Module 4: Engineering Materials - Polymers

⚫ Classification of polymers, molecular weight

⚫ Chemical structure and thermal transitions
⚫ Addition and Condensation Polymerization
⚫ Polymer processing, Polymer additives, blends & composites
⚫ Elastomers and thermosets, Flame-retardants
⚫ Thermoplastics and Fibers: ABS, PVC, PTFE and bakelite
⚫ Biopolymers and biodegradable & Conducting polymers
⚫ Application of polymers as catalyst, catalysts
support, membranes
⚫ Polymer degradation, stability and various
environmental issues

2
Polymer
⚫ The word polymer is
derived from the classical
Greek words poly meaning
“many” and meres meaning
“parts.”
⚫ Simply stated, a polymer is
a long-chain molecule
that is composed of a
large number of repeating
units of identical
structure.

3
Polymer
⚫ The monomer is the repeat unit
of the polymer, and a typical
polymer may have from hundreds
to hundreds of thousands of
repeat units.
⚫ Synthetic polymers are created by
chemical reactions in the
laboratory; natural polymers (or
biopolymers) are created by
chemical reactions within
organisms.

4
Synthetic polymers such as plastics, rubbers, and
specialized glasses have revolutionized everyday
life

Plastics Synthetic
rubbers
5
6
Degree of polymerization
Degree of polymerization (n) (or the number of
repeat units in a chain) is defined as the ratio between
the molar mass of the polymer and molar mass of the
repeat unit.

𝑛𝐴 → (𝐴)𝑛

7
Molecular weight of polymer
⚫ Even though any given chain within
a sample of a polymer has a fixed
molar mass, the degree of
polymerization often varies
considerably from chain to chain.
⚫ For this reason, polymer chemists
use various definitions of
average molar mass, and a
common one is the number-
average molar mass:

8
Molecular weight of polymer
⚫ Number-average molecular
weight

⚫ Weight-average molecular
weight

9
Calculate Mn and Mw
No. of moles of ith Molar mass of ith
polymeric chain (Ni) polymeric chain (Mi)
250 12500
325 14520
175 16500
200 17250

=14927.89 =15142.17

10
Polydispersity Index (PDI)
⚫ Ratio of Mw and Mn is known as Polydispersity Index
(PDI)
𝑴𝒘
𝑷𝑫𝑰 =
𝑴𝒏

11
Polydispersity Index
No. of moles of ith Molar mass of ith
polymeric chain (Ni) polymeric chain (Mi)
250 12500
325 14520
175 16500
200 17250

PDI=1.014

12
Classification of Polymers

13
Classification of Polymers
⚫ Based on their thermal processing behavior:
⚫ Thermoplastics and thermosets

⚫ Based upon mechanism of polymerization

⚫ Addition and condensation polymers

⚫ Based on polymer chain backbone

⚫ Homochain and heterochain polymers

⚫ Based on polymer structures

⚫ Copolymers of different types
14
Thermoplastics and Thermosets
⚫ Thermoplastic polymers melt or deform on heating.
This may seem like a weakness because it means that
they are not suitable for high temperature
applications. Example: Polyethylene
⚫ Thermoset polymers can maintain their shape
and strength when heated. Example: Bakelite
⚫ The name “thermosetting” comes from the fact that
these polymers must be heated to set or “lock in” their
structures. But once this has been done, the materials
offer increased strength and do not lose their shape
upon further heating.

15
Thermoplastics and Thermosets

16
Thermoplastics and Thermosets

17
Addition and condensation
polymers
⚫ An addition polymer is a polymer that forms by
simple linking of monomers without the co-generation
of other products.

⚫ Condensation polymers are any kind

of polymers formed through a condensation reaction
— where molecules join together—losing small
molecules as byproducts such as water or methanol.

18
Addition Polymerization

⚫ Steps in addition
polymerization:
⚫ Chain initiation
⚫ Chain propagation, and
⚫ Chain termination
19
Addition Polymerization: Chain
Initiation
⚫ An addition polymerization begins with
the generation of a free radical.

20
 Addition Polymerization: Chain
Propagation
⚫ This free radical then attacks the double bond in a
monomer molecule, forming a new radical that
now includes one monomer unit.

⚫ The resulting radical

attacks the double
bond of another
monomer, breaking
it and forming an
additional single
bond.

21
Addition Polymerization: Chain
Termination
⚫ Eventually, a radical will be eliminated, either by
encountering another radical or by some other
reaction. This stops the polymer molecule from
growing longer and is referred to as chain termination.

22
Condensation Polymerization
⚫ In this reaction, there are two functional groups on the
monomer, which can react together to form the
polymer and some small molecules.
⚫ Those small molecules then split off, and the
remaining parts of the two monomers are joined
together. (The term condensation polymer originates
from the fact that the small molecule eliminated is
often water.)

23
Condensation Polymerization

24
Condensation Polymerization

25
Based on backbone: Homochain
and Heterochain Polymers
⚫ Polymers having all carbon atoms along their
backbone are important examples of homochain
polymers.
⚫ They may be further classified depending upon
whether there are single or double bonds along their
backbone.
⚫ Carbon-chain polymers with only single bonds along
the backbone are called polyalkylenes (or
polyalkylidenes). Examples of polyalkylenes include
polystyrene, the polyolefins (e.g., polyethylene and
polypropylene), and poly(vinyl chloride). 26
Homochain Polymers

Polystyrene Polyethylene
27
Heterochain Polymers
⚫ Heterochain polymers that contain more than one
atom type in their backbone are grouped according to
the types of atoms and chemical groups (e.g., carbonyl,
amide, or ester) located along the backbone.
⚫ The most important classes of organic
heterochain polymers are listed in the next
slide.
⚫ Another important class of heterochain polymers
includes polysiloxanes. These have a –Si–O–
backbone with methyl or other substituent groups
attached to silicon. 28
29
Based on Polymer Structure
⚫ Based on how monomers repeat, polymer can be
of various types.
⚫ Polymers with two different repeating units in
their chains are called copolymers.
⚫ Depending on how these two different unit
arragnes, copolymers can be of several types.
⚫ Random copolymer
⚫ Alternate copolymer
⚫ AB-block copolymer
⚫ ABA-triblock copolymer
⚫ Graft copolymer
30
Copolymers

31
Copolymers
⚫ AB-block copolymers: Copolymers that contain a
long block of one monomer (A) followed by a block of
the other monomer (B).

-A-A-A-A-B-B-B-B-A-A-A-A-B-B-B-B-

⚫ ABA-triblock copolymers: ABA-triblock copolymers

have a central B block joined by A blocks at both
ends.

32
Copolymers
⚫ Graft copolymers: Copolymers that can be
prepared by polymerizing a monomer in the
presence of a fully formed polymer of another
monomer.

33
What is the degree of
polymerization (DP) of low density
polyethylene (LDPE) having an
average molecular weight (M) of
27,974?

34
A polymer has polydispersity index of 1.98. Find
out the weight average molecular weight (Mw)
of the polymer from the following data:
No. of different types Molar mass of each
of molecules (Ni) type of molecules (Mi)
150 82500
230 95000
355 35000
490 40200
𝑴𝒘
𝑷𝑫𝑰 =
= 54161.63 𝑴𝒏
Mw = 107240.03 35
Question
Classify the following polymers based
on their backbone.
Write the monomeric units for each.
(i) (ii)

36
Write the structure of the polymer formed from each
monomer unit (wherever possible)
37
Draw the Stucture of polymers

38
39
Find out corresponding monomers
of thepolymers given below?

40
Find out corresponding monomer of
the polymer given below?

41
42
Properties of Polymers:
Amorphous vs Crystallites
⚫ Many important synthetic polymers
such as polystyrene and poly(methyl
methacrylate) consist of long, flexible
chains of very high molecular
weight.
⚫ In many cases, individual chains are
randomly coiled and intertwined with
no molecular order or structure. Such
a physical state is termed
amorphous.
43
Crystallinity
Polymer chains with very regular
structures, such as linear polyethylene and
isotactic polypropylene, can be arranged in
highly regular structures called
crystallites.

Crystalline-melting
temperature or Tm is a
temperature at which
crystalline–amorphous
transition occurs.

44
Glass Transition Tempeture (Tg)
⚫ The glass–liquid transition, or glass transition, is
the gradual and reversible transition
in amorphous materials from a hard and
relatively brittle "glassy" state into a viscous or
rubbery state
⚫ The glass-transition temperature Tg of a material
characterizes the range of temperatures over which
this glass transition occurs.

45
Concept of Tg – in Chewing Gum
⚫ At body temperature the gum
is soft and pliable, which is
characteristic of an
amorphous solid in the
rubbery state.
⚫ If you put a cold drink in
your mouth or hold an ice
cube on the gum, it becomes
hard and rigid.
⚫ The glass transition
temperature of the gum is
somewhere between 0 °C
and 37 °C. 46
Glass Transition Tempeture (Tg)

⚫ Glass transition temperature is lower than the melting

temperature, Tm, of the crystalline state of the
material, if one exists.
47
Glass Transition Tempeture (Tg)

48
Comparison of Tg with Melting
Crystalline-melting temperature or Tm is a temperature at which
crystalline–amorphous transition occurs. The glass transition is NOT
the same as melting.
⚫ Glass Transition
⚫ Property of the amorphous region

⚫ Below Tg: Disordered amorphous solid with immobile molecules

⚫ Above Tg: Disordered amorphous solid in which portions of

molecules can wiggle around
⚫ Melting
⚫ Property of the crystalline region

⚫ Below Tm: Ordered crystalline solid

⚫ Above Tm: Disordered melt

49
Factors Influencing Tg
⚫ The value of Tg depends on the mobility of the
polymer chain - the more immobile the chain, the
higher the value of Tg

⚫ Anything that restricts rotational motion within

the chain should raise Tg

⚫ A polymer chain that can move easily will change from

a glass to a rubber at a low temperature
⚫ If the polymer chains don't move as easily, then it
will require a relatively high temperature to change
the compound into a rubbery form
50
Factors Influencing Tg
⚫ Chain Stiffness:
Poly(ethylene
adipate)
Tg = -70oC

Poly(ethylene terephthalate)

Tg = 69oC

51
Factors Influencing Tg
⚫ Intermolecular Forces: Stronger intermolecular
forces lead to a higher Tg
Polypropylene

Tg = -20oC

Poly(vinyl chloride)

Tg = 81oC

52
Factors Influencing Tg
⚫ Pendant Groups:
Bulky pendant groups, such as a benzene ring, can
catch on neighboring chains like a "fish hook" and
restrict rotational freedom. This increases Tg
Polypropylene

Tg = -20oC

Polystyrene

Tg = 100oC

53
Factors Influencing Tg
⚫ Pendant Groups:
Flexible pendant groups, such as aliphatic chains,
tend to limit how close chains can pack. This increases
rotational motion and lowers Tg.
Poly(methyl methacrylate)
Tg = 105oC

Poly(butyl methacrylate)

Tg = 20oC
54
Which one of these has high Tg?

55
Question
⚫Which polymer from each of the following
pair is expected to have a higher glass
transition temperature? Explain with reasons.
⚫(i) Polyethylene and polyacetylene

56
Synthesis, properties and applications
of various types of polymers
⚫ Plastics
⚫ Fibers
⚫ Resins
⚫ Elastomers / Viscoelastomers

57
Plastics: Polyethylene (PE)
⚫ Synthesis:

58
Properties of Polyethylene

LDPE

59
HDPE

60
Plastics: Polyvinyl chloride (PVC)
⚫ Synthesis:

61
Plastics: Polytetrafluoroethene
(PTFE)
⚫ Synthesis:

62
Properties and Uses of PTFE

63
Plastic: Acrylonitrile-Butadiene-Styrene
(ABS)

ABS is a tough, heat-resistant thermoplastic.

Polystyrene provides ease of processing, glossiness, and
rigidity.
Acrylonitrile adds chemical resistance and hardness,
and butadiene provides impact resistance.
64
Acrylonitrile-Butadiene-Styrene (ABS)

ABS is a tough, heat-resistant thermoplastic.

Polystyrene provides ease of processing, glossiness,
and rigidity.
Acrylonitrile adds chemical resistance and
hardness,
and butadiene provides impact resistance.

ABS is the standard material of choice for the strong plastic

cases of computers, televisions, and other household
electronic goods and sometimes is used as an alternative to65
 Synthesis and applications of ABS

ABS is the standard material of choice for

the strong plastic cases of computers,
televisions, and other household
electronic goods and sometimes is
used as an alternative to PVC for pipes.

66
Fibers: Nylon-6,6
⚫ Nylon-6,6 is a type of polyamide or nylon.

⚫ It, and nylon 6, are the two most common for textile
and plastic industries.
⚫ Nylon-6,6 is made of two monomers each containing
6 carbon atoms, hexamethylenediamine and adipic
acid, which give nylon-6,6 its name.

67
H-Bonding in Nylon-6,6

68
Fibers - Cellulose
Structure of Cellulose

⚫ Cellulose is one of many polymers found in nature. Wood, paper,

and cotton all contain cellulose. Cellulose is an excellent fiber.
⚫ Wood, cotton, and hemp rope are all made of fibrous cellulose.

⚫ Cellulose is made of repeat units of the monomer glucose. This is

the same glucose which your body metabolizes in order to live,
but you can't digest it in the form of cellulose.
⚫ Because cellulose is built out of a sugar monomer, it is called
a polysaccharide.
69
H-Bonding in Cellulose

70
Resins: Bakelite
⚫ Bakelite was the
first plastic made from
synthetic
components.

⚫ It is a thermosetting phenol
formaldehyde resin,
formed from a
condensation reaction of
phenol with for
maldehyde.

71
Synthesis of Bakelite

72
Synthesis of Bakelite

73
Structure of Bakelite

74
Bakelite: Properties and Uses

75
⚫ Elastomers can be broadly classified as belonging
to one of three groups:
⚫ Diene elastomers,
⚫ Non-diene elastomers, and
⚫ Thermoplastic elastomers.

76
Diene Elastomers

77
Nondiene Elastomers
⚫ A number of important elastomers do not have the
unsaturated chain structure characteristic of the
diene elastomer.

⚫ These nondiene elastomers include

polyisobutylene (butyl rubber), polysiloxane
(silicone rubber),
fluoroelastomers such as Viton, polyurethane
elastomers such as Spandex, and elastomers
derived from ethylene and propylene (EP and
EPDM elastomers).

78
Example: Silly Putty
⚫ Silly Putty is a toy based
on silicone polymers that have
unusual physical properties.
⚫ It bounces, but it breaks
when given a sharp blow, and
it can also flow like a liquid.
⚫ It contains a viscoelastic
liquid silicone which makes it
act as a viscous liquid over a
long time period but as an
elastic solid over a short time
period.
79
80
Linear vs Cross linked elastomers

81
Question
⚫How can you classify polymers
based on amount of crosslinking?

Ans:
Thermoplastics
Elastomers
Thermosets
82
Biopolymers
⚫ Biopolymers are polymers produced by living organisms; in
other words, they are polymeric biomolecules.
⚫ Biopolymers contain monomeric units that are covalently
bonded to form larger structures.
⚫ There are three main classes of biopolymers, classified
according to the monomeric units used and the structure
of the biopolymer formed:
⚫ Proteins and polypeptides, which are polymers of amino
acids; and
⚫ Polynucleotides (RNA and DNA), which are long
polymers
composed of 13 or more nucleotide monomers;
⚫ Polysaccharides, which are often linear bonded
polymeric carbohydrate structures 83
Polypeptide and Proteins
⚫ Polypeptides are chains of amino acids. Proteins
are made up of one or more polypeptide
molecules.
⚫ Proteins are heteropolymers containing up to 20
different types of amino acids of the general
structure

⚫ where R is a hydrogen atom in the case of the simplest

amino acid glycine or any of a wide variety of
substituent groups such as CH3 (alanine) or an alkyl
group as in
the case of leucine. 84
Polypeptide and Proteins

85
Polypeptide and Proteins
⚫ Write the structure of the di-peptide formed
by combining the following amino acids:

86
Polypeptide and Proteins
⚫ Write the structure of the tri-peptide formed
by combining the following amino acids:

87
A protein has 120 amino acid residues.
How many peptides bonds are
present in the protein backbone?

88
Biodegradable polymer
⚫ Biodegradable polymers are a
special class of polymer that breaks
down after its intended purpose by
bacterial decomposition process to
result in natural byproducts such as
gases
(CO2, N2), water, biomass, and inorganic
salts
⚫ These polymers are found both naturally
and synthetically made, and largely
consist of ester, amide,
and ether functional groups.
⚫ Used in medical industries, and as
packing materials 89
Degradation process
⚫ Aerobic
degradation

⚫ Anaerobic degradation

90
Conductive Polymer
⚫ Polymers obtained by the usual methods
of polymerization are mainly insulators.

⚫ A number of polymers are electrically conductive or

can be made to be conductive by doping with an
electron donor or acceptor.

⚫ Applications: (a) polymeric electrodes for lightweight

batteries, (b) variable-transmission windows, (c)
electrochromic displays, (d) sensors, and (e)
nonlinear optical (NLO) materials.

91
Conductive Polymer
⚫ Polyacetylene with molecular weight up to 1 million can
be prepared through a complicated process involving a
metathesis polymerization.
⚫ The cis isomer of polyacetylene can be transformed
to the more stable trans isomer by heating, as
follows:

⚫ The trans isomer has higher conductivity (4.4 × 10-5 S cm-1)

than the cis isomer (1.7 × 10-9 S cm-1).
92
Other Conductive Polymer

Poly(p-phenylene) (PPP) Polythiophene (PT) Polypyrrole

(PPy)

93
⚫ Match the following!

Linear Chain Polymer Polyester

Branched Polymer Bakelite

Heterochain polymer Low density polyethylene (LDPE)

Thermoset Polystyrene

Homochain polymer High density polyethylene

(HDPE)

Polyethylene terephthalate Nylon 6,6

94
⚫ Match the following!

Linear Chain Polymer Polyester

Branched Polymer Bakelite

Heterochain polymer Low density polyethylene (LDPE)

Thermoset Polystyrene

Homochain polymer High density polyethylene

(HDPE)

Polyethylene terephthalate Nylon 6,6

95
Which one of the following will have high
glass transition temperature? Give the
reason

96
Which of the following are not formed
through condensation polymerization
process?
⚫ Polystyrene
⚫ ABS
⚫ Proteins
⚫ Bakelite
⚫ Resole
⚫ Cellulose

97
Three polymers are provided in the following table.
These polymers differ in R-Groups as indicted in the
structure and in the table. Arrange the polymers in
increasing order of glass transition temperature (Tg)

98
Question
Which polymer from each pair will
show a higher glass transition
temperature?
Give reasons.

99
Question
Which polymer from each pair will
show a higher glass transition
temperature?
Give reasons.

100
Under UV light many polymer slowly
and spontaneously degrades into its
monomers. Comment on the sign of
ΔS, and ΔG.

101
Question
Write the structure of the polymers
formed from the following reactions:

102
Draw the structure of the copolymer
formed from the following monomers.

103
Draw the structure of two monomers
from which the following copolymer was
synthesized:

104
Question
Calculate the degree of polymerization of
acrylonitrile, if the molecular weight of polymer is
1.31 × 105 g/mol.

Molar
mass: 106
Which one the following will show high
glass transition temperature (Tg)?
Provide reason.

106
Separate the polymers given below into fiber,
plastic and thermosetting (or resin) categories.
Write the polymer strength increasing order
for following polymers. Justify your answer
with explanation.

107
Question
Structures of four polymers are given below.
Identify each polymer as conductive and
non- conductive organic polymers and
provide the reasons.

108
Question
Kevlar fiber has 5 times more impact
strength than steel. Discuss the possible
reasons.

109
Cellulose, diacetate cellulose, and triacetate
cellulose: Arrange them according to their
Tg.
The structure of cellulose is
given:

110
What is thermodynamic driving force
for an elastomer to return to its
original shape and size upon removal
of load?

111
Which would be more likely to be softened
by heat?
a) Unvulcanized rubber or ebonite

Unvulcanize
d rubber

Ebonite

112
When you compare cellulose and
nitrocellulose structure, which one is expected
to have higher Tg and more fiber character.

113
In which of the following polymers
hydrogen bonding will predominate?
a) Natural rubber
b) Linear polyethylene
c) Cellulose
d) Cellulose nitrate

114
 Which one of the following polymer
is conducting?

Poly(p-phenylene) (PPP) Polysilazanes Polypyrrole

(PPy)

Polytetrafluoroethene Polythiophene (PT) 116

Which one of the following polymer
is conducting?

116
Which one of the following polymers
will be more hydrophobic?
Polystyrene and polymethylmethacrylate

117
Which one will have high degree of
crystallinity? Provide explanation

118
Draw the structure of tetrapeptide: Ala-Phe-Val-
Gly. The structure of the amino acids are provided
below and the three letter codes are given in
parenthesis of each amino acids

119
Polymer Processing

120
Polymer Processing

121
Polymer Processing

122
Polymer Processing

123
Polymer additives
⚫ Typically, commercial plastics are mixtures of one or
more polymers and a variety of additives such as
plasticizers, flame retardants, processing lubricants,
stabilizers, and fillers.
⚫ The exact formulation will depend upon the
specific application or processing requirement.
⚫ For example, poly(vinyl chloride) (PVC) is a thermally
unstable polymer having high modulus, or stiffness,
typical of other glassy polymers at room
temperature.

124
Plasticizers
⚫ Plasticizers, particularly for No Plasticizer
PVC, constitute one of the
largest segments of the
additives market.
⚫ The principal function of a
plasticizer is to reduce the
modulus of a polymer at
the use temperature by
lowering its Tg.

125
Flame Retardants
⚫ Flame retardants are added to alter the
combustion process in some way.
⚫ Inhibition of the vapor-phase combustion of the
fuel gases
⚫ Alteration of the thermal-degradation pathway by
providing a low energy process that promotes solid-
state reactions leading to carbonization
⚫ Formation of a protective coating to insulate
against thermal energy
⚫ Classes of flame retardants include organochlorine
compounds, organobromine compounds,
organophosphorus, antimony oxides, boron compounds,
and especially alumina trihydrate (ATH). 126
Other Important Additives

127
Other Important Additives

128
Polymer Blends
⚫ A polymer blend, is a member of a class of materials
analogous to metal alloys, in which at least two polymers
are blended together to create a new material with different
physical properties.
⚫ Immiscible polymer blends (heterogeneous polymer
blends): If the blend is made of two polymers, two glass
transition temperatures will be observed.
⚫ Miscible polymer blends (homogeneous polymer blend):
Polymer blend that is a single-phase structure. In this
case, one glass transition temperature will be observed.
⚫ Examples: polyphenylene oxide (PPO) – polystyrene (PS),
polyethylene terephthalate (PET) – polybutylene
terephthalate (PBT)
129
Write the structure of the
monomer unit

130