METAL FINISHING

Introduction: The term metal finishing involves many processes carried out to modify the surface
properties of a metal by depositing a layer of another metal or a polymer. No single metal or alloy
can have all ideal properties like corrosion resistance, wear resistance, mechanical, electrical and
thermal properties. Therefore metal finishing is one of the method employed to improve the
properties.
Definition: It is a process in which a specimen metal (article) is coated with another metal or a
polymer in order to modify the surface properties of the specimen.
Example: [a] Electroplating of metals or alloys. [b] Electroless plating of metals or alloys
Technological importance of metal finishing:
[1] To get a decorative surface. Example: Gold plating on copper.
[2] To prevent corrosion. Example: Zinc coating on iron.
[3] To modify the surface properties such as thermal resistance, hardness, brightness, brittleness,
etc. Example: Chromium or nickel coating on iron.
[4] To impart ware resistance
[5] To get better electrical conductance
[6] To prepare electrical component such as PCB
[7] Generally coated meatl is more economica. For example pure gold is more costlier than rold
gold.
Two main technique of metal finishing are:
[a] Electroplating & [b] Electroless plating
ELECTROPLATING
Definition: Electroplating is the deposition of a metal, over the surface of another metal or alloy
or any conductor with the help of electrical energy.
In this process a metal is deposited on another metal or alloy by passing a direct current through
an electrolyte solution containing metal ions to be deposited.
Theory of Electroplating
Important components of electroplating:
• Anode: The anode, or positively charged electrode, in the circuit is the metal that will form
the plating.
• Cathode: The cathode is also called the substrate. Cathode is the substrate which get
coated
 • Electroplating bath: consist of electrodepositing electrolytic solution, additive , buffering
agent.
• Power source: DC power source.
Working Principles:
The article to be plated is made as cathode (substrate) and the metal to be plated on cathode is
made as anode.
Electroplating is carried out in an electrolytic cell. It consists of two electrodes the metal to be
coated is taken as cathode and connected to negative terminal of a DC power source.
Anode is connected to positive terminal of the power source. The electrodes are dipped in an ionic
solution of the metal to be plated.
Under the influence of direct current a ions move towards anode and get oxidized at the anode
surface if the anode is inert .if the anode is dissolvable the electrode itself get oxidized.
Anode reaction: M Mn+ + ne-
On applying direct current, cations move towards cathode and get reduced to metal atoms and
deposited over cathode.
Cathode reaction: Mn+ + ne- M
Diagrammatically general electroplating process can b represented as below;

Hence, plating is an redox reaction, where oxidation occurs at anode and reduction at cathode.
Commonly used coating metals are Zn, Cu, Cr, Ni, Ag, Pt, Au etc...
For example if you want plate copper over iron key following arrangement required
Factors influencing the nature of electro deposit
The nature of electro deposit is affected by several factors, the important among them are:
1. Current Density: It is defined as the current per unit area of electrode surface. It is expressed
in amperes per square meter( Am -2)
At low current density, surface diffusion is fast as compared to the electron transfer, hence metal
is deposited slowly and takes long time for deposition.
At high current density (when current density is increased), surface diffusion may not reach most
favorable portions but electron transportation may be predominates, it results in a rough, powdery,
loose deposit. This also causes hydrogen evolution on the surface of cathode , this results in
dispersed powders containing oxides and hydroxides of the metal, hence a spongy and burnt
deposit is formed.
Hence for a particular deposition optimum current density is determined and used to get a good
deposit.
2)pH of Electrolytic Bath
At low pH values, evolution of hydrogen gas occurs on the cathode, which results in burnt deposit.
At higher pH values, the electrode surface gets coated with insoluble hydroxides.
Therefore pH range of 4 to 8 is used i.e., slightly acidic or slightly basic (alkaline).
The pH is maintained by using a suitable buffer.eg: Borate buffer is used in Ni plating and citrate
buffer in gold plating.
3)Temperature
At high temperature, the rate of evolution of hydrogen gas at cathode increases, this results in
spongy and loose deposit, also sometimes causes the decomposition of organic additives.
At low temperature, electroplating results a powdery deposit.
Hence moderate temperature is preferred, at this temperature the surface diffusion is more than
hydrogen evolution. Hence plating of metals is generally carried out between 35 0C and 600C.
4) Concentration of Metal ion
The metal ion concentration is normally kept low (1-3 mol dm3) because firm and adherent deposits
can be obtained.
If the metal ion concentration is high, mass transfer of ions occurs from bulk electrolytic solution
to the electrode surface, this results in powdery deposit.
5. Organic Additives
These are the substances added to electroplating bath to improve the nature of deposit . There are
different types of organic addives which are;
i) Brighteners : These are the chemical substances that are added to plating bath to get bright
and lustrous (glowing) deposit. For a deposit to be bright, the light falling on the surface should be
reflected. This happens when the grain size (single particle size) is lower than the wavelength of
incident light. Commonly used brighteners are: molecules containing C≡N, N=C=S.
ii) Wetting Agents During electroplating hydrogen is evolved at the cathode. Wetting agents are
added to remove released hydrogen gas. If hydrogen gas not removed it may get entrapped within
the plated metal and try to escape after plating, this may cause the breakage in deposit. Example
for wetting agent is sodium lauryl sulfate.
iii) Levellers Levellers help to produce a uniform deposit on the surface by getting adsorbed at
regions where rapid deposition occurs. Eg: Sodium allyl sulphonate is used as leveler for Ni
deposition.
6. Throwing Power (TP) of plating bath:
Definition: The ability of a plating bath to give a uniform and even deposit on the entire surface
of object is measured by its throwing power.
This is particularly important in objects of complex shapes.eg: plating in holes and breakings
(bends) takes place less uniformly than on even surfaces.
Determination of TP
The throwing power of a plating bath is determined using Haring-Blum cell. Haring-Blum cell
consists of plating bath solution and anode at the center cell.
Two cathodes are placed at distances C1 and C2 from anode (C1 > C2) as shown in figure.
The surfaces of two cathodes away from anode are insulated (deposition occurs only on the surface
of cathodes which is towards anode). Before starting the experiment weight of the individual
cathodes is noted. Electroplating process is carried out and the weights deposited on cathode 1
(W1) and cathode 2 (W2 ) are noted.
Then throwing power can be calculated by using the equation

Where X = C1/C2 & Y = W2/W1

When the amount deposited is same (W1= W2), irrespective of the placement of electrodes ,
throwing power is 100% and is considered to be very good.
Worked Example:
1. In a electroplating of chromium, cathode 1 and cathode 2 were kept at distance of 18cm and 9
m respectively from anode. After deposition it is observed that, %TP is 15 weight deposite at first
cathode is 4gm and is . Calculate weight deposited at second cathode.

Ans: 11%
2. For a electroplating bath using Haring – Blum cell, it is observed that percentage of TP value
is 89.9%. The distances beteween the two cathodes are 4.5cm and 7.3cm from the anode and the
weight deposited on cathode 1 is 61mg calculate weight deposited on other electrode.
Ans:35mg
Electroplating Process
The plating process is carried out by pretreating the object.
Pretreatment (surface preparation):
It is necessary to clean surface of metal electroplating in order to get a good deposit. The impurities
found on the surface may be grease, oxide film, oil, dust etc Various methods are available to clean
the surface of metal:
1) Solvent cleaning: Organic solvents (like CCl 4, toluene, trichloro ethylene, etc) are used to
remove impurities like oil, grease, etc.. from the surface of metal. The process involved is: solvent
is vapourized by heating process, these vapours are then made to condense on the metal surface to
be cleaned. The condensed liquid dissolves and washes away the impurities present.
2) Acid cleaning(pickling): It is used to remove oxides. After the removal of organic impurities,
the substrate is immersed in dilute HCl or H2SO4, this removes oxides.
3) Alkali cleaning: This method is employed to remove old paint from the metal surface using
alkali solutions (i.e., solution of NaOH, sodium silicate, sodium carbonate etc..) Alkali reacts with
oil, grease and removes it.
4) Water wash & drying: Finally electroplating surface washed with water and dried.
Electroplating of Nickel (Watt’s Bath)
Watts solution for electroplating was developed by Oliver P. Watts in 1916. Now it is most popular
nickel electroplating solution. Plating operation in Watts solutions is low cost and simple.
Anode - Pure nickel
Cathode - Object to be plated
Bath composition - Nickel sulfate (240-300 g/l) + Boric acid (30-45 g/l)
Temperature - 40-65°C
Current density - 20-100 A/ft²
pH - 3 – 4.5
Brighteners - Benzene sulphonic acid
Leveller - Allyl sulfonic acid
Main reaction
Anode: Ni Ni2+ + 2e-
Cathode: Ni2+ + 2e- Ni
Diagrammatically nickel electroplating can be represented as below;

Uses
• Decorative appearance - Lustrous bright, satin semi-bright or black nickel coatings may be
obtained by different plating methods.
• Corrosion protection - Nickel plated object shows better corrosion resustance
• Wear resistance. Nickel deposited on a part made of a softer metal protects the part from wear.
• Coinage -Nickel plating widely used in coinage application
• Ferromagnetism. Ferromagnetic parts (steel) may be plated by nickel without changing their
magnetic properties.
ELECTROLESS PLATING
Definition: It is a technique of depositing a metal from its salt solution on a catalytically active
surface of the substrate using a suitable reducing agent without the use of electicity.
The reducing agent converts the metal ions to metal which gets plated over the catalytic surface.
M+ + reducing agent (donate electron) → M + oxidized product
The driving force in this process is autocatalytic redox reaction on preheated catalytic surface.
The main advantage of this method is irregular shapes can be plated uniformly.
Advantages:
1) No electrical power required.
2) Plating may also be obtained on insulator and semiconductor.
3) Better throwing power compared to electroplating.
4) Coatings have unique mechanical, chemical and magnetic feature.
5) No hydrogen gas liberates at cathode, this results in good deposit.
6) Levellers are not required.
Disadvantages:
 1) Generates more waste than other plating techniques.
2) Deposit is contaminated with oxidized product.
3) Rate of deposition is slow.
Difference between electroplating and electroless plating
Following table indicates main differences between electroplating and electroless plating
Property Electroplating Electroless plating
Driving force Electrical energy(current) Autocatalytic redox reaction
Anode Separate anode is used Catalytic surface of substrate
Cathode Object to be plated Object to be plated(treated to make surface
catalytically active)

Reactions Aanode: M → Mn+ + ne- M+ + reducing agent (donate electron) → M

Cathode: Mn+ + ne- → M + oxidized product
Reducing agent Reducing agent not required Reducing agent required
Applicability Only for conductors To conductors, semiconductors and insulators
Electroless plating of copper on PCB (printed circuit board):
An important application of electroless copper plating is manufacture of printed circuit boards
(PCB). The base metal (substrate) used in this method is insulator (plastic material). In electroless
plating copper can be deposited spontaneously in presence of suitable reducing agent on both metal
and insulators. Insulators like plastic and glass before electroless plating are nedd to be
catalytically activated.
Catalytically activation can be done by dipping in the solution containing stannous chloride
(SnCl2) and HCl then followed by dipping in palladium chloride (PdCl 2) solution. On drying, a
layer of Pd is formed on surface. So now article to be electroless plated is catalytically activated.
Electroless Plating bath composition ,condition and reaction involved in electro less plating of
copper are given as follows;
1) Coating solution : Copper sulphate solution (CuSO4)
2) Reducing agent: Formaldehyde
3) Complexing agent: EDTA
4) Buffer: NaOH + Rochelle salt (double salt of potassium sodiumtartarate)
5) pH : 11
6) Optimum temperature : 250C
The overall manufacturing of PCB can be shown as below

FUEL
A fuel is defined as naturally occurring or artificially manufactured combustible carbonaceous
material which serves particularly as source of heat and light.
Classification of fuels
Fuels are classified into two types
1) Based on their origin they are classified into
a) Primary fuels
b) Secondary fuels.
Primary Fuels: There are naturally occurring fuels which serves as source of energy without any
chemical processing. Ex: Wood, Coal, Crude oil, Natural gas, Peat, Lignite, Anthracite..
Secondary Fuels: They are derived from primary fuels & serves as source of energy only after
subjecting to chemical processing. Ex: Charcoal, Coke, produsergas, Petrol, Diesel etc.,
2) Bases on their physical state fuel are classified into
a) Solid
b) Liquid
c) Gaseous fuels.
Solid Liquid Gaseous
Primary fuel Wood, Coal Crude oil Natural gas
Secondary Fuels Coke, Charcoal Petrol, Diesel LPG, Producer gas
Define Calorific Value. Explain the types
Calorific value is defined as the amount of heat liberated when a unit mass of fuel is burnt
completely in presence of air or oxygen.
Calorific value is of two types as follows:
1) Higher calorific value. (HCV) or Gross calorific value. (GCV)
2) Lower calorific value. (LCV) or Net calorific value. (NCV)
1) HCV: It is the amount of heat liberated when a unit mass of fuels burnt completely in the
presence of air or oxygen and the products of combustion are cooled to room temperature. Here it
includes the heat liberated during combustion and the latent heat of steam. Hence its value is
always higher than lower calorific value.
2) LCV: It is amount of heat liberated when a unit mass of fuel is burnt completely in the presence
of air or oxygen and the product of combustion are let off completely into air. It does not include
the latent heat of steam. Therefore, it is always lesser than HCV
Determination of calorific value of solid fuel using Bomb calorimetric method
A small quantity of a fuel is weighed accurately (M Kg) and is placed in the Bomb. The bomb is
placed in known amount water taken in a copper calorimeter. The initial temp of water is noted
with the help of thermometer. Oxygen gas is pumped under constant pressure through the O2 valve
provided. The fuel is ignited by passing electric current through the wires provided. As the fuel
undergoes combustion and liberates heat, which is absorbed by surrounding water. The water is
stirred continuously to distribute the heat uniformly and the final temp attained by water is noted
gross calorific value of the fuel is calculated as follows:
Calculation
Mass of the fuel = M Kg.
Initial temp of the water = t1 0C
Final temp of the water = t2 0C
Change in temp = Δt = (t2 – t1) 0C
Water equivalent of calorimeter = W Kg
Mass of the water taken = wkg

Worked Example
Calculate the gross and net calorific values of a coal sample from the following data obtained in a
Bomb calorimetric experiment.
(i) Weight of coal= 0.5 g
(ii) Weight of water taken in calorimeter = 250g
(iii) Water equivalent of calorimeter = 100g
(iv) Latent heat of steam= 587 Cal/g
(v)Percentage of hydrogen = 1%
(vi) Rise in temp= 0.80C
(vii) Specific heat of water= 4.187kj/kg/ 0C
 (W + w ) ∆ t x 4.187
𝐆𝐂𝐕 =
M

(250+100 )x 0.8 x 4.187

GCV =
0.5

GCV = 2344 J/gm

NCV = GCV – 0.09 x %H2 x 587 x 4.187 J/ Kg
= 2344 – 0.09 x 1 x 587 x 4.187
= 2344 – 221.2
= 2122 . 8 J/gm
What is Petroleum cracking?
Cracking is a process that involves breaking of the chains of high boiling hydrocarbons of high
molecular weight, to yield simpler, low boiling hydrocarbons of molecular weight.
Fluidized bed catalytic cracking method
The catalyst such as Alumina & SiO2 is finely powered and mixed with steam and it is pumped to
cracking chamber. The feedstock (gas oil, heavy oil) is preheated to 500 0C and forced into the
cracking chamber along with the catalyst by a steam blast where a floating turbulent bed forms. In
cracking chamber, the higher molecular weight hydrocarbons are broken down into simpler
fragments. The products are withdrawn and sent to fractionating column for separation. The
catalyst becomes inactive after cracking process. It is sent to catalyst activation chamber and it is
activated by burning carbon deposited on the catalyst by air blast at 600 0C. The catalyst can be
used again and the process is continuous.

FUEL CELL
Definition
Fuel cells are galvanic cells in which chemical energy of fuel is directly converted into electrical
energy.
Classification of Fuel cells Depending on temperature, these are classified into three types as
follows.
1] Low temp fuel cells: Which operates at the temp range below 100 oC
2] Moderate temp fuel cells: Which operates at the temp range about 100 oC to 250 oC
3) High temp fuel cells: Which operates at the temp range about 500 oC
There are two important fuel cells of commercial interest.
1. HYDROGEN - OXYGEN (H2 - O2) FUEL CELL.
Construction
Hydrogen - oxygen fuel cells consisting of two porous graphite electrodes, which are impregnated
with an electro catalyst such as finely, divided Pt or Ni. Concentrated KOH is used as an
electrolyte.

Working
Hydrogen gas and oxygen gas are continuously supplied to the anode and cathode respectively.
The hydrogen undergoes combustion generating electric current. The cell delivers an emf of 1.23V.
The cell reactions are as follows.
Anode Reaction: H2 → 2 H+ + 2 e-
Cathode Reaction: 2H + + 1/2 O2 + 2 e - → H2O
Overall Reaction: H2 + 1/2 O2 → H2O
Uses: The H2-O2 cells are used in Space vehicles, military, and mobile power systems.
Drawback: Production and storing of hydrogen gas. removal of water
2. METHANOL - OXYGEN FUEL CELL
CONSTRUCTION
Methanol-Oxygen fuel cells are a type of direct methanol fuel cell (DMFC) that generate electricity
through the electrochemical reaction between methanol and oxygen.
Anode: Anode is a porous carbon impregnated with platinum catalyst. At the anode methanol is
passed and oxidized.
Cathode: Cathode is a porous carbon impregnated with silver catalyst. A t cathode oxygen is
passed.
Electrolyte: The electrolyte typically used in methanol-oxygen fuel cells is a sulfuric acid

WORKING
Methanol is supplied to the anode where it undergoes oxidation. This process releases electrons
and protons, producing carbon dioxide and water as byproducts. Electrons released from the anode
passes through an external circuit, generating an electric current that can power devices or systems.
At cathode oxygen is supplied. Here, it reacts with water molecules and protons that have travelled
through an electrolyte. This reaction generates water as the main output.
Anode: CH3OH + H2O → CO2 + 6H+ + 6e-
Cathode: 3/2 O2 + 6H+ + 6e- → 3H2O
Overall Reaction: CH3OH + 3/2 O2 → CO2 + 2H2O
USES
1.Methanol-oxygen fuel cells are employed in portable electronic devices such as laptops,
smartphones, and tablets.
2. Potential power source for vehicles.

POLYMER
The term "polymer" derives from the ancient Greek word (polus, meaning many, much) and
(meros, meaning "parts"), and refers to a molecule whose structure is composed of multiple
repeating units, from which originates a characteristic of high relative molecular mass and
attendant properties.
Thus polymers can be defines as “Polymers are the high molecular weight compounds obtained
by repeated union of simple molecule (Monomers)”.
nM - (M)n- , where M= monomer
Monomer is a simple repetitive unit which when joined together in large numbers gives rise to a
polymer. These are the building blocks of Polymer.
Ex: Vinyl chloride, ethene, propylene etc.
Polymerization: Polymerization is a process of chemical union of large number of monomers to
form a polymer. During polymerization the monomers are linked through covalent leakages to give
raise to polymer. Based on the type of polymerization reaction, it is classified into two types as
follows.
i) Addition Polymerization
ii) Condensation Polymerization
1. Addition reaction: in this process polymers are formed without elimination of any simple
molecues.
Viz; When large number of ethene molecules undergoes addition polymerization reactions,
polyethylene polymer is obtained without the loss of any simple molecule.

2. Condensation reaction: in this process polymers are formed with the loss of simple molecules
like water, ammonia, phenol, HCl etc.
Free Radical Mechanism:
Addition polymerization (of simple unsaturated) involves a chain reaction, which can be explained
on the basis of free radical mechanism taking ethylene as example. The mechanism involves 3
steps
a) Initiation: When the initiators such as dibenzoyl peroxide are heated or exposed to sunlight,
they undergo hemolytic decomposition forming highly reactive species known as free radicals.
This free radical attack the double bond of the monomer (like ethylene) and initi ates the chain
reaction.

b) Propagation: The monomer free radicals formed further react with the ethylene monomers
leading to chain propagation

c) Termination: At some stage chain propagation stops by coupling or disproportionation.

i) Coupling: Coupling reaction also takes place when growing chain polymer reacts with another
free radical like C6H5*.

ii) Disproportionation: Here the transfer of hydrogen atom takes place from one growing chain
polymer to another leading to the formation of two short dead polymers namely, saturated and
unsaturated dead polymers.
Glass Transition Temperature (Tg):
If a polymer is cooled, it becomes harder and brittle and it breaks into pieces at -700C (Glassy
state). When warmed, the polymer regains its softness and becomes flexible (Rubbery state). Glass
transition temperature is a temperature at which a polymer transforms from glassy state to rubbery
state.

(Tg = Glass transition temperature, Tf = Fluid polymer temperature)

The relationship between Tg, and Tf with specific volume of the polymer can be shown as follows

Factors affecting glass transition temperature:

1. Chain flexibility:
Linear polymer chains have a high degree of freedom for rotation hence more chain flexibility and
low Tg.
Aromatic or cyclic groups on the backbone of carbon atoms hinder the freedom of rotation and
causes an increase in Tg.
For Example
 -----------[CH2-CH2]n ---------- in polyethylene free rotation of C-C chain therefore
Tg = -1200C

in polystyrene free rotation hindered therefore increasing Tg = 1000C

2. Cross-linking and branching: A small amount of branching will tend to lower Tg and a high
density of branching reduces chain mobility and elevates the Tg. The cross linking brings the
polymer chain closer, lowers free volume and restricts molecular motion and hence rises Tg. Eg

Poly(α-methyl) styrene presence of methyl side group increases the Tg = 170 0C

In Polystyrene there is no cross linking hence it has low Tg = 100 0C

3. Intermolecular forces crystallinity: The presence of large number of polar groups in the
molecules lead to strong intermolecular cohesive forces which restrict the segmental motion. As a
result, Tg increases.
For example.

in polypropylene, there is no polar groups giving less Tg = -180C

(NH – (CH2)6- NH -OC – (CH2)4 – CO-)n in Nylon due to the presence of polar groups
(-CO-NH-) increases Tg = 570C
4. Molecular mass: Higher the molecular mass more is the restriction in the molecular freedom.
However, Tg is not significantly affected by molecular masses beyond 20,000.
5.Plasticizers: Presence of plasticizers reduces the Tg. generally, addition of plasticizers increases
flexibility of the polymer matrices decreasing Tg. Eg: addition of diisooctyl phthalate to PVC
decreases the Tg from 800C to less than room temperature.
Significance of Tg:
1). It is used as a measure for evaluating the flexibility of a polymer.
2). Tg is very useful in choosing the right processing temperature for fabrication (moulding,
calendaring and extrusion)
3). Tg is very useful in determining the coefficient of thermal expansion, heat resistant, refractive
index, electrical property, etc.,
Preparation and applications of some commercial thermoplastic polymers:
1) Polytetrafluroethylene (trade name Teflon)
Teflon is the trade name of poly tetra fluro ethylene. The monomers for the preparation of Teflon
are tetra fluro ethylene. Teflon is prepared by emulsion polymerization method using ammonium
persulfate as initiators under pressure.

Uses:
1. In non- stick pans and utensils
2. As insulators in electrical appliances
3. As coating materials
4. As adhesives

2) Polyurethane
They are addition polymers with wide variety of applications. Polyurethane’s have a characteristic
urethane linkage –NHCOO- such a linkage is formed by the reaction of diol with diisocyanate.
Ployurethanes are produced by the polymerization of disocyanate and diol or triol (or the addition
reaction between 2, 4-tolylene diisocyanate with glycol). During the addition the ‘H’ atom of the
OH group get attached to N atom to form NH-C-O group as shown below.
Uses:
1. As insulators in electrical appliances,
2. Polyurethane foams are used in cushions and automobiles
3. Polyurethane elastomers are used in tyre resoling and gymnasium floors
4. Polyurethane fibers are used in swimming suits, sports articles etc.
4. Bakelite (Phenol – formaldehyde) Polymer
Phenol - formaldehyde polymers (also called Bakelite) are the oldest synthetic polymers. These
are obtained by the condensation reaction of phenol with excess of formaldehyde in the presence
of base catalyst.
Uses
1. It is used as insulator in electrical appliances
I2. It is also used to make various kitchenware products like frying pans etc.
3. It is also used to make jewelry articles and toy
POLYMER COMPOSITE
A composite is a physical mixture of two or more structurally different components, which
combine to form a new class of material for structural applications.
They are made of two components
Fibres- They are the fibrous materials which give a network structure to the composites.
Eg: Glass fibre, carbon fibre, boron fibre and kevlar.
Matrix- Matrix is the material capable of embedding, encapsulating, adhering and reinforcing.
Eg: Polyesters, polycarbonates and polyvinyls.

Advantages of polymer composites

1. They are light in weight.
2. They have high strength to weight ratio.
3. They are much stronger and durable than steel and aluminium.
4. They have good corrosion resistance.
5. They have high temperature resistance.
6. They have high fatigue strength.
7. They are most suitable for aerospace applications.
Preparation & uses of Carbon fibre
Carbon fibre prepared from polyacrylonitrile involves three stages:
1. First polyacrylonitrile (PAN) is heated carefully to form a polycyclic chain.
2. It is then roasted at 400-7000C, adjacent chains join together losing more H2 gas to become
aromatic.
3. Temperature is raised to around 2000 0C till all N2 is expelled giving ribbon- like pure carbon
fibre in the graphite form.
 NANOSCIENCE
"There is plenty of room at the bottom" - Richard Feynman, 1959.
In 1959, a lecture by physicist Richard Feynman suggested that new materials with fundamentally
different properties could be developed by building and manipulating materials at their basic
molecular or atomic level.
Definition: Nanoscience or Nanotechnology is the creation, manipulation, and use of materials in
the 1 - 100 nanometers (nm) size range.
Materials in this size range have two special properties because of their small dimensions and high
surface area.
 1nm = 10-9m
Properties at nanoscale:
1. Percentage of surface atoms
As particle sizes and layer thicknesses approach the nm size scale, special properties begin to
emerge. For example, as particles get smaller in diameter a greater percentage of the atoms in
the particle reside on the surface of the particle.

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2. Nanoscale and Melting Point
At nanoscale materials can melt at lower temperature.
In nanoscale, most of the atoms are on the surface rather than inside the particle. Because of
this, the atoms on the surface are not held together as strongly as the ones inside. This means
that even at lower temperatures, the surface atoms can vibrate a lot more compared to the atoms
in bigger particles and can melt at lower temperature.
The gold nano particle at few nm can show M.P. as low as 200-300 oC (actual M.P. of gold is
approx. 1300 oC).
3. Surface area to volume ratio:
Nanoscale components have very high surface area to volume ratio making them ideal for use
in composite material, in storage data, chemical energy storage etc.
4. Antimicrobial activity:
Nanoscale metals, like gold, silver etc. show excellent anti-microbial activity. Enhanced
anti-microbial activity of nano particles like silver, gold may be due to following reason.
(i). Nanoparticles being smaller in size show good interaction/ intimacy with nano sized
infection producing microorganism.
(ii). It can destroy protein covering the coat of microorganisms.
(iii). It influentially reduces the oxygen supply thereby affecting the mitochondrial reaction of
bacteria.
Note: Catheters are usually soaked with Ag nanoparticles which helps in destroying infection
producing bacteria/germs.
5. Dominance of electromagnetic force:
Because of mass of nanoscale objects is so small, gravitational force become negligible.
Whereas electromagnetic force depends on size of the object, at nanoscale electromagnetic
force is very strong.
6. Optical property (color of the nanoparticles):
By varying the size of the particles to nano scale the emission wavelength can be adjusted to
any color. By making particles very small (nano scale), we can change the color of light they
emit or reflect. This technology can be used in dyes, paint display and chemical sensor,
sunscreen etc. Gold nano particle exhibit following different color
2 nm - clear (transparent)
5nm- deep red
50 nm- wine red
100 nm - brownish greys
200 nm - greyish orange.
For example, normal Zno and TiO2, - both metal oxide are used in sunscreen because they
absorb UV that is dangerous to skin but TiO2 (50nm) particle absorbs harmful UV radiation as
well as transparent to visible light.
7. Tensile strength: At nanoscale tensile strength is more, for example carbon nanotube
100 times stronger than steel. High tensile strength of some nano structures like CNT may be
due to the following factors.
(i). Existence of covalent bond
(ii). Strong electrostatic force of attraction
(iii). More number of atoms at the surface.
8. At nanoscale material like aluminums metal becomes combustible.
9. At nano dimension opaque metal like copper becomes transparent.
10. Noble metals like Au, Hg become more active. Can be used as catalyst.
Classification
3. of nanomaterials:
1. Zero dimensional nanomaterials/ 0D): Nanoparticle which have nano dimension (1 - 100
nm) in all the three dimension like fullerene. Example fullerene
2. One dimensional nanomaterials /1D): Nanosheet or layers which have nano scale
(1 - 100 nm) in two dimensions where as other one dimension has macro scale. Example
Nanorods
3. Two dimensional nanomaterials / 2D: Those materials which nanoscale (1 -100 nm) in
one dimension whereas in two dimension it has macro scale. Example Nanosheet
4. Three dimensional nanomaterials (3D): Materials which have all three dimensions in
macro scale with coating / dispersion of nanoscale (1 - 100 nm). Example nanoparticles
Synthesis / fabrication of nanomaterials / particles:
Generally, there will be three types of approaches to prepare/ fabricate nanostructured object/
particles.
1. TOP-DOWN APPROACH
2. BOTTOM-UP APPROACH
Top-down & Bottom-up Fabrication of Nanostructures
Top down
Top-down fabrication is like making something smaller from a bigger thing. It's a
process where we start with a larger piece and cut or shape it until we get the small thing
we want. Think of it like carving a statue from a big block of stone. In the world of tiny
things, this is how we make very small structures from larger ones.
In electronics, like making computer chips, this method is widely used. It involves steps
like growing crystals, using tools to carve or draw patterns on the material, adding
layers, and cutting away parts we don't need. This technique has been very import ant,
especially in making things smaller for electronics.
Example: Ball milling technique, Photolithography technique
Bottom-up
Bottom-up fabrication is the opposite to top down. It starts from very tiny things and
builds bigger structures. It's like putting together tiny building blocks to make something
bigger. This approach starts from small components like atoms or molecules and builds
larger structures from them.
Example: Sol- gel technique, preparation of CNT
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Mechanical grinding (Ball Milling)

This method is a typical example of a top-down method of synthesis of nanomaterials. The
mechanical grinding method is a very popular, simple, inexpensive and extremely scalable
method to synthesis all classes of nanomaterials.
This process involves the crushing and grinding of large particles into smaller nano -
sized particles with the assistance of high-speed rotating balls in a milling chamber.
Here, zirconia and almnina are widely used as a high-speed rotating ball for synthesizing
the nano materials.
Advantages
Using this method, it is possible to scale up to tonnage quantity of material.
Disadvantages
Contamination of milling ball.

Sol - Gel method

The sol-gel method is a way to make tiny materials called nanomaterials by mixing a liquid
solution to create a gel and then transforming it into a solid.

Procedure
1. Precursor Preparation
Select an appropriate metal oxide precursor, typically a metal alkoxide or metal salt.
Dissolve the precursor in a suitable solvent, such as water to initiate hydrolysis and
condensation reactions.
Hydrolysis involves the reaction of the precursor with water or alcohol, leading to the formation
of metal hydroxide or alkoxide groups.
Condensation involves the linking of these metal hydroxide or alkoxide groups, resulting in the
formation of a network of interconnected particles.
2. Sol Formation:
The hydrolysis and condensation reactions continue until a colloidal dispersion of metal oxide
nanoparticles formed known as a sol, is formed.
3. Gel formation
The sol is then subjected to aging or heating to promote further condensation leading to the
formation of a wet gel.
4. Drying and Calcination
The wet gel is then dried to remove the solvent and obtain a xerogel.
The xerogel is further calcinated at a high temperature to remove any residual organic
compounds and promote the formation of a crystalline metal oxide nanoparticle structure.
It can be schematically represented below
Advantages of Sol-Gel Method:
• Simple and versatile technique
• Controllable particle size and morphology
• Homogeneous and pure nanoparticles
• Low temperature synthesis
• Suitable for thin film deposition
Disadvantages of Sol-Gel Method:
• Longer synthesis time compared to some other methods
• Requires careful control of reaction parameters
• Limited to certain types of materials
• Prone to cracking or shrinkage during drying and calcination
CARBON NANOTUBE (CNT)
Definition: A CNT is described as a seam less cylinder made by rolling one or several layers
of graphite sheets into a tubular structure.

Generally, CNTs can be divided into two classes: single-walled carbon nanotubes (SWNTS)
and multi-walled carbon nanotubes (MWNTS). A SWNT consists of only one layer of graphite
sheet, and the diameter of a SWNT is usually smaller than 2nm while a MWNT consists of up
to dozens of concentric sidewalls, and the diameter of a MWNT may be as large as tens of
nanometers.
PREPARATION OF CNT
Principle: CVD involves the formation of nanomaterials from the gas phase at elevated
temperature - usually onto solid substrate or catalyst.
Procedure: The CVD technique involves the decomposition of a hydrocarbon in the presence
of a catalyst, typical hydrocarbons are acetylene and methane, which is decomposed in a
furnace reactor at temperatures ranging from 880 to 750°C. The hydrocarbon enters the reactor
with an inert gas at high temperature, as the hydrocarbon decomposes, carbon deposits onto
the substrate which is supported by the common catalyst used such as iron, nickel or cobalt.
Carbon has a low solubility in these metals at high temperatures and thus the carbon will
precipitate to form nanotubes,

Uses
1. In hydrogen storage
2. In bone grafting
3. In sports article like golf stick
4. In sensor device system
5. In drug delivery
APPLICATIONS OF NANOTECHNOLOGY
Cancer therapy
What is cancer?
A group of diseases characterized by uncontrolled growth and spread of abnormal cells.
When cells undergo division, it usually forms its replication of normal healthy cells but some
cells during cell division due to mutation may produce abnormal cells. This abnormal cell
further undergoes multiplication division giving large group of abnormal cells causing cancer.
Cooking of cancer cells using gold nano shell
Nanogold shell can be used to kill cancer cell.
At first gold nanoparticle (10 - 15 nm) is coated to silica (glass. SiO2) core and then this, core
coated (attached) with special amine. amines are attached with gold nanoparticles (less than 2
nm), to this gold nanoparticle cancer specific antibody attached to form gold nano shell
(roughly 15nm). This shell can best absorb infrared light (800 - 1050 nm) and heated up
When gold nano shell injected into the cancer patient body attached antibodies to the gold –
nano shell as shown in the figure attaches to the oncoprotein surface of the cancer cell. Now
these nano-shells are illuminated with IR radiation of 800-1050nm (as it mentioned earlier nano
gold shell can absorb infrared wavelength). By absorbing IR light gold nano shell heated up
which in turn destroys cancer cells.
 CORROSION SCIENCE
Definition: corrosion Corrosion is defined as the destruction or deterioration of a metal
through chemical or electrochemical reactions under the influence of surrounding.
Ex: Rusting of iron- Fe2O3 3H2O
Corrosion of metal depends on the environment to which metal is exposed. The corrosion of
metal can be either dry corrosion or wet corrosion
Differences between dry corrosion or wet corrosion
Dry corrosion Wet corrosion
occurs in the absence of liquid/moisture occurs when liquid/moisture present
temperature is not exact parameter often associated with high temp
corrosion takes place by direct chemical corrosion takes place by electrochemical
attack by gases like' oxygen, nitrogen process ie, through oxidation & reduction

Explain the electrochemical theory of corrosion

According to electrochemical theory, corrosion of metals occurs due to the following changes,
when they are exposed to the environment. This can be explained taking iron as example.
1) Metals by nature contains impurities hence number of minute galvanic cells are formed
which acts as anodic and cathodic areas.
2) At anode the metal undergoes oxidation and electrons are liberated which migrates towards
cathodic region
Anodic reactions:
At anode the metal undergoes oxidation-liberating electrons. Ex: when iron is exposed to the
environment it undergoes oxidation as
Fe Fe2+ + 2e_
Cathodic reactions
The different cathodic reactions are,
a) In acidic medium: In acidic medium and in the absence of oxygen, hydrogen ions are
reduced to hydrogen gas
2H+ + 2e- H2
b) In alkaline medium: If the solution is alkaline and in the absence of oxygen the cathodic
reaction is,
2 H2O + 2e- 2OH- + H2
c) In neutral and aerated medium: when the solution is neutral and aerated, hydroxyl ions
are formed as follows.
2H2O + O2 + 4e- 4OH
Overall reaction
Formation of corrosion product: The hydroxyl ions migrate towards anode and react with metal
ions and forms corrosion product. In the case of iron OH- reacts with Fe2+ ions and forms an
insoluble hydrated ferric oxide known as brown rust.
Fe2+ + 4OH- 2Fe(OH)2
2Fe(OH)2 + O2 + 2H2O 2 (Fe2O3. 3H2O)
Rust
Different types of corrosion
The corrosion can be mainly classified as follows
1. Differential metal corrosion or Galvanic corrosion.
2. Differential aeration corrosion
3. Stress corrosion
Differential Metal Corrosion (Galvanic corrosion)
This type of corrosion occurs when two dissimilar metals are in contact with each other in a
corrosive conducting medium. The two metals differ in their tendencies to undergo corrosion
The one with the lower electrode potential (-ve potential) act as anode thereby undergoes
corrosion and the one with the higher electrode potential (+ve potential) act as cathode which
is safe. The potential difference between the two electrodes is the driving force for corrosion.
Example:
1. Iron metal in contact with copper metal,
2. Brass tap in contact with Iron pipe
3. Bolt & nut
Differential aeration Corrosion
This type of corrosion occurs when a metal is exposed to differential air or oxygen
concentration. The part of the metal exposed to higher concentration of O 2 acts as cathode and
the part of the metal exposed to lower concentration acts as anode consequently poorly
oxygenated anode undergoes corrosion. There are two types of differential aeration corrosion:
1. Water line corrosion
2. Pitting corrosion
Water line corrosion

Water line Corrosion is observed in the cases of ocean ships, water storage steel tanks where
in apportion of the metal is always under water. The part of the metal below water acts as anode
and undergoes corrosion the part of the metal exposed to atmospheric oxygen acts as cathode
which is safe. A distinct brown line is formed just below the water level due to the deposition
of rust.
Example:
1. Ocean Ships,
2. Water storage steel tanks
3. Submerged dam pillar
Pitting corrosion
This is one of the destructive forms of corrosion leading to the formation of pits or holes. Pitting
corrosion results when small particles of dust / impurities/water drop get deposited on the metal
surface. The metal surface covered by the dust will be less aerated when compared to exposed
surface. Thus, the covered portion becomes anode. In the presence of electrolytes and moisture,
corrosion starts beneath the dust forming a pit.

Example
1. Pin stapled to paper
2. Part of nail inside the Wall
Factors affecting the rate of corrosion
1. Anodic to cathodic areas
If a metal has small anodic and large cathodic area the rate of corrosion increases. This is
because when anode is small the electrons liberated during oxidation are completely consumed
on large cathodic surface for the reduction reactions and rate of corrosion increases.
2. Nature of corrosion product
If the nature of corrosion product forms, a protective layer on the metal surface, it prevents the
further corrosion of metal. If the corrosion product does not form protective layer it leads to
further corrosion of metal. For example, Al, Cr, Ti, V etc. forms protective metal oxide layer
on their surfaces which prevents further corrosion of the metal.
3. Hydrogen overvoltage (OV)
The voltage at which hydrogen gas liberated at cathode is known as hydrogen overvoltage. A
metal with low hydrogen overvoltage is more susceptible to corrosion. It is due to the fact that,
better the evolution of hydrogen gas at cathode, accelerates anodic reaction in turn increases
corrosion rate.
4. Anodic and cathodic polarization
The process where there is a variation of electrode potential of the electrode, due to the
inadequate supply of ions from the bulk of the solution to the electrode is known as polarisation.
Polarization of anode and cathode increases corrosion rate decreases.
5. Moisture
More the moisture content in the surrounding corrosion rate increases
6. Oxygen content
Oxygen concentration increases cathodic reaction which in turn accelerate anodic reaction
hence corrosion rate increases.
Corrosion Control methods
1. Metal coatings - two types; Galvanization & Tinning
2. Inorganic coatings – two types; Anodization & Phosphating
3. Cathodic protection - two types; Sacrificial anode method & impressed current method
Galvanization
The process application of zinc coating on iron or steel to prevent from corrosion is called
Galvanization.
The process involves;
• The article is cleaned with organic solvent to remove oil and grease this process is called as
degreasing.
• The article is then dipped in dil. H2SO4 for 10-15 min at 60 -70 0C to remove scales or any
rust impurities this process is called pickling.
• The article is washed well with water and dried using drier.
• It is then dipped in a bath of molten zinc maintained at 450 0C the surface is covered with
ammonium chloride flux to prevent the oxidation.
• The article taken out is found have a coating of zinc
• It is then passed through a pair of hot rollers to squeeze out the excess zinc adhered to the
article

Uses
Pipes, fencing wires nails, bolts, nuts, buckets, mugs, RCC pillars, etc.
Tinning
The process of application tin coating on iron or steel to prevent from corrosion is called
tinning. The process involves;
• The article is cleaned with solvent to remove oil and grease this process is called as
degreasing.
• The article is then dipped in dil. H2SO4 for 10-15 min at 60-700C to remove scales or any rust
impurities this process is called pickling.
• The article is washed well with water and dried using drier.
• It is then dipped in a bath of ZnCl 2 flux to help the prevention of oxidation of the molten tin.
• Then the article is dipped in a bath of molten tin, where the surface is covered with palm oil.
The palm oil to helps tin adhere to the article.
• The article taken out is found have a coating of tin
• It is then passed through a pair of hot rollers to squeeze out the excess tin adhered to the
article
Schematic diagram shown below
Anodization
Formation of oxide layer on the surface of the metals is known as anodization.
Process: First the aluminium article is subjected to pre- treatment like degreasing, pickling,
polishing, washing and drying.
Basic requirements
Anode: Aluminium connected to positive terminal.
Cathode: Steel or copper.
Electrolyte: 5-10% sulphuric acid.
Temperature: 350C
Applied voltage: 0- 50 Volt
Electrode reactions
At anode: 2Al + 3H2O Al2O3 + 6H+ + 6e-
At cathode: 6H+ + 6e- 3H2
Overall: 2Al + 3H2O Al2O3+3H2
So formed oxide layer Al 2O3 protects the metal from corrosion.
Uses
Anodized articles used in soap boxes, Tiffin carriers, mug, bucket, Window panes etc
Cathodic protection
During corrosion, anode undergoes corrosion and cathode is unaffected. The principle of
cathode protection is to reverse the flow of electrons. The technique of offering protection to
the metal by making it as cathode (by providing electrons) is called cathodic protection. They
are of two types
a) Sacrificial anode method
b) Impressed current method
Sacrificial anode method
In this method the metal to be protected is connected to a more anodic metal, as a result anodic
metal under goes corrosion and original structure becomes cathode hence, protected.
Here, the more active anode sacrifices to protect the original metal so this method is called as
sacrificial anode method. The active anode is replaced when it completely corrodes. The
method is used for protecting buried pipeline, ship hulls, industrial water tank & steel rods in
RCC columns.

Impressed current method

In this method the metal to be protected is connected to negative terminal of the D.C source
and inert material (such as resin bonded graphite rod, silicon - iron alloy, platinized Ti) is
connected to positive terminal of the D.C source.
During the process a current is applied in opposite direction to nullify the corrosion current.
The corroding metal is thus converted from anode to cathode and is hence protected. The
impressed current is derived from a D.C source with an anode like graphite.