Engineering materials

&
Applications
 Outline

1. Polymers

2. Conducting polymers

3. Optical fibers

4. Organic light emitting diode (OLED)

 Polymers
❖ Large molecules (macromolecules) that are made by the linkage of small
molecules (monomers) together in various ways are simply called polymers.

❖ The process of making polymers is generally known as polymerization.

Polymer comes from Greek

words
Poly - Many
Mers - Parts
Polymers - applications
 Degree of polymerization (DP)
❖ Degree of polymerization is simply the number of monomeric units present in the
the polymer.

❖ It is the measured by taking the ratio between molecuar weigtht of the polymer
and the molecular weight of monomer.
 Functionality principle
❖ The functionality of a monomer is defined as the number of covalent bonds that
a monomer can form with other monomers in the polymerization.
❖ It gives us the information about the number of binding sites of a monomer to
use in polymerization.
❖ A monomer must be bifunctional atleast. Monofunctional monomers can not
participate in polymerization.
❖ A double bond in ethylene must be treated as bifunctional.
Examples :
Acetic acid -- CH 3COOH -- Monofunctional
Malonic acid -- HOOCCH 2COOH -- Bifunctional
Ethanol -- CH 3CH 2OH -- Monofunctional
Ethylene glycol -- HOCH 2CH 2OH -- Bifunctional
Glycine -- H 2 NCH 2COOH -- Bifunctional
Ethylene -- H 2C=CH 2 -- Bifunctional
 Classification of Polymers
❖ Polymers are classified into different types based on their following properties.
We can see some of the important ones in the below table.
Basis of classification Polymer type

Origin/source Natural, Semi-synthetic and Synthetic

Thermal response Thermoplastic, Thermosetting

Mode of formation Addition, Condensation

Structural arrangements Linear, Branched, Cross-linked

Application and physical properties Rubbers, Plastics, Fibres

Backbone Organic, Inorganic

Crystallinity Non-crystalline, Semi-crystalline, Crystalline

 Classification of Polymers
Based on Origin/source
1. Natural polymers: These are the naturally available polymers.
eg: Natural rubber, natural silk, starch, cellulose etc.

2. Semi-synthetic polymers: These polymers are derived from naturally occuring polymers
but they are chemically modified.
eg: Vulcanized rubber, Cellulose derivatives (nitrates, diacetates) etc.

3. Synthetic polymers: These are man-made polymers by using chemical subatances in the
laboratories or industries.
eg: Polyethylene, Polystyrene, Polyvenylchloride, Polyesters etc.
 Classification of Polymers
Based on Thermal response
1. Thermoplastic polymers:
• These are soft on heating and become hard upon cooling.
• In this manner, they can be moulded in desired shapes.
• Molecules are held together with relatively weak intermolecular forces.
• They remain soluble and fusible even after many cycles of heating and cooling.
eg: Polyolefines, Linear polyethers and polyesters, PVC, nylon etc.

2. Thermosetting polymers:
• These are hard and infusible on heating.
• They can not be remoulded on heating.
• These are cross-linked polymers.
eg: Phenolic resines, epoxy resines, diene rubbers, unsaturated polyesters etc.
 Classification of Polymers
Based on Mode of formation
1. Addition polymers:
• These polymers are formed by the simple addition of monomers to each other by a chain
mechanism without removing any biproducts/small molecules.
• These molecules contain only the -C-C- linkage.
eg: Polyethylene, Teflon, PVC etc.

2. Condensed polymers:
• They are formed from intermolecular reactions between bifunctional or poly-functional
monomers having reactive functional groups such as -OH, -COOH, -NH2 etc.
• Small molecules/biproducts are eliminated during each step in this condensation.
• These polymers also contain elements like oxygen, nitrogen, sulfur etc. as well in their
back bone.
eg: Polyethers, polyamides, polyesters, phenolic and epoxy resins etc.
 Classification of Polymers
Based on structural arrangement
1. Linear polymers:
• These polymers are formed as a result of linkage of monomers with each other in straight
manner.
• They exist in the form of long chains without any side chains
• They have high density and strength. They are also fusible.
eg: Polyethylene, PVC, Nylon 6 etc.

2. Branched polymers:
• These polymers exist in the form of straight chains along with different side chains.
• These are the result of uncontrolled polymerization or by the design of the polymerization.
• Due to their irregular packing, these polymers have low density, low strength and less
melting points (more fusible).
eg: Low density polyethylene (LDPE)
 Classification of Polymers
Based on structural arrangement
3. Cross-linked (or) Network polymers:
• These polymers are formed when monomeric units are linked together in a 3D-network.
• Hence, the links are cross links.
• They are hard, brittle, insoluble and infusible.
eg: Bakelite, Formaldehyde resins, Vulcanized rubber etc.
 Classification of Polymers
Based on Applications and Physical structure
1. Fibres:
• Fibres are formed when the polymer is drawn into a filament like material.
• These are the strongest among the polymers that we mentioned in this category.
• They have high intermolecular attractive forces like hydrogen bonding.
• They occupy the foremost place and importance in industry
eg: Wool, Silk, Polyester and acrylic fibres etc.

2. Plastics:
• These polymers are generally hard, stiff, rigid and dimensionally stable.
• These are formed by the application of heat and pressure.
• The intermolecular forces between polymer chains are intermediate.
• These are weaker than fibres.
eg: Polystyrene, PVC etc.
 Classification of Polymers
Based on Application and Physical structure
3. Rubbers (Elastomers):
• These are rubber like elastic solid materials and the weakest among the three.
• The intermolecular forces that hold the polymeric chains are very weak and permit them to
be stretched.
• These are weak in strength, dimensionally unstable.
• The cross-linking of these rubbers is generally called vulcanization.
eg: Natural rubber, Vulcanized rubber etc.

Vulcanized rubber
Natural rubber
 Classification of Polymers
Based on the Backbone
1. Organic polymers:
• Organic polymers are the ones whose backbone is made up of carbon atoms.
• Most of the synthetic polymers are organic.
eg: Poly ethylene, Nylon, Cellulose etc.

2. Inorganic polymers:
• Inorganic polymers are the ones whose backbone is not made up of carbon atoms.
eg: Glass, Silicone rubber etc.
 Types of polymerization

❖ Polymerization process is an intermolecular reaction by which bifunctional or

polyfunctional monomers are linked with each other to form polymers (big molecules).

❖ In polymerization, a variety of reaction mechanisms are involved to make longer chains

which are nothing but polymers.

❖ We will mainly discuss about the following types of polymerization:

1. Addition polymerization (chain growth)
2. Condensation polymerization (step growth)
 1. Addition (or) Chain growth polymerization
❖ Polymerization of molecules of same or different monomers containing double (or triple)
bonds without making a byproducts is termed as addition (or) chain growth
polymerization.
❖ Addition polymerization involves the opening of a π-bond of one monomer to link with an
other monomer.

❖ Addition polymerization can undergo in three different ways.

a) Free-radical polymerization
b) Cationic polymerization
c) Anionic polymerization
 1. Addition polymerization – Free radical
A) Free-radical polymerization:
• This mechanism involves three stages, i.e., initiation, propagation and termination.
• Very common initiators (I) are peroxides and azo compounds.
• Disproportionation may also be possible along with recombination in the termination step.
• For example, we can see the free-radical vinyl polymerization below.
 1. Addition polymerization - Cationic
B) Cationic polymerization:
• Catalysts with Lewis acidic character (eg. AlCl3, BF3 etc.) initiate this polymerization.
• It involves initiation, propagation, termination - chain transfer steps.
• For example, we can see the cationic isobutene polymerization below.

• Step-1: Initiation
 1. Addition polymerization - Cationic
• Step-2: Propagation

• Step-3: Termination occurs by chain transfer

 1. Addition polymerization - Anionic
C) Anionic polymerization:
• Strong nucleophile (eg. n-BuLi, Grignard reagents etc.) initiate this polymerization.
• It involves initiation, propagation, termination steps.
• For example, we can see the anionic venyl polymerization below.

• Step-1: Initiation
 1. Addition polymerization - Anionic
• Step-2: Propagation

• Step-3: Termination but alive

In many cases, this polymerization would be stopped eventually there are no more monomer
molecules left to add.
If someone comes some time later and supply more monomer into the container, they would
add to the chain and the chain would grow some more.
Some chains of polystyrene have been known to stay active like this for years.
In order to stop them, something like water, which reacts with the carbanions, has to be added
to the polymer. Systems like this are called living anionic polymerizations.
2. Condensation (or) Step growth polymerization
❖ Condensation polymerization is the process which takes place under suitable conditions
allowing bifunctional or polyfunctional monomers to condense in such a manner that the
growth of the molecule takes place in controlled, distinguishable step-wise manner.
❖ This process is always associated with the elimination of small byproducts (usually water,
ammonia, methanol etc.) at each step of the reaction.

❖ eg. Nylon 6,6

2. Condensation (or) Step growth polymerization
❖ eg. Phenol-Formaldehyde resin

❖ eg. Terylene (Decron)

 Addition vs Condensation
Addition polymerization Condensation polymerization
Monomers must have double or triple bonds Monomers must have two similar or different
functional groups

Polymerization is via addition of monomers Polymerization is via the condensation of

monomers

No byproducts are produced Small byproducts are produced

Homo-chain polymers are obtained Both Homo and Hetero-chain polymers are
obtained
Thermoplastic polymers are formed mostly Thermosetting polymers are formed mostly

It follows free-radical, cationic or anionic It follows the condensation mechanism such as

mechanisms. esterification.

The molecular weight of the resulting polymer is a The molecular weight of the resulting polymer is
multiple of monomer’s molecular weight not the multiple of monomer’s molecular weight

Reaction results high molecular weight polymers at Molecular weight increases steadily with the
once reaction
 Biodegradable polymers
❖ When we dump the waste, some part of that disappears from the site after a point of time. But
the other part does not undergo any degradation.
❖ Based on their biodegradation, Polymers are generally divided into two types. Biodegradable and
non-biodegradable polymers.
❖ The polymers which can be decomposed by the action of micro-organism (such as bacteria,
fungi, algae etc.) are known as Biodegradable Polymers.
❖ Biodegradable polymers are found both natural and synthetically made. They largely consist of
ester, amide, ether like functional groups.

Biodegradable

Non-biodegradable
❖ Polysaccharides (starch, cellulose etc.), silk, gelatin, wool etc. are examples of natural
biodegradable polymers.
❖ Polyesters like poly glycolic acid, poly lactic acid etc. are examples of synthetic biodegradable
polymers.
❖ By the action of microorganism, the decomposed biodegradable polymers result in simple
natural products like gases, water, biomass etc.
❖ Polyethylene, polystyrene etc. are examples of non-biodegradable polymers.
 Biodegradation
Enzymatic degradation
 Biodegradable polymers
❖ Advantages:
• Reduction in carbon emission
• Lesser energy consumption during their manufacture
• Eco-friendly disposable solution (less land filling during decomposition)
• Increases soil organic content

❖ Disadvantages:
• Needs specific conditions for their decomposition
• If they are mixed with regular polymers, they get contaminated and can not be used further
 Average molecular weight in characterization
❖ The molecular weight of polymers is important because it correlates with the mechanical
properties of polymers.
❖ The properties like chemical resistance, strength, viscosity, melting point, processing ability etc.
of polymers generally depend upon their molecular weight.

❖ A polymer material is mostly a mixture of molecules with variation in chain lengths. They have a
distribution of molecular weights.
❖ The molecules produced in polymerization reactions have lengths that are distributed in
accordance with a probability function which is governed by the mechanism of the reaction and
by the conditions under which it has been carried out.

❖ Therefore, the concept of average molecular weight is introduced instead of simple molecular
weight in polymers.
❖ Polymer molecular weight is defined as a distribution rather than a specific number because
polymerization occurs in such a way to produce different chain lengths.

❖ Number average molecular weight (Mn) and Weight average molecular weight (Mw) are the two
ways with which we can characterize the polymer molecular weights.
 Number average molecular weight (Mn)
❖ The number average molecular weight is simply the ratio between the total weight of all the
polymer molecules and the total number of polymer molecules in a sample.
❖ The mathematical expression given by 
 ni M i
ni = number of molecules = n1, n2 , n3 ..etc. Mn = i =1

M = Molecular weight  ni
i =1

❖ In this case, all the molecules are treated equally irrespective of their size and shape.
❖ Colligative properties, freezing point, osmotic pressure depend upon number of molecules and
hence on the number average molecular weight.
❖ Usually, a polymer contains many number of molecules with variation in their chain length.

❖ E.g. A polymer has 10 molecules of molar mass 50,000 and 10 molecules of 100,000 molar mass
(ideal and simple case). What is the number average molecular weight?

10(50000) + 10(100000) 500000 + 1000000

Mn = = = 75, 000
10 + 10 20
 Weight average molecular weight (Mw)
❖ The weight average molecular weight is little complicated than number average molecular
weight. It is mathematically represented by

 wi M i
i =1
Mw =  wi = niMi
 wi
i =1

❖ In general, weight average molecular weight is greater than the number average molecular
weight.
❖ In this case, molecules are treated based on their size/weight.
❖ Light scattering, ultracentrifugation of polymer compounds depend upon the size of molecules
and hence on the weight average molecular weight.

A polymer has 10 molecules of molar mass 50,000 and 10 molecules of 100,000 molar
mass (ideal and simple case). What is the weight average molecular weight?

𝑀ሜ 𝑤 = 83,333
 Polydispersity index
❖ If the polymer contains molecules of similar size with similar mass distribution, then it is
monodisperse (e.g. natural polymers).

❖ If the polymer contains molecules of irregular size and inconsistent mass distribution, then it is
polydisperse (most synthetic polymers).

❖ Polydispersity index is also known as heterogeneity index.

Monodisperse Poly-disperse
 Polydispersity index
❖ Polydispersity index (PDI) is the ratio between weight average molecular weight and the
number average molecular weights.
Mw
PDI =
Mn
❖ It gives an idea of lowest and the highest molecular weight species as well as the distribution
pattern of different molecular weights.
❖ PDI index equal to ‘1.0’ indicates that the range of molecular weights in the polymer sample is
narrow.
❖ The more PDI value (greater than 1.0) is an indication of wide range of molecular weights.
Conducting Polymers
❖ Polymers are generally known as plastic materials and most of them are
insulators.
❖ Polyethylene, PVC, Teflon etc. are a few examples of organic polymers and
they are good electrical insulators
❖ Polymeric materials are used in many ways in day to day life starting from
containers to clothing.
❖ As they do not conduct electricity, electric wires are coated with polymers to
protect them as well as us from short circuits.
❖ The previously showed polymers act as insulators because the electrons are
strongly bound and there is no conjugation.
❖ Until the year 1977, electrical conductivity in polymers was considered to be
absurd.
 Conducting polymers
❖ In 1977, Hediki Shirikawa, Alan Macdiarmid and Allan Heeger found a
way to create electrical conductivity in polymers after an extensive
research work.
❖ Organic polymers which can conduct electricity are called conducting
polymers (acts as synthetic metals).
❖ Chemistry Nobel prize for the year 2000 was awarded to the above three
scentists for their pioneering work in the field of conducting polymers.

Alan J. Heeger Alan G. Hediki

MacDiarmid Shirikawa
❖ Polyacetylene is the first example of conducting polymers
 Conducting polymers - classification
Conducting polymers

Coordination or
Intrinsically conducting Extrinsically conducting inorganic conducting
Polymers Polymers polymers

Conjugated conducting Doped conducting Conductive element

polymers polymers filled polymers
Blended
conducting
polymers

P-doping n-doping
 Intrinsically conducting polymers
❖ These type of conducting polymers have a solid backbone made
up of a large conjugated system which is responsible for
conductance.

❖ These are generally two types.

a) Conjugated conducting polymers

b) Doped conducting polymers (p-doped & n-doped)
 Intrinsically conducting polymers
a) Conjugated conducting polymers
❖ These organic polymers essentially contain a conjugated π-electron
backbone.
❖ Presence of lone pairs may also be a part of this conjugated system.

poly acetylene
polyphenylene vinylene (PPV)

❖ Overlap of orbitals of conjugated π-system over the entire backbone

results in the formation of valence bands and conduction bands.
 Intrinsically conducting polymers
a) Conjugated conducting polymers
❖ Under the influence of electric field, conjugated π-electrons of the
polymer get excited from valence band to conduction band and
move through the polymeric material.
 Intrinsically conducting polymers
b) Doped conducting polymers
❖ Doping is the process by which conductivity of the polymer may
be increased by creating +ve (or) -ve charge on the polymer
backbone by oxidation (or) reduction.

❖ During doping process, an organic polymer (insulator or

semiconductor) having small conductivity is converted to a
polymer which is in the metallic conducting range.

❖ Doping is usually two types:

a) p-doping
b) n-doping
 Intrinsically conducting polymers
b) Doped conducting polymers
❖ p-doping (oxidative):
• p-doping involves the creation of a positive charge on the
conjugated backbone of an organic conducting polymer.
• In this process, the conducting polymer is treated with a Lewis
acid (FeCl3 or I2 vapor etc.) due to which the oxidation takes place
and creates the positive charge.
• The delocalization of positive charges create and increase the
electrical conduction in conducting polymers.
Polymer + Lewis acid → p-doped polymer

(CH) x + 2FeCl3 → (CH) +x FeCl 4− + FeCl2

Polyacetylene

(CH) x + 3I 2 → 2(CH) +x I3−

 Intrinsically conducting polymers
b) Doped conducting polymers
❖ p-doping:

Polythiophene

P-doped polythiophene
 Intrinsically conducting polymers
b) Doped conducting polymers
❖ n-doping (reductive):
• n-doping involves the creation of a negative charge on the
conjugated backbone of an organic conducting polymer.
• In this process, the conducting polymer is treated with a Lewis
base due to which the reduction takes place and creates the
negative charge.
• The delocalization of negative charges create and increase the
electrical conduction in conducting polymers.

Polymer + Lewis base → n-doped polymer

 Intrinsically conducting polymers
Advantages & Limitations
❖ Advantages:
• High conductivity
• High ability to store the charge
• High ability to undergo ion exchange
• They can absorb visible light to give colored products
• Transparent to X-rays

❖ Limitations:
• Less conductivity compared to metals
• Poor mechanical strength
• Less stable at high temperatures
 Extrinsically conducting polymers
❖ These conducting polymers are created by the addition of external
ingredients like carbon black, metal oxides or metallic fibers.
❖ There are two types:
a) Conductive element filled polymers:
• Polymer acts as a binder to hold the conducting elements together
in solid entity
• The minimum concentration of the conductive filler which is
added to the polymer to start conductivity is called the percolation
threshold.
• These are cheaper
• Lightweight
• Mechanically durable and strong
• Easily processable in different forms, shapes and sizes
 Extrinsically conducting polymers
b) Blended conducting polymers:

• These polymer are obtained by blending (mixing) a conventional

polymer with a conducting polymer either physically or
chemically.
• They can be easily processed
• Mechanically durable and strong
 Conducting polymers -- Applications
❖ Conducting polymers have wide range of applications:

• In rechargeable batteries
• In making analytical sensors for pH, glucose, ammonia etc.
• In photo voltaic devices
• In telecommunication systems
• In microelectronic devices
• In bio-medical field
OLED
 What is OLED’s (or) Organic LED?
❖ OLED stands for Organic-Light Emitting Diodes

❖ An OLED is an electronic device made by placing a series of

organic thin films between two conductors.

❖ When electrical current is applied, a bright light is usually emitted.

❖ It is 200 times smaller than a human hair with a thickness of 100-

500 nm.
 OLED -- Structure

❖ Anode and cathode materials

❖ Layers of organic material
between two electrodes
❖ Organic layers are electrically
conductive due to delocalization
of electrons (conjugation)
❖ Based on their conductivity, they
are called organic
semiconductors
❖ All the above system (OLED) is
laid on a substrate (supporting
plastic/glass)
 OLED -- Structure
❖ Organic layers in
OLED are in two
forms with different
roles

❖ One is conductive
layer (transports holes
from the anode; eg.
Polyaniline)

❖ Other one is emissive

layer (transports
electrons from the
cathode; eg.
Polyfluorine)
 OLED – How does it emit light?
❖ A voltage is applied across the OLED
❖ A current of electrons flow from cathode to the anode through
organic layers
❖ Cathode injects electrons into the emissive organic layer ---------
electron rich
❖ Anode withdraws electrons from conductive organic layer ---------
creates holes

Light emission

Cathode
Emissive layer
V
Conductive layer
Anode
 OLED – How does it emit light?

❖ Holes from HOMO of conductive layer jump to HOMO of emissive

layer and recombine by transition of electrons from LUMO.
❖ Holes are generally more mobile than electrons in organic layers. So,
the hole-electron recombination occurs close to the emissive layer.
❖ The relaxation due to the decay of excited state emits some radiation
in the form of light
 OLED – Advantages
❖ Thinner and lighter than Liquid crystal display (LCD)
❖ Brighter than LCD (OLED emits light but LCD needs backlight)
❖ Easier to produce and make in larger sizes
❖ Large field of view
❖ More flexible
Optical fibers
 What are optical fibers?
❖ An optical fiber is a transparent fiber which is made up of glass
with the diameter slightly thicker than that of human hair.
❖ They are flexible and can be bent or twisted
❖ Light waves are used to carry the information from one end to the
other end (high frequency compared to radio waves)
❖ They are much better (less loss) than metal electrical cables
❖ Field of applied science and engineering which design optical
fibers is called fiber optics
 Fiber optical technology
❖ Mainly they have three parts:
(a) Source of light
(b) Transmission medium
(c) Detectors

❖ The core contains transparent thin glass surrounded by a cladding

material
 Fiber optical technology
❖ Sources of light:
▪ Light emitting diodes/LED
▪ Lasers

❖ Lasers give high intensty and high frequency light

❖ LED’s are economical
 Physics & Principle
❖ Refraction of light: Bending of light as it travels from one medium to
another.

❖ Refractive index of the medium: Speed of light in vacuum is divided by

speed of light in medium

❖ Critical angle: It is the angle of incidence where the angle of refraction

is 90o.
 Total internal reflection
❖ Light is kept in the core by the phenomeon of total internal reflection
❖ The optical fiber mainly consists of a core surrounded by a cladding
layer
❖ The refractive index of the core must be greater than that of cladding.
❖ TIR phenomenon confines the light only to the core in optical fiber

❖ Conditions for Total internal reflection (TIR):

▪ The light has to be travelled from more dense medium to the less dense
medium
▪ The angle of incidence must be greater than the critical angle

❖ Because the light must strike the boundary with an angle greater than the
critical angle, only light that enters the fiber within a certain range of
angles can travel down the fiber without leaking out
Total internal reflection
 Optical fibers - Advantages
❖ Less weight, less volume and cheaper
❖ High speed and large data transmission capacity
❖ No signal leakage
❖ Immune to electromagnetic interference since they do not pick up line
currents
❖ Low signal attenuation
❖ Much better than metallic electrical cables
 Optical fibers - Applications
❖ Communication: Optical fibres are used as a medium for
telecommunication.
❖ Medical: Used as light guides, imaging tools and also as lasers for
surgery
❖ Defence: Wiring in aircrafts, submarines and also field networking in
defence sector. Optical fibres are highly secure.
❖ Networking: Used to connects users and servers. They are helpful due
to their high speed and accurate data transmission
❖ Industrial: Used for wiring in automobiles
❖ Broadcasting: Used as cables for wiring HDTV, internet and other
applications.
Thank you