is time dependent.
 When the load is removed, material does not return to its original
dimensions completely, so deformation is irreversible.
𝒅𝝐
𝝈=𝜸 where, 𝛾 = viscosity,
𝒅𝒕 d𝜖/dt = strain rate

 but low strain rate, Polymers show combined behavior of elastic and plastic deformation
depending on temperature and strain rate.
 At low temperature and high strain rate, elastic behavior is observed, and at high temperature the
viscous behavior is observed.
 Combined behavior of viscosity and elasticity
is observed at intermediate temperature and
strain rate value.
 This behavior is termed as viscoelasticity, and
the polymer is termed as viscoelastic.

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4. Chemical Properties:
 Different side groups on the polymer can lend to:
a. Ionic bonding
b. Hydrogen bonding
 Polymers containing amide or carbonyl groups can form hydrogen bonds between
adjacent chains.
 Dipole bonding is not as strong as hydrogen bonding.
 Example: Polyesters have dipole –dipole bonding between the oxygen atoms in C=O
groups and the hydrogen atoms in C-H groups.
 Generally, polymeric materials are noncorrosive in nature. Because, upon exposure to
liquid, they may experience by swelling or dissolution.
 Polymers may deteriorate by swelling and dissolution.

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Polymer Degradation:
• It is a change in the properties (Strength, colour, shape, molecular weight etc.) of polymer or
polymer based product under the influence of one or more environmental factors such as heat, light,
moisture and chemical.
• Covalent bonds in polymer are rupture as a result of environmental factors.
• Due to the chemical complexity of polymers, their degradation mechanism are not well understood.

Polymer can degrade by exposure to Types of degradation

1. High temperature ⇒ Thermal degradation
2. Shear action ⇒ Mechanical degradation
3. Oxygen, ozone and chemicals ⇒ Chemical degradation
4. Electromagnetic, ultrasonic radiation ⇒ Light induced degradation
5. Moisture (Liquid) ⇒ Hydrolysis or swelling & dissolution

ADVANCED COMPOSITE LAB 37

Comparison of the properties of ceramics, metals and polymers:
Properties Ceramic Metal Polymer
Hardness High Low Low

Elastic modulus High High Low

High temperature strength High Low Low

Thermal expansion Low High High

Ductility Low High High

Corrosion resistance High Low Low

Resistance to wear High Low Low

Electrical conductivity Intermediate High Low

Density Low High Low

Thermal conductivity Intermediate High Low

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Some Common Application of Polymers:

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Summary:

 Polymers are organic, macromolecules made up of repeating units.

 Material properties controlled by degree of cross-linking.
 Different classes of polymers and they are affected by molecular
weight and crystallinity.
 Mechanical properties are generally quite poor and temperature
dependent.
 Polymers have different applications, hence widely used.
 Very easy material to process and have low cost.

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