4-Important engineering materials

Important Engineering Materials
Important Engineering Materials 1

Nanomaterials

History
• In 1959, physicist and Nobel prize laureate Richard Feynman presented

"There's Plenty of Room at the Bottom" at a meeting of the American Physical
Society and introduces the concept of nanotechnology – without naming it as
such.
• In his famous speech, Feynman talked about the problem of manipulating and
controlling things on a small scale and he asked the question: "Why cannot we
write the entire 24 volumes of the Encyclopedia Britannica on the head of a
pin?"
Origin
• Nano comes from the Greek word for dwarf.
• The prefix nano means a factor of one billionth (10-9) in the metric system and
can be applied, e.g., to time (nanosecond), volume (nanoliter), weight
(nanogram) or length (nanometer or nm).
• In its popular use nano refers to length, and the nanoscale usually refers to a
length from the atomic level of around 0.1 nm up to 100 nm.
• Nanostructures or nanomaterials are forms of matter at the nanoscale.

Nano size
• For example a single human hair is about 50,000 - 100,000 nm

thick.
• If you line up 7 oxygen atoms or 3-4 water molecules, you'll get Carbon nanotube
Human hair
about one nanometer.
• A red blood cell is approximately 7,000 nm wide.
• Viruses which cause infections are in the range of 20 – 400

nanometers
Nanotechnology
• The term broadly refers to such fields as biology, physics or
chemistry, or any scientific field, or a combination thereof,
that deals with the deliberate and controlled manufacturing
of nanostructures.

Historical use of nanomaterials
• Chemists have dealt with naturally occurring nanoparticles all along.
• Ex. Tire manufacturers used nanoparticles - carbon black - to improve the
performance of tires as early as the 1920s.
• Medieval artists used gold nanoparticles to achieve the bright red color in church
windows (gold particles in nanometer size are red, not golden).

Facts
• Nanocrystalline nickel is as strong as hardened steel
• Much of nanoscience requires that you forget what you know

and start learning all over again.
• Two principal factors cause the properties of nanomaterials to

differ significantly from other materials:
1. Increased relative surface area and
2. Quantum effects

Increased relative surface area
• An important aspect of nanomaterials is their surface area.
• When compared to the same mass of material in bulk form, nanoscale materials
have a relatively larger surface area.
• This can make materials more chemically reactive (in some cases materials that
are inert in bulk form are reactive when produced in their nanoscale form), and
affect their strength or electrical properties.

• To understand the effect of particle size on surface area, consider an American
Silver Eagle coin.
• This silver dollar contains 31 grams of coin silver and has a total surface area of
approximately 3000 square millimeters.
• If the same amount of coin silver were divided into tiny particles – say 10
nanometer in diameter – the total surface area of those particles would be 7000
square meters
• 7000 square meters = 7×109 square millimeters

• Thus, when the amount of coin silver contained in a silver dollar is
rendered into 10 nm particles, the surface area of those particles is
about 2.33 million times (7 billion square millimeters divided by the
3000 square millimeters) surface area of the silver dollar!

Quantum Effects
• The so-called quantum size effect describes the physics of electron properties at
nano size.
• This effect does not come into play by going from macro to micro dimensions.
• However, it becomes dominant when the nanometer size range is reached.
• Quantum effects can begin to dominate the behavior of matter at the nanoscale -
particularly at the lower end (single digit and low tens of nanometers) - affecting
the optical, electrical and magnetic behavior of materials.

Quantum Effects
• The causes of these drastic changes are due to the weird world of quantum
physics.
• The bulk properties of any material are merely the average of all the quantum
forces affecting all the atoms that make up the material.
• When things become smaller and smaller, we eventually reach a point where the
averaging no longer works and we have to deal with the specific behavior of
individual atoms or molecules - behavior that can be very different to when these
atoms are aggregated into a bulk material.
Quantum Effects
• Materials reduced to the nanoscale can suddenly show very different

properties compared to what they show on a macroscale.
• For instance, opaque substances become transparent (copper); inert

materials become catalysts (platinum); stable materials turn
combustible (aluminum); solids turn into liquids at room temperature
(gold); insulators become conductors (silicon).

• These factors (increased relative surface area & quantum effects)
can thus change or enhance properties such as:
i. Reactivity,
ii. Strength and
iii. Electrical characteristics.
•Also as particle decreases in size, a greater proportion of atoms are

found at the surface compared to those inside.
THREE TYPES OF CARBON NANO PARTICLES
• Graphite
• Fullerenes
• Nanotubes

GRAPHITE
Introduction:- Graphite is a polymorph of carbon
having crystal structure and used as lubricant.
Structure
i. It is composed of hexagonally arranged carbon
atoms.
ii. Within the layer each carbon atom is bonded
to three coplanar neighboring carbons atoms
by strong covalent bonds
• The fourth bonding electron participate in a weak Vander wall
type of bond between the layers.
• The planar surface layers do not have covalent links, which

gives graphite its lubricating properties.
• Also the fourth electron is free to move from one layer to

another which give graphite electrical conductivity.

Properties of Graphite
• High electrical conductivity.
• High strength.
• Chemically stable
• High thermal conductivity.
• High resistance to thermal shock
• Good lubricant

USES of Graphite
• It is used in heating elements for electrical furnaces high temperature
refractories and insulators, in chemical reactor vessels.
• It can be used as electrode for arc welding, in metallurgical crucibles,
in casting molds for metal alloys and ceramics.
• It is used for electrical contacts, brushes and resistors.

• It can be used as electrodes in batteries and in air purification
devices.

FULLERENE
• Introduction:-fullerene is a polymorphic form of carbon
discovered in 1980's named after architect Buckminster
Fuller.
• It is a discrete molecular form with a hollow spherical cluster

of less than 300 carbon atoms & are commonly known as
“buckyballs”. It includes the most common fullerene,
Buckminster fullerene, C60
FULLERENES ARE THE THIRD ALLOTROPIC FORM OF
CARBON MATERIAL (AFTER GRAPHITE AND DIAMOND)

STRUCTURE of Fullerene
• Fullerenes are spherical carbon-cage molecules with sixty
(C60) or more carbon atoms. They measure about 0.7-1.5 nm
in diameter.
• Each cluster molecule is composed of groups of carbon

atoms that are bonded to one another to form both hexagon
and pentagons, which are arranged such a way that no two
pentagons touch each other. C60 is also known as
Buckminster Fullerene.
STRUCTURE of Fullerene
• The family of fullerene has increased & now it consist of
C70,C76,C84,C240 and so on. They are a class of closed

carbon molecule.
• Fullerene contains 12 pentagons and a variable no. of

hexagons .
HEXAGONS= (NO. OF CARBON ATOMS - 20) / 2

• Giant fullerenes, or fullerenes
with more than 300 carbon
atoms, include single-shelled or
multi-shelled carbon structures,
onions, and nanotubes.

PROPERTIES of Fullerene
• This material is electrically insulating, however with proper
impurity additions, it can be made highly conductive and semi
conductive.
• They have closed structure – the ability for holding (trapping)

molecules inside in it.
• Ex. one could also bind specific antibiotics to the structure to

target drug resistant bacteria and even target certain cancer
cells such as melanoma.
USES of Fullerene
• Fullerene can be used in light emitting diodes in different
electronic equipment and computing.
• It can be used as additive in grease and other lubricants.
• It can be a good conductor of electricity and heat
• It is now used as rocket fuel to bear the huge pressure in the
propellants.

Recent Applications
• Antioxidants & Biopharmaceuticals Fullerenes are known to behave like a “radical
sponge”
• Zelens Dermatological Research, launched a skin care cream based on the C60
fullerene.
• Fullerenes are powerful antioxidants, reacting readily and at a high rate with free
radicals, which are often the cause of cell damage or death.
• Thus, it halts the ageing process by reacting with free radicals. It can also be used as
facial moisturizer.
Carbon Nano Tubes (CNTs)
• It is an allotrope of carbon discovered in 1991 by Japanese scientist

Iijima .
• Carbon particles as graphene sheets are made into tubular form which
are called as Carbon nanotubes (CNTs).
• Carbon nanotubes (CNTs) are produced ranging from single to tens of

nanometers in diameter and several micrometers in length.
STRUCTURE of CNTs
• It is a seamless cylinder composed of carbon atoms in a regular
hexagonal planar arrangement, closed on both ends by
hemispherical end caps.
• Diameter <<< Length
• The chemical bonding in nanotube are entirely sp2 bonds, similar to

that in graphites.
• Hexagonal carbon rings are arranged in either zigzag or armchair

manner.
Single walled carbon nanotube types
• Zig zag type: the border has zig zag pattern, it possesses a
plane of symmetry and hence is achiral
• Arm chair type: the border has arm chair type arrangement,
it possesses a plane of symmetry and hence is achiral
• Chiral: no specific border pattern, does not possess a plane

of symmetry
PROPERTIES of CNTs
• They have outstanding mechanical and electronic properties and are
good thermal conductors.
• The tensile strength, or breaking strain of CNTs is 6-7 times that of

steel. They are among the stiffest and strongest fibers known.
• CNTs can be metallic or semiconducting depending on their structure.

Some CNTs are the most efficient electrical conductors ever made,
while others behave more like silicon.

PROPERTIES of CNTs
• The lightness of carbon nanotubes, give them great potential for use in
nanoelectronics, sensors and nanomechanical devices.
• Single-walled CNTs exhibit different electrical properties (than
multiwalled CNTs) and are prime candidates for applications in
nanoelectronics.
• Due to their structure they also have high elasticity.

USES of CNTs
• In catalyst support
• Batteries fuel cells
• Electrode in electrochemistry
• CNT based microscope
• Diode, transistors and capacitors
• Membranes for molecular transport
• Due to its highly absorbent property it can be used in air, gas and
water filtration.
• It has also been used as a conducting additive to impart conductivity
in plastics.
Nanocomposites
• A plastic nanocomposite is being used for "step
assists" in the GM Safari and Astro Vans. It is
scratch-resistant, light-weight, & rust-proof, and
generates improvements in strength and reductions
in weight, which lead to fuel savings and increased
longevity.
• In 2001, Toyota started using nanocomposites in a
bumper that makes it 60% lighter and twice as
resistant to denting and scratching.
Scratch-resistant
• Coatings - Engineers discovered that adding aluminum silicate
nanoparticles to scratch-resistant polymer coatings made the
coatings more effective, increasing resistance to chipping and
scratching.
• Scratch-resistant coatings are common on everything from cars

to eyeglass lenses..

Nanocrystals
• Metal nanocrystals might be incorporated into car
bumpers, making the parts stronger, or into
aluminum, making it more wear resistant.
• Metal nanocrystals might be used to produce
bearings that last longer than
their conventional counterparts,
• New types of sensors and components for
computers and electronic hardware.
Smith & Nephew
• Markets an antimicrobial dressing covered with
nanocrystalline silver. The nanocrystalline coating of
silver rapidly kills a broad spectrum of bacteria in as
little as 30 minutes.
• Improved chemical & biological sensors, medical
diagnostic devices, microscope, new targeted drug
therapies, enhanced medical imaging.
• Clothing - By coating fabrics with a thin layer of zinc oxide nanoparticles,
manufacturers can create clothes that give better protection from UV
radiation.
• Some clothes have nanoparticles in the form of little hairs or whiskers that
help repel water and other materials, making the clothing stain-resistant.
• Swimming pool cleaners and disinfectants – Enviro Systems, Inc.-

developed a mixture (called a nanoemulsion) of nano-sized oil drops
mixed with a bactericide. The oil particles adhere to bacteria, making the
delivery of the bactericide more efficient and effective.
Sunscreen Many sunscreens contain nanoparticles of zinc oxide or
titanium oxide.
Self-cleaning glass
A company called Pilkington offers a product they call Activ

Glass, which uses nanoparticles to make the glass
photocatalytic and hydrophilic.
• An Oregon State University-led research team has successfully used
nanotechnology to deliver diagnostic imaging agents to cancerous
tumors.
• The specially designed “peptide” – or compound comprised of amino
acids – attaches directly to cancer cells in animals by targeting the
tumors’ low pH levels.

Bridgestone engineers developed
this Quick Response Liquid
Powder Display, a flexible digital
screen, using nanotechnology.

LIQUID CRYSTALS
Development of liquid crystal materials has
revolutionized electronic display boards &
monitors.

Liquid crystal state
• In some substances the tendency toward ordered
arrangement is so high that on heating they pass through an
intermediate state before forming a clear or transparent liquid
• This intermediate state is known as the liquid crystal state.
• The liquid crystal state is intermediate between solid and true

liquid state.
• These substances which have arrangements similar to solids

but have the freedom of motion like liquids are called liquid
crystals Important Engineering Materials 50
• Ex. Cholesteryl benzoate (C6H5COOC27H45) when heated undergoes
two sharp phase transformations one after the other.
• It fuses sharply at 145C to give a turbid or cloudy liquid which on

further heating changes suddenly in to clear transparent liquid at
178C.
• These changes reversed on cooling.

Cholesteryl benzoate Cholesteryl benzoate Cholesteryl benzoate
(Solid) (liquid crystal) (liquid)
(mesomorphic state)
Important Engineering Materials (178⁰C) 51
(145⁰C)
• This turbid liquid show anisotropy (which implies different
physical or mechanical properties in different directions)
• The anisotropy of liquid crystals is particularly seen in their

optical behavior.
• True liquid, on contrary are isotropic.
• Since anisotropic properties are associated with crystalline

state, the turbid liquids are called Liquid crystal.

Vapour Pressure- temperature curves for a substance undergoing mesomorphic change

• Liquid crystals are thus substances that exhibit a phase of
matter that has properties between those of a conventional
liquid and a solid crystal.
• For instance, a liquid crystal may flow like a liquid, but have the
molecules arranged and/or oriented in a crystal-like way.
• When viewed under a microscope using a polarized light source

(light waves in which the vibrations occur in a single plane),
different liquid crystal phases will appear to have a distinct
texture.

• Each “patch” in the texture corresponds to a certain
domain where the LC molecules are oriented in a
different direction.
• Within a domain, however, the molecules are well

ordered.
• The solid state has longer range of ordered

arrangement of molecules and definite orientation
and when it changes to the mesomorphic state, it
retains the orientations but shorter ordered
arrangement results.
Molecular arrangement
(Longer range of (Shorter range of (Random

ordered ordered arrangement in the
arrangement) arrangement) true liquid state)

Liquid Crystal Phases
• Positional order (whether molecules are arranged in any sort of ordered lattice) and
• Orientational order (whether molecules are mostly pointing in the same direction).

It’s a temporary phase
• Liquid crystal materials may not always continue to
exist in a liquid-crystal phase.
• Ex. Water on cooling can give ice but the ice will
return back to water unless continuous freezing is
done.
• The phenomenon Important

is thus reversible.
Engineering Materials 58
Melting
Transition
Substances Point
Point (C)
(C)
Anisaldazine
165 180
(CH3OC6H4CH:N:CHC6H4OCH3)
p-azoxyanisole
116 135
(CH3OC6H4NONC6H4OCH3)
p-azoxyphenetole
137 167
(C2H5OC6H4NONC6H4OC2H5)
Diethylbenzidine
115 120
(C2H5NHC6H4C6H4NHC2H5)
p-methoxy cinnamic acid
170 186
(CH3OC6H4CH:CHCOOH

Classification of LCs
• Liquid crystals can be classified as :
1. Thermotropic LCs: composed of organic substances and exhibit

phase transitions as a function of temperature.
2. Lyotropic liquid crystals: organic substances and exhibit phase

transitions as a function of temperature and concentration of the
substance in a solvent.
3. Metallotropic liquid crystals: (organic + inorganic) substances

and exhibit phase transitions as a function of temperature,
concentration, and the inorganic : organic composition ratio.
Classification of LCs
• Liquid crystals can be classified as :
4. Columnar liquid crystals

1. Thermotropic LC
• Thermotropic LCs exhibit a variety of phases (smectic or nematic) as temperature
is changed.
• At high temp, thermal motion will destroy the delicate cooperative ordering,
pushing the material into a conventional liquid phase (isotropic).
• At too low temp, most LC materials will form the conventional solid crystal
(anisotropic).

1. Thermotropic LC
• On heating a particular type of LC molecule within a phase
(also called a mesogen) may exhibit various smectic phases
followed by the nematic phase and finally the isotropic true
liquid phase as temperature is increased.
• Ex. p-azoxyanisole (118⁰C - 136⁰C)

Smectic LC phases
• Smectic phases are found at lower temperatures than the nematic phases.
• The word comes from the greek word “smecticus” meaning soap like properties.
• Smectic phases form well-defined layers that can slide over one another in a
manner similar to that of soap.
• These phases are liquid-like within the layers.

Smectic LC phases
• Within the layered structure of a smectic phase a variety of
molecular arrangements are possible.
• The inter layer attractions are weak as compared to lateral

forces of attraction between molecules (mesogens).
• When a stress is applied or allowed to flow, layers slide over

one another like soap but still retain their parallelism.
• Ex. Ethyl-p-azoxy benzoate (114⁰C - 121⁰C)
Ethyl-p-azoxy cinnamate (140⁰C - 175⁰C)

Smectic LC phases
• The smectics are thus positionally ordered along one
direction.
• In the Smectic A phase, the molecules are oriented roughly

along the normal layer, while in the Smectic C phase they
are tilted away from the layer.
• There is a very large
number of different smectic
phases, all characterized by
different types and degrees
of positional and
orientational order.
Smectic A phase Smectic C phase
Smectic phases which possess both orientational and positional order
Smectic LC phases
• Properties:
• They don’t flow as normal fluid (i.e. non-Newtonian)
• They flow in layers, as one layer gliding over the other
• The existence of the layers indicates that order is still there but in
distorted form
• They show X-ray diffraction but in one direction only
• Ex. Ethyl-p-azoxy benzoate (114⁰C - 121⁰C)
Ethyl-p-azoxy cinnamate (140⁰C - 175⁰C)

Nematic LC phases
• These are the most common LC phases.
• The word nematic comes from the greek word “nema”

meaning thread like.
• In a nematic phase, the rod-shaped organic molecules

(mesogens) have no positional order, but they self-align to
have long-range directional (orientational) order with their
long axes roughly parallel

Nematic LC phases
• Thus, nematic phases possess only orientational order

unlike the smectic phases which possess both
orientational and positional order.
• The rod like molecules tend to align parallel to each

other with their long axes all pointing roughly in same
direction.

Nematic LC phases
• The fluidity of the nematic mesophase is due to the

ease with which the molecules can slide past one
another while still remaining parallel.
• Nematics possess dielectric anisotropy i.e. different

dielectric constant in the different direction of
orientation.

Nematic LC phases
• Nematics have fluidity similar to that of ordinary true liquids

(which are isotropic)
• Nematic phases can be easily aligned by an external magnetic
or electric field.
• An aligned nematic has the optical properties of a uniaxial
crystal and this makes them extremely useful in liquid crystal
displays (LCD).
• Ex. p-azoxy anisole
Nematic LC phases
• When these crystals are viewed along lines of force

in a strong magnetic field, the turbidity disappears
and if field is removed they appear turbid again.
• e.g. p-azoxy phenetole (137C – 167C), p-azoxy

anisole (116C – 135C), p-methoxy cinnamic acid
(170C – 186C)

Nematic LC phases
• Properties:
• Nematics have fluidity similar to that of ordinary (isotropic) liquids. They show
normal or Newtonian flow behavior. Nematics have more fluidity than smectic types
• The concept of viscosity is applicable in this casebut is low as compared to the

liquids
• In polarized light the thread-like structures are visible
• They are affected by strong magnetic field
• e.g. p-azoxy phenetole (137C – 167C), p-azoxy anisole (116C – 135C), p-methoxy
cinnamic acid (170C – 186C)
Cholesteric (or Chiral nematic) LC phase
• This phase is called the cholesteric because it was first observed for
cholesterol derivatives (cholesteryl esters)
• These are optically active and similar to nematic kind in arrangement

but show strong colour effect in polarised light.
• The optical activity of these liquid crystal phases is many times higher
than of its solid crystalline variety.
• Only chiral molecules (i.e. those that have no internal planes

of symmetry) can give rise to such a cholesteric LC phase.

• These LC phases have some smectic and some nematic
characters.
• In this type of LC phase the molecules (or mesogens) are

twisted about an axis. The twist may be right / left handed.
• The mesogens are arranged in layers like the smectics
• This LC phase exhibits a twisting of the molecules (in layers)

perpendicular to the director, with the molecular axis being
parallel to the director.
• Thus, the mesogens in each layer are twisted with respect to
those in the above or the below layer.
• The twisting is due to the presence of a chiral centre in the

mesogens which produces intermolecular forces that favor the
alignment of one layer of mesogens at a slight angle to the
another.
• The structure can be visualized

• The structure can be visualized as a stack of very thin
nematically arranged mesogens layers.

• An important property of
the cholesteric (chiral
nematic) mesophase is the
pitch, ‘p’.
p
• The chiral pitch, ‘p’, refers to
the distance over which the
LC molecules undergo a full
360° twist.
• Ex. Cholesteryl benzoate

(145⁰C - 178⁰C) Important Engineering Materials 78
• Properties:
• They show many characteristics of Nematic liquid crystal, and also show color effect
in polarized light
• They are also called twisted Nematic
• Pitch of the helix of twisted Nematic structure is responsible for the color of the light
radiation diffracting from the liquid crystal

2. Lyotropic LCs
Lyotropic LCs exhibit phase transitions as a function of
concentration of the mesogen in a solvent (typically
water) as well as temperature.
• Ex. Soap, biological cell membranes, are few examples

of lyotropic LCs.

2. Lyotropic LCs
Lyotropic LCs exhibit phase transitions as a function of
concentration of the mesogen in a solvent (typically
water) as well as temperature.
• Ex. Soap, biological cell membranes, are few examples

of lyotropic LCs.

3. Metallotropic LCs
• Liquid crystal phases can also be based on low-melting inorganic
phases like ZnCl2 that have a structure formed of linked
tetrahedra and easily form glasses
• The addition of long chain soap-like molecules leads to a series of

new phases that show a variety of liquid crystalline behavior both
as a function of the inorganic-organic composition ratio and the
temperature
4. Columnar LC phases
• Columar LC mesophases are shaped like discs
instead of rods
• This mesophase is characterized by stacked

columns of the molecules (mesogens)
• The columns are packed together to form a two

dimensional crystalline array as shown in the figure

Application of Liquid Crystals
• Orientation of nematic liquid crystal is easily changed by electric field or pressure
and the changed orientation have different light transmission and reflection
• When an electric field is applied, on a thin LC film with the help of electrodes, the
patterns of molecules becomes visible. This principle is used in LCD screens of
calculators, reading displays, computer and mobile screen etc.

• The feature of smectic liquid crystals is the distance between
planes or layers having molecules, in the same orientation.
When a beam of light strikes these planes, the properties of
reflected light depend upon the distance between the layers.
• The distance between the plane is highly temperature sensitive

and therefore colour of the reflected light depends upon
temperature. This principle is utilized to detect temperature
changes as small as 0.01C.
Temperature → Distance between planes → Colour of reflected light
• Cholesteric liquid crystal are used for detecting tumors in human body.
• Liquid-crystal are used as convenient solvents for spectroscopic study of

anisotropic solids.
• Recording /Sensing temperature changes: Thermotropic chiral LCs
whose pitch varies strongly with temperature can be used in
thermometers, since the color of the materials will change as the pitch
is changed.
• Liquid crystal colour transitions are used on many aquarium and pool
thermometers.

Polymers

• Polymer (Greek: poly=many; mer=part)
• Made up of large molecules (high molecular weight)
characterized by repeating units called monomers (low
molecular weight) held together by covalent and non-
covalent bonds

• Polymerization
Fundamental process in which low molecular weight
compounds combine to form giant molecules/
macromolecules of high molecular weight
• Synthetic polymers: eg polyethylene, nylon

• Natural polymers: eg nucleic acids and proteins

Tacticity: Orientation of side groups on the monomeric
units in polymer takes place in orderly/disorderly fashion w.r.t
main chain
Isotactic: Functional groups (FG) are all on the same
side of the main chain, FG= Y
molecules pack best with other molecules of the same shape

Syndiotactic: Functional groups occupy alternating position
Nice arrangement to make crystal pack
Atactic: Functional groups arranged in random manner

No regular array to make a nice crystal

Addition Polymerization
• It yields product that is an exact multiple of the original
monomer unit
• Polyethene (PE)

Mechanism
• Initiation: Free radicals formed from H2O2 through the
addition of heat
• Free radical acts to open the C=C double bond by joining to one
side of the monomer.
• This allows the monomers to react with other open monomers
on their other side.

• Propagation: Process continues with successive addition of
monomer units to the chains
• Termination: Through a combination of two chains

Condensation/Step Polymerization
• Formation of polymers from polyfunctional monomers
of organic molecules with elimination of small
molecules like water, HCl, ammonia
• Functional group of one monomer unit reacts with
functional group of the other

Copolymerization
• Specific type of addition polymerisation
• Monomers of more than one type are involved thereby
giving variety of polymers
• Eg. Styrene-Butadiene rubber (Buna-S)

Plastics
ThermoPlastics/Thermosoftening Polymers
• Some polymers when heated become soft and can be
moulded into any shape that can retain on cooling
• PVC, PE, nylon sealing wax, etc
Thermosetting polymers
• On heating, polymers undergo a chemical change and
become an infusible mass which cannot be reshaped
• Egg yolk, polyester, resins

Thermoplastic polymers Thermosetting polymers
They soften on heating and harden on They are fusible on initial heating, but
cooling turn into hard infusible mass on heating
further
Can be reshaped and recycled Cannot be reshaped and recycled

Formed by addition polymerization Formed by condensation polymerization
Linear in structure Three dimensional in structure
They are soluble in some organic solvents Insoluble in organic solvents
Moulded articles are taken out after cooling Moulded articles are taken out from the
the mould to avoid deformation of the mould even when they are hot.
article
Compounding of Plastics
Unusual for a finished high polymeric articles to solely
consist of high polymers alone
Mixed with ingredients known as additives resulting in
useful functions and imparts useful properties to the finished
products
Main types of compounding ingredients are
▪ Resin: Binder, which holds different constituents/additives
together. Natural or synthetic resins used in this case
▪ Plasticizers: Low MW organic liquids added to polymer to
improve its flexibility; Added 8-10% of total bulk of plastics (oils,
camphor, dioctyl phthalates)

• Stabilizers: Most polymers do not possess chemical
stability→ change colors & decompose
• Stabilizers are additives which chemically stabilize the polymer
and thus arrest degradation
• Organic, inorganic, organometallic compounds like CaO, BaO,
Organo-tin compounds
• Fillers/Extenders: Inert material added to enhance
mechanical strength-- asbestos powder, saw dust, cotton pulp, clay,
etc
• Lubricants: Glossy finish to product, Prevents plastics from
sticking to fabrication equipments; oils, waxes, soaps, etc

• Catalysts
Antioxidants like H2O2, benzoyl peroxide, ZnO, NH3, Ag, Pb,
are added to the polymeric matrix to accelerate the cross linking
in thermosetting plastics while moulding process
• Coloring materials
Organic dyes and pigments impart desired color for aesthetic
appeal of the finished polymeric material. Some colors are added
to impart UV protection to the finished products.

Conducting Polymers
• Polymers are poor conductors of electricity, due to non-
availability of large number of free electrons
• Polymers with polyconjugated structures are insulators
in pure state, but can be converted into polymers with
electrical conductivities comparable to metals.
Polymers today are synthesized at par to conductivities

of metallic conductors
Conducting polymers are finding increased use due to
their light weight, easy to process and good mechanical
properties.
Conditions
Polymer should consist of alternating single and double
bonds called conjugated double bonds
• Excitation of  electrons in electric field
• Disturbance in polymer matrix by
- Either by removing electrons from material
• Or inserting electrons into the material.
The process is known as doping
• By doping with electron donor like alkali-metal ion or electron
acceptor like AsF5, Iodine, etc polymers turn conductive
materials

Types of conducting polymers
1. Intrinsically conducting polymer (ICP)
• Polymers with conjugated  electrons
• In an electric field the electrons get excited and are transported through
solid polymeric matrix.
• Overlapping orbitals of conjugated  electrons over the entire polymer

forms valence and conduction bands
2. Doped conducting polymer
Polymer matrix has to be disturbed –
• Removing electrons (oxidation) by electron acceptors like AsF5,
Iodine, etc
• Inserting electrons(reduction) by electron donors like alkali-metal
ion Li, Na, Ca
• The conductivity is increased by creating either a positive or

negative charge on the polymer backbone.
(i) P-doping: treating ICP with Lewis acid, thereby oxidation process
sets in and positive charge created on polymer backbone.
• Iodine molecule attracts an electron from polyacetylene chain and

becomes I3-
• Polyacetylene molecule, now positively charged is a radical cation
• Lonely electron of the double bond, from which an electron was
removed, can move easily.
• As a consequence, double bond successively moves along the
molecule–

(ii) N-doping: treating an ICP with a lewis base, thereby reduction process takes place
and negative charge created on polymer backbone
Examples:
• Industrially conducting polymers are: Polyquinoline, polyanthrylene, polythiophene,
polybutadienylene, polyacetylenes etc
• Used in making button cells, photovoltaic devices, sensors,
biomedical devices.

3. Extrinsically conducting polymers
(i) Conducting element-filled polymer: Here, polymer acts as a binder that binds
the conducting elements like carbon black, metal oxides, metallic fibres that
conduct electricity
(ii) Blended conducting polymer: This polymer is made by blending a conventional
polymer with a conducting polymer
4. Coordination conducting polymers
A metal atom with polydentate ligand, which is a charge transfer complex is bound
to the polymer to make it conducting.

Smart Materials
Conducting
Battery technology Telecommunication
Polymers
Aerospace

Self healing polymers
• Inspired from biological systems → ‘Wound healing’
• Inherent ability of polymers to repair damage caused by
mechanical usage over time
Terminator Polymers
• Chemistry World posted a video of the product in action,
showing someone cutting a piece of the polymer in two with a
scalpel, pressing the pieces back together and leaving it on a table
for two hours at room temperature. The person is unable to pull
the material apart with their hands upon returning.
• This is the next generation breakthrough in polymers.

• Autonomic healing: A propagating crack ruptures the
microcapsules, releasing the healing agent into the crack
plane by capillary action. Polymerization is initiated by
contact with the embedded catalyst or initiator, bonding
the crack faces, and restoring structural continuity.

• Non-autonomic healing: Partially self-contained; healing capability is
designed into the material, but additional external stimuli such as heat or
UV-radiation is required for the healing to occur.

Applications
• Nissan Motor Co. Ltd has commercialized world’s ﬁrst
self-healing clear coat for car surfaces-trade name of this
product is ‘Scratch Guard Coat’
• Self healing concretes– in progress
• Self-healing materials are now used as composites in
aircrafts.

4-Important engineering materials

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4-Important engineering materials

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Important Engineering Materials

Important Engineering Materials 1

Important Engineering Materials 2

• In 1959, physicist and Nobel prize laureate Richard Feynman presented

• Nanostructures or nanomaterials are forms of matter at the nanoscale.

Important Engineering Materials 4

• For example a single human hair is about 50,000 - 100,000 nm

• A red blood cell is approximately 7,000 nm wide.

• Viruses which cause infections are in the range of 20 – 400

• The term broadly refers to such fields as biology, physics or

chemistry, or any scientific field, or a combination thereof,

that deals with the deliberate and controlled manufacturing

Important Engineering Materials 6

• Chemists have dealt with naturally occurring nanoparticles all along.

• Ex. Tire manufacturers used nanoparticles - carbon black - to improve the

performance of tires as early as the 1920s.

windows (gold particles in nanometer size are red, not golden).

Important Engineering Materials 7

• Much of nanoscience requires that you forget what you know

• Two principal factors cause the properties of nanomaterials to

1. Increased relative surface area and

Important Engineering Materials 8

have a relatively larger surface area.

affect their strength or electrical properties.

• 7000 square meters = 7×109 square millimeters

• Thus, when the amount of coin silver contained in a silver dollar is

rendered into 10 nm particles, the surface area of those particles is

about 2.33 million times (7 billion square millimeters divided by the

3000 square millimeters) surface area of the silver dollar!

Important Engineering Materials 11

• However, it becomes dominant when the nanometer size range is reached.

Important Engineering Materials 12

• Materials reduced to the nanoscale can suddenly show very different

• For instance, opaque substances become transparent (copper); inert

Important Engineering Materials 14

ii. Strength and

iii. Electrical characteristics.

•Also as particle decreases in size, a greater proportion of atoms are

Important Engineering Materials 16

• The planar surface layers do not have covalent links, which

• Also the fourth electron is free to move from one layer to

Important Engineering Materials 18

• High thermal conductivity.

• High resistance to thermal shock

Important Engineering Materials 19

• It is used for electrical contacts, brushes and resistors.

Important Engineering Materials 20

• It is a discrete molecular form with a hollow spherical cluster

CARBON MATERIAL (AFTER GRAPHITE AND DIAMOND)

• Each cluster molecule is composed of groups of carbon

C70,C76,C84,C240 and so on. They are a class of closed

• Fullerene contains 12 pentagons and a variable no. of

HEXAGONS= (NO. OF CARBON ATOMS - 20) / 2

Important Engineering Materials 23

with more than 300 carbon

atoms, include single-shelled or

multi-shelled carbon structures,

onions, and nanotubes.

Important Engineering Materials 24

• They have closed structure – the ability for holding (trapping)

• Ex. one could also bind specific antibiotics to the structure to

Important Engineering Materials 26

• It is an allotrope of carbon discovered in 1991 by Japanese scientist

• Carbon nanotubes (CNTs) are produced ranging from single to tens of