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Nano-Materials
Nano materials are defined as a set of substances where at least one dimension is less
than approximately 100 nanometers. A nanometer is a billionth of a meter. Nanomaterials are of
interest because at this scale unique optical, magnetic, electrical, and other properties emerge.
These emergent properties have the potential for great impacts in electronics, medicine, and
other fields.
Synthesis of Nanomaterials:
Sol-gel process: The sol-gel process, involves the evolution of inorganic networks through the
formation of a colloidal suspension (sol) and gelation of the sol to form a network in a
continuous liquid phase (gel). The precursors for synthesizing these colloids consist usually of a
metal or metalloid element surrounded by various reactive ligands. The starting material is
processed to form a dispersible oxide and forms a sol in contact with water or dilute acid.
Removal of the liquid from the sol yields the gel, and the sol/gel transition controls the particle
size and shape. Calcination of the gel produces the oxide.
Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors
such as Si(OEt)4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel
chemistry based on the hydrolysis and condensation of metal alkoxides M(OR) can be described
as follows:
MOR + H2O → MOH + ROH (hydrolysis)
MOH + ROM → M-O-M + ROH (condensation)
Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is
widely employed to prepare oxide materials. The sol-gel process can be characterized by a series
of distinct steps.

1. Formation of different stable solutions of the alkoxide or solvated metal precursor.

2. Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by a
polycondensation reaction that results in a dramatic increase in the viscosity of the solution.
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3. Aging of the gel during which the polycondensation reactions continue until the gel transforms
into a solid mass, accompanied by contraction of the gel network and expulsion of solvent from
gel pores. The aging process of gels can exceed 7 days and is critical to the prevention of cracks
in gels that have been cast.
4. Drying of the gel, when water and other volatile liquids are removed from the gel network.
5. Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing the
gel against rehydration. This is normally achieved by calcining at temperatures up to 800 0C.
6. Densification and decomposition of the gels at high temperatures (T>800 0C). The pores of
the gel network are collapsed, and remaining organic species are volatilized. The typical steps
that are involved in sol-gel processing are shown in the schematic diagram above.
Carbon nanotubes:
Carbon nano tubes (CNTs) which are hollow fibres. CNTs are extended tubes of rolled
graphene sheets (a planner network of inter connected planar hexagonal rings of carbon atoms)
which are typically closed at their ends by semi-fullerene-like structures. Defects in the
structures result in bends and transitions overall. The diameter of carbon nanotube remains in
the order of one nanometer but can go up to several microns to centimeters long. There are two
forms of CNTs namely:
1) Single-walled carbon nanotubes (SWCNT):
These are different types depending on the matter in which the graphene sheets are
rolled. The basic varities being zigzag, armchair, and chiral. Identification of a particular variety
can be made by following the pattern across the diameter of the tube and analyzing their cross-
sectional structure.
2) Multi-walled carbon nanotubes (MWCNT) :
It consists of several concentric Single-walled carbon nanotubes (SWCNT) with different
diameters. The forms are more complex here as each SWCNT can have different structures
resulting in a variety of sequential arrangements.
The simplest form being the one in which the concentric layers are identical but of
different diameters. In other varieties, two or more types of concentric SWCNTs remain arranged
in a different orders. These can have either regular layeres or random layeres.
Characteristics:
1) These materials have high thermal and electrical conductivity. Here, motion of electrons
fall under the regime of ballistic transport. It is the transport of electrons in a medium
with negligible electrical resistivity due to scattering. Ballistic transport is observed when
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the mean free path of the electron (the average length that the electron can travel freely,
i.e, before hitting against the walls.
2) Their mechanical strength is very high
3) Stable at high temperature
4) Stable against strong acids and other chemicals present in atmosphere.
Applications:
1) In conducting polymerscreens,
2) In electronics such as memory, semiconductor components and transparent conducting
films for touch screens, displays and solar cells.
3) To build ultra-capacitors in which energy storage capacity is much higher than the
traditional capacitors.
4) Used for preparation of structural materials such as
a) Textiles: CNT is used to make waterproof and tear-resistant fabrics
b) Body armor: Bullet proof jackets can be made using CNT fibres
c) Concrete: CNT in concrete increases its tensile strength and halt crack propagation.
d) Sports equipment: Stronger and lighter tennis rackets, bicycle parts etc.
Applications of nanomaterials:
Nanomaterials having wide range of applications in the field of electronics, fuel cells,
batteries, agriculture, food industry, and medicines, etc. It is evident that nanomaterials split
their conventional counterparts because of their superior chemical, physical, and mechanical
properties.
1) As materials: Nano tubes of MoS2 and WS2 are used as solid lubricants and NbSe2
becomes super conductor at low temperature.
2) Carbon nano tubes (CNT) are use full in lithium batteries, fluorescent displays, in
computers.
3) As sensors: Nanomaterials can be used as sensors for gases such as NO 2 and NH3.
4) In Chemistry: Nano particles are used as catalysts in chemical industry due to the high
surface area, nano-catalysts tend to have exceptional surface activity.
5) In Medicine: Nano materials find applications in the field of medicine such as disease
diagnosis, drug delivery and molecular imaging, Longer-Lasting Medical Implants
6) Nanocoatings: Surface coating with nanometre thickness of nanomaterial can be used to
improve properties like wear and scratch-resistant, hydrophobic properties.
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Scanning Electron Microscopy:

Principle:

When a beam of electrons interact with solid surface various components are resulted such as back
scattered electrons, secondary electrons, x-rays and luminescence etc.

The surface of a sample is scanned in raster pattern with a beam of electrons and the x-ray emission
is measured.

A raster scanning involves 1. Swept of e- beam on surface in a straight line in x-direction, 2. Returned
to its starting position, 3. Shifted downward in the y direction by a standard increment. This process is
repeated until a desired area of the surface has been scanned.

Instrumentation:

The same instrument can be used for both SEM and Scanning elctron microprobe.

• Electron Gun: Tungsten filament source, or field emission guns are used to generate e - beam
with 1 to 30Kev. The magnetic condenser and objective lens systems reduce the spot size to a
2–10 nm when it reaches the specimen. Objective lens determines the size of the beam hitting
the sample surface. The condenser lens system, is responsible for the throughput of the
electron beam reaching the objective lens and the objective lens determines the size of the
beam hitting the sample surface. SEM contains two pairs of electromagnetic coils located
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within the objective lens. One pair deflects

the beam in the x direction and the other pair
deflects it in the y direction. The entire
sample surface can be irradiated with the
electron beam and the signals to the scan
coils can be either analog (Cathode ray
Tube CRT) or digital.

Magnification is M = W/w . W = Width of

CRT display and w = width of a single line
scan (ie; spot size). The magnification
achievable to a range from about 10X to
100,000X.

Applications:

SEM is one of the most versatile technique, and can be used to-

1) Image morphology of samples, 2) Image compositional and some bonding differences, 3)

Examine wet and dry samples while viewing them (Only with environmental SEM), 4) View Frozen
Material (SEM with a Cryo-stage), 5) Generates X-rays from samples for micro elemental analysis, 6)
View/Map grain orientation/crystallographic orientation and study related information like heterogeneity.

Limitations

(1) SEM operates at high vacuum. So, the sample which cannot tolerate the vacuum cannot be
studied with the help of SEM. (2) Strong insulating samples cannot be directly studied. Such samples
should be coated with very thin layer of gold or carbon. This coating results some unwanted lumps of
coating material and these lumps are known as artifacts.

Transmission Electron Microscopy (TEM):

TEM was the first type of electron microscope to be developed and it is patterned exactly on the light
microscope except for it uses a focused beam of electrons instead of light to see through the specimen.
Developed by Max Knoll and Ernst Ruska, Germany, 1931.
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MICROSCOPE OPTICAL TEM

RESOLUTION 200 nm 0.2 nm
MAGNIFICATION 1000X
5,00000X
Transmission Electron Microscopy (TEM):

Working Principle:

It is a microscopy technique whereby a beam of electrons

is transmitted through an ultra-thin specimen, interacting
with the specimen as it passes through. An image is
formed from the interaction of electrons transmitted
through the specimen; the image is magnified and focuses
onto an imaging device, such as a fluorescent screen, on a
layer of photographic film, or to be detected by a sensor
such as a CCD camera

• Electron Gun: A beam of electrons of very short

wavelength emitted from a tungsten filament.
Optical system is enclosed in vacuum so as to
avoid collision with air molecules and scattering of
electrons. Tungsten filament is heated to emit electrons which are accelerated by the voltage in the
anode. Higher anode voltage, higher electron speed, shorter wavelength and increased resolution.

• Magnetic columns: placed at specific intervals in the column. Acts as electromagnetic condenser lens
system and focuses the electron beam.

• Specimen: Stained with electron dense material. Placed in vacuum. Electron beams pass through the
specimen and are scattered by internal structures.

• Transmitted beam: carries information regarding the structure of the specimen.

• Magnetic lenses: magnify the spatial variation in the information (image).

• Image recorder: fluorescent screen, photographic plate, light sensitive sensor like CCD camera.

• Image display: real time on a monitor or computer.

Applications:

• Examination of small particle in size ranges of 10 – 100 nm.

• The transmission of unscattered electrons is inversely proportional to the specimen thickness.
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• Orientation, atomic arrangements and phases present: Given by incident electrons that are scattered by
specimen atoms in an elastic fashion.
• These electrons follow Bragg's Law nλ=2dSinθ
• The incident electrons that are scattered by the same atomic spacing will be scattered by the same angle.
These scattered electrons can be collated using magnetic lenses to form a pattern of spots; each spot
corresponding to a specific atomic spacing (a plane). Diffraction pattern of a monocrystalline sample
Selected area electron diffraction
Limitations of TEM
• Sampling: Very small sample size. But fortunately we are dealing with nanostructures.
• Interpreting transmission images: TEM presents 2D images of 3D specimens.
• Electron Beam damage and Safety: TEM is a potentially dangerous instrument that generates radiation
level that is enough to kill human being.
• Specimen preparation: Your specimens have to be thin, very thin (has to be electron transparent) to get
any useful information.

Polymers

Polymers are macromolecules or large molecules or high molecular weight compounds

obtained by the repeating union of large number of small molecules.

The word polymer is coined from Greek words. Poly means many and mers means parts.

E.g. Polyethylene, polystyrene

Monomer: A repeating unit in the polymeric chain is called as a monomer. It is the basic unit
which makes up the polymer.

Polymerization: The chemical reaction or the process of the formation of polymers from the
monomers is called polymerization.

Degree of polymerization: The degree of polymerization, or DP, is usually defined as the

number of monomeric units in a polymer.

Classifications based on inter molecular forces: The intermolecular forces present in

polymers are van der Waal’s forces and hydrogen bonding. Although, these are weak forces, but
these forces have collective effect all along the chain of polymers. Polymers are thus classified
into four categories on the basis of magnitude of these intermolecular forces in them.
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1) Elastomers: The polymers which can be stretched to at least twice its length on applying
force and returns to its original shape and dimensions as soon as stretching force is released are
called as elastomers. In these polymers, the chains are held together by weakest intermolecular
forces which permit the polymers to be stretched. A few ‘cross-links’ are introduced between the
chains which help the polymers to regain its original position, when the force is released.
e.g., vulcanized rubber.
2) Fibres: Those polymers which can be drawn in the form of long filaments with high tensile
strength (resistance to lengthwise stress), high rigidity or stiffness are called flbres. These
polymers possess high tensile strength and are used in making fibres. This is due to the strong
inter nuclear forces like hydrogen bonding which operate. These forces also lead to close packing
of chains and thus give crystalline nature. Because of that, these polymers show sharp melting
points. E.g. nylon-6,6 (a polyamide).
3) Thermoplastics: These are polymers in which the intermolecular forces of attraction are
mid-way between those of elastomers and fibres. Due to that, these can be easily moulded by
heating. In thermoplastic polymers, the cross-linking does not exist between chains. Examples
of these polymers are polyethylene, polystyrene etc.

4) Thermosetting polymers: These are prepared from low molecular mass semi fluid
substances. When heated in a mould, they get highly cross-linked to form hard infusible and
insoluble products. Once the polymer is moulded cannot be re-moulded. The common example is
bakelite.

Thermoplastic resins Thermosetting resins

1 These resins become soft on heating During fabrication process these resins are
and rigid on cooling reversibly moulded. Once they are solidified they
cannot be softened.
2 The heating and cooling do not alter These resins are permanent setting resins.
the chemical nature of these resins
because the changes involved are
purely of physical nature.
3 Thermoplastic resins are formed by Thermoset resins are formed by step
chain polymerization polymerization.
4 They consist of long chain linear They have three-dimensional network
polymers with weak secondary van structures.
dar Waal’s forces of attraction in
between.
5 They are softened on heating readily The bonds retain their strength on heating
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because the secondary force of hence do not soften on heating.

attraction between the individual
chains can break easily by heat,
pressure or both.
6 They can be reshaped They cannot be reshaped
7 These plastics can be reclaimed from cannot be reclaimed from waste
waste.
8 Thermoplastic resins are soft, weak Thermoset resins are hard, strong and more
and less brittle brittle.
9 These resins are usually soluble in Due to strong bonds and cross links, they
organic solvents. are insoluble in almost all organic solvents.
10 E.g.: Polyethylene, polyvinyl chloride E.g. Bakelite, Nylon etc.
etc.

Some important Thermoplastics:

1) Polyvinyl chloride (PVC):
Poly vinyl chloride is produced by free radical chain polymerization of vinyl chloride in the presence of benzoyl
peroxide or hydrogen peroxide.

Vinyl chloride is prepared by treating acetylene with hydrogen chloride at 60-80 0C, and in the presence of a
metal oxide catalyst.

Properties:
1. PVC is a colorless and chemically inert powder.
2. Resistant to acids, alkalis, but soluble in chlorinated solvents such as ethylene chloride.
3. PVC is strong, brittle and resistant to atmospheric conditions like O 2, CO2 and moisture.
4. PVC is not stable to heat and U.V. radiation and undergoes degradation.
Engineering applications:
1. PVC treated with plasticizers is called plasticized PVC and used for electrical insulations.
2. Injection moulding PVC is used to make toys, articles like tool handles, radio and telephone components,
chemical containers and thermal insulating foams used in buildings, cinemas and aircrafts.
3. Plasticized PVC is obtained by adding plasticizers such as tricresyl phosphate, trioctyl phosphate is used for
making continuous sheets employed for packing rain coats, table cloths and curtains.
4. The PVC is rigid, highly resistant to chemicals and brittle in nature. The PVC is used for making safety
helmets, refrigerator components, tires, cycle and motor cycle mudguards.
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Thermosetting Resins:
Phenolic resins or pheno plasts: These are condensation polymerization products of phenolic derivatives (phenol,
resorcinol) with aldehydes (like formaldehyde, furfural).
Most important member of this class is Bakelite or phenol-formaldehyde resin.
Bakelite is an important thermoset resin named after the scientist Bakeland who synthesized this resin in the
year 1909. lt is prepared by the step polymerization of phenol with formaldehyde in the presence of an acid or alkali
as a catalyst. The polymerization takes place in three stages
I stage: Phenol is made to react with formaldehyde in presence of acid / alkali to produce non-polymeric mono, di,
and tri methylol phenols depending on the phenol formaldehyde ratio (P/F ratio).
II stage: The mono, di, and tri methylol phenols are heated to produce two types of straight chain resins by
condensation of the methylol group with hydrogen atom of benzene ring to form linear polymer, novolac.
III Stage: During moulding, hexamethylenetetramine [(CH 2)6N4] is added. The addition of hexamethylenetetramine
(HMTA) provides formaldehyde, which converts the soluble and fusible novolac into a hard, infusible and insoluble
solid of cross-linked structure of Bakelite.

Properties:
1. Bakelite plastic resin is hard, rigid and strong.
2. lt is a scratch resistant and water resistant polymer.
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3. Bakelite has got good chemical resistance, resistant to acids, salts and many organic solvents, but it is
attacked by alkalis due to the presence of - OH group
4. lt is a good ion exchanging resin
5. Bakelite is an excellent electrical insulator.
6. lt is a very good adhesive.
7. Bakelite has very good corrosion resistance, resistant to atmospheric conditions like O 2, CO2, moisture etc.
Engineering applications: Bakelite is used widely.
1. For making electrical insulator parts like switches, switch boards, heater handles etc.
2. For making moulded articles like telephone parts, cabinets for radio and television.
3. For making tarpaulins, wood laminates and glass laminates.
4. As an ion exchange resin in water purification by ion exchange method

NATURAL RUBBER:
The main source of natural rubber is the species of tree known as Hevea brasiliensis. It is a polymeric material
having elastic character. India ranks 5 th and produces about 2.7% of the total world production. Most of the Indian
production comes from Kerala. Natural rubber is the polymer of isoprene.
X-ray diffraction studies have shown that isoprene units are arranged in natural rubber in cis-form.
Processing of Natural Rubber:
The milk of rubber trees is called latex. It is a colloidal emulsion containing about 25-40% of rubber. The latex
is collected by cutting the bark of the rubber trees. The latex is diluted with water and filtered to eliminate dirt present
in it. Acetic acid or formic acid (about 1kg per 200kg of rubber material) is added and the rubber is coagulated to soft
white mass. The coagulated mass (coagulum) is washed. The coagulated rubber hydrocarbon is called crude rubber. It
is then rolled out into sheets.

(i) Crepe Rubber: To the crude rubber, a small amount of sodium bisulphite is added to bleach the colour and
passed into rollers which produce 1 mm or more thickness sheets resembling crepe paper and dried in air about 40-
50 0C. This rubber is called as crepe rubber.
(ii) Smoked Rubber: The coagulum is poured in large tanks, which have vertical partition and kept undisturbed for
16hrs. The resulting rubber sheets/slabs are passed through rollers and placed inside smoke rooms maintaining a
temperature 40-50 0C for 4 days. The dried rubber sheets are called smoked rubber (amber in colour) and are sent to
rubber factories for further processing.
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Drawbacks of Crude Rubber or Raw Rubber: Crude rubber obtained

from the latex contains the following drawbacks.
(i) It becomes soft at high temperature and is brittle at low
temperature.
(ii) It shows large water absorption capacity.
(iii) It shows little durability.
(iv) It shows high elasticity.
(v) It attacks easily by oxidizing agents.
(vi) It swells in organic solvents.
(vii) It possesses tackiness.
(viii) It shows low tensile strength.
All the above drawbacks of raw rubber can be rectified by the process of
vulcanization.
Vulcanization: The vulcanization process was discovered by Charles Good year in 1839.
The process by which sulphur is added to raw rubber at 110 0C-140 0C to improve the quality of rubber is
called vulcanization. The added sulphur combines chemically at the double bonds of rubber chains and cross-links
the linear polymer chains, resulting in a three-dimensional network structure. Thus, the rubber loses plastic state and
acquires an elastic state. The stiffness of vulcanized rubber depends on the amount of sulphur added. e.g., A flexible
type rubber contains about 3-5% of sulphur, whereas hard rubber (ebonite or vulcanite) contains about 32% of
sulphur.
Other vulcanizing agents used are hydrogen peroxide, sulphur monochloride, benzoyl peroxide, benzoyl
chloride, etc.
Advantages of Vulcanization:
Vulcanization process brings excellent changes in the properties of rubber, i.e., vulcanized rubber has
1. Good tensile strength. 2. High stiffness.
3. Low water absorption tendency. 4. Slight tackiness.
5. Higher resistance to oxidation. 6. Good durability.
7. Good resistance to change in temperature. 8. Good resistance to swelling in organic solvents,
etc.
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Polymers for Electronics: Polymer resists for integrated circuit fabrication,

lithography and photolithography.

Polymers for Electronics:

Polymer resists:
Polymer resists or simply called resists are polymer resins that contain a photoactive (light-sensitive)
compound (PAC) and an alkaline-soluble resin. These polymer resists are used as thin films in the
manufacture of silicon chips or integrated circuits. The main applicability of these polymers arises due to
the ease and ability to design and synthesize these materials with the precise functionalities and required
properties for a given application. Hence, these polymers were extensively used in the lithographic
imaging for the fabrication of integrated circuits. Radiation sensitivity (ultraviolet light) is the key property
required of materials used for imaging the individual elements of an integrated circuit, known as the
microlithographic process and the technology used to fabricate electronic devices and is critically
dependent on the polymer-organic materials chemistry used to generate the radiation-sensitive imaging
materials.
The resists are of two types. They are positive and negative resists and each contain sensitizer,
resin, solvent, and additives.
A positive photoresist is a type of photoresist in which the portion of the photoresist that is
exposed to light becomes soluble in the photoresist developer usually a solvent. The unexposed portion of
the photoresist remains insoluble in the photoresist developer. General chemical resistance is less than the
negative resist and positives are more costly to produce. However, images from these resists are
extremely accurate, require minimal processing technique, and involve few processing steps.
A negative photoresist is a type of photoresist in which the portion of the photoresist that is
exposed to light becomes insoluble in the photoresist developer. The unexposed portion of the photoresist
is dissolved by the photoresist developer. The negative resists characteristically have high chemical
resistance, good image reproduction qualities and are of low cost. They are widely used in the
manufacture of circuit boards and microelectronic devices for these reasons. Due to their high chemical
resistance, the negative acting resist are generally more difficult to remove than other resists.
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Lithography: Lithography (or patterning) refers to the series of steps that establish the
shapes, dimensions, and location of the various components of the integrated
circuit (IC). The current progress in IC design, with the decreased dimensions
(miniaturization) of the chip and increased density of transistors, is possible
only if smaller areas on the wafer surface can be patterned. This is primarily
the function of lithography.

Process:
The process begins by coating a substrate with a light-sensitive organic material. A patterned mask
is then applied to the surface to block light, so that only unmasked regions of the material will be exposed
to light. A solvent, called a developer, is then applied to the surface. In the case of a positive photoresist,
the photo-sensitive material is degraded by light and the developer will dissolve away the regions that
were exposed to light, leaving behind a coating where the mask was placed. In the case of a negative
photoresist, the photosensitive material is strengthened (either polymerized or cross-linked) by light, and
the developer will dissolve away only the regions that were not exposed to light, leaving behind a coating
in areas where the mask was not placed.
Optical Lithography:
The vast majority of lithographic equipment for IC fabrication is optical equipment using ultraviolet
light (λ  0.2 μm to 0.4 μm) or deep ultraviolet light. There are basically two optical exposure methods:
shadow printing and projection printing.
Photolithography, also called optical lithography or UV lithography, is a process used
in microfabrication to pattern parts on a thin
film or the bulk of a substrate (also called
a wafer). It uses light to transfer a geometric
pattern from a photomask (also called
an optical mask) to a photosensitive (that is,
light-sensitive) chemical photoresist on the
substrate. A series of chemical treatments then
either etches the exposure pattern into the
material or enables deposition of a new material
in the desired pattern upon the material
underneath the photoresist. In
complex integrated circuits, a CMOS wafer may
go through the photolithographic cycle as many
as 50 times.
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CONDUCTING POLYMERS
Polymers are poor conductors of electricity and generally used as electrical insulators.
However, there are polymers with improved electrical conductivity prepared by the addition of
some additives such as conducting metals like copper and silver or other materials.
An organic polymer with highly delocalized π-electron system, having electrical
conductance is called a conducting polymer.
For example, polyacetylene, polypyrrole, polyaniline.
Classification of conducting polymers:
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Intrinsic conducting Polymers:

These polymers are characterized by intensive conjugation of double bonds in their structure i.e. the backbone
of the polymer.
Again, intrinsic conducting polymers are two types as given below.
1) Conducting polymers having conjugation: Such polymers having conjugated double bonds in the backbone
possess their conductivity due to л electrons. In л bonding the overlapping of the orbitals is lateral over the entire
backbone resulting in the formation of valence bands and conducting bands which were separated by a significant
Fermi energy gap. The electrical conductivity takes place in an electric field, conjugated ∏ electrons of the polymer
get excited and gets the sufficient energy to jump the gap and reach into conduction band.

Examples:

All the above polymers possess conductivities around 10 -10 Scm-1 which is sufficient for their use in any
engineering applications.
2) Doped conducting polymers: The conducting polymers having л electrons in their backbone can easily be
oxidized or reduced because they possess low ionization potential and high electron affinities. Hence, their
conductance can be increased by introducing a positive charge or negative charge on polymer backbone by oxidation
or reduction. This process is similar to semiconductor technology and is called doping. Doping is again two types.
1. Creating a positive site on polymer backbone called p-doping
2. Creating a negative site on the polymer backbone called n-doping.
p-Doping: p-Doping is done by oxidation of a conducting polymer like polyacetylene with a Lewis acid or iodine
vapor. This is also called oxidative doping.

During oxidation process the removal of ∏ electron from polymer back bone lead to the formation of a delocalized
radical ion called polaron having a hole in between valence band and conducting band as shown below.
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The second oxidation of the polaron results in two positive charge carriers in each chain called bipolaron,
which are mobile because of delocalization. These delocalized charge carriers are responsible for conductance when
placed in electric field.

n-Doping: n-Doping is carried out by reduction process by the addition of an electron to polymer backbone by using
reducing agents like sodium naphthalide Na +(C10H8)-. Formation of polaron and bipolaron takes place in two steps,
followed by recombination of radicals, which yields two charge carriers on the polyacetylene chain responsible for
conduction as shown below.
The electron added to polyacetylene by reductive doping does not go into the conducting band but goes into
an intermediate electronic state within the band gap of radical anion (polaron).

Bipolaron contains electrons in the energy levels residing in the band gap. The dianion lowers its energy by
segregating into two negative solitons at the mid gap energy levels. The presence of holes in the band gap allows
facile jumps of electrons from valence band into the conduction band. This leads to the generation of conduction
pathways. As a consequence, the conductivity increases significantly.
Polyanilines exist in several oxidation states as far as electrical conductivities are concerned varying from 10 -11
S/cm to > 105 S/cm. The flexible dark blue films of conducting polyaniline are made by protonic doping i.e.
protonation of amine nitrogen atoms in the backbone. Doping is a reversible process deprotonation can also be done
by treatment with alkali. Emeraldine salt is also known as synthetic metal because it possesses metallic conductivity,
metallic luster and metallic sound.
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Advantages of intrinsic conducting polymers:

The following are the advantages of the intrinsic conducting polymers.
1. These polymers possess good conductivity. 2) They can store a charge
3) lon-exchange is possible with these polymers. 4) They absorb visible light to give coloured products.
Extrinsically Conducting polymers:
The conductivity of these polymers is due to the presence of externally added ingredients in them. Again, the
extrinsically conducting polymers are two types.
1) Conducting element filled polymers: The polymer acting as a binder to hold the conducting element such as
carbon black, metallic fibres, metallic oxides etc. Minimum concentration of conducting filler is added so that the
polymer starts conducting. This minimum concentration of conductive filler is called percolation threshold. At this
concentration of filler, a conducting path is formed in polymeric material. The most preferred filler is the special
conducting grade C black has very high surface area, more porosity and more of filamentous properties.
Advantages of conducting element filled polymers:
1. These polymers are low cost polymers. 2) They are light in weight and mechanically durable.
3) These polymers are strong with good bulk conductivity. 4) They are fabricated very easily to any design.
Applications of conducting element filled polymers are used in hospitals and operation theatres.
The disadvantage of the conducting element filled polymers is that addition of 10% carbon black will
drastically decrease the tensile strength, elongation strength and impact strength of the polymer.
Blended conducting polymers: The conventional polymer is blended with a conducting polymer to improve
physical, chemical, electrical and mechanical properties along with the processing properties. Examples: 4O% of
polypyrrole in a conventional polymer gives higher impact strength. These blended polymers are used in
electromagnetic shielding.
Applications of conducting polymers:
1. The conducting polymers are used in rechargeable batteries, small in size (button size), producing current
density up to 50 mA/cm2.
2. Conducting polymers are also used for making analytical sensors for pH, O 2, NO2, SO2, NH3 and glucose.
3. The conducting polymers are used for making ion exchangers. These membranes made of conducting
polymers show selective permeability for ions and gases hence they are used for control release of drug.
4. The conducting polymers are used making electronic displays and optical fibres.
5. They are used for electron beam lithography.
6. The conducting polymers are applicable in photovoltaic devices.
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Drugs
A drug (French-Drogue a dry herb) is defined as “any chemical agent which
affects living protoplasm and is intended for use in the treatment, prevention of
disease.”
Drug classes that are defined by their therapeutic use include:

 Analgesic  Antibiotic  Anticoagulant  Antidepressant

 Anticancer  Antiviral  Antidiabetic  Sedative
Aspirin: Is an analgesic or painkiller used to achieve analgesia, relief from pain
Synthesis:
The synthesis of aspirin is classified as an esterification reaction. Salicylic acid is treated
with acetic anhydride, an acid derivative, causing a chemical reaction that turns salicylic
acid's hydroxyl group into an ester group (R-OH → R-OCOCH3). This process yields aspirin
and acetic acid, which is considered a byproduct of this reaction. Small amounts of sulfuric
acid (and occasionally phosphoric acid) are almost always used as a catalyst.

Physical properties
Aspirin, an acetyl derivative of salicylic acid, is a white, crystalline, weakly acidic substance, with
a melting point of 136 °C
Applications:
 Aspirin, also known as acetylsalicylic acid (ASA), is a medication used to treat pain, fever,
or inflammation. Specific inflammatory conditions in which aspirin is used include Kawasaki
disease, pericarditis, and rheumatic fever.
 Aspirin given shortly after a heart attack decreases the risk of death. Aspirin is also used
long-term to help prevent further heart attacks,
 For pain or fever, effects typically begin within 30 minutes.
Disadvantages:
 Aspirin is a nonsteroidal anti-inflammatory drug (NSAID) but also suppresses the normal
functioning of platelets.
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Paracetamol: Antipyretic is medication used to lower body temperature when a fever is present
Synthesis:
Paracetamol is made by reacting 4-aminophenol with ethanoic anhydride (more commonly called
acetic anhydride) in the presence 3-4 drops of H 2SO4. This reaction forms an amide bond and
ethanoic acid as a byproduct. When the reaction is complete the paracetamol is then isolated
and purified.

 Paracetamol, also known as acetaminophen or APAP, is a medicine used to

treat pain and fever.
 It is typically used for mild to moderate pain relief. Evidence for its use to relieve fever in
children is mixed.
 It is often sold in combination with other medications, such as in many cold medications.
 In combination with opioid pain medication, paracetamol is also used for severe pain such
as cancer pain and pain after surgery.
Disadvantages:
 Paracetamol is generally safe at recommended doses. Serious skin rashes may rarely occur,
and too high a dose can result in liver failure.

Atenolol:
Synthesis:
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Applications:
 Atenolol, is a medication of the beta blockers type, primarily used to treat high blood
pressure and angina.
 Lowering high blood pressure helps prevent strokes, heart attacks, and kidney problems.
 This medication is also used to treat chest pain (angina) and to improve survival after
a heart attack. It works by slowing down the heart and reducing its workload.
 Other uses include the prevention of migraines.
 Atenolol is used for a number of conditions including hypertension, angina, long QT
syndrome, acute myocardial infarction, supraventricular tachycardia, ventricular tachycardia,
and the symptoms of alcohol withdrawal.
Disadvantages:
 Atenolol was the main β-blocker identified as carrying a higher risk of provoking type 2
diabetes.
 Antihypertensive therapy with atenolol provides weaker protective action against
cardiovascular complications