Unit III – Engineering Materials

Course Instructor: Dr. Shailesh Dhoke

 Specialty Polymers

 BIODEGRADABLE POLYMERS: POLY (HYDROXYBUTYRATE -

HYDROXYVALERATE) i.e PHBHV

 POLYMER COMPOSITES :– FIBRE REINFORCED PLASTICS (FRP)

 ENGINEERING THERMOPLASTICS: – POLYCARBONATE

 CONDUCTING POLYMERS : POLYACETYLENE

 ELECTROLUMINISCENT POLYMERS :- POLYPHENYLENE VINYLENE (PPV)

Polymers are compounds of very high molecular weights formed by the combination of a
large number of small repeating units called monomers.
The word ‗polymer‘ is derived from the Greek word poly meaning ‗many‘ and mer
meaning ‘part’.
The process by which the simple molecules (monomers) are converted into polymers is
called polymerisation. For example, many ethylene molecules combine to form a giant
molecule of polythene.
n CH2 CH2 Polymerisation ( CH —CH ) n
Ethylene (monomer) Polythene(polymer)
where n = number of monomers in the polymeric chain.

The number of repeating units in a polymeric chain is called ‘degree of

polymerisation’. In the above example, ‘n’ is the degree of polymerisation.
Classification
1. Based on Origin
Natural polymers: They are polymers that occur in nature. For example, starch (polymer
of a-D-glucose), cellulose (a polymer of b-D-glucose), proteins (polymer of a-amino acids)
and natural rubber (a polymer of poly-cis-isoprene).

Synthetic polymer: It is a polymer that is prepared artificially in the laboratory. For

example, polyethylene (PE), polyvinylchloride (PVC), nylon, terylene, bakelite, synthetic
rubber, etc.
2.On the basis of monomer composition
(a) Homopolymer If a polymer consists of identical monomers, it is termed as homopolymer.
nA (A)n

(b) Copolymer If a polymer is made up of more than one type of monomers it is called a
copolymer.
nA+mB A—A—B—B—A—B
Depending on the arrangement of the monomeric units, the copolymers may be further classified as

(i) Random copolymers The monomeric units are randomly arranged.

A — B — B — A —B — A — A — B — B — A — B —

(ii) Alternating copolymers The monomeric units are arranged in an alternating manner.
A—B—A—B—A—B

(iii) Block copolymers The monomeric units are arranged in blocks.

A—A—A—A—B—B—B—B

(iv) Graft copolymers They are branched copolymers in which the backbone is formed of one
type of monomer and the branches are formed of the other types of monomers.
A—A—A—A—A—A—A–A
B
B
B
3. On the basis of chain structure
(i) Linear polymer It has no branching other than the pendant groups associated with
the monomer. Linear polymers are well packed and therefore have high densities. For
example, polythene, nylons and polyesters.

(ii) Branched polymers These are polymers in which the monomers are joined to form
long chains with side chains or branches of different lengths. They are irregularly packed
and have low densities. If the side chain is different from parent chain, they are called
graft polymers. For example, low-density polyethene, glycogen, etc.

(iii) Cross-linked polymers These are polymers in which the monomer units are linked
together to form a three-dimensional network. These polymers are hard, rigid and brittle.
They are also called network polymers. For example, bakelite, vulcanised rubber, etc.

4. Based on chain composition

(i) Homochain polymer Polymers having all carbon atoms along their backbone are
called homochain polymers. For example, polyethene, PVC, rubber, etc.

(ii) Heterochain polymer If the polymeric chain contains a heteroatom, then they are
called heterochain polymers. For example, nylon (polymeric chain contains nitrogen
atom) and terylene (polymeric chain contains oxygen atom).
5. Based on polymerisation mechanism
(i) Addition polymers Those polymers that are obtained by the addition of monomeric
units are called addition polymers. The molecular weight of such a polymer is an exact
multiple of the molecular weight of the monomer.

n (monomer) polymer
Molecular weight of polymer = n × molecular weight of monomer. For example,
polyethene, PVC, etc.

(ii) Condensation polymers A polymer formed by the condensation of two or more than
two monomers with the elimination of simple molecules like water, ammonia and
hydrochloric acid is termed as a condensation polymer.
The molecular weight of such a polymer is not an exact multiple of the molecular weight of
the monomer. For example, Nylon 66 is obtained by the condensation of two monomers,
hexamethylenediamine and adipic acid with the loss of water molecules.
6. Based on molecular forces

(i) Elastomers They are polymers held by weakest intermolecular forces and have elastic
behavior. For example, natural rubber. These can be stretched to at least thrice their original
length but return to their original shape and dimension as soon as the stretchingm force is
removed.

(ii) Fibres These are polymers whose polymeric chains are held together by strong
intermolecular forces like hydrogen bonds or dipole–dipole interactions. They are
crystalline in nature and have high tensile strength. For example, nylon 66, polyster, silk,
etc.

(iii) Thermoplastics They are linear, long-chain polymers that soften on heating and
harden when cooled. The intermolecular forces of these polymers are intermediate between
those of elastomers and fibres. There is no cross-linking between the polymeric chains.
They can be processed again and again.
For example, polyethene (PE), polystyrene, PVC, teflon, polypropylene, etc.

(iv) Thermosetting plastics They are polymers that can change irreversibly into hard and
rigid materials on heating and cannot be reshaped once they set. They form hard, infusible,
insoluble products because of cross-linkages. For example, bakelite, melamine, Etc.
 Molecular Weight of Polymers
As the chain growth and termination is a random process, all the polymeric chains formed
are of different lengths. Under such a situation, it becomes difficult to express the
molecular weight of the polymer.

Hence, the molecular weight can be expressed as average of the molecular weights
contributed by individual molecules present in the sample.

The molecular weight of a polymer is expressed in two ways.

(i) Number average molecular weight Mn
If n1, n2, n3, … are the numbers of molecules with molecular masses M1, M2, M3, …,
respectively, then the number average molecular weight is

where ni is the number of molecules or number of moles of molecules having molecular

weight Mi.
Unit III – Engineering Materials

Lecture 1 - Biodegradable polymers:

Course Instructor: Dr. Shailesh Dhoke

 Biodegradable polymers:
 The synthetic polymers like polypropylene, polyethylene, polyamides, and
polycarbonates are used for large number of consumer, engineering and medical
applications.
 Degradation of these polymers is done by Thermal, Mechanical or Chemical processes
which give harmful products.
Disposal of such polymer waste has become a major issue. It is a major source of
environmental pollution.
Biodegradation of polymer has significant potential to tackle the problems associated with
plastic waste disposal. Also, reduce need of synthetic nonbodegradable polymers.
 Biodegradation of polymer is a process carried out by biological systems (usually
bacteria or fungi) in which polymer chain is cleaved via enzymatic activity
 A degradable material in which degradation results from the action of microorganism and
the material is converted to water, CO2 or N2 ,biomass, and inorganic salts
 A ―biodegradable‖ polymer have the ability to break down long polymer
chain safely, reliably, and relatively quickly by means biological activity,
into raw materials of nature and disappear into nature.

 If the long chain of polymer is broken into small fragments then these
fragments get metabolized by bacteria and other microorganisms.

Degradation
Biodegradable polymers are the degradable plastics in which degradation
results from the action of naturally occurring microorganisms such as
bacteria, fungi and algae.
 Why some polymers are biodegradable and some are not?
• Presence of easily hydrolysable groups in the main chain/backbone
• Presence of hydrophilic groups
• Low crystallinity Main chain containing groups
such as ester, amide, thioester
• High porosity
 Typical Degradation Mechanism
Degradation steps.
1) Water-sorption.
2) Molar Mass Reduction
3) Loss of Weight
4) Reduction of Mechanical Property (Modulus & Strength)
The first step is a fragmentation step, in which a high molar mass macromolecular chain is broken
down to oligomers having polar functional chain ends and monomers, with the loss of specific
polymer properties, such as molar mass and strength. This step can take place due to hydrolysis (with
or without enzymatic catalysis), oxidation, or any other means, depending on the chemical structure
of the polymer backbone and the environment in which the polymer is being disposed and/or used.

In the second step, oligomers with polar chain ends and monomers are mineralized by
microorganisms forming ultimately carbon dioxide (CO2), methane, water, and biomass .

The product varies depending on the availability of oxygen.

Two-step process of biodegradation—first step is fragmentation and the second step is the mineralization by microorganisms
 Factors responsible for biodegradation of Polymers
 Microorganisms: Bacteria, Fungi and Algae are responsible for biodegradation
of polymers by breaking C- C bond. The process takes place at very slow rate.
 Environment: For the degradation of polymers by the action of microorganisms
suitable conditions are required like temperature, moisture, pH, oxygen, salts
(concentration and type), pressure, light etc are important.
 Nature of polymer: For biodegradation, nature of polymer is also important
because the processes like hydrolysis, oxidation taking place during the
biodegradation depends upon the type of polymer.
 For ex. Polymers containing amines or carboxylic functional groups undergo
biodegradation easily as they have tendency to absorb water, swell and degrade.
However, if a polymer is water soluble that does not mean it is biodegradable.
 Factors affecting biodegradation of polymers
 Naturally occurring polymers are biodegradable.
 Synthetic addition polymers with carbon as the only atom in the backbone do not
biodegrade at molecular weight above 500.
 If an addition polymer chain contains atom other than carbon in the backbone, it may
biodegrade depending on attached functional groups.
 Synthetic condensation polymers are generally biodegradable to some extent depending
on functional groups (ester > ether > amide>urethane).
 Morphology: Amorphous polymers > Crystalline polymers.
 Molecular weight: Low MW Polymers > High MW Polymers.
Hydrophilic polymers degrade faster than hydrophobic Polymers.

The biodegradation of the polymer proceeds by hydrolysis and oxidation. The presence of
hydrolysable and /or oxidisable linkages in the polymer main chain, the presence of
suitable substituents, correct stereo configuration, balance of hydrophobicity and
hydrophilicity contribute to the biodegradation of the polymer
 Classification of biodegradable polymers
They can be classified into following types.
1) Natural biopolymers: originating from plant or animal resources. For ex. Cellulose,
starch, protein, collagen etc.

2) Biosynthetic polymers: produced by the fermentation process of microorganisms. For ex.

polyvinyl alcohol, hydroxyethylcellulose polymer, polycaprolactone, polylactic acid (PLA),
Polyhydroxybutyrate polymer (PHB), Polyhydroxyvalerate polymer (PHV) and
poly(hydroxybutyrate hydroxyvalerate) (PHBV) a copolymer of hydroxybutyrate and
hydroxyvalerate. PHBV is a biodegradable aliphatic polyester.

3) Synthetic biopolymers: Polymers possessing biodegradable properties are produced

synthetically. For ex. Polycaprolactone, Polylatic acid.
 Application of Biodegradable Polymers
 As packing material: find applications in food packaging, foam for industrial packaging, film
wrapping, disposable plastic packaging material such as cups, glasses, disposable food service
items etc.
Medical applications: Polymers like HB-HV, polylactic acids are used in controlled drug delivery
because of biocompatibility and biodegradability. They are also used in absorbable skin grafts and
bone places to support the body recovery systems. Cell transplantation using biodegradable
polymer scaffolds.
 Use in orthopaedic fixation devices. Biodegradable polymers are used to join fractured bones.
 They provide the required strength to the bone and after the bone heals and can take the load,
they harmlessly degrade over time. This prevents the patient from an additional operation for
removal, as would be required if a metallic device was used.
 In controlled drug delivery, the polymer slowly degrades into smaller fragments releasing the
drug gradually and in a controlled manner.
 It is used in dental devices, biodegradable vascular stents, biodegradable soft tissue anchors,
etc.
 Biodegradable polymers are also being increasingly used in the manufacture of plastic bags,
toys and other plastic products. These polymers gradually degrade in the environment (or in
landfills) and leave the environment ‗greener‘.
 Agricultural applications: Time released coatings for fertilizers and pesticides. They are also
used in making films for moisture and heat retention.
 Poly (HydroxyButyrate - HydroxyValarate): PHB-HV
Two types of Polyhydroxyalkanoates (PHA) are known, Polyhydroxybutyrate
(PHB) and Polyhydroxyvalerate (PHV). These are extracted from bacteria, which they
produced by fermenting sugars (sucrose, glucose and lactose) obtained from waste or plant
based feed stocks.
1. Polyhydroxybutyrate (PHB): PHB is produced by the fermentation of glucose by
the bacterium Alcaligenes eutruphus (A-eutrophous) or Bacillus megaterium. This
bacterium uses globules of PHB as an energy storage medium similar to that of fat in
animal or starch in plants.

Properties of PHB:
 Brittle, Highly crystalline, Water soluble
 Non toxic polymer which is relatively resistant to hydrolytic degradation.
 It shows good O2 permeability and is rapidly biodegradable.
 High melting temperature (Tm = 180 oC).
 2. Polyhydroxyvalarate (PHV): PHV can be
produced by bacterium A.eutrophus as well as
bacterium P. oleovorans, depending upon the type
of carbon structure available during fermentation.

Poly (Hydroxybutyrate - Hydroxyvalarate) [PHB-HV]

or [PHBV] or [HB-HV] co-polymer:
PHB is a brittle material which is somewhat difficult to process, as it decomposes
around 200 oC. Addition of hydroxyvalarate (HV) to the polymer leads to several
improvements in the properties as follows –
 Drop in melting temperature.
 Reduction in average crystallinity.
 Increased flexibility and toughness
 Increased impact strength
 Improved higher extension at break
Biosynthesis of PHBHV:
This copolymer of hydroxybutyrate and hydroxyvalarate is produced by
bacterium A. eutrophus when grown in the presence of glucose and either
propionic acid or valeric acid.
It is also known by trade name Biopol.

Chemical structure of PHBHV

PHBHV or PHBV or Biopol or HB-HV

 Physical properties of PHBHV

 Physical properties of Biopol copolymer vary with HV content of polymer.

 Polymer flexibility, Toughness , tensile strength, melting point increases on
increasing HV content by 0.2%.
 Melting point reaches minimum at about 30 % mole hydroxyvalarate
 The resistance of PHBV to oils is very good.
 Polymer is moisture resistant and impermeable.
 However, it is susceptible to hydrolysis above pH = 9 and below pH = 3, it can
be dissolved in number of chlorinated solvents like chloroform and methylene
chloride.
 Biodegradation of PHBV

 PHBV shows complete biodegradation in both aerobic and

anaerobic conditions.
 In aerobic condition PHBV produce CO2 and water.
 In anaerobic condition it produce Methane and CO2
 The rate of degradation depends on moisture, nutrient supply,
temperature, pH etc.
 Applications of PHBV
1. Medical applications:
PHBV are used for controlled drug delivery.
These HB-HV copolymers are suitable as matrices for controlled release of
drugs due to their favorable biocompatibility and biodegradation properties.
The polymer slowly degrades to smaller fragments, thus release drug in
controlled manner.
PHBV are currently used for internal suture. It is non toxic, biodegradable so
it does not required to removed after recovery.
2. Disposal Personal Hygiene : As sole structural material or as part of
degradable composite.
3. Packaging – PHBV can be used for packaging films, blow moulded bottles
and as a coating paper.