Unit – III

Engineering

(Cement) Materials

A material possessing adhesive and cohesive property and capable of bonding materials like
stone, bricks, building blocks etc.

Cement have a property of setting and hardening under water by virtue of a certain chemical
reactions with it and are therefore called ‘hydraulic cements.’

Cement is a most widely used metallic material of today’s age. It is used for construction of
buildings, bridges , highways, dams, house etc.

A tiny ground mixture of calcium silicate and aluminates of different composition which
hydrates when mixed with water, forms rigid continuous structure with a good compressive strength.

Raw Materials :

1. Calcareous material which supplies lime, for example- chalk, limestone, cement rocks marine cells etc.

2. Argillaceous material which supplies silica, alumina and iron oxide. for example-clay shales, blast
furnace, slag etc.

3. Gypsum salt (CaSO4. 2H2O).

Ingredients of cement and their Functions .

(Functions of the Constituents of Cement )

1. Lime and Silica :

It provide strength to cement.

2. Alumina : (Al2O3)
 It helps to quick setting to cement but excess of alumina weakens the cement.

3. Iron Oxide :

It gives color, strength and hardness to cement.

4. Gypsum :

It helps to retard the setting of cement but enhances initial setting of cement time.

5. SO3 :

It imparts soundness to cement when present in a small amount.

6. Alkalies :

It requires in small amounts, excess may cause cement efflorescent.

Classification of cement :

1. Natural Cement

2. Pozzolana Cement

3. Slag Cement

4. Portland Cement

5. Special Cement

1. Natural Cement :

It is made by clacining a naturally occurring argillaceous limestone at a high temperature and

During this process, silica and alumina combine with calcium oxide to form a calcium silicate and
aluminates natural cement is quick setting and of relatively low strength mortar made from it is used in
laying bricks and setting stones. It is also used in dams and foundations.
2. Puzzolana Cement :

These are materials which when mixed with lime, without the use of heat form hydraulic
cementing material.

3. Slag Cement :

It is made from blast furnace slag and hydrated lime. It sets more slowly than portland cement.
They have lower strength and poor abrasion resistance, It is used to limited extent for making concrete
in bulk construction.

4. Port land Cement :

“An extremely finely ground product obtained by calcining together at about 15000C to 17000C
and intimate and properly proportioned mixture of argillaceous (clay containing) and cal carious (lime
containing) raw materials without the addition of anything subsequent to calcinations, excepting the
retarder gypsum.”

Its most important and reliable cementing material used for constructional works. It was
discovered in 1824 by Joseph Aspidin, (a brick layer of leeds).

It was so named because paste of a cement with a water on setting and hardening resembled in
colour and harness of Portland stone. (A lime stone carried in dorest).

‘It is finely ground grayish mixture of calcium silicates and aluminates with a small amount of
gypsum, which is capable of setting and hardening by chemical reaction with water.’

Manufacturing of Cement :

Cement is manufactured by two processes.

A) Wet Process

B) Dry Process
A) Wet Process :

Wet process for manufacturing of cement is used to a very large extent than dry process. Wet
process involves following steps.

1. Crushing and grinding :

The raw material as per the chemical composition are crushed and then ground in a ball mill.
The grinding is done in presence of 30% to 40% water. This gives the mud like mixture (paste) called as a
slurry. The slurry is collected in a storage tank, where it is analyzed for proper composition and can be
corrected by adding required amount of deficient raw material. Slurry is fed at the upper end at the long
rotary kiln as shown in the figure.

Fig

2. Burning and Calcinations :

The slurry is then calcinated in rotary kiln. The modern rotary kiln is the long cylinder lined with
a fire bricks. [The length of the kiln ranges from 90 to 120 meter and diameter from 2.5 to 3 meters].

The rotary kiln ranges from 30 to 150 meters and diameter from 2 to 5 meters. The rotary kiln is
slightly inclined (about 5 to 60) to the horizontal. It is based on the heavy friction rollers. The kiln is
rotated at a speed of about 1 rpm.

The slurry is added from the upper end of the rotary kiln while the burning fuel (powdered coal
or oil or natural gas) and air is introduced from the lower end of the kiln. A long flame is produced
which is forced to the interior part of the kiln by blower of firing fan.

The temperature in the lower part is about (15000C to 17000C) and it decreases in the upper
part of the kiln. The temperature of the top being about 4000C. The hot gases from the flame heat the
elements of the slurry and convert them in to water vapors.

Due to the slope and slow rotation of kiln, the slurry continously moves towards the hottest
end. The slurry moves in the kiln into different zone of increasing temperature.
1) Drying Zone :

The upper part of rotary kiln is known as a drying zone where temperature is about 4000C. In
this zone most of the water evaporates and escape with some gases through chimney.

2) Preheating zone :

The upper central part of the kiln having the temperature about 7000C.

MgCO3  MgO + CO2 

3) Calcinating Zone :

Lower central part of the kiln at a temperature 10000C, Lime stone is decomposed.

CaCO3  CaO + CO2

4) Clinkering Zone :

The material lastly enters in to the hottest zone (1500-17000C) where lime and clay reacts with
each other forming silicates and aluminates.

2CaO + SiO2  Ca2SiO4 (C2S)

Dicalcium silicate

3CaO + SiO2  Ca3SiO4+O2

3CaO + Al2O3  Ca3Al2O6 (C3A)

3CaO + Al2O3 Fel2O3  Ca4Al2Fe2 O10 (C4AF)

Tetra calcium alumino ferrite

These aluminates and silicates then combined together to form hard, grayish stones called as
cement clinkers. Its an exothermic reaction.
3) Cooling of hot clinkers :

The hot clinkers from the kiln are then cooled in a rotary steel cooler (the rate of cooling should
be moderate which gives high strength to the clinker. The not air so produced is economically used for
drying the coal before pulverization.)

4) Grinding the clinkers with gypsum :

The cooled cylinders then ground with a 2-3% gypsum in to fine powder in a steel ball mill is
stored in a concrete stored, ‘Silos then it is fed to automatic packing machines where it gets packed in
bags and then sent for marketing.’

Properties of Cement :

The properties of cement are following –

1) Setting and hardening of cement :

The setting and hardening are mainly due to hydration and hydrolysis of compounds present in
cement. When cement is mixed, with water, anhydrous compounds get hydrated forming plastic mass
called “Cement Plast.” It becomes rigid within a short time, which is known as ‘Initial Set’. The solubility
of hydrated compounds is less and so these are precipitated as gels and crystals. The following reactions
occur during this process.

C2S + xH2O  C2S.x.H2O (gel)

C 2S + x H 2O  C2S.x H2O + Ca(OH)2 Crystal

C4AF+7H2O  C3A.6H2O+CF.H2O

(Crystal) (Gel)

The setting and hardening of cement is due to the formation of gels and crystals which binds the
inert particles (like sand and crushed stones) in a compact rocklike material. So the process of
solidification consists of setting first and then hardening. Setting is defined as stiffening of the original
plastic mass due to initial gel formation and hardening is the development of strength due to
crystallization. So after setting, hardening starts due to the slow progress of crystallization of the mass.

Gypsum which is added to the cement, retards the initial setting by forming a compound which
does not have quick hardening property.

3CaOAl2O3+ x.H2O + y. CaSO4.H2O 3CaO.Al2O3. XYCaSO4 (x+2) H2O

(Gypsum)

(Where x = 10 to 33 & y= 1 to 3)

Again the strength developed by cement plast, is depend upon the amount of gel formed and extent of
crystallization.

Generally the setting times of C2S (dicalcium silicate), C3S (tricalcium silicate)

C3A (Tricalcium alluminate) and C4AF (Tetracalcium alumino ferrite) are 28 days, 7 days, 1 days and 1
day respectively. So C3A and C2AF are responsible for initial setting (1 to 7 days) C3S is responsible for
first setting (7 to 8 days) and C2S is responsible for final setting (28 days or more).

Abnormal type of set is sometimes observed where cement stiffens quickly but without evolution of
sufficient heat and may convert in to fluid. Such a setting is called as a ‘false setting’.

The block diagram for setting and hardening may be represented as below-
 Unhydrated Cement

Hydration

Metastable gel Crystalline hydration product

 

Stable gel  Crystalline Product

Heat of Hydration of cement

When water is mixed with cement, hydration, hydrolysis and gelatin reaction start and some
heat is liberated simultaneously.

On an average 500kj/kg of heat is evolved during complete hydration of cement. The heat of
hydration of various constituents of cement are as follows.

Constituents Heat of Hydration Kj/Kg

C 3A 880

C 3S 500

C4AF 420

C 2S 250

Consequently in order to avoid the shrinkage cracks on setting and hardening it is quite necessary to
pour concrete in position in such amounts that the heat liberated during hydration dissipated as quickly
as possible.

Soundness of cement :
 Cement undergoes some changes when allowed to dry or some expansions when continuously
stored in water. If the cement on hydration produces only very small volume change, then it is said to be
sound and if produces a large volume change, it is said to be ‘unsound.’

Unsoundness is due to the slow hydration of cement, it takes place in a poor quality cement due
to presence of excessive quantities of lime Ca(OH)2, crystalline magnetia (MgO) and sulphate in it.
Unsoundness in cement is measured by –

Le-Chatelier’s Method :

This methods is used for determination of soundness i.e. volume change. In this method, the
test paper piece of specific dimensions is placed in the boiling solution of cement and water for 3 to 5
hours and its expansions is then measured for a good cement, unsoundness 10 mm maximum is
desirable.