UNIT· Ill

113 II Engineering Materials

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Weightage : 9 Marks (ESE)

I Part A : Speciality Polymers

13,1 Introduction I
Q.1 How copolymer of hydroxybutyrate and hydroxyvalerate is
produced ? Give the structure, properties and applic ations of
copolymer. llE [SPPU : Marks 7]

(Marking scheme Copolymer preparation 2M, structure of

copolymer-lM, properties - 2M, application - 2M)
Ans. : Preparation of copolymer of hydroxybutyrate and
hydroxyvalarate :
Copolymer of h ydroxybutyrate and hydroxyvalarate is produced by
A.eutrophus when grown in the presence of glucose and either
propionic acid or valeric acid. Biopol is trade name of HB-HV or
PHBV copolymer.
• Structure of HB-HV or PHBV copolymer :
CH3 0 CH 2 -CH3 0
I II I II
- + o -CH -CH2 - C - O - CH - CH 2 -C-h-
PHBV

• Properties of HB-HV or PHBV copolymer :

1. Physical properties of Biopol copolymer vary with
h ydroxyvalerate content of polymer . As HV content increases
in the range of 0.2 %, polymer flexibility, toughness
increases.

(3 - I)

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2. Melting point of PHBV drops as compare to

hydroxyvalerate.
3. Incorporation of HV into PHB allows flexibility,tensile
strength and melting point to cover a range from, values of
typical p olyp rop ylene (low H V) to those typical polyeth ylene
(high HV).
4. The resistance of PHBV to oils is very good.
5. PHBV is moisture resistant and impermeable.
6. It is susceptible to hydrolysis above pH 9 and below pH 3,
it can be dissolved in number of chlorinated solvents like
chlorofo rm and methylene chloride.
• Applications of HB-HV or PHBV copolymer :
1) Medical applications - PHBV a re used for controlled drug
delivery.
These HB-HV copolymers a re suitable as matrices fo r controlled
re lease of dru gs du e to their favoura ble biocompatibility and
biodegrad ation properties. The polym er slowly degrades to
smaller fragments thus release drug in controlled manner. PHBV
are currently used for internal suture. Tt is non-toxic,
biodegrad able, so it is does not h ave to be removed after
recovery.
2) Disposable personal hygiene - PHBV can be u sed as sole
structural ma terial or as a p a rt of d egradable comp osite.
3) Packaging - PHBV can be used for films, blow m oulded bottles
and as a coating on paper.
Q.2 What are engineering thermoplastics ? State advantages of
engineering thermoplastics. Give structure and four properties and
two applications of polycarbonate. ~ [SPPU : Marks 7]

(Marking scheme : Definition - IM, Advantages of thermoplastics - 2M,

Structure of polycarbonate - 1M, Properties of polycarbonate - 2M,
applications - IM)

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Ans. : • Engineering thermoplastics Engineering thermoplastics

are group of materials obtained from high polymer resins w hich
provide one or more outstanding properties when compared with
the commodity thermoplastics such as polstyrene, polyethylene,
polypropylene etc.
• Advantages of Engineering thermoplastics :
i) High thermal stability
ii) Excellent chemical resistance
iii) High tensile stren gth
iv) High impact strength
v) High flexibility
vi) Hig h mechanical strength
vii) Light weight
viii) Readily mouldable into complicated shapes.
ix) High diamensional stability etc.
• Structure of polycarbonate :
CH 3 0

-+o--0-?--0-o-~-h-
cH3
Polycarbonate

• Properties of polycarbonate : It is an a morphous polymer with

attractive engineerin g properties such as,
i) It has a very high impact strength and tensile strength over
wide range of temperature.
ii) It is a highly transparent plastic. It has higher light
transmittance (about 88 %) than many types of glasses.
iii) It is resistant to water and many organic compounds but
are soluble in number of organic solvents and alkalis.
iv) It has a good heat resistance (useful upto 140 °C).

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v) It has low combustibility. It has high meltingpoint. It melts

around 265 °C.
vi) Polycarbonates have limited chemical and scratch resistance
and it has a tendency to yellow wi th long term u ltraviolet
exposure.
vii) It has a good thermal and oxidative stability in melt.
• Applications of polycarbonate :
A] Construction material : Polycarbonates have high light
transmittance, high impact strength and tensile strength.
They are used as a substitute for window glass. They are
also used in domelights, flat or curved glazing and sound
walls.
Bl Electrical and electronic components : Being good electric
insulator, having heat resistant and flame retardant
properties, it is used in various products associated with
electrical and telecommunica tion hardwa re.
They can be used for making electrical insulators, industrial plugs,
sockets, switches, covers of cell phones, laptops, pagers etc.
Q.3 What are b iodegradable polymers ? Give important features of
biodegradable polymer. How biodegradable polymers are
classified ? Give suitable example for each type. ~ [SPPU : Marks 71

(Marking scheme : Definition - lM, important fea tures - 3M,

Classification with example - 3M)
Ans. : • Biodegradable polymers : Biodegradable polymers are the
polymers w hich are degraded by biological means such as
microorganisms.
• Important features of biodegradable polymer :
i) Naturally occuring poly mers are biodegradable.
ii) Synthetic addition polym ers with only carbon atom main
chain are not biodegrable at molecular weight above 500.
iii) If polymer chain contains a tom other than carbon in the
backbone, it may biodegrade d epending on attached
functional groups.

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iv) Synthetic polycondensation polymers are generally

biodegradable to differen t extent depending on functional
groups involved (ester > ether> amide).
v) Amorphous polymers are more suseptible for biodegradation
compared to crystalline polyn1ers.
vi) Generally lower molecular weight polymers tmdergo
biodegradation easily compared to high molecular weight
polymers.
vii) Hydrophilic polymers degrade faster than hydrophobic.
• Classification of biodegradable polymers Biodegradable
polymers can be di vided into 3 classes.
l) Natural biopolymers - Originating from plant or animal
resources,. For e.g. cellulose, stard1, protein etc.
2) Biosynthetic biopolymers - Produced by fermentation
process by micro organisms. For e.g. polyhydroxy alkanotes
(Polyhydroxy butyrate, polyhydroxy valerate).
3) Synthetic biopolymers - Polymers possessing biodegradable
properties are produced synthetically.
For e.g. polycaprolactone, polylactic acid.
Q.4 What are conducting polymers ? What are the structural
requirements for a polymer to be conducting ? Explain intrinsically
and extrinsically conducting polymers with example.
BE [SPPU : Marks 7]

(Marking scheme : Definition - 1M, Structural requirements-2M,

Explanation of intrinsically and extrinsically conducting polymers with
example - 2M each)

Ans. : Conducting polymers : Conducting polymers are synthetic

polymers which show conductivity unlike many synthetic polymers
due to high planarity and conjugation p resent in them.
• The structural requirements for a polymer to be conducting are
a) having high planarity a nd b) presence of conjugation.
• Intrinsically Conducting Polymers (ICP) Some synthetic
polymers can conduct electricity on their own because of their

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structural features. Such polyme rs are known as Intrinsically

conducting polymer.
• These polymers (ICP) are linear, have high planarity in structure
and possess conjugation (alte rnate do uble bond and single bond)
in the polymer chain. When electric field is a pplied, conjugated
electrons (d elocalised electrons) of the polymer get excited and
can be transported through the polymer through resonance.
Increase in conjugation, in creases the conductivity to a larger
extent.
For example :
i) Trans - polyacetylene

H H H H

ii) Polyaniline

~NH--0--NH~

iii) Polyparaphenylene

Conductivity can also be observed in arom atic, heteroatomic system

due to d elocalised electron pair.

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For example :
1. polypyrrole

2. polythiophene

• Extrinsically conducting polymers - These are conducting

polymers whose conductivity is achieved because of externally
added ingredient in them. It can be achieved in 2 ways -
i) Conductive element filled polymer : Metallic fibres, metal
oxides or carbon black can be mixed in the polymer during
moulding process. Polymer acts as a binder to hold the
conducting elements.
Conducting plastics containing carbon black finds uses in wires
and cables, antistatic devices, video discs, audio records etc.
ii) Blended conducting polymer : It is obtained by blending
conducting polymer with conventional polymer, physically or
chemically.
Q.5 What is doping ? How conductivity of intrinsically conducting
polymers (ICP) can be increased using doping process ? Explain
with suitable example and state the different dopants used.
!ti" [SPPU : Marks 7)

OR What is doping ? How conductivity of intrinsically conducting

polymers (ICP) can be increased using doping ? !ti" [SPPU : Marks 5]

(Marking scheme : Definition-lM, explaination of doping process-2M,

p-doping with example-lM,n-doping with example-lM)
Ans. : Doping : Intrinsically Conducting Polymer (ICP) possess low
conductivity, but their conductivity can be improved by creating

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positive or negative charges on the polymer chain by oxidation or

reduction. This technique is called doping.
Conductivity of intrinsically conducting polyme rs (ICP) can be
increased using doping process. There are two types of doping
techniques used as follows -
i) P-doping : It includes doping of ICP with a Lewis acid.
Oxidation (removal of electrons) takes place and positive charge
is developed on polymer chain increasing conductivity.
Lewis acids like 12 , Br2 , FeCI3 , PF6 , AsF5 can be used as
p-dopa nts.
Polyacetylene can be doped as follows using iodine as a dopant,
2 (C 2 H 2 )n+3 12 Oxidation
------> 2 [ (C 2 H 2 )n+ 13 ]

ii) N-doping : It includes treating of ICP with a Lewis base.

Reduction (addition of e lectrons) takes place and negative
charge is developed on polymer chain, increasing conductivity.
Lewis base like lithium, sodium metals, naphthyl amines can be
used as n-dopants.

Q.6 Give structure, properties and applications of polyphenelyne

vinylene (PPV).Explain construction and working of basic polymer
LED based on polyphenelyne vinylene (PPV) . ~ SPPU : Marks 7]

(Marking scheme structure-IM, properties- IM, applications-IM,

Explaination-3M, diagmm-IM)
Ans. : Structure of polyphenelyne vinylene (PPV) : Polyphenylene
vinylene (PPV) is a conducting polymer with conjugated system.
Highly oriented PPV films a re obtained by soluble polymeric
precursor. The structure of PPV chains resembles that of other
higher oriented rigid rod polymers, where, the molecules are
oriented along the the fiber axis (often the s tretching d irections).

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Properties :
1. PPV is a diamagnetic material.
2. It h as a very low intrinsic electrical conductivity (10 - 13 S/cm).
3. The electrical conductivity increases upon doping with iodine,
ferric chloride, alkali metals or acids. However, the stability of
these doped material is relatively low.
4. Alkoxy substituted PPV shows ease of oxidation and have much
higher conductivities. Large side chain substitutions lower the
conductivity.
5. PPV is water insoluble, but its precursors can be manipulated
in aqueous solution .
6. It gives bright yellow-green fluorescence on application of
electric field.
Applications :
i) PPV is capable of electroluminescence. Due to its stability,
processibility and electrical as well as optical properties, PPV is
used in Organic Light Emitting diode (OLEO). Devices based
on PPV as emissive layer, emit bright yellow-green fluorescent
light and derivatives of PPV are used when light of different
colour is required.
ii) PPV is also used in organic solar cells, photovoltaic devices,
sensors etc.

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Construction and working of basic polymer LED based on

polyphenelyne vinylene (PPV) :
• Construction : Semiconducting polymers, with electron system
such as PPV exhibit electroluminescence. To generate light with
these mate rials, a th in film of semiconducting polymer is
sandwitched between two electrodes. Indium Tin Oxide (ITO) is
commonly used anode material. It is transparent electrode
material which is deposited on glass/plastic substrate. Metals like
calcium, magnesium, aluminium are used for cathode.
• Working : Electrons and holes are then injected from the cathode
and anode respectively into polymer. Driven by the electric field,
the charge carrie rs move through the polymer over certain
distance and recombination takes place.
• The recombination of these charge carriers results in
luminescence. The band gap (energy d ifference between valence
band and conduction band) determine the wavelength and the
colour of emitted light.

Aluminium, magnesium
or calcium

Indium tin Glass / Plastic substrate

oxide

D Light D
Fig. Q.6.1 Device structure of single layer polymer electroluminescent
diode (Polyer LED)

Q.7 Give the structure of cis and trans isomer of polyacetylene.

How cis polyacetylene is converted into trans polyacetylene ? How
conductivity of trans-polyacetylene can be improved ? Explain with
reactions involved. ~ [SPPU : Marks 7]

(Marking scheme : Structure of cis and trans isomer-2M, conversion of

cis form to trans form-2M, improvement in conductivihJ of trans
form-3M)
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Ans. : Structure of polyacetylene -

• The polymer consist of a long cha in carbon atoms with
alternating single and double bonds between them. Each carbon
possesses one hydrogen atom. Polyacetylene is observed in two
forms, cis-polyacetylene and trans-polyacetylene.
H H H H

" C=C/ " C=C/ /

/ \=(
I \
\=c
I \
H H H H

Cis-polyacetylene Trans~polyacetylene

• Cis-polyacetylene is converted into trans polyacetylene by raising

the temperature of the film of cis isomer, to about 200 °C, further
isomerization takes place to form more stable trans fo rm.
• Tran s-polyacetylene has hig her conductivity (4.4 x 10-5 S cm)
than cis-polyacetylene (1.7 x 10- 9 S/cm). Doping of trans form
with AsF5 , I2 increases conductivity to about 400 S/cm. Doped
polyacetylene has condu cti vity comparable to that of good
conductor such as copper and silver.
There are 2 types of doping carried out on trans-polyacetylene as
follows :
i) Oxidation with 12 (p-doping)

i) Oxidation, known as 2 (C2H2ln + 312 ----- 2 [ (C2H2)~ 1;]

p-doping. Polyacetylene
ii) Reduction with alkali metals like Na (n-doping)

ii) Reduction, known as (C2H2ln + Na ----- (C2H2)~ Na

n-doping. Polyacetylene
Q.8 What are electroluminescent Polymers ? Give applications of
electroluminescent Polymers. Explain construction and working of
basic polymer LED based on polyphenelynevinylene (PPV).
~ [SPPU : Marks 7)

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(Marki11g scheme Defi11itio11-1M, applications-1M, construction-3M,

working-1M,diagram-1M)
Ans. : • Electroluminescent polymers Electroluminescent
polymers are the polymers which emit light in response to the
passage of an electric current or a strong electric field.
• Applications of electroluminescent polymers
Electroluminescent polymers have potential appJjcations in Light
Emitting Diode (LED) devices.(Flat panel displays for computer
monitors, televisions screens, mobile phone displays) and colour
pixels in ink jet printing e tc.
Construction and working of basic polymer LED based on
polyphenelyne vinylene (PPV) :
• Refer Q.6.
Q.9 How Fibre Reinforced Polymer composite (FRP) is prepared ?
Which are the factors that influence properties of FRP ? Give
advantages, limitations and applications of Glass fibre reinforced
polymer composite. ~ [SPPU : Marks 71

(M/lrki11g scheme : Preparation of FRP-1M, factors i11flue11ci11g properties

of FRP-1M,Glass fibre reinforced polymer composite ndvnntages-1M,
li111itatio11s-IM, application-lM)
Ans. : Preparation of FRP : Fibre reinforced polyme r is a
composite material prepared from a polymer matrix which is
reinfo rced with fibres.
• Factors influencing properties of FRP :
i) Nature, orien tation and distribution of fibres
ii) Nature of polymer matrix
iii) Strength of interfacial bon ds between fibre phase and
polymer matrix phase.
• Glass fibre reinforced polymer composite -
Advantages : They show improved properties as,
i) High tensile strength and impact resistance
ii) Lower densities

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iii) Excellent resistance to corrosion and chemicals.

Limitations :
i) Since polymer matrix deteriorates or flows at high temperature,
they show applicahons in limited temperature range.
ii) Since the material do not possess desired stiffness and rigidity,
they can not be e mployed as structural components.
Applications :
• They are used in automobile parts, storage tanks, industrial
flooring, plastic pipes etc. They are extensively used in
automobiles to reduce vehicle weight and boost fuel efficiency.
Q.10 What are polymer composites ? What are the constituents of
polymer composite? What are the types of polymer matrix ? State
important functions of matrix phase. ~ [SPPU : Marks 7]

(Marking scheme : Definition-lM, constituents of composite-2M, Types of

mntrix-2M, functions of matrix-2M)
Ans. : Polymer composite is the material which is made up of
polymer matrix and reinforcing materials being put together with
a defined interface.

Constituents of composites
Two essential constituents of polymer composites are,
A) Polymer matrix phase - It gives a continuous body constituent,
surrounding the othe r phases and gives a bulk form to the
composite. Commercial the rmoplastic and thermosetting
materials are used as polymer matrix.
For e.g. Epoxy resins, polyamides (nylons) etc.
B) Reinforcement / Dispersed phase They are structural
conshtuents Like fibres, sheets, particles which are embedded in
matrix phase and provide high strength, rigidity and enhance
matrix properhes.
Polymer matrix : Polymer is commonly used matrix material
due to its processibility, light weight and desirable mechanical
properties.
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Polymer matrix materials can be of 2 types :

i) Thermoplastics : Thermoplastics are the one which can be made
soft on heating and hard on cooling. Thermoplastic composites
can be pre-fabricated into semi-finished items and later can be
converted to final shape. The advantages of thermoplastic
composites a re, they have high toughness, high impact
resistance, good chemical resistance. TI1ey have high reparability
and recyclability. For e.g. Polyolefins, Polyimides,Vinylic
polymers, Polyphenyles e tc. are commonly used thermoplastic
matrix materials.
ii) Thermosetting : They have three dimensional network like
structure, After curing, they get fina l shape w hich cannot be
changed. On further heating, they decompose but do not
become soft. TI1ey are most suitable for fibres composites and
structural engineering applications. Thermosetting polymers
used as matrix material are Epoxy resins, Phenolic resins,
Polyesters etc.
Functions of matrix phase are :
i) It binds the dispersed phase/reinforcement together.
ii) lt helps in distributing externally applied load to the
reinforcement.
iii) It prevents the development of cracks due to its plasticity and
softness.
iv) It protects the reinforcement/dispersed phase from chemical
achon and keeps them properly oriented under the action of
load.
Q.11 What are polymer composites ? What are the constituents of
polymer composite ? What is carbon fibre reinforced polymer
composites ? Give advantages and applications of carbon fibre
reinforced polymer composites. I& [SPPU : Marks 7)

(Marking scheme : Definition-1M, constituents of composite-2M , carbon

fibre reinforced polymer composites definition-1M, advantages-2M,
application-IM)
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Ans. : • Polymer composite is the material which is made up of

polymer matrix and reinfmcing materials being put together with
a defined interface.
• Constituents of composites : Two essential constituents of
polymer composites are,
A) Polymer matrix phase : It gives a continuous body
constituent, surrounding the other phases and gives a bulk
form to the composite. Commercial thermoplastic and
thermosetting materials are used as polymer matrix. For e.g.
Epoxy resins, polyamides (nylons) etc.
B) Reinforcement / Dispersed phase : They are structural
constituents like fibres, sheets, particles which are embedded
in m atrix phase and provide high strength, rigidity and
enhance matrix properties.
• Carbon fibre reinforced polymer composites - They use carbon
fibre reinforced in polymer matrix like epoxy or polyester resins.
Carbon fibres are obtained by pyrolysis of cellulose/acrylonitrile
in an inert atmosphere. Carbon fibres have much higher elastic
modulus than glass fibres and show bettte r resistance to
te mperature and corrosive chemicals. However, they are short
fibres and are more expensive.
• Advantages : They show improved properties as,
i) Excellent resistance to corrosion
ii) High elastic modulus
iii) Low density
iv) High temperature resistance
Applications :
1) They are used as structural components (like wings, body,
stabilizer) of aircrafts and helicopters.
2) They are used in making sports goods (rackets, archery, racing
bicycles), laptops, fishing rods, musical instruments (violin
bows, guitar pickguards) etc.

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Q.12 Give classification of composites based on reinforcement.

State the properties and any four applications of polymer
composites. I& [SPPU : Marks 7]

(Marking scheme : Differe11t types based on reinforce1nenl with cxnmple-

3M, Four general properties- 2M, four applications- 2M)
Ans. : Classification of composites :
Based on reinforcement forms, composites can be classified as,
1) Particle reinforced composites / Particulate composites - These
are composed of particles distributed or embedded in the matrix
body. Metallic or non-metallic particles can be added to polymer
matrix to improve mechanical strength. For e.g. Carbon black
rei nforced rubber show improvement in tensile stren gth,
toughness and abrasion resistance and are used in
manufacturing automobile tyre. Concrete concrete or wood
particle boards are other examples of this category.
2) Fibre reinforced composites - These are composed of fibres
embedded in the matrix material, These can be further divided
into 3 categories - Continuous aligned, discontinuous aligned
and discontinuous randomly oriented fibre composites.
3) Structural composites - Properties of structural composites
depend not only on the constituent materials but also the
geometrical design of formation.
• Properties of Composites :
Polymer composites possess
i) High tensile strength
ii) High stiffness
iii) High thermal stability
iv) Cheap and easily fa bricable
v) Low thermal expansion
vi) High impact resistance
yji) High oxidation resistance
viii) High abrasion resistance

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• Applications of Composites -
Becau se of high stren gth, high im p act resistance, low coefficient of
expansion, low cost and ease in fabrication, po lym e r com posites are
used in variety of ap plications as,
i) In automobile body and parts, turbine engines, pumps, valves
etc.
ii) ln fabrication of roofs and floors, furniture (plywood ).
iii) In manufacturing sports goods (rackets), toys, musical
instruments.
iv) In marine application s - shafts, hulls, propellers e tc.
v) In components of rockets, aircrafts, helicopters etc.
vi) In electronic a pplication s - communication antenna, electronic
circuit boards (PCB).
Q.13 What are engineering thermoplastics ? State important
advantages of engineering thermoplastics. Give two examples of
engineering thermoplastics . lti!f" [SPPU : Marks 51

(Marking sche111e : definition-l M, advan tages-3M,exmnples-IM)

Ans. : Engineering thermoplastics : Engineering thermoplastics are

group of ma te rials obtained from high p olymer resins w hich
provide one or more outstanding prop erties when compared w ith
the commodity thermoplastics such as polstyrene, polyethylene,
polypropylene etc.
• Advantages of Engineering thermoplastics :
i) High thermal stability
ii) Excellent chemical resistan ce
iii) High ten sile strength
iv) High impact strength
v) High flexib ility
vi) High mech anical strength
vii) Light w eig ht
viii) Readily mouldable into complicated shapes.

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ix) Hig h dimensional stability etc.

• The important examples of engineering polymers
Polycarbonate, Polysulfones, Teflon,
Acrylonitrile-Butadiene-Styrene resin (ABS resin)
Q,14 What are biodegradable polymers ? Give important features of
biodegradable polymers. Give the structure of PHB and PHV.
~ [SPPU : Marks 51

(Marking scheme : Definilion-lM, important features-2M, structure of

PHB-1M and PHV-lM)
Ans. : • Biodegradable polymers : Biodegrad able polymers are the
polyme rs w hich are degraded by biological means such as
microorganisms.
• Important features of biodegradable polymer :
i) Naturally occurin g polymers are biodegradable.
ii) Synthetic addition polymers w ith only carbon atom main
chain are not biodegrable at molecular weight above 500.
iii) If polymer ch ain contains atom other than caTbonin the
backbone, it m ay biodegrade d epending on attached
functional groups.
iv) Synthetic polycondensation polyn1e rs are generally
biodegradable to different extent depending on functional
groups involved (ester > ether > amide).
v) Amorphous polymers are m ore suseptible for biodegradation
compared to crystalline polymers.
vi) Generally lower molecular weight polymers unde rgo
biodegradation easily compared to high molecular weight
polymers.
vii) Hydrophilic polymers degrade faster than hydrophobic.

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• Structure of PHB :

CH3 0
I II
- CH - CH2 - C T
__l__
r,

Polyhydroxybutyrate (PHB)

• Structure of PHV :
0
II __]__
C Trl

Polyhydroxyvalarate

Q.15 How Polyhydroxybutyrate (PHB) is produced using biological

route ? Give the structure of PHB and state which properties of
PHB are improved on addition of PHV . BE [SPPU : Marks 5]

(Marking scheme : Production of PHB-2M, structure-IM, improved

properties-2M)
Ans. : • Preparation of PHB using biological route : PHB is
produced by the fermentation of glucose by the bacterium
Alcaligenes eutrophus (A_eutrophous).These bacterium uses
globules of PHB as an energy storage medium similar to that of fat
in animal or starch in plants.
• Structu re of PHB :
0
II __]__
C Trl

Polyhydroxyvalarate

• Properties of PHB that are improved on addition of PHV are as

follows :
i) Drop in melting temperature.

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A G ulde for Enginee ring S tude nts

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