CEMENT

A material possessing adhesive and cohesive properties and capable of bonding

materials like stones, bricks, building blocks etc. The principle constituents of
cement used for constructional purposes are compounds of Ca and Al+Si. The

cements have properties of setting and hardening under water.

Classification:
1) Natural cement: It is made by calcining a naturally occuring lime stone at
high temperature and subsequently pulverising the calcined mass. During
calcination, silica and alumina combine with calcium oxide to form the
corresponding calcium silicates and aluminates.
Properties:
1. It is of quick setting and relatively of low strength
2. Used for laying stones and setting stones.
3. Used for construction of dams and foundations.
2) Puzzolona cement: These are materials which when mixed with lime, without
the use of heat, form hydraulic cementing materials. These are made by simply
mixing and grinding natual puzzolona consisting of glassy material, produced by
rapid cooling of lava and slaked lime.
3) Slag cement: This is produced by mixing blast furnace slag and hydrated lime
and grinding with small quantity of gypsum.
4) Portland cement: This is produced by the mixing of calcareous matter (lime
containing matter) and argillaceous matter (clay containing matter) and
powdered with addition of 2-3% gypsum
Properties: It most important and reliable cementing material, used for
constructional work.

Manufacture of portland cement:

Raw materials:
 Calcarious matter, CaO(lime stone, chalk, marl etc)
 Argillacous matter, Al2O3 and SiO2(clay,slate etc)
 Powdered coal or fuel oil
 Gypsum Functions of the ingredients of cement:
 lime: Its proportion must be properly regulated. Excess or lesser amount of lime
reduces strength of cement and makes it quick setting
 Silica: Gives strength to cement
 Alumina: Makes the cement quick setting
 Gypsum: It enhances the initial setting time of cement.
 Iron Oxide: Provides color, strength, hardness to the cement.
 Alkalies: If present in excess, causes cement efforescent.
Manufacture of portland cement involves the following steps:
1) Mixing of raw materials:
a). Dry process: The raw materials and clay are crushed into small pieces,then
these are ground to fine powder. Each separate powdered ingredients is stored in
a separate hopper. Then, the powdered materials are mixed to get dry raw mix,
which is stored in storage bins and kept ready to be fed in a rotary kiln.
b). wet process: The calcareous raw materials are crushed , powdered and
stored in a big storage tanks. The argilaceous material is thouroughly mixed with
water in wash mills and made into slurry. The powdered lime and clay slurry are
mixed in requisite proportions and then fed to a rotary kiln.
2). Burning: It is done in rotary kiln, which is a steel tube lined inside with
refractory bricks. The kiln is laid in slightly inc lined position towards the lower
end. Theupper part of kiln temperature is 400 degree Celsius but the
temperature gradually increases upto 1750 degree Celsius at the bottom. The
raw slurry from the wet process and the dry process is passed into the rotary kiln
through the lower end. The following reactions takes place in the rotary kiln.
a). Drying zone: The upper part of the kiln where the temperature is only 400oC
and the slurry gets dried.
b). Calcination zone: It is the central part of kiln where the temperature is around
1000oC. lime stone of dry mix or slurry undergoes decomposition to form quick
lime and CO2
=CaCO3---------- CaO+ CO2
c). Clinkering zone: In the lower part of the rotary kiln, the temperature is
between 1500- 1700 oC. here the lime and clay combine to form calcium
silicates and aluminates
2CaO+SiO2--------------------2CaO.SiO2(dicalcium silicates)
 3CaO+SiO2--------------------3CaO.SiO2(tricalcium silicates)
3CaO+Al2O3--------------------3CaO.Al2O3 (tricalcium aluminates)
4CaO+Al2O3+Fe2O3-----------4CaO.Al2O3.Fe2O3(tetra calcium alumino ferrite)
The aluminates and silicates of calcium fuse together to form hard greyesh
stones called clinkers. The cooled clinkers are collected in trolleys.
3). Grinding: The cooled clinkers are ground to fine powder in ball mills together
with 2-3% gypsum. The mixture of clinkers and gypsum powder is called cement.
Here,gypsum acts as a retarding agent for easily setting cement.
4). Packing. The ground cement is stored in silos, from which it is fed into
automatic packing machine

Setting and Hardening of cement :

When mixed with water, cement sets to a hard mass. It first forms a plastic mass
which hardens after some time due to 3-dimensional cross-links between the --Si-O-
Si-- and --Si-O-Al-- chains. The first setting occurs within 24 hours whereas the
subsequent hardening requires a fortnight, when it is covered by a layer of water.
This transition from plastic to solid state is called setting. The term ‘Hardening’
refers to the gain of strength of a set cement paste, although during setting the
cement paste acquires some strength.
Reactions Involved in Setting of Cement :
On hydration silicates and aluminates of calcium get converted to their respective
hydrated colloidal gels.
3CaO.Al2O3 + 6H2O -----------------> 3CaO.Al2O3. 6H2O
Tricalcium aluminate hydrated colloidal gel of tricalcium aluminate

2CaO.SiO2 + xH2O ----------------------------> 2CaO.SiO2.xH2O

Hydrated colloidal gel of dicalcium silicate

At the same time, hydrolysis precipitates calcium hydroxide and aluminium

hydroxide.
3CaO.SiO2 + H2O ----------------------------> Ca(OH)2 + 2CaO.SiO2
Tricalcium silicate dicalcium silicate

This calcium hydroxide binds calcium silicate particles together. On the other hand,
aluminium hydroxide fills the interstices (an intervening space) rendering the mass
impervious (not affording passage to a fluid).
3CaO.Al2O3+ 6H2O ----------------------------> 3Ca(OH)2 + 2Al(OH)3
Tricalcium aluminate aluminium hydroxide

Role of gypsum - Gypsum reacts with tricalcium aluminate.

3CaO.Al2O3+ 3CaS04 + 2H2O ----------------------------> 3CaO.Al2O3.3CaS04.2H2O
Calcium sulpho aluminate

Note: The fast-setting tricalcium aluminate is removed to slow down the setting process. A quick setting will give rise to crystalline hydrated

calcium aluminate. A slower setting yields the colloidal gel that imparts greater strength to the set mass. Thus gypsum helps in regulating the

setting time of cement.