Engineering Chemistry Notes (21CHE12/22)

Module-III ENGINEERING MATERIALS

Polymers introduction Nanomaterials

Polyurethanes Synthesis of Nanomaterials
Polymer composite Sol-gel process
Kevlar fibers Precipitation method
Conducting polymers Fullerene materials
Factors influencing the conductivity of Carbon nanotubes
organic polymer. Graphene
Biodegradable polymers

Engineering materials

Naturally occurring or man-made material that find use in construction of buildings and manufacture of tools
and equipment’s are called engineering materials
POLYMERS
Introduction
Polymers are the high molecular weight compounds obtained by repeated union of simple molecules
(Monomers). Ex: Starch, silk, wool, Polyvinyl chloride, Polyethylene, Nylon 6,6 etc.
Classification of polymers.
Polymers are classified into two types as follows:
i) Natural polymers: These are the polymers obtained naturally by plants and animals.
Ex: Silk, wool, natural rubber, protein, starch, cellulose, etc.
ii) Synthetic Polymers: These are artificially prepared polymers also known as manmade polymers.
Ex: PVC, Nylon 6.6, Polyethylene, Phenol formaldehyde resin etc.,
Important Terms used:
 Monomer: These are the simple molecules, which combine with each other to form polymers. These
are the building blocks of Polymer.
 Polymerization: The process of linking of monomers to form polymers with or without the
elimination of by-products is called as polymerization.
 Degree of Polymerisation (n): The total number of monomers present in a single chain of polymer
is called as degree of polymerization.
 Functionality: The total number of bonding sites or functional groups present in a monomer is called
functionality of the monomer

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Polyurethanes
Synthesis: Polyurethane often abbreviated PUR and PU refers to a class of polymers composed of
organic units joined by urethane links. Polyurethanes are produced by the polymerization rection of di-
isocyanate and diol or triol (or the addition reaction between di-isocyanate with glycol). In the production of
polyurethane foams, glycol, di-isocyanate, catalyst (tertiary amines), water and surfactants are mixed
together and heated.

O O O O

H H
C N R N C + HO R OH C N R N C O R O
n
Diisocyanate (excess) Diol Polyurethanes

Properties Applications
High resistant to oxidation by air, ozone. Flexible foams are used for cushions in
automobiles & furniture
The foams are available in both rigid & flexible Rigid foams are used to reinforce hallow structural
forms. units.
Resistant to organic solvent but easily attached by Fibers of Polyurethanes are used in lightweight
hot acids and alkalis. garments and swimsuits because of their stretching
property
Share good electrical insulating property These are used to coat gymnasium floor and dance
floor.
Thermally stable These are used in tyre treads and industrial wheels.

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3.3 Polymer composite

A polymer matrix composite (PMC) is a composite material composed of a variety of short or
continuous fibers bound together by an organic polymer matrix. PMCs are designed to transfer loads between
fibers of a matrix. Some of the advantages with PMCs include their lightweight, high stiffness and their high
strength along the direction of their reinforcements.
Kevlar fibres:
Kevlar fiber is a heat-resistant and strong synthetic fiber, it is typically spun into ropes or fabric
sheets that can be used as such, or as an ingredient in composite material components. Kevlar is
synthesized in solution from the monomers of 1,4 benzene dicarbonoyl chloride & 1,4-
phenylenediamine in a condensation reaction yielding hydrochloric acid as a by-product.

O O O O
n Cl Cl + n HN NH H H
C C 2 2 C C N N

-2nHCl

n
terphthaloyl chloride p- phenylene diamine Kevlar

Properties Applications
Kevlar is crystalline, light weight and nonflammable. Used in reinforcement material for some tyres.
Resistant to heat, impact and scratch. Used in boat hulls and aerospace industry.
Good Chemical resistance. Used in formula one racing car tanks.
Good tensile strength. Used in bullet proof vests and combat helmets.

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Conducting polymers
These are the organic polymers having the conductivity band similar to that of conductors with highly
delocalized Pi electron system. Ex: Polyaniline, Polypyrrole, Polythiophene, Polyacetylene, etc. Conducting
polymers are obtained by doping an oxidizing or reducing agent into organic polymers. With the carbon
backbone consisting of alternate double bond & single bonds doping results in delocalization of electrons
responsible for conduction.

Mechanism of conduction in Poly aniline

Protonic acid doping:

The synthesis of conducting polyaniline is a typical example of this type of doping technique. In this
technique current carrying charged species (-/+) are created by the protonation of imine nitrogen. Polyaniline
is partially oxidized, first using a suitable oxidizing agent into a base form of aniline which contains
alternating reduced and oxidized forms of aniline polymer backbone. This base form of aniline when treated

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with aqueous HCl (1M) undergoes protonation of imine nitrogen atom; creating current carrying charged
sites (+ve) in the polymer backbone. These charges are compensated by anions (Cl -) of the doping agent,
giving the corresponding salt. This type of protonic acid doping of polyaniline results in an increase of
conductivity by approximately 09-10 orders of magnitude.
Applications:
Conducting polymers are highly promising materials to be used in electric and electronic applications, some
of the applications are.
1. As electrode material for commercial rechargeable batteries, for higher power to weight ratio (coin
type of batteries)
2. As conductive tracks of on printed circuit boards
3. As sensors: Humidity sensor, Gas sensor, Biosensor for glucose, Galactose etc.
4. In electro chromic display windows.
5. In information storage device.
6. In light emitting diodes.
Factors influencing the conductivity of organic polymer

1. Effect of Dopant: It has been observed that as addition of dopant causes more charging sites hence
conductivity will be going to increases.
2. Effect of Temperature: as temperature increases electrons in valance band gains kinetic energy
hence more electrons will move from conduction band to valance band.
It has been observed that conductivity is increases by Temperature
3. Effect of Band Gap: It has been observed that conductivity increases with decreasing band gap.
Metals have zero band gaps, while insulators like many polymers have large band-gaps (1.5 to 4 eV)
which impede electron flow.

Biodegradable polymers
“These are polymers which can be decomposed by micro-organisms”. They contain functional groups similar
to the functional groups present in biopolymers like starch, cellulose etc.
Polylactic acid, also known as poly (lactic acid) or polylactide (abbreviation PLA). PLA has become a
popular material due to it being economically produced from renewable resources. The monomer is typically
made from fermented plant starch such as from corn, cassava, sugarcane or sugar beet pulp.
“The direct condensation of lactic acid monomers can also be used to produce PLA. This process needs to
be carried out at less than 200 °C”

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Properties Applications
It is amorphous glossy polymer They are used as parts of medical device.
Lactic acid is colorless or yellow syrupy liquid They are used to replace tissues
It has melting point range from 130-180 0C They are used in Tooth reconstruction
The high surface energy of PLA results in good Used to deliver drugs to body parts
printability, making it widely used in 3D printing

Nanomaterials:
The term nano originated from the Greek nanos which means ‘dwarf’.
It is one billionth of a meter. The size of the materials at least in any
one of its dimension ranges between 1 to 100 nm is called nanomaterial.
Size-dependent properties
1. Surface area:
The total surface area (or) the number of surface atom increases with reducing size of the particles. The
physical and chemical properties property of nanomaterials is size dependent, because in nano scale more
surface area will be exposed compared to bulk materials. If the bulk materials are subdivided into
nanomaterials, the collective surface area is greatly increased as shown in the figure.
Change in surface to area volume on breaking down the molecules affects the physical, chemical,
mechanical and other properties invariably.
At Nano-scale, the material properties change - melting point, fluorescence, electrical conductivity,
and chemical reactivity Surface size is larger so a greater amount of the material comes into contact with
surrounding materials and increases reactivity
2. Catalytic properties
Nanomaterial-based catalysts are usually heterogeneous catalysts broken up into metal nanoparticles
in order to enhance the catalytic process. Metal nanoparticles have high surface area, which can increase
catalytic activity. The catalytic activity of the catalyst increases with increase in surface area hence the
nanomaterial’s exhibits better catalytic activity.
 Example, Gold in macro medium is inert catalyst, where as in Nano scale it acts as a good catalyst.

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 Iron oxide and cobalt nanoparticles are used with active materials like alumina to convert gases
such as carbon monoxide and hydrogen into liquid hydrocarbon fuels using the Fischer-Tropsch
process.
 In magnetic chemistry, nanoparticles can be used for catalyst support for medicinal use. Besides
conventional catalysis, nanomaterials have been explored for mimicking natural enzymes.
 The nanomaterials with enzyme mimicking activities are termed as nanozymes.
 The nanozymes have found wide applications in many areas, from biosensing and bioimaging to
therapeutics and water treatment.
3. Optical properties
Band gap increases with the decrease in size of materials due to less overlapping of orbitals. Thus,
same nanomaterial with different size shows different color. Example: Gold exhibiting golden color in its
regular structure shows various colours like, blue, red, green etc. In its various Nano size.
 The particles are so small that electrons are not free to move about as in bulk gold – because this
movement is restricted, the particles react differently with light.
 Large ZnO particles – block UV light – scatter visible light – appear white Nano sized ZnoO particles
– block UV light – so small compared to the wavelength of visible light that they don’t scatter it –
appear clear.

4. Electrical properties
As the size decreases the energy bandgap increases thus some nanomaterials exhibit electrical properties that
are absolutely exceptional.
 For example, Carbon Nano tubes can be conductors or semiconductors depending on their Nano
structure.
 Nanotubes are long, thin cylinders of carbon – They are 100 times stronger than steel, very flexible,
and have unique electrical properties

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 Their electrical properties change with diameter, “twist”, and number of walls – They can be either
conducting or semi-conducting in their electrical behaviour.

Synthesis of Nanomaterials:

1 Top-down process: Bulk materials are broken into nano sized particle. E.g., Ball milling.
As the name suggests, the top-down approach means from top (larger) to bottom(smaller). In top-down
approach; a bulk piece of material is taken. Then carving and cutting is done until desired shape is
achieved. Example: Different kinds of lithographic techniques cutting (such as electron beam, photo ion
beam or X-ray lithography cutting), etching, grinding, ball milling and sol gel technique.
2 Bottom-up process: Nano materials are produced by building of atom by atom. Eg., CVD, Sol-gel,
Precipitation method.
As the name suggests, the bottom-up approach means from bottom (smaller) to top or up(larger).
Example: all cell use enzymes to create DNA by taking constituent molecules and binding them together
to make the final component.

Sol-gel process
The sol-gel process is shown in figure, it involves the evolution of networks through the formation of
a colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase (gel).

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Metal or metalloid element surrounded by various reactive ligands is processed to form a dispersible
oxide to form sol in contact with water or dilute acid. Removal of the liquid from the sol yields the gel. The
sol/gel transition controls the particle size and shape.

Sol-gel synthesis may be used to prepare materials with a variety of shapes, such as porous structures,
thin fibres, dense powders and thin films.
Metal alkoxides are used as precursors in sol-gel operation. The metal alkoxides are hydrolysed in
alcohol solution containing a controlled amount of water. The sol gel chemistry can be represented by
following two reactions:

Hydrolysis: M-OH + H2O M-OH + R-OH

Condensation: M-OH + X-OM M-OM + X-OH

Where M= metal; X = H or R (alkyl group)
Solgel process can be characterized by series of distinct steps:
Step-1: Formation of stable alkoxide solution (the sol)
Step-2: Formation of oxide- or alcohol-bridged network (the gel) by condensation method.
Step-3: Aging of gel by heating until the gel transforms to sloid mass.
Step-4: Drying of gel. (Water and other volatile liquids are removed from the gel network.
Step-5: Dehydration, during this step, M-OH groups are removed, and stabilize gel by rehydration,
Step-6: Heating at high temperature (>8000C). The pores of the gel network are collapsed, remaining

organic species are volatilized.

Precipitation method:
In this method an inorganic metal salt, such as chloride, nitrites etc., are dissolved in suitable solvent
(Nucleation). These metallic salts are precipitated out as hydroxides using a suitable base
(Precipitation) in suitable solvent under constant and continuous stirring. The obtained precipitate is
dried and heated at high temperature in muffle furnace (Calcination) to obtain the metal oxide
nanoparticles. The size of nanomaterial
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can be controlled by varying the stirring speed, time and temperature of heating. Schematic diagram of
precipitation method is shown in figure.
Synthesis of nanomaterial by precipitation method.
Principle: Iron oxide nanoparticles were synthesized by precipitation method and it is the most convenient
way to synthesize iron oxide nanoparticles Fe3O4 from aqueous Fe2+/Fe3+ salt solutions by the addition of a
base under inert atmosphere at room temperature.
Procedure: Magnetic nanoparticles of Fe3O4 were synthesized using co-precipitation method by mixing of
FeCl2.4H2O (1.72 g) and FeCl3.6H2O (4.70 g) salts in 50 mL de-ionized water. Ammonia solution was
added dropwise into the salt mixture until the solution reached pH 10, and the black precipitate was obtained.
During this process, the mixture solution was stirred by a magnetic stirrer. The process was finished by
washing the black precipitate of Fe3O4 with de-ionized water to remove any alkali metals, and separated by
magnetic decantation. Afterward, it was suspended in 125 mL of de-ionized water. Before being
characterized, the black precipitates of Fe3O4 in de-ionized water were dried. Properties of various
nanomaterials
Fullerene materials:
A fullerene is a pure carbon molecule composed of at least 60 atom s of carbon.
Because a fullerene takes a shape similar to a soccer ball, it is sometimes referred to
as a buckyball. Fullerenes are seen as promising components of future micro-
electromechanical systems ( MEMS ) and in nanotechnology.
 The fullerene is the reference to a family of carbon allotropes, molecules
composed entirely of carbon, in the form of a hollow sphere, ellipsoid, tube, or plane. Spherical
fullerenes are also called Bucky balls.
 Fullerenes are similar in structure to graphite, which is composed of stacked sheets of linked
hexagonal rings, but may also contain pentagonal (or sometimes heptagonal) rings that would prevent
a sheet from being planar.
 Fullerenes with a closed mesh topology are informally denoted by their empirical formula Cn, often
written Cn, where n is the number of carbon atoms. Ex: C60, C70.
Properties of Fullerene
 Highest tensile strength of any known 2D structure or element, including cross-section of diamonds
which have the highest tensile strength of all known 3D structures.
 Also has the highest packing density of all known structures (including diamonds)
 Resistant to high temperatures.
 Possesses semiconductor properties.
 Superconducting at low temperatures
Applications

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 Fullerene molecules can be used for drug delivery into the body, as lubricants, as catalysts.
 They have many chemical synthetic and pharmaceutical applications.
 Chemical derivatives of fullerenes have fascinating electrical and magnetic behaviour including
superconductivity and ferromagnetism
 Fullerene molecules have very a high surface area / volume ratio and may be used in the development
of new types of catalysts in the chemical industry.
 Fire resistance, High thermal conductivity may lead to better heat sinks for electronics
 Television screens Bucky paper may be more efficient than CRT and LCD displays
Carbon nanotubes:
Carbon nanotubes (CNTs) were discovered in 1991 by Sumio Ijima of the NEC laboratory in Japan,
during high resolution transmission electron microscopy (TEM). These are molecules that are unique for
their size, shape, and remarkable physical properties. They can be thought of as a sheet of graphite (a
hexagonal lattice of carbon) rolled into a cylinder.
Carbon nanotubes (CNTs) are cylindrical molecules that consist of rolled-up sheets of single-layer
carbon atoms (graphene). They can be single-walled (SWCNT) with a diameter of less than 1 nanometre
(nm) or multi-walled (MWCNT), consisting of several concentrically interlinked nanotubes, with
diameters reaching more than 100 nm. Their length can reach several micrometres or even millimetres.
Like their building block graphene, CNTs are chemically bonded with sp 2 bonds, an extremely strong
form of molecular interaction. This feature combined with carbon nanotubes natural inclination to rope
together via van der Waals forces, provide the opportunity to develop ultra-high strength, low-weight
materials that possess highly conductive electrical and thermal properties.

Synthesis of CNT

Chemical vapor deposition process of producing nanotubes uses a target substrate containing catalysts in a
quartz tube; a hydrocarbon gas breaks apart and deposits carbon on the substrate. Through this method carbon
nanotubes are produced using base growth mechanism.

Properties of CNT

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• Nanotubes are long, thin cylinders of carbon.

• They are 100 times stronger than steel, very flexible, and have unique electrical properties
• Their electrical properties change with diameter, “twist”, and number of walls
• They can be either conducting or semi- conducting in their electrical behaviour.
• A broad range of electrical, thermal, and structural properties depending on the tube diameter, length,
and chirality, or twist.
• Semiconducting like silicon or a 1000 times better electrical conductors than copper.
• Transport heat twice as good as diamond. Tensile strength 20 times that of steel and still
Applications of CNT
• Their mechanical tensile strength can be 400 times that of steel.
• They are very light-weight – their density is one sixth of that of steel.
• Their thermal conductivity is better than that of diamond.
• They have a very high aspect ratio greater than 1000, i.e. In relation to their length, they are extremely
thin.
• A tip-surface area near the theoretical limit (the smaller the tip-surface area, the more concentrated
the electric field, and the greater the field enhancement factor).
• Just like graphite, they are highly chemically stable and resist virtually any chemical impact that
makes them extremely resistant to corrosion.
• Their hollow interior can be filled with various nanomaterials, separating and shielding them from
the surrounding environment - a property that is extremely useful for nanomedicine applications like
drug delivery.
Graphene
Graphene is an allotrope of carbon that exists as a two-dimensional planar sheet, it is technically a
non-metal but is often referred to as a quasi-metal due to its properties being like that of a semi-conducting
metal. Each carbon atom is covalently bonded (sp2 hybridized) to three other carbon atoms in a hexagonal
array, leaving one free electron per each carbon atom
There are 3 main ways to synthesize graphene, they are:
1. Chemical Vapor Deposition
2. Chemical or Plasma Exfoliation from natural Graphite
3. Mechanical cleavage from natural Graphite
Properties Of Graphene
The properties of graphene are unique due to its all-carbon structure and nanoscale geometry.
1. Electronic Properties: Because graphene has a delocalized pi-electron system across the entirety of
its surface, the movement of electrons is very fluid.

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2. Thermal Properties: The repeating structure of graphene makes it an ideal material to conduct heat
in plane. Interplane conductivity is problematic and typically other nanomaterials such as CNTs are
added to boost interplane conductivity.
3. Mechanical Strength: Graphene is one of the strongest materials ever discovered with a tensile
strength of 1.3 x 1011 Pa. In addition to having an unrivalled strength, it is also very lightweight (0.77
mgm-2).
4. Flexibility/Elasticity: The repeating sp 2 hybridized backbone of graphene molecules allow for
flexibility, as there is rotation around some of the bonds, whilst still providing enough rigidity and
stability that the molecule can withstand changes in conformation and support other ions
Applications of Graphene
1. Graphene is used in Sensors
2. Graphenes are used in anticorrosion coatings and paints
3. Graphenes are used in lightweight, thin, and flexible electric/photonics circuits,
4. It is used in Solar panels
5. Used in electron emission displays.

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