UNIT-3

ENGINEERING MATERIALS AND POLYMER CHEMISTRY

Syllabus: Steel – Types of Steel, chemical composition – applications of alloy steels

Cement: Portland cement, constituents, Manufacture of Portland Cement, chemistry of

setting and hardening of cement (hydration, hydrolysis, equations).
Polymer Chemistry: Concept of polymerization – Types of Polymerizations, Chain growth
polymerization-mechanisms of free radical and cationic polymerizations, Thermoplastic
resins and Thermosetting resins: examples- Polyethylene, Styrene, Nylon 6,6 and Bakelite.
and applications, Conducting polymers: – Examples-and applications.

Introduction

Steel is basically an alloy of iron and carbon with a small percentage of other metals such as
nickel, chromium, aluminium, cobalt, etc. The density of steel is in the range between 7,700
and 8,050 kg/m3. The presence of carbon creates a robust molecular structure. Depending on
the temperature, it can take two crystalline forms: body-centered cubic and face-centered
cubic.

Pure iron is often ductile, soft, or easily formed due to the iron atoms in the crystal structure
slipping past one another. Here the presence of carbon and other elements act as hardening
agents which prevent the dislocation of atoms. As a result, the amount of carbon and other
elements present in the alloy makes up for the final physical qualities of the alloy. These
qualities include quenching behavior, need for annealing, tempering behavior, hardness,
tensile strength, and yield strength. Evident production of steel dates back to the sixth century
BC, produced in South India, known as Wootz steel.

Modern evolution led to the use of blast furnaces, which was followed by the use of electric
furnaces for processing steel. Steel making process consists of a primary process involving
pig iron production. It is melted iron from iron ore which contains more carbon than optimum
for steel. The secondary steel-making process involves refining and alloying the steel. It can
either initialize with the use of scrap steel or be a continuation of the primary process. This is
among the world’s most important engineering and construction materials, as it is used in
every aspect of our lives.
Properties of Steel

The following are the general properties of steel.

1. Tensile Strength
2. Ductility
3. Durability
4. Malleability
5. Conductivity

Types of Steel and Applications

Various types of Steel are manufactured with variable carbon content from 0.2 to 2.1 percent
by weight, classification depending on the composition and physical properties.
The major types of steel are-
1. Carbon steel: Carbon steel generally consists of less than 2 % carbon and traces of
manganese, sulfur, silicon, and phosphorus. Carbon content influences carbon steel's
characteristics, and alloying elements cause only minor changes. Plain carbon steel can be
further classified into four categories depending on the carbon present. The detailed
classification is as follows:
Low Carbon Steel- In low-carbon steel types of steel, the amount of carbon is limited to 0.30.
It is the most commonly used grade. This type can be machined and welded easily. It also has
ductility higher than high-carbon steel. These are used in pipes, bolts, and wires.
Medium Carbon Steel- In medium carbon steel, the carbon content is between 0.30 to 0.45 %.
The increase in carbon content indicates an increase in hardness and tensile strength and a
decrease in ductility. But, because of the higher carbon content, its machining and welding
properties become lower than low-carbon steel due to the increased hardness. These are
found in gears and railroad tracks.
High Carbon Steel- High carbon steel contains 0.45 to 0.75%. These types of steel have
complicated welding and machining properties. So, heat treatment is necessary for any
molding work to produce acceptable welds. It is also used to control the mechanical
properties of steel after welding.
2. Alloy Steel: Alloy steel is a type of carbon steel, which consists of one or more elements
other than carbon, added to produce the desired characteristic. Each added element
contributes its separate attribute to the final product. Generally, elements such as silicon,
boron, chromium-molybdenum, manganese, nickel, and vanadium are added as external
elements. There are two types of alloy steel, namely low alloy steel and high alloy steel.
Low alloy steel- In low alloy steel, the carbon content is generally between 0.15% to 0.25 %,
suitable for welding purposes. Some of the alloying elements used are manganese, nickel,
chromium, molybdenum, silicon, vanadium, and boron, and the less common alloying
elements are aluminum, cobalt, copper, titanium, tungsten, tin, and zirconium. Low alloy
steel is preferred for better hardenability and increased corrosion resistance in specific
environments. Difficulty in welding is a particular drawback for these types of steel. If the
carbon content is decreased up to 0.10 percent, along with other alloying materials, the
strength of the material can be increased. The versatility of these makes them hem essential in
modern industrial development. Typical applications include electrical wiring, heat
exchanger, anti-drill plates, high-strength safes, pipelines, electrical transformers, and
permanent magnets.
High alloy steel- Generally, steel having other elements more than 8% of total weight other
than carbon and iron is known as high alloy steel. High alloy steel has two chemical
elements, one carbon and the other an added element. The properties of these types of steel
depend on the percentage of the chemical elements present in it. One of its significant
advantages is its high corrosion resistance and reliability. These types of high-carbon steel are
extensively used in driers, pipelines, couplings, valves, bolts, salt manufacturing, nuclear
power plants, heat exchangers, centrifugal separators, exhaust gas desulfurized,
petrochemical, pharmaceutical, and semiconductor cleaning equipment.
3. Stainless Steel: Stainless steel is a type of steel that is corrosion and rust-resistant.
Chromium is the element that sets it apart, which is responsible for the materials’ luster.
Stainless steel has a chromium content of more than 10.5% and can go up to 30% in some
applications. It is commonly known for its role in medical equipment and appliance
manufacturing, also with kitchen appliances. Stainless steel can act differently when
chromium is electroplated onto another metal, producing a tough, polished coating. This is
classified into four categories, with each serving a different purpose.
Martensitic Alloys- Martensitic alloys are extremely tough but prove to be corrosive. These
are formed by a rapid cooling process, ideal for heat treatment, and are found in cutlery,
medical instruments, and pliers.
Ferritic Alloys- Ferritic alloys contain low amounts of carbon and nickel. These are less
expensive and are extensively used in the automotive industry because of their chromium-
induced strength and sheen.
Austenitic Alloys- These consist of higher chromium and nickel content, which helps to
improve the corrosion resistance and become nonmagnetic. Most commonly used in the
commercial kitchen industry because of its durability and ability to be cleaned easily.
Duplex Alloys- Duplex alloys are a mixture of austenitic and terrific alloys, which results in
the doubling of strength while also inheriting both properties. Due to the high chromium
content, these are highly resistant to corrosion and are known for their ductility.

4. Tool and Die Steel: Tool and die steel ideally has a carbon content range between 0.7% to
1.5%. These are manufactured in carefully controlled conditions to produce the desired steel
quality. Tool steels are heat-treatable and very high carbon steels (either carbon or alloy) with
high hardness, strength, and wear resistance. Elements forming hard and stable carbides are
added to the composition to increase the hardness of the steel tool. Processes such as
tempering, adding high heat, cooling quickly, and heating make the tool steel extremely hard
and heat-resistant. These are extensively used in high-impact environments and are very
abrasive. These are mainly used for making hummers, drills, cutters, shear blades, chisels,
forging dies, drills, and razors. Tool and die steels can be classified depending on their use,
composition, mechanical properties, and heat treatment method. Various grades of tool and
die steel are available for different application purposes. The added element plays a role in
determining the particular application it’s suited for.

Chemical Composition

Steel is an alloy of iron and other elements. Some elements are intentionally added to iron to
attain specific properties and characteristics. Other elements are present incidentally and
cannot be easily removed. Such elements are referred to as “trace” or “residual” elements.
Many product specifications have mandatory requirements for reporting certain elements,
which vary. Generally, steel contains elements like Carbon, Manganese, Phosphorous,
Sulphur, Silicon, Copper, Nickel, Chromium, Molybdenum, Vanadium, Niobium, Titanium,
Aluminum, Nitrogen, Boron, Tin, and Calcium.
Examples-
1. Brass is an alloy of copper and zinc
2. Bronze is an alloy consisting primarily of copper, commonly with about 12–12.5% tin

POLYMERS
 Polymers are high molecular weight organic compounds in which many simple units
repeat themselves in a regular fashion. The simple units are called as monomers. For
any compound to be recognized as a true monomer, it should possess at least two
functionalities (Not two functional groups necessarily---- as in some compounds, one
functional group gives rise to only one functionality while in some compounds, one
functional group gives rise to two functionalities), e.g.,
CH3OH has one functional group and one functionality (Not a true monomer)
CH2=CH2 has one functional group and two functionalities (A true monomer) HO-
CH2-CH2-OH has two functional groups and two functionalities (A true
monomer)
Therefore, what is actually required for polymerization, is presence of at least two
functionalities and not two functional groups, in the monomer.

Classification of Polymers
Polymers have been classified on different basis as follows:

(A). Classification on the basis of Origin/Source

On this basis, polymers have been broadly classified into two types:

1. Natural Polymers
They occur naturally and are found in plants and animals.
Examples: Proteins, Nucleic acids, Sta

2. Synthetic Polymers
These are man-made polymers. Plastic is the most common and widely used synthetic
polymer.
e.g., Nylons, Polythene, PVC, Synthetic rubbers, etc.

(A). Classification on the basis of Structure

On this basis, polymers have been broadly classified into three types:

1. Linear Polymers
Polymers comprising of long and straight chains are called as linear or straight chain
polymers. e.g., High density polyethene (HDPE)
2. Branched-chain Polymers
Polymers comprising of linear chains with branches are called as branched chain
polymers. e.g., Low-density polyethene (LDPE).

3. Cross-linked Polymers
Polymers in which various individual chains are connected by covalent bonds (cross links)
are called as cross-linked polymers. These polymers are formed from bi-functional and tri-
functional monomers and the additional functionality produces the cross links.
e.g., Bakelite, Nylon-6,6 and Urea-Formaldehyde.

(A). Classification on the basis of nature of Monomers

On this basis, polymers have been broadly classified into two types:

1. Homo-polymers
Polymers which are comprising of only one type of monomers are called as homo-
polymers. e.g., Polyethene, PVC, Nylon-6, etc. This can be represented as:
-A-A-A-A-A-A-A-A-A-A-A-A-A-A-, or -(A-)n-

2. Co-polymers
Polymers which are comprising of more than one (generally two) types of monomers
arecalled as homo-polymers. e.g., Nylon-6'6, Terylene, SBR, etc.
Co-polymers have further been classified into four types based on relative arrangement
 of the monomer units with respect to each other. These are:
i). Alternate Co-polymers: Polymers comprising of alternating A and B
units. The order is regularly followed throughout the chain. This can be
represented as:

ii). Block Co-polymers: Polymers comprising of regular alternating blocks of

A and B units. The order is regularly followed throughout the chain. This
can be represented as:
-A-A-A-A-A-B-B-B-B-B-A-A-A-A-A-B-B-B-B-B-

iii). Graft Co-polymers: Polymers in which the main chain is comprising of

one type of monomers and the other monomer forms the branches.
Therefore, for being a graft co-polymer, the polymer must be branched.
This can be represented as:
B B B

-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-B
B B

iv). Random Co-polymers: Polymers in which no regular order of

arrangement is followed by the monomer units. This can be represented
as:

-A-A-A-A-A-B-B-A-B-B-B-B-B-B-B-A-A-A-

The most common type of co-polymers are alternate co-polymers.

(A). Classification on the basis of Inter-molecular Forces

On this basis, polymers have been broadly classified into four types:

1. Elastomers
Polymers in which intermolecular (inter-chain) forces are very weak (van der Waals
forces) are called as elastomers. These are rubber-like solids weak interaction forces
are present. e.g., Rubber.
2. Fibres
Polymers in which intermolecular (inter-chain) forces are very strong (Hydrogen bond or
dipole-dipole interaction) are called as Fibres. These are strong, tough, with high tensile
strength. e.g., Nylons, Terrylene, etc.

1. Thermo-plastics
Polymers in which intermolecular (inter-chain) forces are intermediate are called as
thermo- plastics. These polymers on heating become soft and on cooling again become
hard and retain their original shape. In this case, the intermolecular forces, on heating,
get weaken and the polymer becomes soft and vise-versa. It is purely a physical change
and physical changes are generally reversible. Therefore, these polymers are recyclable,
i.e., they can be moulded and re-moulded again and again. e.g., Polyethene, Polyvinyl
chloride, Polystyrene, etc.
2. Thermo-settings
Polymers in which there is extensive cross linking, are called as thermo-settings. These
polymers on heating become soft and on cooling again become hard but do not retain their
original shape. In this case, the cross links get broken and rearranged on heating. It is
purely a chemical change and chemical changes are generally irreversible. Therefore,
these polymers are not recyclable, i.e., once moulded, they cannot be moulded again.
These polymers greatly improve the material’s mechanical properties. e.g., Bakelite,
Epoxy resins, etc.

Addition Polymers
Polymers which are formed by addition reaction are called as addition polymers. e.g., Poly
ethane, Teflon, Polyvinyl chloride, etc. For addition polymerization to take place, the
monomer must be unsaturated. Taking the example of polyethene, the addition
polymerization reaction can be shown as:

Addition polymerisation *
CH2 ) H2C C *
n( H2C H2

n
 Addition polymerization is a chain reaction, which once initiated, propagates itself till
the chain is not terminated. It involves three steps: Chain initiation, Chain propagation
and Chain termination. Addition polymerization can take place via three different types
of mechanisms: I). Cationic Mechanism II). Anionic Mechanism III). Free
Radical Mechanism

I). Cationic Mechanism: In this mechanism, the reaction is initiated by an electrophile

resulting in the formation of a carbocation as intermediate, thus known as cationic
mechanism. The reaction can be terminated by a nucleophile. We can summarize that in
this reaction, Initiator is Electrophile, Intermediate is Carbocation, Inhibitor (Terminator)
is Nucleophile. The mechanism can be shown as:

Anionic Mechanism: In this mechanism, the reaction is initiated by a nucleophile resulting

in the formation of a carbanion as intermediate, thus known as anionic mechanism. The
reaction can be terminated by an electrophile. We can summarize that in this reaction,
Initiator is Nucleophile, Intermediate is Carbanion, Inhibitor (Terminator) is Electrophile.
The mechanism can be shown as:
I). Free Radical Mechanism: In this mechanism, the reaction is initiated by a free
radical resulting in the formation of a free radical as intermediate, thus known as free
radical mechanism. The reaction can be terminated by a free radical. We can summarize
that in this reaction, Initiator is Free radical, Intermediate is Free radical, Inhibitor
(Terminator) is Free radical. The mechanism can be shown as:

In case of free radical mechanism, in addition to the normal chain termination by

introducing a free radical, there are also other ways wherein the chains can terminate
themselves. These are:

i). By Coupling: There is possibility that two propagating chains can collide with
 each other and couple. In this way, both the chains are terminated, and the polymer chain
obtained has molecular weight more than expected.

ii). By Dis-proportionation: There is possibility that a hydrogen radical from one

propagating chain can be abstracted by another, thereby terminating both the chains,
however, unsaturation is created in the chain from which H-radical is being abstracted.

Classification of Plastics

Plastics or resins are classified into two kinds

(1) Thermoplastics (2) Thermosetting.

Thermoplastics:

These can be softened on heating and hardened on cooling. They soften on heating and
remain soft as long as they are hot. On cooling, they regain their original rigidity and
hardness. Repeated heating and cooling does not alter the chemical nature of these materials.
The changes involved are only physical and temporary.

These are formed by addition polymerization and have long chain molecular structure.

Examples: PVC, polystyrene, poly Acrylonitrile, etc.

Thermosetting Plastics:

These become hard on heating during the moulding process and once they are solidified they
cannot be soften even heating. These are permanent setting resins. They acquire three
dimensional cross-like structures. They are hard, strong and more brittle than thermoplastics.
These are formed by condensation polymerization.

Example: (Nylon 6,6) Bakelite, polyesters, etc.

Differences between thermoplastics and thermosets

Thermoplastics Thermosetting plastics

They are formed by addition

Formed by condensation polymerization.
polymerization.

They consist of long-chain linear They have 3 D network.

Polymers. Structure

They soften on heating and harden on They do not soften on heating. On prolonged
cooling. heating charring of polymer is caused.

They are usually soft, weak, and less They are usually hard and strong.
brittle. and more brittle.

They cannot be reclaimed.

They can be reclaimed from waste.
from wastes.

They are soluble in some organic They are insoluble in almost.

solvents. all organic solvents.

Examples: PVC, PS, polyethylene, Examples: Nylon, Bakelite, U-F resin,

Polypropylene etc. Polyesters etc.

Preparation, properties, and uses of thermoplastic and thermosetting resins

THERMOPLASTICS
1. Polyethylene or Polyethene:

Preparation:

This can be obtained by the polymerization of ethylene at 1500 atm and a temperature
150 – 250 °C in the presence of traces of oxygen.

1500 atm
n H2C CH2 H2C CH2
250 °C n
Ethylene Low density
polyethylene
35 atm (LDPE)
60-200 °C

H2C CH2
n
High density
polyethylene
(HDPE)

Types and properties of polyethylenes:

Basing on condition employed, polyethylenes are of two types

1. Low Density Polyethylene (LDPE): Polymerization of ethylene at 1500 atm pressure and
250 °C in the presence of peroxide results in LDPE, having a density of 0.920 g/cm 3.

2. High Density Polyethylene (HDPE): Polymerization of ethylene at 35 atm pressure and

60-200 °C in the presence of ionic salts like triethylaluminium, chromium oxide results in
HDPE, having a density of 0.955 g/cm3.

Uses:

 Polyethylenes are useful in the preparation of insulator parts, bottle caps, flexible bottles,
pipes etc.
 LDPE is used in making film and sheeting. Pipes made of LDPE are used for both
agricultural and domestic purpose.
 Irrigation and domestic water line connections.
 HDPE is used in manufacture of toys and other household articles.
2. Poly Styrene:

Preparation:

This is prepared by polymerisation of styrene (dissolved in ethyl benzene) in

presence of benzoyl peroxide catalyst.

peroxide
n H2C CH H2C CH
n

Styrene Polystyrene
(Monmer) (Polymer)

Properties:

1. It is transparent, light, good light stable, excellent moisture resistance.

2. It is highly electric insulating, highly resistant to acids and has good chemical resistance.

3. It shows low softening range and is brittle.

Uses:

1. It is used in the moulding of articles like toys, combs, buttons, buckles, radio, and T.V
parts

2. Making of some refrigerator parts.

3. Polyamides: Polymers having amide linkages

Nylon 6-6, also referred to as nylon 6,6, is a polyamide from nylon class. Nylons come in
many types, and the two most common for textile and plastics industries are nylon 6 and
nylon 6,6. The polymer is made polycondensation of hexamethylene diamine and adipic acid.
The name Nylon-6,6 is because of existence of six carbon atoms in hexamethylene
diamine and adipic acid.

Synthesis:
O O
n H2N CH2 NH2 n HOOC CH2 COOH HN CH2 NH C CH2 C n H2O
6 4 6 4
n
Hexamethylene Adipic acid Nylon-6,6
diamine
Properties:
1. They are transparent, whitish, and high melting polymers
2. They show high temperature stability and good abrasion resistance.
3. Nylon 6-6 shows high mechanical strength, great rigidity, and good stability under heat is
required.
Uses:
1. It is used for ball bearing cages, electro-insulating elements, pipes, profiles and various
machine parts.
2. Other popular applications are: carpet fibres, apparel, airbags, tyres, zip ties, ropes,
conveyor belts, hoses and the outer layer of turnout blankets.
3. This was used in making tooth brush bristles and lubricant free gears and bearings.

THERMOSETTING RESIN

Bakelite (or) phenol-formaldehyde resin:

Preparation: Bakelite is prepared by condensation reaction between phenol and

formaldehyde in presence of an acid or base. Initially, the reaction between phenol and
formaldehyde results in differently substituted hydroxyl methyl phenol derivatives.
OH OH OH OH OH
O CH2OH CH2OH HOH2C CH2OH
H C H

CH2OH CH2OH CH2OH

Phenol Formaldehyde 2-hydroxy 4-hydroxy 2,4-Dihydroxy 2,4,6-Trihydroxy

methyl phenol methyl phenol methyl phenol methyl phenol

The hydroxyl methyl phenol derivatives undergo self-condensation to form a linear,

thermoplastic polymer called Novolak, which is soluble & fusible in nature.
OH OH OH
CH2OH H CH2OH H CH2OH -nH2O

OH OH OH

n
Novolak
The molding of Novolak in the presence of a promoter hexamethylene tetramine results in a
crosslinked thermosetting plastic called Bakelite.

OH OH OH
OH OH OH

H H H n -n H2O
CH2 CH2 CH2
OH OH OH
CH2 CH2 CH2

OH OH OH
n
OH OH OH n
Bakelite

Properties:

a) Rigid and hard material

b) Good dimensional stability

c) Good thermal stability

d) Excellent electrical insulation property

e) Resistance to corrosion

f) Shows resistance to chemicals but it is attacked by alkalis.

Uses:

i) Used for making insulating materials like switches, switch boards, plugs, etc.

ii) Also used for making mounded articles like telephone arts, TV & radio cabinets, heater
candles

iii) As an adhesive.

iv) As a cation exchanger.

v) For making non-lubricating bearings.

Conducting Polymers

Conducting polymers are organic polymers that conduct electricity and are known as
conducting polymers. They are also known as intrinsically conducting polymers (ICPs) and
they have alternating single and double bonds along the polymer backbone (conjugated
bonds) or are composed of aromatic rings such as Phenylene, naphthalene, anthracene,
pyrrole, and thiophene which are connected through carbon-carbon single bonds.

Examples: Polyacetylene, Polypyrrole, Polyaniline, etc

Conducting polymers come in two forms that are doped conducting polymers and non-doped
conducting polymers. The conductivity of non-doped conjugated polymers is due to the
existence of a conductivity band similar to a metal.

In a conjugated polymer, three of the four valence electrons form strong sigma bonds through
sp² hybridization where electrons are strongly localized.

The remaining unpaired electron of each carbon atom remains in a P𝘻 orbital. It overlaps with
a neighbouring P𝘻 orbital to form a pi bond.
 The pi electrons of these conjugated P𝘻 orbitals overlap to form an extended P𝘻 orbital
system through which electrons can move free (delocalization of pi electrons). However, the
conductivity of non-doped polymers is low.

In the case of doped conjugated polymers, an electron is removed from the valence band by
oxidation (p-doping) or is added to the conducting band by reduction (n-doping).

P-doping increases the mobility of electrons in these delocalized orbitals and the polymer
becomes highly conductive.

Properties of Conducting Polymers

1. Conductivity polymers have high melting and softening points because the mobility of the
repeat units is highly restricted due to the presence of a fully aromatic ring structure and the
absence of free-rotating groups.
2. Conductivity polymers show excellent chemical, thermal, and oxidative stability due to low
hydrogen content and aromatic structure.
3. They can be processed into a highly ordered crystalline thin film that is electrically
conducting upon doping.
4. They are insoluble in many common solvents.
Applications of Conducting Polymers

1. They are used in the manufacturing of chemical sensors, electromagnetic shielding, antistatic
coatings, corrosion inhibitors, etc.
2. They are also used in compact electronic devices such as polymer-based transitions, light-
emitted diodes (LEDs), and lasers.
3. They are used for microwave-absorbent coating particularly radar-absorptive coatings on
stealth aircraft.
4. They are used in the manufacturing of printed circuit board because it protects the copper
from corrosion and prevents its solderability.
 Unit-3 Engineering materials and Polymer Chemistry

Cement

1.1 Definition: “Cement is construction material which possesses adhesive and cohesive
properties and used for binding the building blocks, bricks, stones”.

1.2 Classification:

Classification

Natural cement Puzzalona cement Slag cement Portland cement

Natural cement
Preparation: By calcining the naturally occurring argillaceous lime stone high temperature
and subsequently pulverizing the calcined mass. Calcium and aluminium silicates are formed
by the combination of silica and alumina with calcium oxide.

Properties: i) It possesses hydraulic qualities

ii) It is quite setting cement
iii) It possesses relatively low strength
Applications: i) Mortars used in lying bricks and setting stones
ii) It is also used in large mass concretes such as dams and foundations.

Puzzalona cement: “It is a material which when mixed with lime without the requirement
of heat forms a hydraulic cement”.
 One of the oldest cement invented by romans.
 Used for making concrete for the construction of walls and doms.
 Natural puzzalona is deposit of volcanic ash produced by rapid cooling of lava mixed
with slaked lime. It is a mixture of aluminum silicate, calcium silicate and silicates of
iron. Natural Puzzalona cement is not used directly but used by mixing with Portland
cement.

Slag cement:
Slag cement is mixture of slag i.e. aluminum silicate and calcium.
Preparation: It is made from hydrated lime and blast furnace slag. The mixture is poured into
cold water, granular cement produced is dried and mixed with lime and pulverized to fine
powder.

Properties:
 Slag cement is low setting cement.
 It can be hardened by adding accelerators like clay, salt or caustic soda.
 Poor abrasion resistance and lower strength.
Applications:
 It is used for making concrete for construction in waterlogged area where much
tensile strength is not required.
 Used for making concrete for bulk constructions.

(4) Portland cement:

Portland cement is made by calcinations of calculated amounts of clay and lime followed by
gypsum. It is a mixture of calcium silicate and aluminium silicate with small amount of
gypsum. It is hydraulic in nature.

Note;
Why the name Portland cement?
In 1824, Willium Joseph Aspidin, a bricklayer produced an improved cement by heating a
mixture of limestone and clay and crushing the resulting product to a fine powder. The
powder on mixing with water set to give a hard, stone like mass which resembled the colour
of stone quarried on the isle of Portland, England. So the name Portland cement. It was
patented by him.

Composition of Portland cement:

Chemical composition of cement:
According to Indian standard Institutions, for a good quality of cement the following ratio
should be maintained.

 The ratio of calcium oxide to silica + alumina + ferric oxide should be close to 2.5
and 4.


 The ratio of silica to alumina lies between 2.5 and 4.

 Total percentage of magnesia should be < 6%

 Total sulphur content should not be more than 2.75%
 The ratio of Alumina to Iron oxide should be close to 0.65
  Total loss on ignition shall not exceed 4%.

1.4 Manufacturing of Portland cement

Raw materials: Two types of raw materials

 Calcareous materials (Calcium compounds): Aragonite, Calcite, Marl, Shale and
limestone.
 Argillaceous materials( Si and Al compounds): Silica, Clay, fly ash and shale, in
addition,
 Gypsum, to slow down the setting speed of Al2O3

Different stages in manufacturing of

cement

Crushing Mixing Burning

Dry process Drying

Wet process Calcining

Reactions

Step 1: Crushing
It is done in a crusher to reduce the size of limestone to 3-5 inches.

Step 2: Mixing
Mixing of raw materials can be done either by dry process or by wet process.

(a) Dry process: the raw materials are crushed into roughly 2-5 cm size pieces. Then, these
are ground to fine powder using ball mills/tube mills. Each separate powdered ingredient is
stored in a separate hopper. Then, the powdered materials are mixed in the required
proportions to get dry raw mix which is stored in storage bins called silos and kept ready to
be fed in a rotary kiln.

(b) Wet process: the calcareous raw materials are crushed, powdered and stored in big storage
tanks i.e. silos. The argillaceous materials (clay) is thoroughly mixed with water in wash
mills, to remove any adhering organic matter etc. the basin-washed clay is also stored.
Powdered limestone and washed wet clay are allowed to flow in a channel in the right
proportions. From the channel, the two raw materials are led to grinding mills where they are
mixed intimately to form a paste, called slurry. This slurry contains about 38-40 % water. The
slurry is finally stored in storage tanks and kept ready for feeding to a rotary kiln.

Differences between dry process and wet process

Sl.no Dry process Wet process

1 It is used when the raw materials are quite It can be used for any type of raw
hard materials
2 Fuel consumption is low Fuel consumption is higher
3 Process is slow Process is comparatively faster
4 Cement produced is of inferior quality Cement produced is of superior quality
5 Cost of production is less Cost of production is high
Step 3: Burning
Burning of the raw mix obtained from both dry process and wet process is done in a rotary
kiln. It is a long steel cylinder with length 90-120 m and diameter of 2.5-3.0 m lined inside
with refractory bricks. The kiln is slightly inclined downwards towards the exit end. It can be
rotated at a desired speed as it is mounted on rollers. The raw material is fed to the rotary kiln
from the upper end. As the kiln rotates, the material passes slowly from the upper to the
lower end at a rate controlled by the slope and speed of rotation of the kiln. The kiln is heated
from the lower end. The upper end is cooler. As the material passes through the kiln, its
temperature is raised to the point of clinkering temperature where the actual chemical
reactions take place. In fact there are different zones in the rotary kiln.

(a) Drying zone: In this zone temperature raises to maximum 400°C so that entire moisture
in the slurry gets evaporated.

(b) Calcinations zone: In this zone, the temperature rises to 1000°C and the limestone is
completely decomposed into CaO.
CaCO3 → CaO + CO2 ↑
(c) Reaction zone (Clinkering zone): The temperature of this zone is about 1600°C, the
mixture is partly fused and chemical combinations between lime, alumina, ferric oxide and
silica occurs resulting in the formation of calcium silicates and aluminates silicates occur.

2CaO + SiO2 → 2CaO.SiO2 (C2S)

3CaO + SiO2 → 3CaO.SiO2 (C3S)
2CaO + Al2O3 → 2CaO. Al2O3 (C2A)
3CaO + Al2O3 → 3CaO. Al2O3 (C3A)
4CaO + Al2O3 + Fe2O3→ 4CaO. Al2O3. Fe2O3 (C4AF)

The resulting product is known as cement clinkers and is allowed to cool in a cooler. The
clinkers have the appearance of small greenish black or grey colored.

Step 4: Mixing with Gypsum

The cooled clinker is ground and 3% of gypsum is mixed with it in order to reduce the rate
of setting. After the initial setting, Al2O3 which is a fast setting constituent of clinker, reacts
with gypsum to form the crystals of calcium sulpho aluminate, a water insoluble compound.
3CaO. Al2O3 + 3(CaSO4.2H2O) + 2H2O → 3CaO. Al2O3 3CaSO4.2H2O + 6H2O
Water insoluble compound

Thus the process of setting cement gets retarded and the results in better strength of the mass
which sets.

1.5 Cement Setting and Hardening

Cement has the property of setting to hard mass after being mixed with water which is called
cement paste resulting in hydration compound of cement. This mass then become stiff and
hard. This change of slurry like mass to hard, rock like solid is known as setting of cement.
Setting is stiffening of original plastic mass due to initial gel formation and hardening is
development of strength due to crystallization. It has two stages.

(a) Initial setting:

Due to hydration of C3A and gel formation by C4AF and little by C2S.In 1 day it is finished.

C3A + 6H2O → C3A.6H2O + 880 kj/kg

Crystalline

C4 AF + 7H2O → C3A.6H2O + CF.H2O + 420 kj/kg

Crystalline Gel

C3A + 3(CaSO4.2H2O) + 2H2O → C3A. 3CaSO4.2H2O + 6H2O

(Gypsum, to reduce rate of setting)

(b) Final setting and hardening:

Due to the hydration of C3S to form Tobermonite gel and Ca(OH)2 crystals. This begins to
form within 24 hours and gets completed in 7 days.

C3S + 6 H2O → C3S2.H2O + Ca(OH)2

Tobermonite Gel Crystals

The gel of aluminate begins to crystallize and at the same time, C 2S begins to hydrate in 7 to
28 days with continued hydration of C3S. Thus, the initial set of cement is due to the
hydration of aluminate.

3C2S + 6H2O → 2C3S2.H2O + Ca(OH)2

C3S + 4 H2O → C3S2.H2O + Ca(OH)2
Tobermonite Gel Crystals

The development of early-strength, between 1 to 7 days, is due to the hydration of tricalcium

silicate and the further hydration of aluminate. The increase of strength, between 7 to 28
days, is due to hydration of dicalcium silicate and continued hydration of tricalcium silicates.