UNIT- V

UNIT V: Engineering
Materials, Nanoscience &
Nanotechnology
CONTENTS:
Engineering Materials: Cement Materials and Manufacturing
Process. Lubricants – definition, Properties of lubricants –
Viscosity, Viscosity Index, Saponification Number, Flash Point
and Pour Point.
 CEMENT
 Cement is a material possessing adhesive and cohesive properties
and capable of bonding materials like stones, bricks, building blocks
etc.
 The principal content of cement for construction purpose are,
mixture of calcium silicate and calcium aluminate.
 It has the property of setting to a hard solid structure in several
hours with varying degrees of strength and is capable of bonding
with stones, bricks, etc.,
 CEMENTING MATERIALS
Lime:
Lime is a calcium-containing inorganic material in which carbonates, oxides and
hydroxides predominate.
Lime is calcium oxide or calcium hydroxide.
These materials are derived from rocks, typically lime stone or chalk, are composed
primarily of calcium carbonate.
They may be cut, crushed or pulverized and chemically altered.
"Burning" (calcination) converts them into the highly caustic material quicklime
(CaO) and, through subsequent addition of water, into the less caustic (but still
strongly alkaline) slaked lime or hydrated lime (Ca(OH)2), the process of which is
called slaking of lime.
Lime Cycle:
The process of converting limestone (CaCO3) to quicklime (CaO) by
heating, then to slaked lime (Ca(OH)2) by hydration, and then to calcium
carbonate (CaCO3) by carbonation is called lime cycle.

CaCO3 CaO +CO2

CaO + H2O Ca(OH)2
Ca(OH)2 + CO2 CaCO3 + H2O

The lime cycle for high-calcium lime

 Limestone is extracted from mines. Part of the extracted stone is calcinated at
about 1,000 °C (1,830 °F) to produce quicklime:
CaCO3 + heat → CaO + CO2
 Quicklime is hydrated, that is combined with water, called slaking so hydrated
lime is also known as slaked lime, and is produced according to the reaction:
CaO + H2O → Ca(OH)2
 Dry slaking is when quicklime is slaked with just enough water to hydrate the
quicklime but remain as a powder and is referred to as hydrated lime.
 In wet slaking enough water, but not too much, is added to hydrate the
quicklime and form a putty referred to as lime putty.
 Lime has an adhesive property with bricks and stones. It is used as binding
material and also used in whitewashing as wall coat to stick the white wash on
the wall.
Classification of Cement
There are five type of cements
(a)Natural Cement (b) Slag cement (c) Pozzolana cement
(d) High alumina cement (e) Portland cement
(a) Natural Cement: The cement obtained by high temperature heating (calcining) of
naturally occurring limestone with 20-40% clay followed by pulverization of the calcined
mass is called natural cement. During heating, silica and alumina present in the clay
reacts with lime to produce calcium silicate and calcium aluminates. Natural cement sets
quickly and has low strength.
(b) Slag cement: The cement obtained by mixing of blast furnace slag (mixture of Ca and
Al silicate) with hydrated lime followed by the addition of small quantity of Gypsum
(CaSO4 .2H2O) is called slag cement. Slag cement sets very slowly and has low strength.
(c) Pozzolana cement: The cement obtained by the mixing of pozzolana and
slaked lime (Ca(OH)2) is called pozzolana cement.
Pozzolana is the volcanic ash deposit obtained by the rapid cooling of Lava.
Pozzolana cement harden very slowly.

(d) High alumina cement: The cement prepared by the mixing of lime stone
(CaCO3) and bauxite [Al(OH)2 and AlO(OH)] at 1550-1600ᵒC is called high
alumina cement. High alumina cement has very quick strength developing
ability and high resistance to sea and sulphate waters.
(e) Portland cement:
 The cement produced by the mixing of calcarious matter (lime containing) and
orgillaceous matter (clay containing) with 2-3 % gypsum is called Portland cement.
 Portland cement is defined as a finely powdered mixture of calcium silicates and calcium
aluminates of varying compositions.
 This cement has quick setting and hardening property and was prepared in the year 1824
by Joseph Aspidin.
Chemical composition of portland cement
Composition of Portland cement should satisfy
(a) Ratio of the percentage of lime (CaO) to that of silica (SiO2), alumina (Al2O3) and iron

oxide(Fe2O3), should not be greater than 1.02 and not less than 0.66, when calculated by the
formula: CaO
2.8SiO2 + 1.2 Al2O3 + 0.65 Fe2O3
(b) Weight of insoluble residue should not exceed 2%
(c) Ratio percentage of alumina (Al2O3) to that of iron oxide (Fe2O3) should not be less
than 0.66
(d) Weight of magnesia should not be more than 6%
(e) Total sulphur contents, calculated as SO3 should not be more than 2.75%

(f) Total loss on ignition should not exceed 4%

• If too much lime (CaO) present – after concrete made it will expand and crack
• If too little lime – will have low strength
• If alumina is high – set quickly
• If silica is high – slow hardening, don’t get full strength
 CHEMICAL CONSTITUENTS OF PORTLAND CEMENT
NAME OF THE CONSTITUENT CHEMICAL FORMULA AVERAGE PERCENTAGE
TRICALCIUM SILICATE C 3S 45
DICALCIUM SILICATE C 2S 25
TRICALIUM ALUMINATE C 3A 1
TETRA CALCIUM ALUMINO FERRITE C4AF 9
CALCIUM OXIDE CaO 2
CALCIUM SULPHATE CaSO4 5
MAGNESIUM OXIDE MgO 4
Manufacturing of Portland cement

Raw materials
For the manufacturing of portland cement these five raw materials are
required.
(a) limestone (CaCO3) to quicklime (CaO)

(b) Silica(SiO2) and alumina(Al2O3)

(c) Iron(Fe2O3)
(d) Powdered coal or fuel oil.
(e) Gypsum (CaSO4 .2H2O)
The following steps are involved in For the manufacturing of portland Cement:
(i) Mixing of Raw materials
(ii) Burning

(iii) Grinding
(i) Mixing of Raw materials
The raw material mixing can be done using (i) dry process and (ii) wet process.
(i)Dry process: In this process, the raw materials are ground separately to fine powder in
the absence of water and then are mixed together in the desired proportions. To this
powder water is then added to get thick a paste and then cakes. These cakes are dried
and burnt in kilns.
(ii) Wet process: In this process, the calcarious materials (Lime) are crushed and
powdered. The argillaceous material (clay) is mixed with water and made into slurry.
The powdered lime and clay slurry are mixed in requisite proportions and then fed to a
rotary kiln. The slurry contains 38 – 40% water.
(ii) Burning
In this step, the mixed raw material obtained by the dry process or wet-process undergo
burning in the rotary kiln.
The rotary kiln is a steel cylinder of 90-120 m in length and 2.5-3.0 m diameter with
refractory bricks lined inside it.
The kiln is kept in a slightly inclined position.
The temperature at the upper part of the kiln is 400 °C, however the temperature at the
bottom increases to 1750 °C.
The raw material is passed in to the rotary kiln through the upper end.
The raw material moves from the upper part to the bottom part at a speed of 15km/hour.
The kiln is divided into several zones i.e (a) dehydration/drying zone, (b) calcination zone,
(c) clinkering zone and (d) cooling zone based on its role
While moving towards the lower end, following chemical reactions takes place in the different
zones of the kiln:
(a) Dehydration/Drying zone: It is the upper part of the kiln where the temperature is only
400 °C. In this zone the slurry gets dried (all the water is evaporated).
(b) Calcination Zone: It is the central part of kiln where the temperature is around 1000 °C .
In this zone, the lime stone present in the dry mix or slurry undergoes decomposition to
form CaO (quick lime) and CO2(carbon-dioxide)
CaCO3 + heat → CaO + CO2
(c) Clinkering Zone: This is the lower part of the rotary kiln, where the temperature is
between 1500° C and 1700 °C. In this part CaO (quick lime) and clay (SiO2 and Al2O3)

combine to form dicalcium silicates (2CaO.SiO2 (C2S)), tricalcium silicates (3CaO.SiO2

(C3S)) and calcium aluminates (3CaO.Al2O3 (C3A)). Clinker

2CaO + SiO2 → 2CaO.SiO2 (C2S)

3CaO + SiO2 → 3CaO.SiO2 (C3S)

3CaO + Al2O3 → 3CaO.Al2O3 (C3A)

4CaO + Al2O3 + Fe2O3 → 4CaO. Al2O3.Fe2O3 (C4AF)

(iii) Grinding:
In this step, the cooled clinkers together with 2-3% of gypsum are ground to fine
powder in ball mills. This fine powder mixture containing both clinkers and gypsum is
called portland cement.

Gypsum
Clinker CaSO4 .2H2O
The role of gypsum in portland cement
In the portland cement, gypsum acts as a retarding/inhibiting/delaying agent which helps in
the delay/retard of the cement from its early setting down.

Gypsum reacts with tricalcium aluminate (C3A) to produce calcium sulphoaluminate

which does not undergo rapid hydration, hence, it does not set down easily. So the presence
of gypsum in the cement helps in the delaying in the early/quick setting of the cement. By
adding gypsum at the time of cement preparation, the storage of cement can be done for long
3 CaO.Al2O3
time. + x CaSO4 .2H2O → 3 CaO.Al2O3 .x CaSO4 .2H2O
C3A Gypsum Tricalcium
sulphoaluminate
Where x=32

(iv) Packing:
The cement obtained in the powder form is fed into an automatic packing machine
and then cement packets are obtained.
SETTING AND HARDENING OF CEMENT
Portland cement on mixing with water is converted into
plastic mass called cement paste. Hydration forms gel and
crystalline products.
These particles bind and form rock like material. which sets to a
hard mass.

The process of solidifications consists of (i) setting and (ii) hardening.

(i)Setting :
Stiffening of the original plastic mass due to internal gel
formation is called setting.

(ii) Hardening:
Development of strength due to crystallization is called
hardening.
(a)The initial setting reaction is

3CaO. Al2O3 + 6H2O → 3CaO. Al2O3.6H2O + 880 kJ/Kg

(Hydrated tricalcium aluminate)

4CaO. Al2O3.Fe2O3 + 7H2O → 3CaO. Al2O3.6H2O +

(crystalline) (gel)
CaO.Fe2O3.H2O + 420kJ/Kg
(b) The initial setting and hardening of cement paste is also due to
the formation of tobermonite gel.

2(2CaO. SiO2) + 7H2O → 3CaO.2SiO2.6H2O + 250kJ/Kg

Tobermonite gel

(c) The final setting and hardening of cement past is due to the
formation to tobermonite gel, and crystallization of calcium
hydroxide.

2(3CaO. SiO2) + 6H2O → 3CaO.2SiO2.3H2O + 3Ca(OH)2 + 500kJ/Kg

Tobermonite (Crystalline)
SETTING AND HARDENING OF CEMENT

Cement and water paste

One day

Hydration of C3A and C4AF

Seven days

Gelation of C2S and crystallization of Ca(OH)2

28 days

Gelation of C2S and C3S crystallization of Ca(OH)2

 Lubricants
Introduction:
If we look at the solid surfaces, they appears to be smooth to our naked eye.
if we will see that smooth surface under a high power microscope, this smooth
surface will show many projections and cavities.
Similarly, the surface of the machinery part also looks smooth to the naked eye
But, they have projections and cavities.
So, when the machine will work, the projections and cavities will get interlocked.
Hence, machinery part movement will not occur smoothly.
As a result, there will be a friction between those projections and cavities
Due to the friction, the old projections breaks and deformities arise.
We need to avoid this problem and it can be avoided by using the lubricants
Lubricants
The substances used to decrease the friction between the moving parts of
machine in contact are known as Lubricants.
The friction decreasing process is known as Lubrication or lubricity.
 Functions of Lubricants
i) Lubricants reduces friction
ii) Lubricants reduces the damage of machine parts
iii) Lubricants reduces production of heat in machine parts.
iv) Lubricants reduce the wear and tear of machinery parts
v) Lubricants reduce the maintenance and running cost of machine.
vi) Lubricants act as the coolant
vii) Lubricants increases the efficiency of machine by reducing the loss of energy
viii)By using the lubricants, the relative motion of the moving parts of machine
becomes smooth and noise level of running machine reduces.
ix) Lubricants also act as the corrosion preventers.
x) Lubricants also act as a seal as in piston. Lubricant used between piston and
walls of the container (cylinder) prevents the leakage of hot gases produced
by the internal combustion i.e. it act as seal.
Extreme Pressure lubrication Mechanism:
When the moving/sliding surfaces are
under very high pressure and speed, a high local
temperature is attained under such conditions.
liquid lubricants fail to stick and may
decompose and even vaporize. To meet these
extreme pressure conditions, special additives are
added to minerals oils.
These are called extreme pressure
additives. These additives form more durable films
(capable of withstanding very high loads and high
temperatures) on metal surfaces.
Important additives are organic
compounds having active radicals or groups such
as chlorine (as in chlorinated esters), sulphur (as in
sulphurized oils) or phosphorus (as in tricresyl
phosphate).
These compounds react with metallic
surfaces, at existing high temperatures, to form
metallic chlorides, sulphides or phosphides.
Classification of Lubricants:
Lubricants are classified on the basis of their physical state, as follows;
(a) Liquid lubricants or Lubricating Oils,
(b) Semi-solid lubricants or Greases
(c) Solid lubricants.
(a)Liquid lubricants or Lubricating oils:
Lubricating oils also known as liquid lubricants and further
classified into four categories;
(i) Animal and Vegetables oils,
(ii) Mineral or Petroleum oils and
(iii) Blended oils
(iv) Synthetic oil
Liquid lubricants or Lubricating oils
(i) Animal and Vegetables oils:
 Animal oils are extracted from the crude fat of animals
 Vegetables oils such as cotton seed oil, olive oil and caster oil are extracted from the
cotton, olive and caster seeds.
 These oils have good oiliness and they can stick to the metal surfaces at high
temperature and high pressure.
 But they are costly, get oxidized easily resulting a gummy product and hydrolyze easily
on contact with moisture.
 So, they are rarely used for lubrication.
 They can be used as blending agents in petroleum based lubricants to get improved
oiliness.
(ii) Mineral or Petroleum oils:
The low molecular weight hydrocarbons with 12-50 carbon chain derived from crude oil is
known as mineral or petroleum oils.
These hydrocarbons can be widely used as lubricants, since they are cheap, available in
large excess and stable under the operational condition.
However, these hydrocarbons (mineral or petroleum oil) have a very low oiliness

(iii) Blended oils:

To increase the oiliness of the mineral or petroleum oils, addition of proper additives are
essential
These additive added lubricating oils are called blended oils.
To get blended oils, generally oleic acid, stearic acid, palmetic acid, coconut oil, castor oil,
etc are added to the mineral or petroleum oils.
 The addition of those high molecular weight compounds increases the oiliness of mineral
oil.
iv) Synthetic oils:
Synthetic oils are the liquid lubricant oils made artificially.
They can work under harsh conditions where petroleum oil lubricants fail to work
effectively.
They are used in military jets engines, submarines, rocket motors, and atomic energy plants.
They possess high thermal stability, high flash points, high viscosity index etc.
Characteristics of good lubricating oil
A good lubricating oil should have

High boiling point

Adequate viscosity

Low Freezing point

High oxidation resistance

Good thermal stability

Non corrosive properties

(b) Semi-solid Lubricants or Grease:
A semi-solid lubricant is obtained by mixing a lubricating oil and a thickening agent.
In the semi-solid lubricant the principal component is lubricating oil. They can be either
petroleum oil or synthetic hydrocarbon of low to high viscosity.
For thickening, two types of thickening agents such as soap based or non-soap based
materials are used.
Soap-based thickening agents are the soaps of Li, Na, Ca, Ba, Al and non-soap based
thickening agents include carbon black, silica gel, clays, polyureas and other synthetic
polymers, etc.
The example of semi-solid lubricant is grease.
Grease can support much heavier load at lower speed.
But the internal resistance of grease is much higher than the lubricating oils, so it is better to
use oil instead of grease.
Grease can’t relieve heat effectively from the bearings, so it works at relatively low
temperature.
(c) Solid lubricants:
The lubricants which are used in the dry powder form is called solid lubricants.
The solid lubricants are graphite, molybdenum disulphide (MoS2), tungsten disulphide

(WS2), and zinc oxide (ZnO), soapstone (talc) and mica.

They can be applied in continuously operating situation and san survive up to 650° C.
They can also be used as additives to mineral oils and greases to increase the load carrying
capacity of the lubricant.
Molybdenum Disulphide (MoS2):
MoS2 has a sandwich-like structure
It is stable up to a temperature of 650° C.
 In MoS2, molybdenum (Mo) atoms remain in between the two layers of sulphur (S) atoms.
Poor inter layer attraction helps these layers to slide over one another easily.
Hence , MoS2 acts as a solid lubricant
Graphite:
Graphite has a flat plate like structure and the layers of
graphite sheets are arranged one above the other in
parallel way.
Graphite sheets are held together by weak van der
Waal’s forces.
These parallel layers which can easily slide one over other
make graphite an effective lubricant.
Graphite is a most widely used solid lubricant
It can be used either in the powdered form or in
suspension.
Graphite suspension with oil is called as oildag
Graphite suspension with water is called aquadag
It is soapy to touch; non-inflammable and stable up to a
temperature of 375° C.
 Properties of Lubricants:
Viscosity:
The resistance to flow of liquid is known as viscosity.
The unit of viscosity is poise.
Viscosity of the lubricating oil is its main characteristics which decides whether the
lubricating oil is fit for application or not.
If the viscosity of the oil is too low, a liquid oil film can’t be maintained between
two moving surfaces.
If the viscosity of the oil is too high, excess friction will result.
So to be good a lubricating oil the viscosity of the oil should neither be too low nor
too high. It should be medium.
Effect of temperature on viscosity:
Viscosity of the liquids decreases with the increase in temperature, so lubricating oil
becomes less viscous as the operating temperature is increased.
Viscosity of the good lubricating oil should not change much with the change in
temperature, so that it can be used continuously under various temperature
conditions.
Viscosity Index
The measurement in the rate at which the viscosity of lubricating oil changes with
temperature known as Viscosity Index (V. I).
If the viscosity of lubricating oil decreases rapidly with the increase in temperature,
it has a low viscosity index.
If the viscosity of lubricating oil is only slightly affected with the increase in
temperature its has high viscosity index.
It is used to characterize viscosity changes with relation to temperature in
lubricating oil.
Viscosity index of the oil is measured with the help of two types of standard oils
namely Pennsylvanian oil and Gulf oils having VI 100 and VI 0.

VI
Where VI = Viscosity index of the oil to be measured
U = Viscosity of oil under test at 100°F
L = Viscosity of gulf oil at 100°F and also having same viscosity as the
oil under test at 210°F
H = Viscosity of Pennsylvanian oil at 100°F and also having the same
viscosity as the oil under test at 210°F.
Flash point and Fire point lubricant oil:
Flash point is the lowest temperature at which the lubricant oil produces vapours
when it is ignited for a moment by bringing a tiny flame near to it.
Fire point is the lowest temperature at which the vapours of the lubricant oil burn
continuously for at least five seconds, when a tiny flame is brought near it. In most
cases, the fire points are 5° C to 40° C higher than the flash points.
The flash and fire point do not have any bearing with lubricating property of the oil,
but these are important when oil is exposed to high temperature service.
A good lubricant should have flash point at least above the temperature at which
it is to be used.
This safeguards against risk of fire, during the use of lubricant.
 Cloud Point and Pour Point
The temperature at which the lubricant oil becomes cloudy or hazy in appearance
during its slow cooling, is called its cloud point.
The temperature at which the lubricant oil cease to flow or pour during its slow
cooling, is called its pour point.
Cloud and pour point of lubricant oil indicate its suitability to be used in the cold
conditions.
Lubricant oil used in a machine working at low temperatures should possess low
pour point; otherwise solidification of lubricant oil will cause jamming of machine.
It has been found that presence of waxes in the lubricant oil raise pour point.