UNIT I: FUELS

Part A Questions and Answers

1. Distinguish between GCV and NCV.
Gross or Higher Calorific Value (GCV): The total heat generated when a unit quantity of
fuel is completely burnt and the products of combustion are cooled to room temperature
Net or Lower Calorific Value (LCV): The net heat produced when a unit quantity of fuel is
completely burnt and the products of combustion are allowed to escape
2. What is meant by refining of petroleum?
The process involves removal of impurities and separation of various fractions on the basis of
their boiling points from petroleum.
3. Define cracking. What is the necessity of cracking of petroleum fractions of higher
boiling points?
The process of breaking of heavier compounds into more useful lower fractions by the
application of heat and pressure or by using catalysts is known as cracking.
Crude oil on distillation yields only 16 20% gasoline. This is known as straight run petrol. It
contains mainly n-paraffins. Presence of n-paraffins produces knocking in SI engines.
Hence, in order to improve the quantity and quality, higher fractions are cracked to produce
high quality gasoline.
4. Define octane number of petrol. How can it be improved? (or) What is leaded petrol?
What are the advantages and disadvantages of leaded petrol?
Octane number is defined as the percentage of isooctane in isooctane-n-heptane mixture,
which has the same amount of knocking as a standard binary mixture when tested in
standard engine under standard conditions. It can be improved through the addition of tetra
ethyl lead and oxygenates.
Petrol containing tetra ethyl lead is called leaded petrol. Leaded petrol prevents knocking in
SI engine. But it produces lead bromide in SI engines and causes atmospheric pollution.
5. Define cetane number of diesel. How can it be improved?
Cetane number is defined as the percentage of cetane in cetane - -methyl naphthalene
mixture which has same ignition delay as a standard binary mixture when tested in a
standard engine under standard conditions. Cetane number of diesel oil can be improved
through the addition of Isoamyl nitrite, Ethyl nitrate.
6. What are oxygenates? Give examples.
Oxygenates are organic compounds rich with oxygen that are added to gasoline in order to
boost the gasoline's octane level and to reduce atmospheric pollution associated with
automobile emissions. Examples: Methyl tertiary butyl ether, ethyl tertiary butyl ether.
7. What is CNG? What are its advantages?
CNG is compressed natural gas stored at pressure. It consists of 8090% methane in
gaseous form with small amounts of ethane, propane and butane. CNG is an attractive fuel
due to its clean burning characteristics and very low amount of exhaust pollution.
8. Name the reagents used for absorbing CO
2
, CO and O
2
during flue gas analysis by
Orsats apparatus.
Reagents Absorbents
CO
2
KOH solution
CO Ammoniacal cuprous chloride solution
O
2
Alkaline pyrogallol
9. Calculate the volume of air required for the complete combustion of one litre of CO.
CO + O
2
CO
2
1 litre 0.5 litre

1 litre of CO requires = 0.5 litre of oxygen for complete combustion
The volume of air
required
=
21
100
5 . 0
= 2.38 litre
10. Write the expression to calculate theoretical quantity of air required for combustion of
1kg of a fuel.

fuel solid a of 1kg burning for

required air of quantity minimum The

1
]
1

+
,
_

+ S
8
O
H 8 C 67 . 2
23
100
Part B Questions and Answers
1. Explain a gross and net calorific value? How calorific value of a liquid fuel is
determined by bomb calorimeter?
Determination of calorific value of a solid (or) liquid fuel
Principle: A known weight of the fuel is burnt completely and the quantity of heat liberated is
absorbed in water and measured.
Description: A bomb calorimeter consists of the followings:
(i) A stainless steel bomb: It can withstand a pressure of about 100 atmospheres. It is
provided with two electrodes and an oxygen inlet valve. One of the electrodes acts as support
for the crucible. It is placed in copper calorimeter.
2
(ii) A copper calorimeter: The copper calorimeter contains a known weight of water. It has an
arrangement for inserting a thermometer and stirrer. The calorimeter is surrounded by air
jacket and water jacket to prevent the loss of heat.
(iii) A stainless steel crucible: It holds the weighed pellet of fuel sample. The crucible
is fixed in such a way that the fuse wire touches the fuel sample.
Beckmann's
Thermometer
Oxygen valve
Electrodes
Stirrer
Copper calorimeter
Magnesium fuse wire
Stainless steel
crucible
Water jacket
Air jacket
6V Battery
Ebonite cover
Stainless steel
bomb
Weighed pellet of
given fuel sample
Working: A known quantity of fuel (m gm)is taken in the crucible. The bomb is charged with
oxygen to a pressure of 30 atmospheres and the oxygen charging valve is closed tightly.
Then the bomb is placed carefully in a known amount of water (W gm). The water in the
calorimeter is stirred throughout the experiment and its initial temperature is noted (T
1
C).
Now the fuel is ignited by passing current through the fuse wire. The heat produced by
burning is transferred into the water. The temperature is measured to an accuracy of 0.001C
by a Beckmanns thermometer till the maximum temperature (T
2
C) is reached.
Calculations:
Mass of fuel = m gm
Mass of water in calorimeter = W g
Water equivalent of calorimeter = w g
Initial temperature of water = T
1
C
Final temperature of water = T
2
C
The water equivalent of the calorimeter is determined by burning a fuel of known
calorific value (Example: Benzoic acid, CV = 26565 kcal/kg)
By heat balance, heat produced by the
fuel due to combustion
= Heat absorbed by water and
calorimeter
If x is the calorific value of fuel, heat
produced
= (x m) cal
Heat absorbed by water and
calorimeter
= (W + w) (T
2
T
1
)
(x m) (W + w) (T
2
T
1
)
x =
cal/g
) ( ) (
1 2
m
T T w W +
For calculating the more accurate calorific value of a fuel, the following corrections
3
should be considered. (i) Fuse wire correction (C
1
) (ii) Cotton/Thread correction (C
2
),
Acid correction (C
A
), Cooling correction (T
C
).
HCV, x
cal/g
) ( ) ( ) (
2 1 1 2
m
C C C T T T w W
A C
+ + + +
2. What is meant by crude petroleum? Discuss the principle steps involved in the refining
of crude petroleum?
Definition: Crude Petroleum is a naturally occurring brown to black coloured viscous oil. It is
found under the crust of earth, on shore or off shore. Chemically it is a complex mixture of
parffinic, naphthenic, olifinic and aromatic hydrocarbons. The approximate composition of
petroleum is: 8087%C + 1115%H + 0.13.5%S + 0.50.9%N + 0.10.9%O
Principle: The process of (i) removing impurities and (ii) separating petroleum into more
useful fractions with different boiling point ranges is known as refining of petroleum.

Removal of impurities:
(i) Modern electrical desalting: This process is used to remove dissolved salts like NaCl,
MgCl
2
etc from oil.
(ii) Cottrells process: The highly charged electrodes used in this process cause colloidal
water droplets to combine to form bigger drops, and separated easily from oil.

(iii) Chemical precipitation: This process involves addition of CuO in order to precipitate
sulphur as CuS, which is filtered and removed.
Purified
Petroleum
Oil Heater
450
o
C
Uncondensed
Gases
Petroleum Ether
Gasoline
Naphtha
Kerosene
Diesel
Heavy Oil
Residual Oil
Cracking
Gasoline
Fractionating
Tower
S.S Tray
Chimney with Cap
Oil Vapours
Fractional distillation: Fractional distillation is used to separate out the purified petroleum
into various fractions based on their boiling points.
(i) Pre-heater or Heating still: Here the purified oil is vaporized by heating to a temperature of
450C. The hot oil vapours are introduced through the bottom of fractionating tower.
(ii) Fractional distillation tower or Bubble tower: It is a tall cylindrical tower consists of a large
number of stainless steel trays placed at shorter distances. Each tray is provided with
4
chimneys covered with loose caps. The tower is hot at the lower end and comparatively
cooler at the top. When the oil vapours go up, high boiling point condense at the bottom trays
whereas low boiling point fractions condense at the top trays. Lower fractions are used after
purification while the high boiling point fractions are subjected to cracking operation to get
more useful lower fractions.
The following table summarizes the various fractions obtained by the fractional distillation of
petroleum.
S.No. Name of the
fraction
Chemical
composition
Boiling
point
range
Uses
1. Uncondensed gases C
1
C
4
030C Used as domestic fuel
under the trade name
of LPG
2. Petroleum ether C
5
C
7
3070C Used as solvent for
rubbers, varnishes
3. Petrol or Gasoline,
CV: 11250kcals/kg
C
5
C
8
40120C Used as fuel for IC-
engines
4. Naphtha or Solvent
Spirit
C
9
C
10
120180C Used as solvent for
dry cleaning, used as
fuel
5. Kerosene,
CV: 11100kcals/kg
C
10
C
16
180250C Used as fuel for
domestic heating and
Jet engines
6. Diesel,
CV: 11000kcals/kg
C
15
C
18
250320C Used as fuel for diesel
engines, generators
7. Heavy oil C
17
C
30
320400C Used for cracking to
produce gasoline
8. Heavy oil on refractionation yields:
Lubricating oils Used as lubricant
Petroleum Jelly-Vaseline Used in cosmetics,
medicines
Greases Used as lubricant
Paraffin wax Used in candles, boot
polishes, wax papers
9. Residue on vacuum distillation yields:
Pitch (Asphalt-Bitumen) Used for making tar,
waterproofing of
roofs
Petroleum coke Used as fuel,
electrode rods
3. What is meant by cracking of heavy oil? Explain fluidized bed catalytic cracking.
Definition: The process of decomposition of less volatile heavier compounds into highly
volatile lower fractions by the application of heat and pressure or by using catalysts is known
as cracking.
Fluidized-bed or Moving-bed catalytic cracking: The Cat cracker consists of the following
main parts: Pre-heater, Reactor, Fractional tower, Condenser, Stabilizer and Regenerator.
Name of parts Role in the Cat cracker
5
Pre-heater : Here the heavy oil is vaporized by heating to a temperature of 450C.
Finely powdered synthetic zeolites or bentonites are used as
catalysts and are suspended in hot oil vapors. The mixture is forced
into the reactor.
Reactor : The reactor is a slim and tall tower. It is provided with a centrifugal
separator at the top, which allows only cracked vapors to pass
through and not any solid catalyst particles. It is maintained at 500C.
Cracking occurs at the surface of the catalyst particles. About 70% of
hot oil vapors are cracked into gasoline hydrocarbons. During
cracking catalyst particles are coated with carbon and settle at the
bottom of the reactor.
Fractional
distillation tower
: It is a tall and slim tower. It is used to separate out gasoline and other
lower hydrocarbons from uncracked heavy oil vapors.
Condenser : The gasoline and other lower hydrocarbons are admitted into a
condenser, where they get cooled and recovered as a mixture of
liquids.
Stabilizer : It is used to separate out gasoline from the mixture. The lower
hydrocarbon liquids are recovered as gas, which is subjected for
polymerization to obtain superior type of petrol.
Regenerator : It is a tall tower maintained at 600C. At this temperature, the carbon
is burnt off and the catalyst particles are reactivated. The regenerator
is provided with a centrifugal separator at the top, which allows only
flue gas (waste gas) to pass through and not any regenerated solid
catalyst particles. The reactivated catalysts are again used for fresh
batch of hot oil vapours to continue the process.
Heavy
Oil
Oil Heater
450
o
C
R
e
a
c
t
o
r

5
0
0
o
C
Cracked
Vapours
Condenser
Gas +
Gasoline
Gas for
Polymeris
-ation
Gasoline
Heavy Oil
F
r
a
c
t
i
o
n
a
t
i
n
g

C
o
l
u
m
n
S
t
a
b
i
l
i
s
e
r
------
------
------
R
e
g
e
n
e
r
a
t
o
r

6
0
0
o
C
R
e
g
e
n
e
r
a
t
e
d

C
a
t
a
l
y
s
t
Powderad Catalyst
Spent Catalyst
.....
.....
.....
Flue Gas
4. Explain the causes, mechanism and prevention of knocking in I.C. engines?
Definition: Knocking is a kind of mild explosion which occurs in IC engines due to sudden
increase of pressure developed by spontaneous combustion of fuel and air mixture.
6
Causes of knocking: Knocking in internal combustion engine causes mechanical damage in
cylinder and reduction of power output.
Chemical structure and Knocking: The knocking tendency in IC engines depends upon the
compactness of molecules, double bonds and cyclic structure.
Knocking tendency in SI engines decreases in the following order while knocking tendency in
CI engines increases in the same order.
n-Paraffins Iso-paraffins Olefins Naphthenes Aromatics
It means that the presence of maximum quantity of aromatics and minimum quantity of n-
paraffins in petrol is desirable. It also indicates that the presence of maximum quantity of n-
paraffins and minimum quantity of aromatics in diesel is desirable.
Measurement of knocking in SI engines (or) Octane Number: The quality of petrol is
expressed in terms of octane number. It is defined as the percentage of isooctane in
isooctane-n-heptane mixture, which has the same amount of knocking as a standard binary
mixture when tested in standard engine under standard conditions.
Leaded petrol (or) Octane number Enhancers The octane number of gasoline may be
improved by adding about 1-3ml of ethyl fluid (60% Tetra ethyl lead + 26% Ethylene bromide
+ 9% Ethylene chloride + 2% Red dye) to 1 gallon of petrol. Petrol containing TEL is known
as leaded gasoline.
Measurement of knocking in CI engines (or) Cetane Number: The quality of diesel is
expressed in terms of cetane number. It is defined as the percentage of cetane in cetane -
-methyl naphthalene mixture which has same ignition delay as a standard binary mixture
when tested in a standard engine under standard conditions.
Improvement of antiknock value (or) Cetane number Enhancers: Cetane number of
diesel oil can be improved through the addition of Isoamyl nitrite, Ethyl nitrate.
5. What is flue gas? How it is estimated by Orsats method?
Definition: The mixture of gases (CO
2
, O
2
, CO etc.,) coming out from the combustion
chamber is called flue gas. Usually, the flue gas is estimated by Orsats method.
Significance: Analysis of Flue gas gives an idea about the complete or incomplete
combustion process.
The presence of a high % of CO in the flue gas shows incomplete combustion of the
fuel and also indicates the short supply of oxygen.
If the flue gas contains considerable amount of oxygen, it indicates an excess supply
of oxygen and the possibility of complete combustion.
Description: The Orsats apparatus consists of four main parts:
(i) A 3-way stop cock: It has provisions: for entry of flue gas into the gas burette; to release
air present in the burette; to connect the glass horizontal tube.
(ii) Absorption pipettes: The central part of horizontal tube is connected to three absorption
pipettes via 2-way stop cocks.
Pipette-A contains KOH solution to absorb CO
2
gas
Pipette-B contains alkaline pyrogallol solution to absorb O
2
gas
Pipette-C contains ammoniacal cuprous chloride solution to absorb CO gas
7
(iii) Gas burette (100cc): It is surrounded by a water jacket to maintain gas temperature
constant throughout the experiment
(iv) Water reservoir: It contains an acidified 25% solution of NaCl and coloured with methyl
orange. It is connected to the end of gas burette by means of a rubber tube. By raising
the water reservoir, the gas can be sent to various parts of the apparatus and by lowering
the water reservoir, the gas can be brought back into the gas burette
Determination: The analysis of flue gas generally deals with the determination of CO
2
, O
2
and CO by absorbing them in the respective solution of KOH, alkaline pyrogallol and
ammoniacal cuprous chloride. It is quite necessary to follow the order of absorbing the gases,
CO
2
-first, O
2
-second and CO-last. This is because the absorbent used for O
2
(i.e. alkaline
pyrogallol) can also absorb some amount of CO
2
and the % of CO
2
left would be less.
L
i
q
.
N
H
3
+
C
u
2
C
l
2
P
y
r
o
g
a
l
l
i
c

A
c
i
d
K
O
H

S
o
l
u
t
i
o
n
Levelling Bottle
Water + small amount
Gas Burette
Rubber Tube
Three way
Stop-Cock
of NaCl
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
- - -
_
_
_
_
_
_
-
-
-
-
-
- - - - -
- - - - -
- - - - -
- - - - -
- - - - -
Wooden Box
A B C
- - - - -
(i) Determination of CO
2
gas: To measure the volume of CO
2
, the flue gas is first passed into
the absorption pipetteA via its 2-way stop cock by raising the water reservoir. The
pipetteA absorbs only CO
2
gas present in the flue gas. Then the flue gas is taken back
to the gas burette by lowering the water reservoir. This procedure is repeated several
times in order to ensure complete absorption of CO
2
gas. Now stop cock of pipetteA is
closed. To find the volume of CO
2
gas, the volume of residual (remaining) gas is
measured by equalizing the water level both in the water reservoir and in the burette. Let
the volume of residual gas be X cc.
The percentage by volume of CO
2
gas = (100 X) cc
(ii) Determination of O
2
gas: To measure the volume of O
2
, stop cock of pipetteB is opened
and the flue gas [initial volume = (100X) cc] is passed into it by raising the water
reservoir. The pipetteB absorbs only O
2
gas. Then the flue gas is taken back to the gas
burette by lowering the water reservoir. This procedure is repeated several times in order
to ensure complete absorption of O
2
gas. Now stop cock of pipetteB is closed. To find
the volume of O
2
gas, the volume of residual (remaining) gas is measured by equalizing
the water level both in the water reservoir and in the burette. Let the volume of residual
gas be Y cc.
The percentage by volume of O
2
gas = [(100X) Y] cc
(iii) Determination of CO

gas: To measure the volume of CO, stop cock of pipetteC is
opened and the flue gas {initial volume = [(100X)Y cc} is passed into it by raising the
water reservoir. The pipetteC absorbs only CO gas present in the flue gas. Then the flue
gas is taken back to the gas burette by lowering the water reservoir. This procedure is
8
repeated several times for complete absorption of CO in pipetteC. To find the volume of
CO gas, the volume of residual (remaining) gas is measured by equalizing the water level
both in the water reservoir and in the burette. Let the volume of residual gas be Z cc.
The percentage by volume of CO gas = [(100X) Y] Z cc
(iv) Determination of N
2
gas: The residual volume of gas in the gas burette after CO
2
, O
2
and
CO absorption can be taken as the percentage by volume of N
2
gas.
UNIT II: LUBRICANTS AND ADHESIVES
Part A Questions and Answers
1. Define the terms: Lubricants and lubrication.
Lubricant is a substance, used to reduce the friction between two moving surfaces. The
process of reducing friction between two moving surfaces with respect to one another by
introducing a lubricant between them is called lubrication.
2. What are extreme pressure additives? Give examples.
Extreme pressure additives are used to provide adhering power to oil to maintain thick oil film
under extreme pressures
Examples: Organic chlorine and sulphur compounds.
3. What are oiliness improvers? Give examples.
Oiliness improvers are used to increase oiliness or adhering property of lubricants
Examples: Castor Oil; Palmitic acid; Stearic acid; Oleic acid
4. Define aniline point.
It is the lowest temperature at which an equal volume of aniline and oil sample mixes each
other to form a homogeneous solution. It gives a measure of paraffinic and aromatic content
in oil.
5. Distinguish between soda base grease and lime base grease.
Soda based grease: It is an emulsion of mineral oil and sodium soap. It is slightly water
soluble and is used up to 120

C.
Lime based grease: It is an emulsion of mineral oil and calcium soap. It is water resistant
and used up to 135

C.
6. How does graphic differ from molybdenum di sulphide in lubricating action?
Graphite: It can be used only up to 370

C. Adsorbed water and gases are required for

effective lubrication in vacuum.
MoS
2
: It is used up to 800

C. It does not require adsorbed water and air for lubrication in

vacuum.
7. What are adhesives and adherends?
Substances capable of binding two materials together by surface attachment are called
adhesives.
The materials held together by an adhesive are called adherends.
8. What are the advantages of adhesive bonding over other joining methods?
Any two surfaces can be joined together by an adhesive
9
Adhesive bonding minimizes the chances of galvanic type corrosion of two dissimilar
metals.
9. What are the defects or limitations or disadvantages of adhesive bonding?
There is no single and general purpose adhesive which can join all types of surfaces
Adhesive strength is generally lower than other joining methods like welding
10. What is meant by specific adhesion?
If the attachment of surfaces takes place by either physical or chemical forces of attraction, it
is called specific adhesion.
Part B Questions and Answers
1. Explain the mechanism of lubrication.
(i) Fluid-film lubrication (or) Thick-film lubrication (or) Hydrodynamic lubrication
When two metallic surfaces are perfectly separated by thick fluid film of about 1000 in order
to avoid direct metal to metal contact in turn to reduce friction, then the process is termed as
fluid film lubrication.
Velocity
Thick Layer
of Lubricant
Load
Since the frictional force generated in the movement of metal surfaces is only due to internal
resistance of the particles of lubricants, its coefficient of friction is as low as 0.001 to 0.003.
This type of lubrication depends upon mainly viscosity of lubricants and it must have a
minimum viscosity and it must remain in place (a good oiliness).
This type of lubrication is used in machineries working under low load and fair speed
conditions. Delicate instruments and light machines like watches, clocks, sewing machines
and scientific equipments are required this type of lubrication.
Examples: Hydrocarbon oils blended with long chain polymers are considered as fluid film
lubricants.
(ii) Boundary lubrication (or) Thin-film lubrication
When two metallic surfaces are perfectly separated by an adsorbed thin layer of boundary
lubricants of only 2 to 3 molecules thick in order to avoid direct metal to metal contact in turn
to reduce friction, then the process is termed as boundary lubrication.
10
Velocity
Load
Adsorbed
Thin Layer
of Lubricant
Since the load is carried by a thin layer of adsorbed lubricant, its coefficient of friction is 0.05
to 0.1. This type of lubrication depends upon mainly oiliness of lubricants. It also should have
low viscosity index, high resistance to heat and oxidation.
This type of lubrication is used in machines working under heavy load and slow speed
conditions. Railway track joints, gears, rollers, tractors are required this type of lubrication.
Examples: Graphite, MoS
2
as emulsions are considered as boundary lubricants.
(iii) Extreme pressure lubrication
When two metallic surfaces are separated by an extreme pressure additive in order to
withstand heavy load and high temperatures, the process is known as extreme pressure
lubrication.
The machines working under extreme conditions (heavy load and high speed) generate very
high local temperatures. This causes the lubricants to stick on to the surface and decompose.
Hence the lubricating oils are blended with special additives are known as extreme pressure
additives. Extreme pressure lubrication is used in (i) wire drawing (ii) making tough metals.
Examples: Chlorinated esters; sulphurized fats or oils; tricresyl phosphate
2. Explain the following properties of lubricants and give their significances (i) Viscosity
index (ii) Flash and fire point (iii) Cloud and pour point.
(i) Viscosity-index (VI)
Definition: Viscosity index is defined as the average decrease in viscosity per degree rise of
temperature between 100 and 210
o
F. A good lubricant should have minimum change in
viscosity for a wide range of temperature (high VI).
Example (i): Gulf coast oil. This oil mainly consists of naphthenic hydrocarbons and shows a
large change in viscosity with temperature. Thus, its VI value is arbitrarily fixed as zero.
Example (ii): Pennsylvanian oil. This oil mainly consists of paraffinic hydrocarbons and shows
relatively a small change in viscosity with temperature. Thus, its VI value is arbitrarily fixed as
100.
Determination of Viscosity-Index: The VI of a test oil is determined by comparing with the
above two standard oils. The viscosity of test oil is compared at 100
o
F with zero viscosity-
index Gulf coast oil and 100 viscosity-index Pennsylvanian oil, both having the same viscosity
at 210
o
F.
where,
L is the viscosity (in seconds) at 100
o
F of the standard oil having VI of zero
U is the viscosity (in seconds) at 100
o
F of the test oil
H is the viscosity index (in seconds) at 100
o
F of the standard oil having VI of 100.
11
Viscosity Index Improvers: Viscosity-index of lubricating oil can be increased by the
addition of linear polymers such as polyalkyl styrene, polyisobutylene, n-hexanol etc.
- - - - - - - - - - - - - - - - - - - - - - - - -
-

-

-

-

-

-

-

-

V
i
s
c
o
s
i
t
y
Temperature
100
o
F
L
210
o
F
U
H
(ii) Cloud point and Pour point
Cloud Point: When petroleum oil is cooled under specified conditions, the temperature at
which the oil becomes cloudy or hazy is called its cloud-point.
Significance: On cooling the oil, the impurities (wax, asphalt) present in oil crystallize out,
and making the oil turbid. Knowledge of the cloud-point is useful in locating the lowest
temperature up to which a machine can be operated without any risk of jamming.
Pour Point: When petroleum oil is cooled without any disturbance, the temperature at which
the oil just ceases to flow is called its pour point.
Significance: On cooling the oil below the cloud-point, the oil itself crystallizes out and
minute crystals of wax become interlocked and the flow is therefore arrested. Knowledge of
pour point is essential for fixing the lowest temperature up to which the flow of lubricant is
reliable.
Pour-Point Depressant: A good lubricant must have low cloud-point and pour point. Pour
point of a lubricant can be lowered by lowering the viscosity of the oil, or by dewaxing, or by
adding suitable chemical called pour-point depressant. Examples: Paraflow and Santapour .
(iii) Flash point and Fire point
Flash Point: It is the lowest temperature at which the oil gives off enough vapours that will
flash if a small flame is brought near to it.
Fire Point: It is the lowest temperature at which the oil gives off enough vapours that must
burn continuously for at least five seconds when a small flame is brought near to it.
Significance: Knowledge of flash point and fire-point is useful in providing safeguards
against fire hazards during use, transport and storage of the lubricating oil.

3. Write a note on greases?
Definition: Grease is a semi-solid lubricant prepared by adding suitable metallic soap to
petroleum oil or synthetic oil. The metallic soap is also called as gelling agent.
Grease is used under the following situations:
Where the machine is worked under heavy load and slow speed operations (Rail axle
boxes).
12
Where frequent lubrication is not possible (automobile wheel bearings).
Where spilling of oil from the bearings is undesirable (in preparing paper, textile etc.).
In places where the lubricants have to prevent the entry of dirt or moisture.
(i) Calcium based Grease or Cup-Grease: It is an emulsion of petroleum oil and calcium
soap. It is water-resistant. It can be used only up to 70

C. It is used for lubricating pumps

and tractors.
(ii) Soda based Grease: It is an emulsion of petroleum oil and sodium soap. It is slightly
soluble in water. It can be used up to 120

C. It is used in ball bearings.

(iii) Lithium soap Grease: It is an emulsion of petroleum oil and lithium soap. It is
resistant to both heat and water. It can be used up to 135

C. It is used for aircraft

lubrication.
(iv) Axle Greases: It is prepared by adding lime to resin and fatty oils. It is water
resistant. It is used for machines working under low loads and high speeds.
4. Write a note on solid lubricants?
Solid lubricants are used in machineries working at high temperatures and under heavy load
conditions, and other environments, which prohibit the use of oils and greases.
(i) Graphite
Structure: The graphite crystal consists of flat layers of covalently bonded carbon atoms.
Each carbon atom is bonded to three other carbon atoms to form hexagonal layers. The bond
length in the hexagons is 1.42 . The adjacent layers are joined together by weak vander
Waals forces attraction, the layers slide them one over the other.
-

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1
.
4
2

A o
3.40 A
o
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Properties: Graphite is not effective as a lubricant in vacuum. Adsorbed water and gases are
essential for effective lubrication. It can be used as lubricant up to 370
o
C, and above this
temperature, it gets oxidized.
Uses: Graphite is used either as powder or as colloidal dispersions. When graphite is
dispersed in oil, it is called oildag and when it is dispersed in water, it is called aquadag.
Graphite is used in air-compressors, laths, foodstuff industries, railway track joints, internal
combustion engines etc.
(ii) Molybdenum disulphide, MoS
2
Structure: MoS
2
, has a sandwich like structure in which a layer of molybdenum atoms lies
between two layers of sulphur atoms. The atoms in the layer are held by strong covalent
bonds. Presence of intermolecular forces of attraction is responsible for sliding one layer over
another.
13
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3.08 A
o
3.13 A
o
Sulphur atom layer
Molybdenum atom layer
Sulphur atom layer
3.15 A
o
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Properties: Unlike graphite, it does not require the presence of adsorbed gases for effective
lubrication in vacuum. MoS
2
can be used as lubricant up to 800
o
C, and above this
temperature, it gets oxidized.
Uses: MoS
2
can also be used as powder or as colloidal dispersions. It is mainly used in
heavy machineries working under heavy load and high temperatures.
5. What are adhesives? Explain the classification of adhesives with suitable examples.
NATURAL ADHESIVES:
S.No. Name of Adhesive Properties and uses
1. Shellac resin It is a natural resin, dissolved in alcohol and used
as adhesive. It is used for making conveyers, belts
etc.
2. Starch It is prepared from corn, potato, wheat flour etc. It
is used for making office paste, postage stamps,
wall paper, and for note book bindings etc.
3. Protein glues (i) Casein adhesives, soya protein adhesives are
prepared from casein and soya respectively. They
are widely used in wood work industries.
4. Animal glues Animal glues are derived from hides, tendons or
bones of dead animals, which are rich in collagen.
They are used for making furniture, labels, paper
boxes etc.
5. Silicate based adhesive It is prepared by dissolving sodium silicate in
water. It is used for making paper boxes, plywood
etc.
SYNTHETIC ADHESIVES:
S.No. Name of Adhesive Properties and uses
(i) Thermosetting Resins
1. Phenol formaldehyde resin It is fungus, insect and heat resistant. It is used for
making plywood, laminates etc.
2. Melamine formaldehyde resin It is fungus, insect and heat resistant. It is also
used for making plywood, laminates etc.
3. Epoxy resin It is used for bonding glasses, metallic and
ceramic articles. Araldite, the trade name of
epoxy resin used very much in aircraft industry.
4. Silicone resin It is water resistant. It can withstand temperature
14
up to 250
0
C. It is used for bonding metals,
ceramics, plastics etc
(ii) Thermoplastic Resins
1. Cellulose derivatives Cellulose acetate, cellulose nitrate, and ethyl
cellulose are the most important water soluble
cellulose adhesives. Cellulose nitrate mixed with
alcohol is the trade name of Collodion. It is used
in cloth and foot-wear industries.
2. Acrylics (Plexiglass) Methyl acrylic esters adhesives are used for
bonding porous surfaces like paper, cloth, leather
etc.
3. Polyvinyls Polyvinyl acetate, polyvinyl acetal and polyvinyl
butyral are used for bonding non-porous surfaces
like glasses, metals etc.
6. Explain the various physical factors and chemical factors influencing adhesive action.
Physical factors influencing adhesive action
(i) Interfacial Tension: The attraction between the liquid adhesive and adherend surfaces
is maximum when the interfacial tension between the two is minimum.

(ii) Porosity of contacting surfaces: Presence of pores in adherends sometimes disturbs
the equilibrium between solute and solvent of the adhesives. In such a case, poor bond
strength is formed. But in the case of sodium silicate adhesive, presence of pores helps
to absorb the water quickly to form gel. This enhances bond strength.
(iii) Thickness of adhesive film: Thick adhesives with too many voids have poor cohesive
properties. Such adhesives develop weak bond strength. However, viscosity of such
adhesives can be reduced by adding suitable solvent, which can develop good bond
strength.
(iv) Physical characteristics of adhesive film: Adhesives with good tensile strength and
compressive strength develop good bond strength. Adhesives with negligible creep make
the bond strong. Good bond strength is obtained when thermal coefficient of expansion of
adhesive and adherend do not vary much with temperature.
(v) Technique of application of adhesives: Whatever may be the method of application of
adhesive (in the form of powder or liquid, pressure and temperature actually determine
whether full curing of adhesive film takes place or not. The bond strength will be weak
before the proper curing of the adhesive film.
Chemical factors influencing adhesive action
(i) Polar characteristics of adhesives: Adhesives with organic polar groups are used for
bonding organic materials together (plastics, rubbers etc). Further, the addition of polar
molecule to non-polar adhesive enhances its the bond strength.
15
(ii) Degree of polymerization: Partially polymerized semisolid resins develop good bond
strength than the unpolymerized resin or the highly polymerized resin.
(iii) Side chains in adhesive molecule: The bond strength of an adhesive also depends
upon the length of side chain in the adhesive molecule and its structure. In the case of
cellulose esters, maximum bond strength is obtained when fatty acids having side chains
of 6 to 14 carbon atoms are substituted.
(iv) Effect of pH: Protein glues shows better adhesive strength in the presence of lime
whereas vulcanized rubber shows better adhesive strength at a lower pH.

UNIT III PHASE RULE
Part A Questions and Answers
1. Write mathematical statement of phase rule
Gibbs phase rule is mathematically stated as: F = C = P + 2.
Where, P is the number of phases; C is the number of components; F is the number of
degrees of freedom.
2. How many phases, components and degrees of freedom are available in the following
systems?
(i) CaCO
3
(s) CaO (s) + CO
2
(g) (ii) NH
4
Cl (s) NH
3
(g) + HCl (g)
(i)P = 3; C = 2; F = 23 + 2 = 1 (ii) P = 2; C = 1; F = 1 2 + 2 = 1
3. State reduced phase rule.
For solid-liquid alloy system, the variable factor pressure is ignored due to the absence of
gaseous phase. For such a system the phase rule equation is reduced to F = C P + 1 and
it is known as reduced phase rule.
4. State the conditions under which two substances can form a simple eutectic.
The two solids should be completely miscible in liquid state and completely immiscible in
solid state.
They should not react chemically with each other.
5. Mention the differences among melting point, triple point and eutectic point.
Melting point: It is the temperature at which a pure metal starts melting.
Triple point: It is the temperature at which any 3 phases are simultaneously in equilibrium.
Eutectic point: It is the temperature at which a mixture of two solids melts together.
6. Eutectic is a mixture and not a compound. Explain.
Since the two solids are completely miscible in liquid state and are completely immiscible in
solid state, eutectic is a mixture of two solids and not a compound.
16
7. What are the limitations of phase rule?
The influence of factors such as electric, magnetic, gravitational, surface forces is ignored
in phase rule.
The phase rule is applicable only to heterogeneous equilibrium systems.
8. What are the advantages of phase rule?
The phase rule takes no account of the nature or amount of substances.
Phase rule is applicable only to macroscopic systems .Information about molecular
structure is not required.
9. What is peritectic point?
It is the temperature (1495C) at which the liquid melt of composition 0.53 wt% carbon reacts
with ferrite of 0.09 wt% carbon to form austenite of composition 0.17 wt% carbon.
(0.17%C) austenite (0.09%C) ferrite - (0.53%C) melt Liquid
C 1495
+


10. What is ledeburite?
The temperature (1147C) at which the liquid melt of composition 4.3 wt% carbon transforms
into austenite and cementite. This eutectic mixture is called as ledeburite.
Ledeburite
cementite austenite -
C) (4.3% melt Liquid
C 1147
+



11. What is eutectoid point?
It is the temperature (723C) at which austenite of 0.83 wt% carbon transforms into
ferrite and cementite. This mechanical mixture is called as pearlite.
Pearlite
cementite ferrite -
(0.83%C) austenite -
C 727
+

Part B Questions and Answers

1. State the phase rule. Explain the terms involved in it with suitable examples.
Gibbs phase rule is mathematically stated as: F = C = P + 2.
Where, P is the number of phases; C is the number of components; F is the number of
degrees of freedom.
Phase: A phase is a homogeneous, physically distinct, and mechanically separable part of a
system, which is separated from other parts of system by definite boundaries.
Examples:
(i) Freezing water system: It consists of three phases namely liquid water, solid ice and
water vapour.
(ii) Gases: A pure gas or a mixture of any number of gases is considered as a single phase.
This is because gases are completely miscible in all proportions.
(iii) Liquids: If two liquids are immiscible (Benzene and water), they are considered as two
separate phases. If two liquids are miscible (alcohol and water), they are considered as
one liquid phase only.
(iv) Solids: Each solid is considered as a separate phase. For example, a heterogeneous
mixture of CaCO
3
and CaO consists of two phases.
17
Components: It is defined as the minimum number of chemical constituents required to
express the composition of all the phases present in the system.
Examples:
(i) The freezing water system: This system consists of three phases namely ice, water and
water vapour. The chemical composition of all the three phases can be expressed by
chemical constituent, water. Hence it is an example of one-component system.
(ii) Thermal decomposition of CaCO
3
: CaCO
3
(s) CaO(s) + CO
2
(g)
This system consists of three phases namely, solid CaCO
3
, solid CaO and gaseous CO
2
.
The chemical composition of all the three phases can be expressed by any two of the
three chemical constituents. Hence it is an example of two-component system.
Degree of Freedom (Or) Variance of a System: It is defined as the minimum number of
independent variable factors such as temperature, pressure and concentration (composition)
required to describe the system completely.
Examples:
(i) Consider a one component system consisting of two phases: water water vapour:
P = 2; C = 1; and F = C P + 2 = 1 2 + 2 = 1; to define such a system, only one
variable factor (either temperature or pressure) is needed. Hence the system is
univariant.
(ii) Consider a one component system consisting of one phase: water vapour:
P = 1; C = 1; and F = C P + 2 = 1 1 + 2 = 2; to define such a system, two variable
factors (temperature and pressure) are needed. Hence the system is bivariant.
(iii) Consider a one component system consisting of three phases: ice water water
vapour.
P = 3; C = 1; and F = C P + 2 = 3 1 + 2 = 0; to describe this equilibrium system, no
need to specify any variable factors, because all the three phases can occur in
equilibrium only at a particular temperature and pressure. Hence this system does not
have any degree of freedom (invariant or zero variant).
2. Draw and explain the phase diagram of ice-waterwater vapour system. How does the
melting point of ice change with variation of pressure?
18
Temperature
P
r
e
s
s
u
r
e
----------------------------------------------
-
-
-
-
-
-
-
-
-
-
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-
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-----------------------------------
----------------------
-
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-
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-
-
-
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-
-
-
-
-
-----------
Solid Ice
Liquid Water
Water Vapour
O
B A
C
A'
273
o
C 0.0075
o
C
100
o
C 374
o
C
4.58mm
1atm
218atm
V
a
p
o
u
r
i
z
a
t
i
o
n

c
u
r
v
e
S
u
b
l
i
m
a
t
i
o
n

c
u
r
v
e
F
u
s
i
o
n

c
u
r
v
e
0
o
C
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
The water system is an example of one component system. It consists of three phases
namely solid ice, liquid water and water vapour.
Salient features of phase diagram of water system:
(i) Curves: The phase diagram consists of three curves OA, OB and OC. Each curve
separates two phases and hence the system is univariant along the curve (F = CP+2 =
12+2 = 1).
Curve OA: is the vaporization curve because it separates the liquid region from vapour
region. Along the curve OA, water and water vapour are in equilibrium (water water
vapour). The curve OA ends at the point A, which corresponds to the critical temperature
(374

C) and critical pressure (218.5atm) of water. Beyond which the liquid and vapour
phases merge into each other to form a single homogeneous phase.
Curve OB: is the fusion or melting curve because it separates ice and water phases. The
curve OB is slightly inclined towards pressure axis. This shows that melting point of ice
decreases with the application of pressure.
Curve OC: is the sublimation curve because it separates ice and water vapour phases. At
the lower limit, the curve OC terminates at absolute zero (273

C) where no vapour can be

present and only ice exists.
(ii) Point O (Triple Point): The three curves OA, OB, and OC meet at a point O, at which
solid ice, liquid water and water vapour are simultaneously in equilibrium. This is called
triple point (Solid ice Liquid water Water vapour).
At the triple point, the system is invariant (F = CP+2 = 13+2 = 0). The triple point of
water system corresponds to a temperature of 0.0075

C and a pressure of 4.58mm

mercury.
(iii) Areas: The curve is divided into three areas AOB, BOC and COA. Each area represents a
single phase and hence the system is bivariant (F = CP+2 = 11+2 = 2).
(iv) Curve OA' (Meta stable Equilibrium): The curve OA represents the vapour pressure
curve of super cooled water. The process of cooling of water below its freezing point
19
without the separation of solid is known as super cooling. The super cooled water is highly
unstable. It can be converted into solid by a slight disturbance. Hence the system along
the curve OA is said to be in meta stable equilibrium.
3. Explain the construction of eutectic phase diagram by thermal analysis.
Thermal analysis involves the study of cooling curve of various compositions of two solids
during solidification.
(i) Cooling curve for pure metal
Time
T
e
m
p
e
r
a
t
u
r
e
x
s
a a'
E
n
d

o
f

f
r
e
e
z
i
n
g
B
e
g
i
n
n
i
n
g

o
f

f
r
e
e
z
i
n
g
s: The point s represents that a pure metal is in molten state.
sa: Along the line sa, the temperature of the liquid melt decreases gradually with time.
a: It is the point at which the molten liquid metal starts freezing on its surface.
aa: Along the line aa, the temperature of liquid melt remains constant until it is completely
solidified into solid metal. This is because the liquid melt and solid metal have same
chemical composition.
a: The point a indicates the end of freezing.
ax: Along the line ax, the temperature of solid metal again decreases with time.
(ii) Cooling curve for a mixture of solid A and solid B
Time
T
e
m
p
e
r
a
t
u
r
e
s
a
b b'
x
Freezing of either A or B starts
End of freezing
E
u
t
e
c
t
i
c

p
o
i
n
t
20
s: The point s represents that a mixture of solid A and solid B is in molten state.
sa: Along the line sa, the temperature of the mixture containing A and B decreases with time.
a: It is the point at which freezing of base metal (either A or B depends upon their freezing
point) starts from the liquid mixture.
ab: Along the line ab, the composition of molten mixture progressively changes due to
continuous separation of solid A (or solid B) with time.
b: The point at which the liquid mixture (containing both A and B) starts freezing into solid A
and solid B (eutectic mixture).
bb: Along the line bb, the temperature of molten mixture remains constant until it is
completely solidified.
b: The point b indicates the end of freezing of eutectic mixture.
bx: Along the line bx, the temperature of solids again decreases with time.
(iii) Construction of eutectic phase diagram by using cooling curves of solid A and B
So, it is possible to construct a complete phase diagram for the two-component system on
the basis of large number of cooling curves of various compositions.
.......................................................
..........................................................
.......................................................
.......................................................
...........................................................
.......................................................
a
b
c
e
d
f
g
Liquid melt
S
o
l
i
d

A

+

L
i
q
u
i
d

m
e
l
t
S
o
l
i
d

B

+

L
i
q
u
i
d

m
e
l
t
Solid A + Solid B
T
e
m
p
e
r
a
t
u
r
e

Time
100%A 100%B
T
e
m
p
e
r
a
t
u
r
e

Composition
1
2 3
4
5 6 7
.........................
a
b
c
d
e
f
g
1. 100%A 2. 80%A+20%B 3. 70%A+30%B 4. 60%A+40%B 5. 45%A+55%B 6. 30%A+70%B 7. 100%B
4. Draw the phase diagram of lead-silver system and explain the salient features and its
application?
21
O
Liquid melt
Solid Ag +
Liquid melt
Solid Pb + Solid Ag
100%Pb
100%Ag
Composition wt%
T
e
m
p
e
r
a
t
u
r
e

A
B
S
o
l
i
d

P
b


+


L
i
q
u
i
d

m
e
l
t 303
o
C
961
o
C
303
o
C
327
o
C
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
97.4%Pb
+ 2.6%Ag
a
b
Salient features of phase diagram of lead-silver system:
(i) Curves:
Curve AO: Pure Ag melts at 961

C. Addition of Pb lowers the freezing point of Ag along the

curve AO. Therefore AO is the freezing point curve of silver. Along AO, solid Ag and liquid
melt are in equilibrium. Hence the system along the curve is univariant (F = 22+1 = 1).
Curve BO: Pure Pb melts at 327
0
C. Addition of Ag lowers the freezing point of Pb along the
curve BO. Therefore BO is the freezing point curve of Pb. Along BO, solid Pb and liquid melt
co-exist and hence the system is univariant (F = 2 2 + 1 = 1).
(ii) Point O (Eutectic Point): The curve AO and BO intersect at O which is called eutectic point.
At the eutectic point three phases are in equilibrium (Liquid melt Solid Ag + Solid Pb ).
Hence the system is non-variant (F = CP+1 = 23+1 = 0). Below the point O, both silver
and lead exist in the solid state.
Therefore, eutectic point is the lowest temperature at which a mixture of two solids melts
(eutectic = easy melting). The eutectic point of Pb-Ag system corresponds to a temperature
303

C and composition 97.4%Pb+2.6%Ag.

(iii) Areas: The area above AOC has a single phase (molten Pb and Ag). Applying the reduced
phase rule F = CP+1 = 21+1 = 2, the system is bivariant. The area below AO (solid Ag +
liquid melt), below BO (solid Pb + liquid melt) and below O (solid Ag + solid Pb) have two
phases and hence the system is univariant (F = CP+1 = 22+1 = 1).
Application of Pb-Ag System (Pattinsons Process): The process of recovery of silver from
argentiferous lead is called as desilverisation. Desilverisation of lead is based on the formation of
eutectic mixture. Argentiferous lead consists of a very small amount of silver (0.1%). The ore is
heated to a temperature well above its melting point, so that it exists as liquid melt(point a in Pb-
Ag system). When it is allowed to cool, the temperature of the melt falls along the line ab. As
soon as point b is reached, lead is crystallized out. On repeating the process of melting and
cooling, more and more lead is separated along the line BO. At O a eutectic mixture containing
2.6%Ag and 97.4%Pb is obtained. The eutectic alloy is then treated for recovery of silver.
22
5. Draw and explain iron-carbon phase diagram with different phases and invariant
reactions.
Iron-carbon phase diagram consists of: (i) Steel portion: [0.0032.12 wt% C] (ii) Cast iron
portion: [>2.12 6.67wt% C]
F
e
r
r
i
t
e
727
o
C
wt% Carbon
912
o
C
T
e
m
p
e
r
a
t
u
r
e
0.022
0.008
0.83 2.12
1147
o
C
1495
o
C
Austenite
1400
o
C
1538
o
C
0.09
0.17
0.53
4.3
Liquid (Fe+C)
Austenite
+ Liquid
Austenite + Cementite
A
u
s
t
e
n
i
t
e

+

C
e
m
e
n
t
i
t
e
A
u
s
t
e
n
i
t
e

+

F
e
r
r
i
t
e
A
B
C
D
H
E
F
G
Cementite
+ Liquid
J
M
N
I
K
6.67
Cementite + Pearlite
Ferrite +
Pearlite
L
DF+L
DF
DF+A
D
F
+
L
:

D
e
l
t
a

f
e
r
r
i
t
e
+
L
i
q
u
i
d
D
F
:

D
e
l
t
a

f
e
r
r
i
t
e

D
F
+
A
:

D
e
l
t
a

f
e
r
r
i
t
e
+
A
u
s
t
e
n
i
t
e
F: Peritectic point
C: Eutectic Point
M: Eutectoid point
4.3
L
e
d
e
b
u
r
i
t
e
727
o
C
1550
o
C
Salient features of iron-carbon phase diagram:
(i) Curves: The curve ABCD is known as liquidus line. Above this line, only one phase
(liquid) exists. When carbon is added to iron, the melting point of iron gradually
decreases along the liquidus line ABC up to 4.3%. On further addition of carbon, the
melting point of iron increases along the line CH.
The curve AEFGCH represents solidus line below which only solid phase of various
compositions of iron and carbon exists
(ii) Areas: The area AEI represents of -ferrite phase. The area IFGMJI represents of -
austenite phase and the area JKL represents -ferrite phase.
(iii) Phases (Microconstituents of Fe-C System)
Ferrite: It is an interstitial solid solution of carbon in BCC iron. . ferrite is soft,
ductile, and magnetic but has poor strength. At room temperature, the solubility of carbon
is limited to 0.008 wt%, because the BCC iron has relatively small interstitial positions.
The maximum solubility of carbon in BCC iron is 0.022 wt% at 727C. It transforms into
austenite at 912C
Austenite: It is an interstitial solid solution of carbon in FCC iron. austenite is
tough and denser than ferrite. It is non-magnetic. The maximum solubility of carbon in
23
iron is 2.12 wt% at 1147C because the FCC iron has relatively more interstitial positions.
But the solubility decreases to 0.83 wt% at 727C. It transforms into ferrite at 1400C.
Ferrite: It is the interstitial solid solution of carbon in BCC iron. The maximum
solubility of carbon in iron is 0.09 wt% at 1495C. It is a stable phase between 1400C
and 1538C. It melts at 1538C. It has the softest structure. It has no practical
significance in engineering
Cementite (Iron carbide, Fe
3
C): It is the intermetallic compound of iron and carbon. The
maximum solubility of carbon in iron is 6.67 wt% at 1550C. It is white, extremely hard
and brittle phase.
(iv) Invariant Reactions (Critical Points)
Peritectic point: It is the temperature (1495C) at which the liquid melt of composition 0.53
wt% carbon reacts with ferrite of 0.09 wt% carbon to form austenite of composition
0.17 wt% carbon.
(0.17%C) austenite (0.09%C) ferrite - (0.53%C) melt Liquid
C 1495
+


Eutectic point: It is the temperature (1147C) at which the liquid melt of composition 4.3
wt% carbon transforms into austenite and cementite. This eutectic mixture is called as
ledeburite.
Ledeburite
cementite austenite -
C) (4.3% melt Liquid
C 1147
+



Eutectoid point: It is the temperature (723C) at which austenite of 0.83 wt% carbon
transforms into ferrite and cementite. This mechanical mixture is called as pearlite.
Pearlite
cementite ferrite -
(0.83%C) austenite -
C 727
+

UNIT IV ALLOYS AND COMPOSITES

Part A Questions and Answers
24
1. Write the importance (purpose) of making alloys.
To increase the strength of metals: Pure iron is a weak metal whereas carbon is brittle.
When the two are combined, we get a strong and workable alloy called steel.
To increase the hardness of metals: Gold is the soft and ductile metal. When it is alloyed
with copper, we get a hard alloy suitable for making ornaments.
To increase the corrosion resistance of metals: Iron is susceptible to oxidation corrosion.
When chromium is added to iron, it forms a coherent oxide film of chromium oxide and
improves its corrosion resistance.
To lower the melting point of base metals: Alloying of lead with tin reduces the melting
point of the constituent metals by forming a simple eutectic. Such eutectic mixture is
fusible at the lowest temperature and used as solder.
2. What are alloy steels? Why there is a need for alloying steels? What are its
applications?
Definition: The properties of plain carbon steel can be further improved by adding certain
elements like Cr, Ni, Mn, Si, V, W etc. Such admixtures are called alloy steel.
Need (Effect) of Alloying Elements on Steel and Applications:
S.No. Alloying element Properties Applications
1. Chromium, Cr Makes steel stainless,
increases strength, hardness
and corrosion resistance.
Shafts, gears, cutlerys,
surgical instruments
2. Nickel, Ni Improves strength, hardness Crankshafts, axles
3. Manganese, Mn Improves strength, hardness,
deoxidiser
Shafts, gears
4. Silicon, Si Improves strength, deoxidiser Transformer cores
3. Give the composition and the main use of nichrome.
Nichrome has the composition: 70% Fe + 10% Ni + 20% Cr.
Applications: It is used for making boiler parts, gas turbines, heating elements for
electric irons, ovens, room heaters etc.
4. Distinguish between brasses and bronzes.
Brasses are essentially alloys of copper and zinc whereas bronzes are alloys of copper
with any element other than zinc and nickel
Brasses have higher strength than copper while bronzes have higher strength than both
copper and brasses
Brasses have good resistance to atmospheric corrosion and fair resistance to marine
corrosion. Bronzes, in general, have better corrosion resistance than brasses.
5. What are composites? What are the advantages of composites?
25
Composites are hybrid materials formed by integration of two or more materials with superior
structure and better properties than constituent materials.
Composites possess excellent strength, stiffness and are light weight
Composites have high specific modulus
Composites are highly resistant to corrosion
Composites are recyclable, reliable and consume less energy
6. Mention the applications of composites.
Composite materials are extensively used in:
Manufacturing advanced aerospace structures
Light weight construction materials
High speed and fuel efficient transport vehicles
Electronic components and Sporting goods
7. What are the constituents of composites? Mention their functions.
Matrix phase: The matrix phase is the primary phase. It surrounds and holds the individual
reinforcing elements. Examples: Polymers, Metals, Ceramics
Functions:
Matrix phase takes the load and stress and transfers into reinforcements
Matrix phase gives shape to composites
Reinforcement phase: The reinforcement phase is the secondary phase. It carries most of
the loads.
Functions:
Reinforcement phase imparts mechanical properties like light weight, strength, stiffness,
toughness and thermal stability
Reinforcement phase acts as major load bearing constituent
8. What are ceramic-matrix composites?
Ceramic-Matrix Composite (CMC) is material that consists of a ceramic dispersed in another
ceramic dispersed phase (oxides, carbides).
Examples of ceramic matrix: Alumina (Oxide matrix), SiC (Non-oxide matrix)
Examples of reinforcements: Whiskers (Fine single crystal materials) of SiC, TiB
2
, AlN,
ZrO
2
.
9. What are Cermets? Mention their applications.
Cermets are the materials composed of ceramic particles dispersed in a refractory metal
matrix. They are characterized with high tensile strength, high thermal shock resistance, high
density, high modulus, high shape ability etc. Most cermets contain 15-20% metal.
(i) Oxide base cermets are used as high speed cutting tool materials, thermocouple
protection tubes, molten metal processing equipment parts.
(ii) Carbide base cermets are used for gauges and valve parts.
Part B Questions and Answers
26
1. What are alloys? Write an account on ferrous alloys. (or) Write the chemical
composition and uses of (i) heat treatable stainless steel and (ii) non-heat treatable
stainless steel.
Definition: An alloy is a homogeneous mixture of two or more metals. In an alloy, the metal
which is present in excess amount is called base metal and the elements which are present
in least amounts are known as alloying elements.
Ferrous alloys: They contain iron as major component. Common examples are plain carbon
steel and alloy steel.
Plain carbon steel: Plain carbon steel is a binary alloy of iron and carbon.
S.No. Types C (% by Wt) Properties Applications
1. Low carbon steel
(Mild steel)
0.1-0.3 Soft, ductile,
weldable.
Manufacture of bolts, nuts,
and screws.
2. Medium carbon
steel
0.3-0.8 Hard and
tougher than
mild steel,
non-weldable.
Manufacture of automotive
engine components, wheels,
gears, hydraulic fittings,
shafts and axles.
3. High carbon steel 0.8-1.3 Hard, tough. Manufacture of hammers,
dies, and razors.
Stainless steel: Stainless steel is otherwise known as corrosion resistant steel. The stainless
steel is protected against corrosion because of the formation of dense, tough film of
chromium oxide. It is of two types: Heat treatable stainless steel and non-heat treatable
stainless steel.
(i) Heat treatable stainless steel
S.No. Types % Composition Properties and Applications
1. Plain chromium
stainless steel
C: 0.1-0.8
Cr: 12-18
For making cutlery, scissors, surgical
instruments
2. High chromium low
nickel steel
C: 0.1-0.3
Cr: 12-18
Ni: 2%
(ii) Non-heat treatable stainless steel
S.No. Types Composition Properties and Applications
Magnetic type
1. Ferritic
stainless steel
C: 0.1-0.8
Cr: 12-18
For making surgical instruments,
decorative pieces, steam oil pumps.
2. Martensitic
stainless steel
C: 0.8-1.3
Cr: 12-18
For making utensils, springs, cutting
tools.
Non-magnetic type
1. Austenitic
stainless steel
C: 0.5
Cr: 18-25
Ni: 8-21
For making sinks, utensils, dental and
surgical instruments.
2. What are non-ferrous alloys? Write the composition, properties and uses of various
varieties of brass and bronze.
27
Definition: Non-ferrous alloys do not contain iron as a base metal. Common examples of
non-ferrous alloys are copper alloys, aluminium alloys, lead alloys, nickel alloys etc.
Copper alloys: Alloys of copper are generally classified into two groups. (i) Brasses (ii)
Bronzes.
(i) Brasses: Brasses are alloys of copper and zinc.
S.No. Types %Composition Properties and Applications
1. Gilding metal
(or) French gold
Cu: 90
Zn: 10
It is stronger and harder than copper.
For making coins, medals, tokens.
2. Dutch metal Cu: 80
Zn: 20
It is stronger and harder than Gilding metal.
For making cheap jewelry, name plates.
3. Cartridge brass Cu: 70
Zn: 30
It has good combination of strength and
ductility.
For making cartridge cases.
4. Muntz metal Cu: 60
Zn: 40
It is stronger and harder than cartridge
brass.
For making condenser tubes.
5. Admirality brass Cu: 70
Zn: 29
Sn: 1
It is resistant to sea water corrosion.
For making propellers for ships and boats.
6. Naval brass Cu: 60
Zn: 39
Sn: 1
It is resistant to corrosion.
For structural applications especially where
they contact with sea water.
(ii) Brasses: Brasses are alloys of copper and zinc.
S.No. Types %Composition Properties and Applications
1. Common bronze Cu: 90
Sn: 10
It is soft and ductile.
For making coins, statues, ornaments.
2. Gun metal Cu: 88
Sn: 10
Zn: 2
It is strong and resistant to corrosion
For handling liquids, steam and oil under
pressure
2. Phosphor bronze Cu: 89
Sn: 10
P: 1
Phosphorous increases strength and
ductility
For making gears, bearings, turbine
blades.
4. Aluminium
bronze
Cu: 90
Al: 10
It has good resistance to corrosion and
abrasion.
For making coins, gears, propellers.
3. Discuss the various types of aluminium alloys giving their composition, properties and
uses.
28
(1) Wrought Aluminium Alloys: Aluminium alloys, which are shaped by mechanical
working processes such as extrusion, rolling, drawing, forging are known as wrought
alloys.
(i) Non-Heat Treatable Wrought Aluminium Alloys: Alloys which do not respond to heat
treatment are called as non- heat treatable alloys.
AlMn alloys: This alloy possesses very good resistance to corrosion and good
weldability. It is widely used for making utensils, food and chemical handling equipments,
gas and oil tanks, pressure vessels etc.
(ii) Heat Treatable Wrought Aluminium Alloys: Alloys which respond to heat treatment are
called as non- heat treatable alloys.
Duralumin: Duralumin consists of about 95% Al + 4% Cu + 0.5% Mn + 0.5% Mg. Due to
its high strength and low density, it is widely used for making aircraft and automobile
parts. Due to its high ductility and good electrical conductivity, it is used for making
surgical instruments, cables etc.
Magnelium: Magnelium consists of about 70-90% Al+10-30% Mg. It is characterized by
light weight, high tensile strength, good machinability and weldability. It is used in aircraft
and automobile industries.
(2) Cast Aluminium Alloys: Aluminium alloys, which are shaped by casting processes such
as die casting, investment castings are known as cast alloys.
Al-Si alloys: Aluminium alloy with 10% Si possesses casting properties and good
corrosion resistance. They are used in automobile gear boxes, radiators etc.
AlMg alloys: Aluminium alloy with 10% Mg possesses high strength and excellent
corrosion resistance. They are used for large tanks carrying milk, petrol.
4. What is Fiber reinforced polymers (FRP)? Discuss the various types of FRP (PMC) with
suitable examples.
Definition: FRP are composite materials that typically consist of strong fibers embedded in a
resin matrix.

Types of FRP (or Classification of Polymer matrix composites, PMC):

Glass fiber reinforced polymers (GFRP)
Aramid fiber (Kevlar) reinforced polymers (AFRP)
Carbon fiber reinforced polymers (CFRP)
(i) Glass Fiber Reinforced Polymers (GFRP)

Definition: GFRP is a kind of PMC reinforced by Glass fibers
Preparation, Properties and Applications: There are basically four varieties of glass fibers
used in composites. They are E-glass (electrical grade), S-glass (high strength), AR-glass
(alkaline resistant) and Z-glass (zirconia containing glass fibers).
E-glass fibers are used for structural and electrical applications because of their high
electrical insulating properties and good mechanical properties.
29
S-glass fibers retain their strength at higher temperatures and have higher fatigue strength
and are used in defence and aeronautical applications.
AR- and Z-glass fibers possess good resistance to alkaline environments and are used for
structural applications.
(ii) Aramid Fiber (Kevlar) Reinforced Polymers (AFRP)
Definition: AFRP is a kind of PMC reinforced by aramid (aromatic polyamides) fibers.
Preparation, Properties and Applications: Kevlar is the trade name of aramid [Poly (para-
phenylene-terephthalamide)] fibers. Aramid fibres are synthesized by polycondensation of p-
phenylene diamine and terephthaloyl dichloride.
Aramid fibers characterized by high strength and stiffness; light weight and low density; ultra
high modulus. AFRP are used for manufacturing aerospace, automotive and marine
applications.
(iii) Carbon Fiber Reinforced Polymers (CFRP)
Definition: CFRP is a kind of PMC reinforced by carbon fibers.
Preparation, Properties and Applications: Carbon fibers are prepared by carbonization of
rayon or polyacrylonitrile in an inert atmosphere at high temperatures (1600 to 2200C).
Carbon fibers characterized by high strength to weight ratio; very high modulus of elasticity;
light weight; good corrosion resistance; low coefficient of thermal expansion; high electrical
conductivity. CFRP are used for manufacturing automotive, marine and aerospace parts etc.
5. What are metal matrix composites (MMC)? Describe MMC with suitable examples.
Definition: MMC is a material that consists either a ceramic or another metal dispersed in
metal matrix.
Examples of matrix: Al, Mg, Ti, Cu etc.,
Examples of reinforcements: Ceramics Oxides (Al
2
O
3
), Carbides (SiC, TiC), Borides
(TiB
2
); Metals Pb, W, Mo etc.
Characteristics: MMC are characterized by: High strength at elevated temperatures; High
stiffness; High thermal stability; High thermal conductivity etc.
Types of MMC:
S.No. Types Reinforcement Properties and Applications
1. Al-matrix
composites
SiC particles,
Al
2
O
3
fibers
Used for manufacturing automotive parts,
cores for high voltage electrical cables.
2. Mg-matrix
composites
SiC particles Used for manufacturing components for
aircraft parts, gear boxes.
3. Ti-matrix
composites
TiB
2
, TiC Used for manufacturing turbine engine
components, automotive engine components
UNIT V INTRODUCTION TO NANOMATERIALS
30
Part A Questions and Answers
1. Define nanochemistry.
Nanochemistry is the study of synthesis and analysis of materials in the nanoscale range (1
10nm), including large organic molecules, inorganic cluster compounds, and metallic or
semiconductor particles.
2. What are nanomaterials or nanostructured materials?
Materials, which possess grain size less than 100nm in at least one coordinate (dimension),
are known as nanomaterials or nanostructured materials.

3. How are nanomaterials classified on the basis of dimensions?
S.No. Reduction in size in
different coordinates
Size Examples
1. 3 dimensions <100 nm Nanoparticles; Quantum dots
2. 2 dimensions <100 nm Nanotubes; Nanowires
3. 1 dimension <100 nm Thin films; Coatings
4. Define the terms: top-down nanofabrication and bottom-up nanofabrication.
Bottom-up nanofabrication: The building of nanostructures starting with small components
such as atoms or molecules is called bottom-up nanofabrication.
Examples: Chemical vapour deposition; Sol-gel process.
Top-down nanofabrication: The process of making nanostructures starting with larger
structures and taking parts away is called top-down nanofabrication.
Examples: Ball milling; Epitaxy
5. What are carbon nanotubes? Distinguish between SWCNT and MWCNT.
Carbon nanotubes are cylindrical carbon molecules (graphite sheet is folded into a tube),
useful for electronic and mechanical applications. They exhibit unusual strength, unique
electrical and thermal properties.
Single-walled carbon nanotube (SWCNT): If a nanotube has a single cylinder of graphene
sheet (Dia: 1-2nm; Length: 1-100 m), it is known as SWNT.
Multi-walled carbon nanotube (MWCNT): If a nanotube has a number of concentric rings of
graphene sheets (Inner dia: 1-2nm; Outer dia: 2-20nm; Length: 1-100 m: Inter tublar
spacing: 0.34nm), it is known as MWNT.
6. What are the unique properties of CNTs?
CNTs are 100 stronger and about six times lighter than steel
CNTs can conduct electricity like copper and acts as semiconductor like silicon
CNTs can transport heat 10 times higher than silver
31
7. What are nanoparticles? Write the preparation, properties and applications of
nanoparticles.
Definition: Particles or powders with grain size (diameter) less than 100 nm are called
nanoparticles.
Synthesis of nanoparticles by chemical reduction method:
Group VI metal halides like MoCl
3
, WCl
4
can be reduced into their corresponding metals by
using NaBEt
3
H (sodium tri-ethoxy boron hydride) with toluene as solvent at room
temperature.
Properties:
As the particle size decreases, surface to volume ratio increases. This enhances catalytic
activity of nanoparticles.
Size reduction influences thermal properties like melting point. Melting point decreases
with the particle size reduction.
Applications of nanoparticles:
Since Ag nanoparticles have good antibacterial properties, it is used in refrigerators, air-
conditioners, water purifiers etc.
ZnO, TiO
2
nanoparticles are used as sunscreen cosmetics because they absorb uv and
give protection to skin.
8. What are nanowires? Write the preparation, properties and applications of
nanoparticles.
Definition: Nanowires are cylindrical solid wires with a diameter ranging from 10100nm and
a length of few micrometers.
Preparation of nanowires by VLS mechanism: A well accepted mechanism for the growth
of nanowires through gas phase reaction is vapour-liquid-solid (VLS) process.
Mechanism: VLS mechanism follows two step processes:
(i) In the first step, diffusion of vapour phase (reactants) takes place into the liquid phase
(molten nanoparticle catalyst)
(ii) In the second step, super saturation of reactants occurs in the liquid phase which causes
the precipitation of solid phase (nanowire)
Synthesis of Silicon Nanowire: To grow silicon nanowire, gold nanoparticles is used as
catalyst. The substrate is first covered with a coating of gold nanoparticles and heated to a
temperature in a furnace so that it becomes liquid. Simultaneously the precursor (raw
material), silane (SiH
4
) is introduced into the furnace where it vapourises to form silicon
vapour. During the reaction, silicon vapour diffuses and dissolves in molten gold
nanoparticles. When the concentration of silicon becomes supersaturated, the excess
material (silicon) precipitates and grows as nanowires.
Applications:
Nanowires are used in electron devices like field effect transistors, in sensors, and
detectors
Nanowires replace copper in computers and in electronics.
32
9. Mention the important properties and applications of nanoporous materials.
Nanoporous materials have the surface area of 5001000m
2
/gm, which enhances the
chemical reactivity and catalytic activity of various reactions.
They have very low thermal conductivity and are used as thermal insulators.
10. Write the basic principles of Chemical vapour deposition (CVD) and Physical vapour
deposition (PVD) methods?
CVD method involves a transport of reactant gases towards the substrate kept at some
temperature. The reactants crack into different products and diffuse on the surface and
undergo certain chemical reactions. This leads to the growth of thin films, nanowires and
nanotubes.
Physical vapour deposition (PVD) is a technique by which a metal, ceramic or a compound is
converted into gaseous form and then deposited on the surface of a substrate.
Examples: Evaporation, Sputtering, Laser ablation
Part B Questions and Answers
1. Explain plasma arcing method for synthesis of CNTs.
Electric arc discharge method (or) Plasma arcing: Carbon nanotubes are commonly
prepared by striking or producing an arc between graphite electrodes in an inert atmosphere.
The following are the conditions required for CNT formation.
Electrodes : Pure graphite rods
Diameter of electrodes : 5 to 20m
Gap between the electrodes : 1 mm
Current : 50 to 120 Amperes
Voltage : 20 to 25 V
Inert gas pressure : 100 to 500torr
Temperature rise during arc
discharge
: 3000 to 3500C
To Vacuum
+
Gas
Inlet
Graphite Electrodes
In this method, a potential of 2025V is applied across the pure graphite electrodes of 5
20m diameter and separated by 1mm at 500torr pressure of flowing helium gas. Under
these conditions carbon atoms are ejected as vapour from the positive electrode and forms
nanotube on the negative electrode. To produce SWCNT a small amount of Co, Ni, or Fe is
incorporated as catalyst in the central region of the positive electrode. If no catalysts are
used, the tubes formed are multi-walled types.
33
2. Explain any two important properties of cabon nanotubes.
(i) Electrical properties of CNTs
Carbon nanotubes (CNTs) can be both metallic or semiconducting, depending upon the
helicity (chirality) and diameter of the nanotubes. Helicity refers to rolling of hexagonal chains
with respect to the tube axis. Helicity results in three different kinds of CNTs. They are
armchair, zigzag, and chiral nanotubes.
The general rules for the electrical conductivity of the SWNTs are as follows:
Basically, all armchair tubes (n, n) tubes are metallic because of their symmetry.
One out of three zigzag and chiral tubes can be either metallic or semi-conducting
depending upon their chiral vector (n, m).
Metallic properties dominate when
0 m - n
or
integer.
3
m) - (n

Semi conducting properties dominate when

integer.
3
m) - (n

Hence, (7,1) and (5,2) tubes would be metallic, whereas (8,0) and (6,1) tubes would be
semiconducting; the (5,5) armchair tube would always be metallic.
In metallic state, the conductivity of CNTs is very high. It is estimated that CNTs can carry
billion amperes of current per square centimeter. The copper wire fails at one million amperes
of current per square centimeter because resistive heating melts the wire. One reason for
high conductivity of CNTs is that they have very few defects to scatter electrons and offer a
very low resistance.
armchair zigzag chiral
(ii) Mechanical properties of CNTs
(i) Tensile strength: It is a measure of the amount of stress needed to pull a material. The
tensile strength of CNTs is ~100 times stronger than that of steel of the same diameter. (a)
The strength is provided by the interlocking of carbon-to-carbon covalent bonds (b) Each
CNT is one large molecule. It means that, it does not have any weak spots like grain
boundaries, dislocation etc.
(ii) Youngs modulus: It is a measure of stiffness or flexibility a material. CNTs have Youngs
modulus ranging from 1.28 to 1.80TPa whereas steel has 0.21TPa. It means that Youngs
modulus of CNTs is almost 5 to 10 times of steel.
(iii) Thermal conductivity: CNTs have high thermal conductivity. It has been
predicted that, thermal conductivity of CNTs is ten times that of silver.
(iv) Density: CNTs are light weight with a density of about that of steel and 1/2 of
that of aluminium. The density of CNTs is 1.331.44gm/cm
3
.
34
3. Discuss the various steps involved in sol-gel process for the synthesis of nanoporous
materials.
Synthesis of Nanoporous materials by sol-gel process:
Basic principle: Sols are particles in liquid. Gels are nothing but a continuous network of
particles with porous structure filled with a liquid. A sol-gel process involves the formation of
sols in a liquid and then converting the sol particles into a porous network filled with a liquid.
By drying the liquid, it is possible to obtain a thin film or monolithic solid is known as aerogel.
Precursors: The precursors used in sol-gel process for the synthesis of nanoporous
materials are metal alkoxides, M(OR)
4
. They readily react with water to form gels. Egs:
Tetramethoxy silane, [Si(OCH
3
)
4
]; Tetraethoxy silane, [Si(OC
2
H
5
)
4
]
Synthesis of silica aerogel: The process consists of four main steps:
1. Hydrolysis: It occurs through the addition of water and to form silanol, (SiOH) particles.
2. Condensation: The self condensation of silanol groups produces siloxane linkages, (Si
OSi) filled with byproducts of water or alcohol.
3. Polycondensation: The condensation process continues to form poly condensed silica gel
with SiOSi linkages.
Si O Si O Si
Si O Si O Si
Si O Si O Si
O O O
O O O
4. Drying: The gels are subjected to super critical drying in an autoclave. The critical
pressure and critical temperature used are 78bar and 294C respectively in order to
remove liquid from silica gel to form the network structure of silica aerogel.
Precursor, M(OR)
4
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
.
.
.
. .
.
.
.
.
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
.
.
.
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
_ _ _ _ _ _ _ _
Hydrolysis
Sol
Gel
Aerogel
Xerogel
Condensation
Polycondensation
S
u
p
e
r
c
r
i
t
i
c
a
l

d
r
y
i
n
g
R
a
p
i
d

e
v
a
p
o
r
a
t
i
o
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35
4. Explain CVD method for the synthesis of nanotubes.
Chemical vapour deposition (CVD) method:

In chemical vapour deposition (CVD) method, carbon nanotubes (CNTs) are grown by
decomposing an organic gas over a substrate covered with metal catalyst nanoparticles.
A thermal CVD reactor is simple and inexpensive to construct. It consists of a quartz tube
enclosed in a furnace. The substrate material may be silica, mica, quartz, or alumina.
Thermal CVD can be used to grow SWCNT as well as MWCNT.
Substrate
Vacuum
Pump
C
2
H
2
N
2
Furnace
Quartz Tube
Thermal CVD uses acetylene (C
2
H
2
), ethylene (C
2
H
4
), or methane (CH
4
) gas as the carbon
precursors (feed stock or raw material) and Fe, Co, or Ni nanoparticles as the catalyst. The
growth temperature is typically in the range of 500900C. At these temperatures, the carbon
atoms dissolve in the metal nanoparticle catalysts, which finally become saturated. The
saturated carbon then precipitates to form carbon nanotubes at the surface of catalyst coated
substrates. The diameter of the tube is determined by the size of nanoparticles, which work
as catalyst.
5. Explain the basic principle of any two physical vapour deposition (PVD) techniques.
Definition: PVD is a technique by which a metal, ceramic or a compound is converted into
gaseous form and then deposited on the surface of a substrate.
(i) Sputtering: The source materials used in this process are generally an alloy, ceramic or
a compound. In sputtering technique, a high energy atom in its ionized form (usually Ar
+
)
is used to hit the surface atoms of the targeted source material. Then the knocked out
atoms in vapour form are deposited on the surface of the substrates to produce a uniform
coatings.
(ii) Laser ablation: Laser ablation has several advantages, such as high quality SWNT
production, diameter control and the production of new materials.The laser ablation
apparatus consists of a furnace, a quartz tube with a window, a graphite target
doped with small amount of catalytic metals like cobalt and nickel, flow systems for
argon gas to maintain constant pressures and flow rates and a watercooled copper
collector placed somewhat outside the furnace.
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1200
o
C, Furnace
Graphite Target
Nd:YAG Laser
Water cooled
Cu-Collector
Ar Gas
Quartz Tube
A laser beam of a pulsed (or continuous) Nd:YAG (Neodymium-doped-yttrium aluminium
garnet, Nd:Y
3
Al
5
O
12
) or CO
2
is introduced through the window by focusing onto the target
located in the center of the furnace. The furnace temperature is maintained at 1200

C.
Due to the emission of a pulsed (or continuous) laser, the target is vaporized in high
temperature. This leads to the formation of small carbon molecules and atoms. The
argon gas then sweeps the carbon atoms from the high temperature zone to the colder
copper collector where they condense to form carbon nanotubes. The argon flow rate
and pressure are typically 1cm.s
-1
and 500Torr respectively.
6. Write an account on the applications of nanomaterials.
1. Cabon nanotubes (CNTs) can be used as catalyst supports because they can provide the
advantages of large surface areas, high chemical stability and controlled surface
chemistry.
2. CNTs are used in the development of flat panel displays used in televisions and
computers
3. Silver nanoparticles have good antibacterial properties, and hence it is used in
refrigerators, air-conditioners, water purifiers etc.
4. ZnO, TiO
2
nanoparticles are used as sunscreen cosmetics because they absorb uv and
give protection to skin.
5. Silicon and gallium nitride nanowires are used in electron devices like field effect
transistors, in sensors, and detectors.
6. Nanoporous materials have very low thermal conductivity (presence of air in the pores
makes the porous material less conductive) and are used as thermal insulators.
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