Engineering Materials

Module
ENGINEERING MATERIALS
3
Syllabus
Polymers: Introduction, Synthesis and applications of Polyurethanes. Polymer composites-
Introduction, synthesis, properties & applications of Kevlar Fibre,
Conducting Polymers: Introduction, Synthesis & Mechanism of conduction in polyaniline
and factors influencing conductivity of organic polymers.
Biodegradable polymers: Introduction and their requirements. Synthesis, properties and
applications of Poly lactic acid.
Nanomaterials: Introduction, size dependent properties (Surface area, Electrical, Optical and
Catalytic properties). Synthesis of nanomaterials: Top down and bottom up approaches,
Synthesis by Sol-gel, and precipitation method, Nanoscale materials: Fullerenes, Carbon
nanotubes and graphemes –Introduction, properties and applications.
Questions and anwers
1. Define polymers
 The word polymer is derived from Greek words, Poly (many) and meros (Parts or unit).
 These are large molecules which are made from monomers.
2. Define monomers
Monomers are small molecules, mostly organic, that can join with other similar molecules to
form very large molecules or polymers.
3. Define Polymerization
The process of formation of polymers from respective monomers is called polymerization.
4. Explain the synthesis and applications of Polyurethane?
Polyurethane: It is referred to as a class of polymers composed of organic units joined by urethane
links (-NH-CO-O-).
Synthesis of polyurethane: They are prepared by the polyaddition reaction between diisocyanate
and a diol or a triol. During the addition, the H atom of OH group migrates to the nitrogen atom
as shown in the following scheme
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Examples

Application of polyurethanes
 Elastomers: Because of their resistance to oil, grease and corrosive chemicals, they are
used for tyre treads and industrial wheels.
 Fibers: Perol-U is a typical polyurethane fiber used in lightweight garments and swimsuits
because of its stretching property.
 Coatings: It is used as floor coating for gymnasium and dance floors where high abrasion
resistance is required.
 Foams: Polyurethane foams are widely used as cushions for furniture and automobiles.
5. Write a short note on polymer composites?
Polymer composites: It can be defined as a physical mixture of two or more structurally different
homopolymers or copolymers. The widely used polymer matrices are epoxy, polyester, phenolic
resin, etc. The commonly used reinforcements are glass, carbon and aramid (Kevlar- trade name
of Du Pont Company) fibres.
Properties of polymer composites.
 They are light in weight.
 They have high strength to weight ratio.
 They are much stronger and more durable than conventional metals like steel and
aluminum.
 They are most suitable for aerospace applications due to their lightweight.
 They have good corrosion resistance.
 They have high fatigue strength.
Applications of polymer composites
 Composites of phenolic resins and nylon are used in heat shields for space crafts.
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 They are used in aircraft and space industry.

 They are suitable for automotive and railway applications.
 They are used for civil construction works also.
6. Explain the synthesis, properties, and applications of Kevlar fibre?
Kevlar Fibre: It is an aromatic polyamide (aramide) (IUPAC name is poly-
paraphenyleneterepthalamide). Kelvar is synthesized from the monomers 1,4-phenylene-diamine
(1,4-phenylene-diamine) and terephthaloyl chloride through a condensation reaction with the
libration of HCl as a byproduct.

Properties of Kevlar
 Kevlar is crystalline, lightweight, and non-flammable.
 Resistant to heat, impact, and scratch.
 It withstands harsh environmental conditions.
 It has the excellent force and tensile stress resistance.
 High cut resistance
 Textile processibility
 Flame resistance.
Uses of Kevlar fiber
 Used as a reinforcement material for some car tyres and bicycle tyres. It dramatically
reduces the puncture rate.
 Used in the manufacture of lightweight military vehicles.
 Used for the boat hulls and aerospace industry.
 Used in the manufacture of formula one racing car petrol tanks.
 Used in the manufacture of bullet-proof vests and combat helmets.
Disadvantages
 Kevlar textiles tend to absorb moisture.
 It reacts badly under a compressive force.
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7. Define conducting polymer and mention the examples?

Conducting polymer:
An organic polymer with a highly delocalized pi-electron system, having electrical conductance
of the order of a conductor is called Conducting polymers.
Examples: Polyacetylene, polyphenylene vinylene, and polyaniline

 Many of these polymers especially those with a conjugated 𝜋- bond system, often yield
higher conductivity once having undergone the doping process.
8. Explain the synthesis and Mechanism of conduction in polyaniline?
Polyaniline
 Polyaniline (PANI) is a conducting polymer that is formed by the continuous repetition of an
aniline monomer unit.
Chemical synthesis: An aqueous solution of ammonium persulphate is added slowly to a solution
of aniline dissolved in aqueous HCl at a lower temperature (0-50C) under agitation. After 1h the
precipitate formed was removed by filtration. The polymer thus obtained is emeraldine
hydrochloride. The emeraldine hydrochloride was converted into the emeraldine base by stirring
with 0.1 M solution of ammonium hydroxide for several hours.
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Mechanism of conduction in polyaniline

 Conducting polymers can conduct electricity because of their conjugated π-bond system,
which is formed by the overlapping of carbon p-orbitals and alternating. In polyaniline,
Nitrogen Pz orbitals and carbon rings are also part of the conjugated system.
 The organic polymer can be converted into a conducting polymer by doping agents if it has
 Linear structure
 Conjugation in the polymeric backbone (pi-back bone)
 Polyaniline conductivity increased through doping by protonic acids. The protonation occurs
by a general reaction of polyaniline with protonic acids.
 Polyaniline with protonic acids (HCl) will produce charge sites on polymer back bone, which
are current carriers for conduction.
 Treatment of polyaniline with acids increases the electrical conductivity by up to ten orders of
magnitude.
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9. Explain the factors influencing the conductivity of organic polymer?

 The density of charge carriers: The charge carriers are responsible for the conduction. In
polypyrrole, bipolarons trigger the conductivity while in trans-polyacetylene, solitons act as
charge carriers. In conducting polymers, the charge carriers hop not only in the defective area
but also in interchain gaps
 The mobility of electrons: All conducting polymers have conjugate bonds in their backbones,
and these bonds are responsible for the movement of electrons: i.e., a single bond contains a
localized σ bond and a double bond has both σ and weaker π bonds.
 Presence of doping materials (additives that facilitate the polymer conductivity): The
conductivity shows drastic changes depending upon the dopant material, the arrangement of
the polymer chain, and its length. The dopant concentration and pH value enhance the
conductivity; for example, polyaniline shows excellent. There are two types of doping: p-type
doping and n-type doping, and the dopants produce both positive and negative
polarons/bipolarons.
 Mechanical properties: The mechanical properties of polymer materials depend upon the
monomer arrangement and crystallinity. A crystalline polymer has better mechanical
properties compared with amorphous semi-crystalline polymers. The macroscopic mechanical
property of conducting polymers depends upon the microscopic change in the molecular
mobility of macromolecules.
 Electrical and electronic properties: All conducting polymers have conjugate bonds in their
backbones, and these bonds are responsible for the movement of electrons: i.e., a single bond
contains a localized σ bond and a double bond has both σ and weaker π bonds.

10. Explain the biodegradable polymers ?

Biodegradable Polymers: 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.
Examples: Poly β-hydroxybutyrate–co-β-hydroxy valerate (PHBV), Nylon 2–Nylon 6.

 Biopolymers are polymers that are biodegradable.

 The initial materials for the production of these polymers may be either renewable or synthetic.
A degradable material in which degradation result from the action of microorganisms and the
material are converted to water, carbon dioxide and/ or methane. Biodegradation is a process
by which organic substance are broken down by the enzymes produced by living organisms.
 Biopolymer are several different types of degradation that can occur in the environment these
include, biodegradation, photo degradation, oxidation and hydrolysis.
After influencing the degradation of polymers
 Generally, naturally occurring polymers are biodegradable.
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 Synthetic addition polymer with carbon as the only atom in the backbone does not biodegrade
at molecular weight above 500.
 If an addition polymer contains atom other than carbon in the backbone it may biodegrade
depending on the functional groups.
 Synthetic condensation polymers are generally biodegradable to different extent depending on
chain coupling (Ester > Ether > Amide > Urethane).
 Morphology (Amorphous > Crystalline).
 Molecular weight (Lower > Higher).
 Hydrophilic polymer degrade faster than hydrophobic.
11. Synthesis, properties and applications of Poly lactic acid?
Polylactic acid: It is a biodegradable thermoplastic aliphatic polyester derived from renewable
resources such as corn or sugar canes. Lactic acid is produced by bacterial fermentation of
sugarcane or from the conversion of starch from corn. The lactic acid is oligomerized and then
catalytically dimerized to make the lactide monomer. High molecular weight PLA is produced
from the lactide monomer by ring opening polymerization using a stannous octoate catalyst.

 Polymerization of a racemic mixture of Land D Lactides leads to synthesis of poly -DL-

Lactide.
 PDLLA which is not crystalline but amorphous.
 Poly-L-Lactide (PLLA) is the product resulting from polymerization of L, L-Lactide.
 PLLA has a crystallinity of around 37%, a glass transition temperature 50-800C and Tm
173-1780C.
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 PLLA can be processed like most thermoplastic into fiber (using conventional melt
spinning) and film.
 Biodegradation of PDLA is slower than for PLLA due to the higher crystallinity of PDLA.
Applications of polylactic acid
 PLA is used in some biomedical applications, such as sutures, stents, dialysis media and
drug delivery devices.
 Because of its biodegradability, it can be used in the preparation of bioplastics useful for
food packing and disposable tableware.
12. Define nanomaterial?
Nanomaterials have one of its dimensions in the range of 1- 100 nm are known to use for centuries.
13. What are the applications of nanomaterials?
1. The range of commercial products available today is very broad, including stain-resistant and
wrinkle-free textiles, cosmetics, sunscreens, electronics, paints, and varnishes etc.
2. Nanocoatings and nanocomposites are finding uses in consumer products, such as windows,
sports equipment, bicycles, and automobiles.
3. There are UV- blocking coatings on glass bottles that protect beverages from damage by
sunlight, and longer-lasting tennis balls using butyl rubber/nano-clay composites.
4. Nanoscale titanium dioxide for instance is finding application in cosmetics, sunblock cleans,
and self-cleaning windows and nanoscale silica is being used as filler in a range of products,
including cosmetics and dental fillings
 Nanophase ceramics are of interest because they are ductile at elevated temperature as
compared to the coarse-grained ceramics.
 Nano structed semiconductor are known to show various non-linear optical properties.
 Nanosized metallic powders have been used to produce gas tight materials dense parts and
porous coatings.
Magnetic nanocomposites have been used for mechanical Materials in the nanometer scale
exhibit physical properties distinctively
 force transfer, for high density information storage and magnetic refrigeration.
 Nanostructured metal clusters and colloids have a special impact in catalytic applications.
 Nanostructured metal-oxide (MnO2) finds application for rechargeable batteries for cars or
consumer goods.
14. Explain the size-dependent properties? (i)Surface area, (ii)Electrical properties (iii)
Optical properties (iv)Catalytic properties (V) Thermal properties
Materials in the nanometer scale exhibit physical properties distinctively different from that of the
bulk material
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 Surface area
 Electrical properties
 Optical properties
 Catalytic properties
 Thermal properties
Surface Area: When a bulk material is subdivided into individual nanomaterials, the total volume
remains the same, but the collective surface area is enormously increased.
Nanomaterials have a large proportion of atoms existing at the surface. Properties like
catalytic activity gas adsorption and chemical reactivity depend on the surface area. Therefore
nanomaterials can show specific surface-related properties that are not observed in bulk materials.
For example, Bulk gold is catalytically inactive, but gold nanoparticles are catalytically very active
for selective redox reaction.
Electrical properties: Some metals which are good conductors in bulk become semiconductors
or insulators as their size is decreased to the nano level. The reason is that the electronic bands in
bulk material are continuous due to the overlapping of orbitals of billions of atoms. Nanomaterials
very few atoms or molecules are present and so the electronic bonds become separate and
separation between different electronic states varies with the size of nanomaterial
Optical properties: The nanomaterials of different sizes can scatter radiation of different
wavelengths. The Colour of a few colloidal solutions is due to this scattering effect.
In addition to the above, nanoparticles of metals exhibit a unique optical property called as surface
‘Plasmon resonance’. when lights hit the surface of metals particle, electron present on the surface
(Surface plasmon) starts oscillating back and forth in a synchronized way in a small space and the
effect is known as surface plasmon resonance. Depending on the frequency of oscillation
resonating electrons capture radiation of different wavelengths.
Catalytic properties: The catalytic property of materials depends on particle size. If the size of
the particles reduces from bulk to nanoscale, surface to volume increases drastically, which leads
to the very high catalytic activity of the same material.
Example: Catalytic properties of gold nanoparticles. Although bulk gold samples are practically
inert, nanometer-sized gold particles have been proven to be highly active for several reactions,
including
 Low- temperature oxidation of CO
 Partial oxidation of hydrocarbons.
 The water-gas shift reaction.
 Reduction of nitrogen oxides when dispersed over certain oxides and carbides.
Thermal properties (Melting point): The melting point is defined as the temperature at which
the atoms, ions, or molecules in a substance have enough energy to overcome the intermolecular
forces that hold them in a fixed position in a solid.
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As the size of the material decreases to the nanoscale, their melting point decreases.
Because surface atoms are in contact with only fewer atoms in nanomaterials and require lesser
energy to overcome intermolecular forces.
15. Explain the synthesis of Nanomaterials by Bottom-up synthesis and Top-down synthesis?
Synthesis of nanomaterial
There are two approaches to the synthesis of nanomaterials: bottom-up synthesis and top-down
synthesis
Bottom-up synthesis(Construction or Self-assembly)
In this approach, molecular components arrange themselves into more complex assemblies atom-
by-atom, molecule-by-molecule, cluster-by-cluster from the bottom (e.g. growth of a crystal)
Bottom-up approaches, in contrast, arrange molecular components themselves into some useful
conformation using the concept of molecular self-assembly. The bottom-up approach has been
well known to chemists for a long time. This approach plays a very important role in preparing
nanomaterials having very small sizes where the top-down process cannot deal with very tiny
objects.
The bottom-up approach generally produces nanostructure with fewer defects as compared to the
nanostructures produced by the top-down approach. The main driving force behind the bottom-up
approach is the reduction in Gibbs's free energy. Therefore, the materials produced are close to
their equilibrium state.
Top-down approach:
The top-down approach refers to slicing or successive cutting of bulk material to get nano-sized
particles. This approach often uses the traditional workshop or micro-fabrication methods in which
externally controlled tools are used to cut, mill and shape materials into the desired shape and
order.
Example: Nanowires made by lithography are not smooth and can contain a lot of impurities and
structural defects on its surface.
In spite of the defects, the top-down approach plays an important role in the synthesis and
fabrication of nanomaterials. The present state of nanoscience can be viewed as an amalgamation
of bottom-up chemistry and top-down engineering techniques.
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Schematic representation of nanoparticles

16. What is Nano-material? Explain the synthesis of Nanomaterials by the Sol-Gel
technique?
Nanomaterials have one of its dimensions in the range of 1- 100 nm are known to use for centuries
are called Nanomaterials.
For example: Chinese used gold nanoparticles as an inorganic dye into their ceramic porcelains
more than thousand year ago.
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Synthesis by Sol-gel: Sol-gel method of synthesizing nanomaterials is very popular amongst

chemists and is widely employed to prepare oxide nanomaterials.
The sol-gel process can be characterized by a series of distinct steps.
 Preparation of sol
A stable colloidal solution called sol is prepared. (The sol is a liquid suspension of solid particles
ranging in size from 1nm to 1 micron). It is prepared by hydrolysis and partial condensation of
precursors such as metal alkoxide.
M-O-R + H2O → M-OH + ROH (hydrolysis)
Metal alkoxide
M-O-R + M-OH → MOM + ROH (condensation)
Metal alkoxide

 Conversion of Sol to Gel

Further condensation of a sol into a three-dimensional network produces a gel material
(The gel is a diphasic material in which the solids encapsulate the solvent)

 Aging of the Gel

Polycondensation reaction continues until the gel transforms into a solid mass accompanied by
contraction of the gel networks and expulsion of solvent from gel pores. The aging process of gels
can exceed 7 days.

 Drying of Gel
Water and other volatile liquid are removed from the gel network.
If isolated by thermal evaporation, the resulting monolith is termed a Xerogel. If the solvent (such
as water) is extracted under critical or near supercritical conditions, the product is an aerogel.

 Dehydration
To stabilize the gel against any rehydration the surface-bound M-OH groups are removed by
calcining(heating) the monolith at temperature up to 8000C.
The typical steps that are involved in sol-gel processing are shown in the schematic diagram below.
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Advantages of Sol-gel method

 Low temperature route (below 2000C)
 Uniform particle size distribution
 Can easily shape materials into complex geometries in gel state
 Simple, effective method to produce high quality coatings
1. What is nanomaterial? Explain the synthesis of nanomaterials by precipitation method?
Precipitation method
1. Preparation of nanoparticles can be achieved by careful precipitation of the substance from its
solution.
2. In this process, acid or base is added to the precursor solution to adjust the pH to the desired
level.
3. Then a precipitating agent is added to it to initiate nucleus formation. The nucleus formed grows
into particles and gets precipitated. The precipitate is filtered, washed, air dried and calcined to
obtain nanoparticles.
For example:
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Precipitation of Zinc sulphide nanoparticles is carried out from Zinc acetate precursor solution by
adding precipitating agent. Thioacetate (TAA) which provide sulphide ions.
Zn2+ + S2- → ZnS
Advantages of precipitation method:
 This simple and rapid method of preparation of nanoparticles.
 Particle size and crystallinity can be controlled by optimizing conditions
12. Write notes on (i)Fullerenes (ii) Carbon nanotubes and(iii) Graphene’s
Nanoscale materials
FULLERENES
1. Fullerenes is a “0” dimensional carbon allotrope named after Buckminster fuller.
2. Fullerene molecules composed entirely carbon, in forms of a hallow sphere. There are
called Buckyball.
3. The C60 fullerene is often compared to a soccer football
4. Fullerenes have 20 hexagonal and 12 pentagonal rings.
5. Fullerenes is icosahedral symmetry.
6. Fullerenes is SP2 hybridized.

Properties of Fullerenes
1. Fullerence is a black powdery material.
2. Fullerenes are the only known carbon allotropes that can be dissolved in common solvents at
room temperature.
3. Fullerenes is a very tough and thermally stable material.
4. Fullerene can be compressed to 30% of its volume without destroying its cage structure.
Application of fullerene
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1. Fullerene is used as a hydrogen storage material for fuel cells and some secondary batteries.
2. Fullerene is used in the preparation of superconductors.
3. Fullerenes are used as lubricants.
4. Fullerenes are used in tennis racket frames.
5. Fullerenes are used to carry drugs into cells, the cage-like fullerenes molecules could contain a
drug.
CARBON NANOTUBES
Carbon Nanotubes is a 1-dimensional carbon allotrope having a cylindrical structure and a central
hollow core formed by rolling up graphene sheets.
1. The diameter of CNT is 1 – 50 nm and the length is in a few micrometers.
2. Carbon Nano-tube Aspect-ratio (length/Width) is generally greater than 1000.
Types of CNT’s
1. Single-walled carbon nanotubes (SWCNT’s)
They are formed by rolling a graphene layer diameter of 1 to 2nm.

2. Multiwalled carbon nanotubes (MWCNT’s)

(a) They are made by rolling multiple layers of graphene sheets arranged in concentric cylinder
form.
(b) MWCNT’s diameter 2 to 25 nm.
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(c) The open ends of CNT’s are closed with fullerene caps.
Properties CNT’S (carbon nanotubes)
1. CNT’s have outstanding high electrical properties.
2. CNT has the highest tensile strength of any material known.
3. CNT’s has high chemical (Such a lithium storage capacity)
4. CNT’s can be easily functionalized.
5. CNT’s are excellent field emitters; high aspect ratio and small tip radius of curvature are
ideal for field emission.
Application of CNT’s (carbon nanotubes)
1. CNT’s have electrical and thermal hence used as electrode materials for lithium-ion batteries.
2. CNT’s have low density and high mechanical strength hence it is used as composite materials.
3. SWCNT’s(Single-walled carbon nanotubes) have a well-defined diameter of 1.4nm They are
used for the synthesis of nanorods.
4. SWCNT’s(Single-walled carbon nanotubes) is efficiently absorb radiation in the near-infrared
range and convert it to heat. Hence it is used in cancer chemotherapy to kill cancer cells without
affecting nearby healthy tissues.
GRAPHENE’S

1. Graphene is a two-dimensional crystalline allotrope of carbon consisting of a single layer of

carbon consisting of a single layer of carbon atoms arranged in hexagonal.
2. Graphene has high electrical conductivity and acts like a semimetal with a small overlap between
the valence and the conduction bands.
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3. Graphene carbon atoms are densely packed in a regular hexagonal pattern.

4. Graphene atom are about 1-42 Ao a part. Graphene carbon atom is bonded to three carbon atoms
and is SP2 hybridized.
Properties of Graphene’s
1. Graphene has excellent electronic conductivity because its conduction and valence bands meet
at the Dirac points (Zero-gap semiconductor).
2. Graphene has unique optical properties that produce an unexpectedly high opacity for an atomic
monolayer in a vacuum.
3. Thermal transport in graphene is an active area of research which has attracted attention because
of the potential for thermal management applications.
4. Graphene melts at nearly ≈ 4125 K graphene melts into an agglomeration of loosely coupled
doubled bonded chains before becoming a gas.
5. Graphene is the strongest material ever tested, with an intrinsic tensile strength of 130.5GPa
Graphene’s application
1. Graphene is a flexible conductor that holds promise for various device applications including
solar cells, light -emitting diodes (LED) touch panels and smart windows or phones.
2. Graphene has also been used in other fundamental electronic devices, such as capacitors and
field effect transistors (FET’s) in which it can acts as an atomically thin channel.
3. Graphene supercapacitors serve as energy storage alternative to traditional batteries. Among
advantage are fast charging, long life span and environmentally friendly production.
4. Graphenes are used for biological and chemical sensors.
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