Unit V. Engg. Mateials

Unit V : Engineering Materials and Nano Science
Contents
Cementing materials - Lime, Cement, Gypsum, Refractories, Abrasives, Insulators, Liquid crystals
– classification and applications, Lubricants – definition, classification, Extreme pressure
lubrication mechanism, Important properties: viscosity, viscosity index, saponification number,
flash point and pour point.
Introduction to Nano science and nanomaterials, synthesis: sol-gel and hydrothermal methods,
characterization by powder XRD (Scherrers equation) and photo catalytic application – dye
degradation
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.
 On 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.
 Limestone is extracted from quarries or 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. So it is used as binding material. It is
also used in whitewashing as wall coat to stick the white wash on the wall.
CEMENT
 Cement is a material possessing adhesive and cohesive properties and capable of bonding
materials like stones, bricks, building blocks etc.
Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
 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.,
Classification of cement
(a) Natural Cement: This is obtained by calcining naturally occurring limestone containing 20-40%
of clay at a high temperature and subsequently pulverizing the calcined mass.
During heating, silica and alumina present in the clay reacts with lime to produce calcium
silicate and calcium aluminates. Natural cement is quick setting and possesses low strength.
(b) Slag cement: This is produced by mixing blast furnace slag (mixture of Ca and Al silicate) and
hydrated lime and grinding with small quantity of gypsum. Slag cement sets very slowly and
has low strength.
(c) Pozzolana cement: This is obtained by mixing Pozzolana and slaked lime (Ca(OH)2).
Pozzolana is deposits of volcanic ash obtained by rapid cooling of Lava.
Lava – molten mixture of silicates of calcium, iron and aluminium.
Pozzolana cements harden very slowly.
At present used with Portland cement.
(d) High alumina cement: This is mainly a calcium aluminate cement and is prepared by mixing
lime stone and bauxite [Al(OH)2 and AlO(OH)] at 1550-1600 C.
High alumina cement has rapid rate of development of strength and has superior resistance
to sea and sulphate waters.
(e) Portland cement: This is produced by mixing of calcarious matter (lime containing) and
orgillaceous matter (clay containing) and powdered with the addition of 2-3% gypsum.
Portland cement was discovered by Joseph Aspidin of England in the year 1824.
This has quick setting and hardening property when made into a paste with sand and water.
It resembled in colour and hardness to Portland stone, so this cement is called as Portland
cement.
CHEMICAL COMPOSITION OF PORTLAND CEMENT:
Portland cement is defined as a finely powdered mixture of calcium silicates and calcium
aluminates of varying compositions.
According to I.S. 269-1975, composition of Portland cement should satisfy
a) Ratio of the percentage of lime (CaO) to that of silica (SiO2), alumina (Al2O3) and iron
oxide when calculated by the formula:
b) It should not be greater than 1.02 and not less than 0.66.
c) Weight of insoluble residue should not exceed 2%

d) Ratio percentage of alumina (Al2O3) to that of iron oxide (Fe2O3) should not be less
than 0.66
e) Weight of magnesia should not be more than 6%
f) Total sulphur contents, calculated as SO3 should not be more than 2.75%
g) Total loss on ignition should not exceed 4%
If too much lime 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 Average %

formula
Tricalcium silicate C3S 45
Dicalcium silicate C2S 25
Tricalium aluminate C3A 1
Tetra calcium alumino ferrite C4AF 9
Calcium oxide CaO 2
Calcium sulphate CaSO4 5
Magnesium oxide MgO 4
MANUFACTURE OF PORTLAND CEMENT
RAW MATERIALS:
(a) Calcareous materials rich in lime such as lime stone, chalk and marble
(b) Argillaceous materials rich in silica and alumina such as clay, shale, slate etc.
(c) Powdered coal or fuel oil.
(d) Gypsum (CaSO4 .2H2O)
The following steps are involved in manufacture of Portland cement.
(i) Mixing of Raw materials
(ii) Burning
(iii) Grinding
(iv) Packing
(i) Mixing of raw materials
This can be done either by dry process or wet process.
In dry process, the raw materials are crushed in gyratory crushers and ball mills, and then burnt in dry
condition in a rotary kiln.
In wet process, the calcareous 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 contain 38 – 40% water.
(ii) Burning
It is done in rotary kiln which is a steel cylinder, about 2.5 to 3.0m diameter and 90 to 120m length
and line inside with refractory bricks.
The kiln is laid in slightly incline position.
The upper part of kiln temperature is 400° C but the temperature gradually increases up to 1750° C at
the bottom.
The raw slurry from the wet process, or the dry powder from the dry process is passed in to the rotary
kiln through the upper end.
Sample move from top to lower end in the speed of 15m/hour.
While moving towards lowed end, following chemical reactions takes place
(a) Drying zone: The upper part of the kiln where the temperature is only 400 °C and 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 . Lime
stone of dry mix or slurry undergo decomposition to form quick lime and carbon dioxide
CaCO3 + heat → CaO + CO2
(c) Clinkering Zone: In the lower part of the rotary kiln, the temperature is between 1500° C and
1700 °C. Here lime and clay combine to form calcium aluminates and calcium silicates.
2CaO + SiO2 → 2CaO.SiO2 (C2S)
3CaO + SiO2 → 3CaO. SiO2 (C3S)
3CaO + Al2O3 → 3CaO. Al2O3 (C3A)
4CaO + Al2O3 + Fe2O3 → 4CaO. Al2O3.Fe2O3 (C4AF)
The aluminates and silicates of calcium fuse together to form hard grayish stones called clinkers.
(iii) Grinding:
The cooled clinkers are ground to fine powder in ball mills

together with 2-3% of gypsum. The mixture of clinkers
and gypsum powder is called cement. Here, gypsum acts
as a retarding agent for early setting of cement.
The role of gypsum in cement
The presence of gypsum in the cement helps to retard the speed of the initial set.
This is due to the formation of calcium sulphoaluminate (by the reaction between gypsum and C3A)
which does not show any tendency to rapid hydration.
(v) Packing:
The ground cement fed in to automatic packing machines then packed.
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 + CaO.Fe2O3.H2O + 420kJ/Kg
(crystalline) (gel)
(b) The initial setting and hardening of cement past is also due to the formation to 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
REFRACTORIES
 Refractories are inorganic materials and are used as construction materials. It is resistant to
melting or fusion.
 An inorganic materials that can withstand very high temperatures without softening or
deformation in shape is called refractory.
 These are chemically inert, resistant towards corrosion, abrasion etc. by hot gases, molten
gases etc.
 Refractories are used for the construction of lining in furnaces retorts, kilns, crucibles, etc.
which are employed in metallurgical and industrial purposes.
 Refractories are heat-resistant materials that constitute the linings for high-temperature
furnaces and reactors and other processing units. In addition to being resistant to thermal
stress and other physical phenomena induced by heat.
 Refractories must also withstand physical wear and corrosion by chemical agents
Characteristics of a good refractory materials
A good refractory material should
(i) Be infusible at the temperature to which it is to be exposed
(ii) Be chemically inert by actions of corrosive gases, molten metals, slages etc. produce in
furnaces
(iii) Be resistant to the abrasing action of flue gases, flames, slages, etc.
(iv) Not crack and suffer loss in size at operating temperatures
(v) Be able to withstand the overlying load at operating conditions
(vi) Expand and contact uniformly at high and low temperatures.
Classification of Refractories
PROPERTIES OF REFRACTORIES
Thermal expansion:
The refractor tends to expand when temperature increases and contract when temperature
decreases. Thermal expansion affects all dimensions of body. So a good refractory should have less
thermal expansion.
Abrasion resistance:
A good refractory should resist the abrasion action of flue gases, flames, slages etc.
Electrical conductivity:
Generally, Refractories are poor conductors of electricity (Except graphite). So, Refractories should
have low electrical conductivity.
Causes for the failure of refractories
The efficiency of the refractory product mainly depends on its constituent, processing and final curing
I. The most common cause for failure of refractory is chemical reaction with the environment
in which it is operating. For example and acidic refractory should not be used in furnaces using
basic fluxes, slag etc. and vice versa.
II. The porosity of refractory plays an important role in the chemical reaction. The more porous
it is, the greater will be the depth to which the slag will penetrate and destroy the refractory.
III. The deposition of carbon from carbon monoxide in fire clay refractories in a blast furnace is
an important cause of its failure.
IV. As the temperature increases the rate of chemical reaction gradually increases. Sometimes,
rise in temperature beyond the safe limit quickly brings about the destruction of the
refractory.
V. The other important cause is thermal spalling and expansion
Liquid Crystals
Liquid crystals are substances that exhibit a phase of matter that has properties between those of a
conventional liquid, and those of a solid crystal.
Classification of Liquid crystals

LIQUID CRYSTALS
Liquid crystals are basically classified in to two.
I. THERMOTROPIC LC and II. LYOTROPIC LC I. THERMOTROPIC LC II. LYOTROPIC LC
I. THERMOTROPIC LIQUID CRYSTALS

i. NEMATIC LC
Liquid crystals are said to be thermotropic if the liquid
crystalline properties depend on the temperature. ii. CHOLESTERIC LC
iii. SMECTIC LC
i. Nematic liquid crystals
One of the most common LC phases is the nematic, where the molecules
(mesogens) have no positional order, but they have long-range
orientational order.
Most nematics are uniaxial: they have one axis that is longer and
preferred, with the other two being equivalent (can be approximated as
cylinders)
In Greek ‘nematic’ means thread. And hence the thread like structure of
the nematic crystals.
Nematics have fluidity similar to that of ordinary (isotropic) liquids but

they can be easily aligned by an external magnetic or electric field. An
aligned nematic has the optical properties of a uniaxial crystal and this makes them extremely useful
in liquid crystal displays (LCD).
ii. Smectic liquid crystals
In the case of Smectic type LC, the mesogens have both positional order and
orientation order. The smectic phases, which are found at lower temperatures
than the nematic, form well-defined layers that can slide over one another like
soap.
iii. Cholesteric liquid crystals
The cholesteric phase can be defined as a special type of nematic LC in which

the thin layers of the parallel mesogens have their longitudinal axes rotated
in adjacent layers at certain angle.
II. LYOTROPIC LIQUID CRYSTALS
Liquid crystals which are prepared by mixing two or more

substances, of which one is a polar molecule, are known as
lyotropic liquid crystals.
Eg. Soap in water.
Applications of Liquid Crystals
1. Liquid Crystal Displays: Used in display devices (LCDs) such as Laptops, watches, calculators,
clocks, etc.
2. Liquid Crystal Thermometers: Chiral nematic (cholesteric) liquid crystals reflect light and the
color reflected also is dependent upon temperature.
3. Optical Imaging: An application of liquid crystals that is only now being explored is optical
imaging and recording.
4. Some of the liquid crystals are used in hydraulic break/clutch system due to their high
viscosity values.
INSULATORS
The substances which are capable of retarding or prohibiting the flow of heat or electricity or sound
through them are known as insulators or insulating materials.
If insulation is main function, they are called insulators.
If charge storage is main function, they are called dielectrics.
CLASSIFICATION:
Insulators can be broadly classified into three categories etc.
Characteristics of Insulators
A good insulating material should possess the following characteristics properties:
1. Resistivity: It is defined as the resistance offered by a unit cube of the material or it is

reciprocal of conductivity. A good insulators should have low conductivity or high resistivity.
Insulators have resistivity ranging from 109 to 1020 ohm-cm at RT.
2. Dielectric constant: It is the quantitative measure of the ability of a material to store electric
charge in presence of applied electric field. Dielectric constant expresses as the ration of the
capacitance of a capacitor filled with dielectric materials to the capacitance of same capacitor
under vacuum. Dielectric constant should be low for a good insulator.
3. Dielectric polarization: Charge separation of dielectrics under the electric field is called
dielectric polarization. If ‘Q’ is the charge collected in the presence of an applied voltage V,
Then the capacitance of materials is C=Q/V.
4. Dielectric loss: This is caused mainly by internal dipole fraction and by leakage of current
through the material. Dielectric losses should be minimum for an ideal insulator.
5. Thermal expansion and contraction: A good Insulating material possesses least thermal
expansion and contraction, which leads to gaps in the insulator
6. Porosity: Porosity of insulating materials causes increase of moisture holding capacity leading
to adverse an effect on the electrical properties. Hence, dielectrics of high porosity are not
used.
7. External Chemical effects: insulating materials should be chemically inert towards oils, acids,
solvents and alkalis.
8. Dielectric strength: The ability to resist puncture or rupture of an insulating materials with
the applied electric field is called dielectric strength, expressed in volts/mm. Dielectric
strength decreases with increase of thickness of material, humidity and temperature. In the
case of liquid insulators, it increases with increase of viscosity. For ideal insulating material, it
should have high dielectric strength.
9. Not prone to chemical change itself: Chemical alteration may take place by some material
during its use. But such changes should not deteriorate the properties of insulating materials.
Some Insulating materials and their applications:
(a) Simple Gases: Gases like air and nitrogen are considered as insulating materials.
(i) Air it is considered as an important dielectric gas which provides insulation between the
overhead transmission lines without any cost and maintenance charge.
(ii) Nitrogen When chemical resistance or inert medium is needed, nitrogen is a very important
gas in place of air since it causes oxidation. This is used in transformers. High pressure
nitrogen is used as dielectric in electrical capacitors.
(iii) Electronegative gases They have high dielectric strengths than normal gases such as air and
nitrogen. For example, SF6 is 2.35 times and CCl4 is 6.33 times than that of air. Further, these
are non-explosive and non-inflammable. SF6 is used in electrical devices like capacitors and
cables.
(b) Liquid Insulating Materials: These are used mainly for pure dielectric purpose to eliminate air
or other gases particularly as an insulating cum heat transfer medium. Some of the liquid
insulating materials are mentioned.
(i) Mineral oils: They have a better insulating property which is greatly influenced by the
presence of non-hydrocarbon compound nitrogen, oxygen, sulphur, etc. They have low
dielectric constant (~ 2.5) and are used in the transformers.
(ii) Askarels: Askarels are non-inflammable and synthetic insulating liquids which do not
decompose under the influence of electric arc. They are used as transformer fluids. Some of
the examples are chlorinated diphenyl, pentachloro diphenyl and trichloro benzene.
(iii) Fluorinated fluids: They are

non-inflammable, non-
explosive and have very
high chemical stability.
These are better substitute
of mineral and silicone
fluids for heat transfer
from the winding and
magnetic circuits. They are
used in small-sized electric
and radio devices,
electronic transformers,
etc.
(c) Solid insulating materials: Most of the non-metals such as mica, paper, asbestos, polymers
and silk are considered as solid insulators. All the materials are capable of retaining their
insulating properties up to a definite temperature called limiting temperature.
THERMAL INSULATORS
The substances having extremely low thermal conductivities are known as thermal insulators and they
are used to prevent the loss of heat which takes place by conduction, convection or radiation.
Uses:
(a) When the equipments or plants like refrigerators, cold storages etc. are operated at low
temperatures, then thermal insulators prevent flow of heat from the outside environment to
them.
(b) Ovens, boilers, steam carrying pipers etc. need thermal insulators because they prevent loss
of heat to the outer environment.
Characteristics: The important characteristics of a good thermal insulator are
(a) Its thermal conductivity is extremely

low
(b) It should be fire proof
(c) It should resist moisture absorption

and hence it should be water proof
(d) (d) It should have low density
(e) (e) At the working temperature, it

should be physically and mechanically
stable
(f) (f) It should be chemically stable to surrounding conditions of high temperature.
(g) (g) During the use, it should be odourless as far as possible
(h) (h) It should be easily available at economical price.
Abrasives
Abrasives are the substances characterized by their hardness, and which are used to wear down softer
surfaces by cutting, grinding or polishing.
Hardness of an abrasive is most important quality and is measured roughly on Moh’s or Vickers scale.
Natural Abrasives:
1. Diamond: which is crystallized carbon ranks first in hardness, since it can cut into the surface f any
other substance; whereas only another diamond can scratch a diamond. IT is chemically inactive and
not attacked by acids, alkalis or fused potassium chlorate. Diamonds that are off-colour or are
otherwise faulty are borts. Carbonado and borts are used in drill points and in operations where great
hardness is required.
2. Corundum: Corundum is a crystalline form of aluminium oxide (Al2O3) with traces of iron, titanium
and chromium. It is a rock-forming mineral. It is one of the naturally transparent materials, but can
have different colours when impurities are present. Transparent specimens are used as gems, called
ruby if red and padparadscha if pink-orange. All other colours are called sapphire, e.g., "green
sapphire" for a green specimen.
It finds use as abrasives for grinding glasses, gems, lenses, metals and metal cutting.
3. Emery (or corundite): Emery is a dark granular rock used to make abrasive powder. Emery is named
after Cape Emery, Island of Naxos, where it was first discovered. It largely consists of the mineral
corundum (aluminium oxide), mixed with other species such as the iron-bearing spinels, hercynite,
and magnetite, and also rutile (titania). Industrial emery may contain a variety of other minerals and
synthetic compounds such as magnesia, mullite, and silica.
4. Garnet: Garnet is the name used for a large group of rock-forming minerals. These minerals share
a common crystal structure and a generalized chemical composition of A3B2(SiO4)3. In that composition
A can be Ca, Mg, Fe2+ or Mn2+, and B can be Al, Fe3+, Mn3+, V3+ or Cr3+.
5. Quartz: Quartz is the second most abundant mineral in the Earth's continental crust, after feldspar.
It is made up of a continuous framework of SiO4 silicon–oxygen tetrahedra, with each oxygen being
shared between two tetrahedra, giving an overall formula SiO2.
Artificial Abrasives
Silicon Carbide (SiC): Silicon Carbide is the only chemical compound of carbon and silicon. It was
originally produced by a high temperature electro-chemical reaction of sand and carbon. Silicon
carbide is an excellent abrasive and has been produced and made into grinding wheels and other
abrasive products for over one hundred years.
SiO2 + 3C→ SiC + 2CO↑
It is very hard (Moh’s scale = 9.3). Chemically unreactive, can withstand the action of high temperature
without damage, but is not tough and is somewhat brittle. It is mainly used in cutting wheels, abrasive
papers, and clothes.
Alundum: Al2O3 is prepared by subjecting a mixture of calcined bauxite, coke and iron to high
temperature about 4000C in an electric arc furnace. The impurities are settle down at the bottom of
the furnace and after solidification, the hard crystalline alumina is separated crushed and graded.
It is used in abrasive paper and cloth, it is used for finishing woodworks.
Boron carbide or norbide (B4C): It is inert and one of the hardest (about 9 Moh’s) of all artificial
abrasives, and made by heating boron oxide with coke in an electric furnace to approximately 2700°C.
2B2O3 + 7C → B4C + 6CO
It is used on hard materials for making grinding dyes, for cutting and sharpening hard high-speed tools.
LUBRICANTS
The substances which are used to decrease the force of friction between the moving parts of machine
in contact are known as Lubricants
The process of decreasing the force of friction between the moving parts of machine in contact is
known as Lubrication.
Introduction:
When one of machinery moves over another surface, resistance to relative motion of the surfaces
arises.
When we look at the solid surface it appears smooth to naked eye, but this smooth surface shows
irregularities of projections and cavities when viewed under high power microscope.
Projections and cavities in surfaces
When one such surface is placed over another, its projections fall into the cavities of the other and get
interlocked.
Due to this, there is resistance to the relative motion of the surfaces. This is called the frictional forces
or frictional resistance of friction.
In due course of motion, the old projections get broken and deformities arise.
Friction
Friction may be defined as the opposing force that is set up between the surface of contact, when one
body moves over the surface of another body.
Functions of Lubricants
i) Lubricants avoid the damage of the moving parts of machines by minimizing the production
of heat.
ii) Lubricants reduce the wear and tear of machinery by keeping the moving parts of machines
apart.
iii) Lubricants reduce the maintenance and running cost of machine.
iv) Lubricants act as the coolant because it reduces the production heat between the moving
parts of machine in contact.
v) Lubricants increases the efficiency of machine by reducing the loss of energy
vi) By using the lubricants, the relative motion of the moving parts of machine becomes smooth
and noise level of running machine reduces.
vii) Lubricants also act as the corrosion preventers.
viii) 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 mineral 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 and
(c) Solid lubricants.
(a) Liquid lubricants or Lubricating oils:
Lubricating oils also known as liquid lubricants and further classified into three categories;
(i) Animal and Vegetables oils,
(ii) Mineral or Petroleum oils and
(iii) blended oils.
(i) Animal and Vegetables oils:
 Animal oils are extracted from the crude fat and vegetable oils such as cotton seed oil and
caster oils extracted from seeds.
 These oils possess good oiliness and hence they can stick on metal surfaces effectively even
under elevated temperatures and heavy loads.
 But they suffer from the disadvantages that they are costly, undergo easy oxidation to give
gummy products and hydrolyze easily on contact with moist air or water.
 Hence they are rarely used for lubrication. But they are still used as blending agents in
petroleum based lubricants to get improved oiliness.
(ii) Mineral or Petroleum oils:
 These are basically lower molecular weight hydrocarbons with about 12 to 50 carbon atoms.
 As they are cheap, available in abundance and stable under service conditions, hence they are
widely used.
 But the oiliness of mineral oils is less, so the addition of higher molecular weight compounds
like oleic acid and stearic acid increases the oiliness of mineral oil.
(iii) Blended oils:
 No single oil possesses all the properties required for a good lubricant and hence addition of
proper additives is essential to make them perform well. Such additives added lubricating oils are
called blended oils.
 Examples: The addition of higher molecular weight compounds like oleic acid, stearic acid,
palmetic acid, etc or vegetables oil like coconut oil, castor oil, etc increases the oiliness of mineral
oil.
(iii) Synthetic oils:
 Synthetic lubricating oils are used under very severe conditions where petroleum 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.
Characteristic of good lubricating oils:
(1) High boiling point
(2) Low freezing point,
(3) Adequate viscosity for proper functioning in service,
(4) High resistance to oxidation and heat,
(5) Non-corrosive properties and
(6) Stability to decomposition at the operating temperatures.
(b) Semi-solid Lubricants or Grease:
 A semi-solid lubricant obtained by combining lubricating oil with thickening agents is termed as
grease.
 Lubricating oil is the principal component and it can be either petroleum oil or a synthetic
hydrocarbon of low to high viscosity.
 The thickeners consist primarily of special soaps of Li, Na, Ca, Ba, Al, etc. Non-soap thickeners
include carbon black, silica gel, polyureas and other synthetic polymers, clays, etc.
 Grease can support much heavier load at lower speed.
 Internal resistance of grease is much higher than that of lubricating oils; therefore it is better to
use oil instead of grease.
 Compared to lubricating oils, grease cannot effectively dissipate heat from the bearings, so work
at relatively lower temp.
(c) Solid lubricants:
They are preferred where
(1) the operating conditions are such that a lubricating film cannot be secured by the use of
lubricating oils or grease
(2) Contamination (by the entry of dust particles) of lubricating oils or grease is unacceptable
(3) The operating temperature or load is too high, even for grease to remain in position and
(4) Combustible lubricants must be avoided.
They are used either in the dry powder form or with binders to make them stick firmly to the metal
surfaces while in use.
They are available as dispersions in non-volatile carriers like soaps, fats, waxes, etc and as soft metal
films.
 The most common solid lubricants are graphite, molybdenum disulphide, tungsten disulphide
and zinc oxide.
 They can withstand temperature up to 650° C and can be applied in continuously operating
situations.
Molybdenum Disulphide:
 It has a sandwich- like structure with a layer of

molybdenum atoms in between two layers of
sulphur atoms.
 Poor interlaminar attraction helps these layers to
slide over one another easily.
 It is stable upto a temperature of 400° C.
 They are also used as additives to mineral oils and
greases in order to increase the load carrying
capacity of the lubricant.
 Other solid lubricants in use are soapstone (talc)
and mica.
Graphite:
 It is the most widely used of all the solid lubricants and can be used
either in the powdered form or in suspension.
 It is soapy to touch; non-inflammable and stable upto a
temperature of 375° C.
 Graphite has a flat plate like structure and the layers of gra phite
sheets are arranged one above the other and held together by
weak van der Waal’s forces.
 These parallel layers which can easily slide one over other make graphite an effective lubricant.
 Also the layer of graphite has a tendency to absorb oil and to be wetted of it.
Properties of Lubricants:
Viscosity:
 It is the property of liquid by virtue of which it offers resistance to its own flow or
the resistance to flow of liquid is known as viscosity.
 The unit of viscosity is poise.
 It is the most important single property of any lubricating oil, because it is the main
determinant of the operating characteristics of the lubricant.
 If the viscosity of the oil is too low, a liquid oil film cannot be maintained between two
moving/sliding surfaces.
 On the other hand, if the viscosity of the oil is too high, excessive friction will result.
Effect of temperature on viscosity:
 Viscosity of liquids decreases with increasing, temperature and, consequently, the lubricating oil
becomes thinner as the operating temperature increases.
 Hence, viscosity of good lubricating oil should not change much with change in temperature, so
that it can be used continuously, under varying conditions of temperature.
 The rate at which the viscosity of lubricating oil changes with temperature is measured by an
arbitrary scale, known as Viscosity Index (V. I).
 If the viscosity of lubricating oil falls rapidly as the temperature is raised, it has a low viscosity
index.
 On the other hand, if the viscosity of lubricating oil is only slightly affected on raising the
temperature, its viscosity index is high.
The viscosity index: The viscosity index of test oil is measure with the help of two types of standard
oils namely Pennsylvanian oil and Gulf oils having VI 100 and 0 respectively.
Where
VI = viscosity index of the oil under test
L= viscosity of gulf oil at 100°F and also having same viscosity as the oil under test at 210°F
U= Viscosity of oil under test at 100°F
H= Viscosity of Pennsylvanian oil at 100°F having VI, 100 and also having the same viscosity as the oil
under test at 210°F
Flash Point and Fire Point:
 Flash point is the lowest temperature at which the lubricant oil gives off enough vapours that
ignite for a moment, when a tiny flame is brought near it;
 while 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 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 if fire, during the use of lubricant.
Cloud Point and Pour Point:
 When the lubricant oil is cooled slowly, the temperature at which it becomes cloudy or hazy in
appearance, is called its cloud point; while the temperature at which the lubricant oil cease to
flow or pour, is called its pour point.
 Cloud and pour points indicate the suitability of lubricant oil in 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.
Saponification Number
 The Saponification value of an oil is defined as the number of milligrams of potassium hydroxide
required to saponify one gram of the oil.
 This is usually determined by refluxing a known quantity of the oil with a known excess of standard
KOH solution and determining the alkali consumed by titrating the un-reacted alkali.
 Animals and vegetable oils undergo Saponification but mineral oils do not.
 Each of the fixed oil has got its own specific Saponification number, any deviation from this value
in a given sample indicates the probability and extent of adulteration.
Nanotechnology and Nanoscience

What are nanomaterials?
Nanoscale materials are defined as a set of substances where at least one dimension is less than
approximately 100 nanometers. A nanometer is one millionth of a millimeter - approximately 100,000
times smaller than the diameter of a human hair. Nanomaterials are of interest because at this scale
unique optical, magnetic, electrical, and other properties emerge. These emergent properties have
the potential for great impacts in electronics, medicine , and other fields.
Nanotechnology:
Nanotechnology is a technology, which Design, production, characterization, and applications of

Nanostructured materials and also, fundamental understanding of physical properties and
phenomena.
Nanoscience:
Study on fundamental relationships between physical properties and material dimensions on the
nanometer scale.
Classification of Nanostructured Materials
• Nanoparticles (including quantum dots) exhibit quantum size effects. Those are, Nanorods and
nanowires, Thin films, Bulk materials made of nanoscale, building blocks or consisting of
nanoscale, nanostructures.
• According to Siegel, Nanostructured materials are classified as Zero dimensional, one dimensional,
two dimensional, three dimensional nanostructures.
• Nanomaterials are materials which are characterized by an ultra-fine grain size (< 50 nm) or by a
dimensionality limited to 50 nm. Nanomaterials can be created with various modulation
dimensionalities as defined by Richard W. Siegel: zero (atomic clusters, filaments and cluster
assemblies), one (multilayers), two (ultrafine-grained overlayers or buried layers), and three
(Nano phase materials consisting of equiaxed nanometer sized grains) as shown in the above
figure.
Why “nano” play an important role in science and technology?
1. Nanomaterials have superior properties than the bulk substances in

I. Mechanical strength IV. Electrical conductivity
II. Thermal stability V. Magnetic properties
III. Catalytic activity VI. Optical properties
2. A wide range of applications such are
I. Quantum electronics, VI. adsorbents,

II. nonlinear optics, VII. catalysis,
III. photonics, VIII. solar cells,
IV. sensing, IX. Superplastic ceramics…
V. information storage and
processing,
3. Source for new fields such are
Nanofabrication, nanodevices, nanobiology and nanocatalysis.
Why are nanomaterials important?

These materials have created a high interest in recent years by virtue of their unusual mechanical,
electrical, optical and magnetic properties. Some examples are given below:
(i) Nanophase ceramics are of particular interest because they are more ductile at elevated
temperatures as compared to the coarse-grained ceramics.
(ii) Nanostructured semiconductors are known to show various non-linear optical properties.
Semiconductor quantum-particles also show quantum confinement effects which may lead to special
properties, like the luminescence in silicon powders and silicon germanium quantum dots as infrared
optoelectronic devices. Nanostructured semiconductors are used as window layers in solar cells.
(iii) Nanosized metallic powders have been used for the production of gas tight materials, dense parts
and porous coatings. Cold welding properties combined with the ductility make them suitable for
metal-metal bonding especially in the electronic industry.
(iv) Single nanosized magnetic particles are mono-domains and one expects that also in magnetic
nanophase materials the grains correspond with domains, while boundaries on the contrary to
disordered walls. Very small particles have special atomic structures with discrete electronic states,
which give rise to special properties in addition to the superparamagnetism behaviour. Magnetic
nanocomposites have been used for mechanical force transfer (ferrofluids), for high density
information storage and magnetic refrigeration.
(v) Nanostructured metal clusters and colloids of mono- or plurimetallic composition have a special
impact in catalytic applications. They may serve as precursors for new type of heterogeneous catalysts
(Cortex-catalysts) and have been shown to offer substantial advantages concerning activity, selectivity
and lifetime in chemical transformations and electrocatalysis (fuel cells). Enantioselective catalysis
was also achieved using chiral modifiers on the surface of nanoscale metal particles.
(vi) Nanostructured metal-oxide thin films are receiving a growing attention for the realization of gas
sensors (NOx, CO, CO2, CH4 and aromatic hydrocarbons) with enhanced sensitivity and selectivity.
Nanostructured metal-oxide (MnO2) finds application for rechargeable batteries for cars or consumer
goods. Nanocrystalline silicon films for highly transparent contacts in thin film solar cell and nano-
structured titanium oxide porous films for its high transmission and significant surface area
enhancement leading to strong absorption in dye sensitized solar cells.
(vii) Polymer based composites with a high content of inorganic particles leading to a high dielectric
constant are interesting materials for photonic band gap structure.
Two Different Approaches to Nanofabrication
Nanomaterials deal with very fine structures: a nanometer is a billionth of a meter.
This indeed allows us to think in both the ‘bottom up’ or the ‘top down’ approaches to synthesize
nanomaterials, i.e. either to assemble atoms together or to dis-assemble (break, or dissociate) bulk
solids into finer pieces until they are constituted of only a few atoms.
1. Top ⇨ Down: Start with the bulk material and

“cut away material” to make what we want.
2. Bottom ⇨ Up:
Building what you want by assembling it from

building blocks (such as atoms and molecules).
Atom-by-atom, molecule-by-molecule, or cluster-
by-cluster
This is a pure example of interdisciplinary work

encompassing physics, chemistry, and engineering
up to medicine.
NANOPARTICLE SYNTHESIS - SOL-GEL PROCESS

The sol-gel process, involves the evolution of inorganic networks through the formation of a colloidal
suspension (sol) and gelation of the sol to form a network in a continuous liquid phase (gel).
The precursors for synthesizing these colloids consist usually of a metal or metalloid element
surrounded by various reactive ligands.
The starting material is processed to form a dispersible oxide and forms a sol in contact with water or
dilute acid.
Removal of the liquid from the sol yields the gel, and the sol/gel transition controls the particle size
and shape and by calcination of the gel produces the oxide.
Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors such as
Si(OEt)4 (tetraethyl orthosilicate, or TEOS).
The reactions involved in the sol-gel chemistry based on the hydrolysis and condensation of metal
alkoxides M(OR)z can be described as follows:
MOR + H2O → MOH + ROH (hydrolysis)
MOH + ROM → M-O-M + ROH (condensation)
Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is widely
employed to prepare oxide materials.
The sol-gel process can be characterized by a series of distinct steps.
1. Formation of different stable solutions of the alkoxide or solvated metal precursor.

2. Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by a
polycondensation reaction that results in a dramatic increase in the viscosity of the solution.
3. Aging of the gel (Syneresis), during which the polycondensation reactions continue until the gel
transforms into a solid mass, accompanied by contraction of the gel network and expulsion of
solvent from gel pores. Ostwald ripening (also referred to as coarsening, is the phenomenon by
which smaller particles are consumed by larger particles during the growth process) and phase
transformations may occur concurrently with synthesis. The aging process of gels can exceed 7
days and is critical to the prevention of cracks in gels that have been cast.
4. Drying of the gel, when water and other volatile liquids are removed from the gel network. This
process is complicated due to fundamental changes in the structure of the gel. The drying process
has itself been broken into four distinct steps: (i) the constant rate period, (ii) the critical point,
(iii) the falling rate period, (iv) the second falling rate period. If isolated by thermal evaporation,
the resulting monolith is termed a xerogel. If the solvent (such as water) is extracted under
supercritical or near super critical conditions, the product is an aerogel.
Schematic representation of sol-gel process of synthesis of nanomaterials.
5. Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing the
gel against rehydration. This is normally achieved by calcining the monolith at temperatures up
to 8000C.
6. Densification and decomposition of the gels at high temperatures (T>8000C). The pores of the
gel network are collapsed, and remaining organic species are volatilized. The typical steps that
are involved in sol-gel processing are shown in the schematic diagram above.
Advantages:
 Starting materials are in molecular level, and final products prepared are homogeneous
 Products are relatively higher in purity
 Have rheological behaviour, which may be used in the preparation of products with different
applications.
 Controllable degree of porosity
 Easy to prepare various shapes
 Cheap and convenient to carry out.
 Enable synthesis at a low temperature
 Allow for fine control of the product’s chemical composition, especially suitable for preparing
multicomponent materials.
 Enable small quantities of dopants to be introduced in the sol and end up uniformly dispersed in
the final product.
Disadvantages
 Relatively higher in the cost of raw materials.

 Micro-pores may be left after the synthesis.
 Relatively longer in reaction times.
 Organic solvents may be harmful to the human body.
Synthesis of Nanoparticles by Hydrothermal/Solvothermal method
In a sealed vessel (bomb, autoclave etc.) solvents can be brought to temperature were above their
boiling points by the increase in autogenous pressure resulting from heating. Performing chemical
reactions under such condition is referred to as solvothermal synthesis. If the same process is done
with water as solvent is said to be hydrothermal processing.
1. This method is non-conventional method to

obtain Nanocrystalline inorganic materials.
2. A direct precursor product correlation exists

allowing the tailoring of almost any materials
synthesis without the presence of further
structure directing agents.
3. The synthesis method uses the solubility in

water of almost all inorganic solvents at elevated temperatures and pressures, and
subsequent crystallization of the dissolved material from the fluid.
4. As implemented in the name, water at elevated temperatures plays an essential role in the
precursor material transformation.
5. In the high pressure mode conditions, remarkable synthesis results can be obtained because
the solubility of inorganic materials is generally rising with pressure. Temperature, water
pressure and the time of reaction are, therefore, the three principle parameters in
hydrothermal processing.
6. In this hydrothermal technique, methods like rapid expansion of supercritical fluid solution
(RESS) and Rapid thermal decomposition of precursors in solutions (RTDS) are the most
relevant for the synthesis of nanocrystalline inorganic materials.
Pros and cons of hydrothermal route:
Advantages: Disadvantages:
 Difficult to control Morphology and
 Preparing New materials
size
 Easy and relatively cheap
 Not applicable for all materials
 May obtain variation in sizes
Scherrer equation
The Scherrer equation, in X-ray diffraction and crystallography, is a formula that relates the size of
sub-micrometre particles, or crystallites, in a solid to the broadening of a peak in a diffraction pattern.
It is named after Paul Scherrer. It is used in the determination of size of particles of crystals in the form
of powder.
The Scherrer equation can be written as:
Kλ
𝒯=
β cos θ
where:
τ is the mean size of the ordered (crystalline) domains, which may be smaller or equal to the grain
size;
K is a dimensionless shape factor, with a value close to unity.
λ is the X-ray wavelength;
βis the line broadening at half the maximum intensity (FWHM),
θ is the Bragg angle
Applicability
The Scherrer equation is limited to nano-scale particles. It is not applicable to grains larger than about
0.1 to 0.2 μm, which precludes those observed in most metallographic and ceramographic
microstructures.
Photo catalytic application – dye degradation:
The principle behind the photo catalysis involves the photo excitation of the metal oxides with light
energy (Figure 3). In this case, only U.V. Light (𝜆 ≥ 387 nm) greater than the band gap of the anatase
TiO2 (𝐸bg = 3.2 eV) generates electron hole pairs as shown in (1).
The photo induced electrons and holes diffuse to the particle surface of the TiO2, in which they can be
exploited for various redox processes analogous to those of an electrochemical cell.
The positive holes react with water, an electron donors, to produce the most crucial and powerful
oxidizing free radicals, ∙OH. Thus, any organic compound adsorbed on the surface of the
photocatalysts is oxidized by ∙OH (3).
Fig: Overall mechanism of the photo catalytic degradation of organic dye compounds using TiO2
based nanomaterial.
The photo excited negative electrons react with oxygen to become superoxide radicals, O2−∙, and
perform the similar oxidative attack on organic compounds. Consider
In this manner, TiO2 can act as an ideal semiconductor material for photo-catalysis because it is
nontoxic, relatively cheap, and highly photo stable.
☺ ALL THE BEST ☺

Unit V. Engg. Mateials

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Unit V. Engg. Mateials

Uploaded by

Copyright:

Available Formats

Unit V : Engineering Materials and Nano Science

 Lime is a calcium-containing inorganic material in which carbonates, oxides and hydroxides

 Lime is calcium oxide or calcium hydroxide.

 These materials are derived from rocks,

 They may be cut, crushed or pulverized and

 On calcination, converts them into the highly

Pozzolana is deposits of volcanic ash obtained by rapid cooling of Lava.

Lava – molten mixture of silicates of calcium, iron and aluminium.

Pozzolana cements harden very slowly.

At present used with Portland cement.

CHEMICAL COMPOSITION OF PORTLAND CEMENT:

According to I.S. 269-1975, composition of Portland cement should satisfy

c) Weight of insoluble residue should not exceed 2%

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 Average %

MANUFACTURE OF PORTLAND CEMENT

(c) Powdered coal or fuel oil.

(d) Gypsum (CaSO4 .2H2O)

The following steps are involved in manufacture of Portland cement.

(i) Mixing of Raw materials

(i) Mixing of raw materials

This can be done either by dry process or wet process.

The kiln is laid in slightly incline position.

Sample move from top to lower end in the speed of 15m/hour.

2CaO + SiO2 → 2CaO.SiO2 (C2S)

3CaO + SiO2 → 3CaO. SiO2 (C3S)

3CaO + Al2O3 → 3CaO. Al2O3 (C3A)

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

The cooled clinkers are ground to fine powder in ball mills

The role of gypsum in cement

SETTING AND HARDENING OF CEMENT

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

(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 + CaO.Fe2O3.H2O + 420kJ/Kg

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

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

Characteristics of a good refractory materials

A good refractory material should

(i) Be infusible at the temperature to which it is to be exposed

(iv) Not crack and suffer loss in size at operating temperatures

(v) Be able to withstand the overlying load at operating conditions

(vi) Expand and contact uniformly at high and low temperatures.

Causes for the failure of refractories

Classification of Liquid crystals

I. THERMOTROPIC LC and II. LYOTROPIC LC I. THERMOTROPIC LC II. LYOTROPIC LC

I. THERMOTROPIC LIQUID CRYSTALS

i. Nematic liquid crystals

Nematics have fluidity similar to that of ordinary (isotropic) liquids but

ii. Smectic liquid crystals

iii. Cholesteric liquid crystals

The cholesteric phase can be defined as a special type of nematic LC in which

II. LYOTROPIC LIQUID CRYSTALS

Liquid crystals which are prepared by mixing two or more

Eg. Soap in water.

Applications of Liquid Crystals

If insulation is main function, they are called insulators.