Portland Cement

Portland Cement: Portland cement may be defined as the product obtained by pulverizing clinker consisting essentially of
hydraulic calcium aluminates, silicates of varying composition, which hydrates and becomes hard like stone in contact with
water or moist air. Cement clinker is a solid material produced in the manufacture of Portland cement as an intermediary product. Clinker occurs as lumps or nodules, usually 3 millimetres (0.12
in) to 25 millimetres (0.98 in) in diameter.
Composition of Portland cement: Cement is the pulverized hydraulic calcium silicates. The essential constituents of Portland
cement are (a) 3CaO.SiO2 and (b)2CaO.SiO2.
Aluminium and iron are also found in cements and these become the constituents of cement in the form of 3 CaO.Al2O3 and 4
CaO.Al2O3/Fe2O3. All these constituents of cement are abbreviated as:
2 CaO.SiO2 Dicalcium silicate (C2S) Hydraulic cement is cement that sets and hardens by chemical reaction with water (hydration) and
3 CaO.SiO2 Tricalcium silicate (C3S) is capable of doing so under water
3 CaO.Al2O3 Tricalcium Aluminate (C3A)
4 CaO.Al2O3.Fe2O3. Tetracalcium Aluminoferrite (C4AF)
In addition to these above components , Portland cement also contains small amount of magnesium oxide. The general
composition of Portland cement is given below

CaO : 60 to 66%
SiO2 : 17 to 25%
Al2O3 : 3 to 8%
Fe2O3 : 2 to 6%
MgO : 0.1 to 5%
Na2O and K2O : 0.5 to 1.5%q
SO3 : 1 to 3%
 Classification of Portland cement
Depending on the composition, Portland cement may be classified as
(1) Regular, Type-I: This is the common type of Portland cement. It is used for general construction. There are some other
varieties of this type of cement such as white cement, (which contains less ferric oxide), oil-well cement, quick setting cement
etc. These cements are hardened to full strength in about 28-30 days.

(2) Moderate heat of hardening type cement, Type-II: This type of cements are used where moderate heat of hydration is
required or for general concrete construction exposed to moderate sulphate action. The heat liberated from this type of cement
should not exceed 295 and 335 J/g after 7 and 28 days, respectively. These cements are characterized by higher C2S/C3S ratio.

(3) High early strength (HES) Portland cement, Type-III: this type of cement contains lime to silica ratio higher than that of
type-I. This is also ground to finer particle than that of type-I. They contain higher proportion of C3S than the regular cement.
Because of this and their fineness they set quickly and liberate heat faster than the regular cement. As a result, construction
work from this type of cement can be put into service earlier than that from regular type of cement.

(4) Low heat hydration cement, Type-IV: this type of cement contains lower percentage of C3S and C3A, which lower the heat
of hydration. The percentage of C3AF is increased because of the addition of Fe2O3 to reduce the amount of C3A. In fact heat
evolved in this type of cement during the hardening and setting does not exceed 250 and 295 J/g after 7 and 28 days,
respectively. This is 15 to 35% less than the heat of hydration of regular or HES cement.

(5) Sulphate resisting Portland cement, Type-V: This type of cement is used when high sulphate resistance is required
particularly for seawater contact. These cements have lower percentage of C3A than regular cements. As a result, the
percentage of C4AF becomes higher. Therefore, by their composition they resist the action of sulphate ( particularly present in
water as dissolved MgSO4, Na2SO4 etc.), better than other four types.
 Raw materials of Portland cement
The basic raw materials for the manufacture of cement are limestone and clay. In fact limestone and clay supply all the four
principal ingredient of cement such as CaO, Al2O3, SiO2 and Fe2O3. Limestone provides CaO and Al2O3 while SiO2 and Fe2O3 are
obtained from clay. The different substances which are used to provide these materials i.e. for the manufacture of Portland
cement may be broadly classified into two groups:
(a) Calcareous materials: Calcareous materials are rich in calcium. Calcium oxide or lime is one of the major ingredients of this
type of raw materials. The example of calcareous materials are limestone, cement rock, chalk, marine shells, waste calcium
carbonate from industries etc. Calcareous materials should be such that they contain less than 3.3% MgO. Limestone containing
high percentage of MgO is not suitable unless its magnesia content is reduced to less than 5%. Similarly flint from chalk is to be
removed before its use as calcareous raw material.
(b) Argillaceous materials: Argillaceous materials are rich in silica. Argillaceous materials are those substances, which supply
silica SiO2 Al2O3, and Fe2O3 to the cement. The examples of argillaceous materials are clay, shell, blast furnace slag, ash, cement
rock etc. All these materials should contain 2.5 to 4 times more silica than alumina. Among these, shell and clay are most
commonly used. Cement rock is some times used as such without any further addition of additives, since it contains both
limestone and clay minerals, which are the essential ingredient of cement. Sand, waste bauxite and iron ore are sometimes
used in small amount to adjust the composition of mixture.
Process parameters for manufacturing a good quality of cement clinker: During the manufacture of cement it is very
important to maintain the following parameters
𝐶𝑎𝑂
(1) The lime saturation factor = (2.8 𝑆𝑖𝑂 +1.2 𝐴𝑙 𝑂 +0.65 𝐹𝑒 𝑂 ), should be in the range of 0.66-1.2. This will ensure the formation
2 2 3 2 3
of C3S, C2S and C3A, which are responsible for giving strength to cement concrete.
𝑆𝑖𝑂2
(2) Silica modulus = (𝐴𝑙 𝑂 + 𝐹𝑒 ), should be within 2.2 to 3.5.
2 3 𝑂
2 3
(3) Fine grinding of the raw materials, which helps the kinetics of the reaction.
(4) Maintaining MgO content below the specified limit, which ensures that the cement is sound.
 Manufacturing method of Portland cement
The calcareous and argillaceous materials (in required proportions) are finely ground, thoroughly mixed and heated to a
temperature of about 1400-1600oC in a rotary kiln to form cement clinker. This is then cooled and mixed with 2-3% gypsum and
finely pulverized. In general there are two methods of manufacturing Portland of cement clinker:
(a) Dry process and
(b) wet process
Wet process: This process is most commonly and universally used for the manufacture of Portland cement. The total process
may be split up into following steps:
(i) Crushing of raw materials: In this step the raw materials are crushed by
gyratory crushers and are stored.
(ii) Grinding of raw materials: The grinding of raw materials is carried out in
two stages; First, crushing is done by ball mill then by tube mill. Materials from
ball mill are fed into tube mills by means of a screwdriver. In principle the tube
mill is nearly same as ball mill. But the tube mill is continually operative. In this
process the raw materials are fed in one side of the tube mill and they are
taken out from the other side. The size of grinding materials depends upon the
speed of feeding the raw materials. Slower is the speed of feeding, longer will
be the time the materials receive impacts of pebbles and finer will be the
products. The finer the particle size the greater will be surface of contact. As a
result, better quality of cement will be produced. About 80% of the total
electrical energy consumed in the manufacture of cement is used up in
crushing, grinding and blending of materials.
Gyratory crushers
 Ball mill
Tube mill

Rotary kiln

(iii) Storage of slurry: The ground raw materials are mixed together with required amount of water. The slurry formed containing
30-40% water is stored in a basin or tank equipped with agitator.
(iv) Correction vats: From the tank slurry materials are taken to the correction vats. When the vat is full, small amount of the
sample is drawn and analyzed. If the sample is not of the required composition it is then corrected by adding more of the
deficient raw materials. The slurry from the correction vats is taken to kiln feed basin where the slurry is kept in agitation until it
is fed to rotary kiln.
 (v) Rotary kiln: The rotary kiln is a long steel cylinder lined with refractory bricks. The kiln is set inclined downwards so that
the materials move downward to the firing zone and come to the discharge end automatically. The general inclination is 3-60
per a foot length. The kiln having several tires rotates at a speed of 0.5 to 2 rpm. The length and diameter of the kiln vary from
30-50 meters. The slurry of the raw materials enters from the upper end of the rotary kiln while the burning fuel and air are
introduced from the lower end of the metal-to-metal kiln. The slurry gradually moves downwards and enters into different
zones of the kiln of increasing temperature. The operating temperature and the changes of raw materials are briefly described
below:
(a) the upper part of the kiln is known as drying zone. The temperature of this zone is about 4000C. In this zone most of the
water is driven out of the slurry by means of hot gases.
(b) the next lower zone of the kiln is known as preheating zone. In this zone temperature varies from 400-7000C. Here the
clay and magnesium carbonate decompose.
(c) The lower central part of the kiln is known as calcining or decarbonating zone. In this zone temperatue ranges from 700-
10000C. Here limestone is decomposed to CaO and CO2.
CaCO3 CaO+ CO2

(d) the materials then enter the hottest zone of the kiln. This zone is known as burning or clinkering zone. Here the
temperature ranges from 1300-15000C. In this zone lime and clay melt and react with each other forming aluminates and
silicates. The reactions involved in this zone are
2CaO+ SiO2 2CaO SiO2 (C2S)

3CaO+ SiO2 3CaO SiO2 (C3S)

3CaO+ Al2O3 3CaO Al2O3 (C3A)
4CaO+ Al2O3 + Fe2O3 4CaO Al2O3 Fe2O3 (C4AF)
These materials are combined together to from hard, grayish pellets, which is known as cement clinker. The compositon of the
𝐶 𝐴+ 𝐶 𝐴𝐹
cement clinker depends upon the ratio ( 3 𝐶 𝑆4 ), which is known as burnability index. In general the burnability index is
3
kept to a value in between 0.45 to 0.85.

(vi) Cooling the clinker: This is a very important part of the cement manufacturing process. The quality of cement depends
upon the rate of cooling. The hot clinker emerging from the kiln through the clinker conveyor falls into the cooler. In the cooler
atmospheric air passes over the hot clinker thereby cool the clinker and itself gets heated. The hot air so produced, is used for
drying the coal (fuel) before pulverizing. There are different types of such as rotary coolers, planetary coolers, air quench type
coolers etc.
(vii) Grinding of clinker: The cement clinker obtained after cooling consists of granular masses having 0.65-2.0 mm diameter.
This is then finely pulverized with 2 to 6 % gypsum ( which acts as retarder of setting time of cement-water paste). The finer is
the cement the higher will be the strength of concrete made from it. During grinding some other additives are mixed to
improve the quality of cement.
(viii) Storage and Packing: The pulverized cement obtained from grinding mills is packed by automatic machine in jute or
paper bags each holding 50 kg for storage. During packing moisture free compressed air is used to agitate the cement and to
keep it free from compaction by its own weight. The packed cement is then stored in a concrete storage silos.
 Setting and hardening of cement
The setting and hardening of cement-water mass mainly occur by a series of reactions such as hydration and hydrolysis
reactions, which take place when the different components of cement interact with water. Anhydrous components of cement
react with water and undergo hydration. The solubility of these hydrated components is much less. As a result they are
precipitated as insoluble gels or crystals. The gels or crystal have the ability to surround the inert materials, sand or crushed
stones and bind them together very strongly. As a results heat is evolved during setting or hardening of cement. There are
two different theories of hardening of cement.
(i) Crystalline theory of Le-Chatelier: According to this theory, the setting and hardening of cement are due to interlocking of
crystalline products formed during hydration of anhydrous component of cement.
(ii) Colloidal theory of Michaelis: According to this theory hardening of cement is due to the hydration of cement to form
silicate gels and then the hardening of gels develop strength.
Therefore, hardening of cement is mainly due to hydrolysis and hydration of the components of the cement. The chemical
reactions involved in hydrolysis and hydration of cement are shown below:
Hydrolysis: In hydrolysis when water comes in contact with cement, calcium silicates decomposed into calcium silicates of
lower basicity and removes CaO which reacts with water and form Ca(OH)2. Hydrolysis of cement may be represented by the
following equations:
(1) Hydrolysis of tricalcium silicates: Hydrolysis
3CaO.SiO2 + H2O 2CaO.SiO2(aq) + Ca(OH)2
Where water is less
Hydrolysis
2(3CaO.SiO2) + 3H2O 3CaO.SiO2(aq) + 3Ca(OH)2
Where water is less
(2) Hydrolysis of dicalcium silicates:
Hydrolysis
2CaO.SiO2 + H2O CaO.2SiO2(aq) + Ca(OH)2
 Setting and hardening of cement
Hydration: When cement comes in contact with water the main components of cement ( silicates and aluminates) take up
water as hydration in the following manner:
(1) Hydration of dicalcium silicates:
4H2O
2CaO.SiO2 + H2O 2CaO. SiO2.4H2O
(2) Hydration of tricalcium silicates:
6H2O
3CaO.SiO2 + H2O 3CaO. SiO2.6H2O
At least three different hydrated aluminates having three different crystalline structures are found to form. These are
3CaO. Al2O3.6H2O (Cubic )
3CaO. Al2O3.12H2O (Hexagonal )
3CaO. Al2O3.18H2O (Orthorhombic )
Hydrated tricalcium aluminate combines with gypsum to form calcium sulfatoaluminate.
(aq)
3CaO. Al2O3.xH2O + CaSO4.2H2O 3CaO. Al2O3.CaSO4.3H2O

(3) Hydration of dicalcium aluminate:

Hydration
2CaO. Al2O3 2CaO. Al2O3.nH2O (n = 5-9)
(3) Hydration of tetracalcium aluminate:
Hydration
4CaO. Al2O3 4CaO. Al2O3.nH2O (n = 12-14)