CHAPTER ONE

CHEMESTRY OF CEMENTS AND LIMES

1.1 CEMENTS
Cement is a matrix in mortar or concrete.
It is used as a binding material to bind the aggregates to form one unit.
There are three Main types of Cement:
• Portland cement
• High Alumina Cement
• Supersulphate Cement

1.2 PRODUCTION OF PORTLAND CEMENTS

Portland cement is made by heating together about one part of clay or shale with three parts of
either Chalk or Limestone.
There are two characteristics of the manufacturing process:
• to produce a finely divided mixture of the raw materials (chalk/limestone and clay/shale -
maximum particle size approximately 100µm)
• to heat this mixture to produce chemical combination.
These materials are intimately mixed together before heating takes place. The two mixing methods
are:
• the wet process and
• the dry process
1.2.1 The Wet Process
In the wet process, the powders are mixed as slurry with water, much of which is removed by
heating in the kiln. The main outline for the process is as follows:
• The raw materials are converted into slurry with a water content of about 1/3 and pumped
into the tanks from which blends can be taken to obtain the precise ratio of carbonate
required.
• The slurry is fed into the upper end of a large rotating kiln which is slightly inclined to
facilitate the gravitating of the slurry down the kiln.
• There is injection of hot pulverized coal, oil or gas from the lower end of the kiln. The
highest temperature of about 1550 degree Celsius is reached near the bottom end.
 • Cold air is blown over the hot material as it comes out of the kiln (cooling zone) - causing
the C3A and C4AF to finally crystallize to form a solid matrix called CLINKER.

1.2.2 The Dry Process

The dry process is far more economical on heat, using only 1kg instead of 3.5kg of coal per 10kg
of cement. However, it involves a more complicated, mixing process using compressed air The
dry powder then has about 12 per cent of water added so as to form hard pellets about 12mm in
diameter. This process requires non-cohesive materials (Limestone and Shale are normally used).
The process is as follows:
• The raw materials are ground separately and blended to a uniform powder.
• The powder is transferred to silos and mixed to the desired composition.
• Pre-heating of the powder by waste gases in a vertically arranged system of cyclones.
• The pre-heated powder then falls into the rotary kiln where nodules of clinker are formed.
Both processes are identical at the kiln.
Within the kiln the first step is the removal of the water when the cement reaches 100°C. Further
down the kiln at a temperature of about 900°C the carbon dioxide (CO2) is removed as the Chalk
or Limestone decomposes.

CaCO3 + Heat CaO + CO2

At the bottom end of the kiln where the temperature is approximately 1400°C a chemical reaction
takes place between the calcium oxide and clay producing the cement clinker.

FINAL PROCESSING:
• The clinker is then ground in a large steel-ball mill into powdered form whose particle
sizes ranges between 100µm down to 10µm.
• Gypsum (about 5% by weight) is added to the powdered cement to prevent the cement
from flash setting when water is added. Cements of finer particles and those with higher
C3A or C3S contents will require more gypsum.
• The cement is then bagged or transferred to tankers for bulk transport.
An essential property of a Portland cement is that it hardens by a chemical action when mixed with
water. This process is known as HYDRATION. A paste of cement and water first undergoes
gradual stiffening, called SETTING, but the hydration continues long after the paste has become
rigid, resulting in a progressive increase in strength called HARDENING.

1.3 COMPOSITION AND COMPOUND CONTENT OF COMMON PORTLAND

CEMENTS.
There are four major constituents of cement:
Name of Compound Oxide Abbreviation

Tricaicium Silicate Composition

3CaO.SiO2 C3S
Dicalcium Silicate 2CaO.SiO3 C2S
Tricalcium Aluminate 3CaO.Al2O3 C3A
Tetracalcium Aluminoferrite 4CaO.Al2O3. C4AF
Fe2O3
Aside these major compounds, there exist MINOR COMPOUNDS. They include MgO, TiO2,
Mn2O3, K2O and Na2O. These are present in small amounts.
Two of minor compounds are of special interest. They are oxides of sodium and potassium, (Na2O
and K2O) known as the ALKALIS (although other alkalis also exist in cement. These oxides react
with some aggregates, resulting in disintegration of the concrete; affect the rate of the gain of
strength of cement.
It should be noted that the chief chemical constituents in the raw materials for Portland Cements
are:
Lime - 65%
Silica - 20%
Alumina - 5%
Iron oxide - 3%
The above percentages are typical for Ordinary Portland cement. Each compound or chemical
constituent has a function.
For the Raw Materials:
• Lime: high lime content increases setting time but gives high early strength. Too little
reduces strength. Excess, if hard burnt, causes unsoundness.
• Silica: high silica content increases setting time and strength.
• Alumina: high alumina content reduces setting time and increases strength.
 • Iron Oxide: Imparts grey colour
For the Finished Product (Powder Cement)
• Tricalcium Silicate (C3S): gives early strength and high heat.
• Dicalium Silicate (C2S): gives later strength and little heat.
• Tricalcium Aluminate (C3A): gives little strength; great heat. It is unstable, decomposes to
lime in the mist of air and water. C3A is attacked by sulphates to form calcium sulpho
aluminate.
• Tetra - Calcium Alumino Ferrite (C4AF): gives little strength and little heat.
For the Set Cement:
The compounds in it consist of interlacing needles of the hydrated crystals of silicates and
aluminates, together with hydrated forms of the iron compounds and free hydrated lime. The table
below shows a typical chemical composition (in percentages) of three types of Portland Cements
TYPE OF PORTLAND C3S C2S C3A C4AF CaSO4
CEMENT
Ordinary Portland Cement 46 24 11 7 5
Rapid Hardening Portland 74 5 5 4 5
Cement
Sulphate-Resisting Portland 45 23 2 18 4
Cement

APPROXIMATE COMPOSITION LIMITS OF OXIDES IN PORTLAND CEMENT

OXIDE CONTENT %
CaO 60 – 67
SiO2 17 – 25
Al2O3 3–8
Fe2O3 0.5 – 6.0
MgO 0.1 – 4.0
Alkalis 0.2 – 1.3
SO3 1–3
OXIDE AND COMPOUND COMPOSITION OF A TYPICAL PORTLAND CEMENT
TYPICAL OXIDE COMPOSITION % CALCULATED COMPOUND
COMPOSITION %
CaO 63 C3 A 10.8
SiO2 20 C3 S 54.1
Al2O3 6 C2 S 16.6
Fe2O3 3 C4AF 9.1
MgO 1.5 Minor Compounds -
SO3 2
Alkalis (K2O, Na2O) 1
Others 1
Loss of ignition 2
Insoluble residue 0.5

Influence of change in oxide composition on the compound composition

Oxide Percentage in Cement
1 2 3
CaO 66.0 63.0 66.0
SiO2 22.0 22.0 20.0
Al2O2 7.0 7.7 5.5
Fe2O2 3.0 3.3 4.5
Others 4.0 4.0 4.0
Compound
C3 S 65 33 73
C2 S 8 38 2
C3 A 14 15 7
C4AF 9 10 14

Changes in the oxide composition to a large extend affect or influence the compound composition
of cement. In the above table
 • COL. 1 shows the composition of fairly typical rapid-hardening cement.
A decrease of 3% lime content with corresponding increases in the other oxides (COL. 2), results
in a considerable change in the C3S:C2S ratio.
• COL. 3 shows change of 1% in the alumina and iron contents as compared with the cement
of COL. l. Although CaO and SiO2 contents are not changed yet the ratio of the silicate, as
well as the contents of C3A and C4AF is greatly affected.

HYDRATION OF CEMENT
Hydration is the process of chemical combination between the cement and water. Hydration results
in
• Setting - initial stiffening
• Hardening - increases of strength and stiffness. In the presence of water, the silicates and
aluminates of the cement form products of hydration, which in time produce a firm and
hard mass.

SILICATES: The main strength-producing compounds are C2S and C3S. They react with water
as follows:

2(2CaO.SiO2) + 4H2O CaO.2SiO2.3H2O + 3 Ca (OH) 2

C2S + water calcium silicate hydrate + calcium hydroxide

2(3CaO.SiO2) + 4H2O 3CaO.2SiO2.3H2O + 3 Ca (OH) 2

C3S + water calcium silicate hydrate +calcium hydroxide

Although both compounds produce the same hydration products, in practice a range of similar
products may be obtained depending on the constituents, any impurities in them and the prevailing
conditions. Both the chemical and physical nature of these materials has a decisive effect on the
behaviour of the cement product.
The calcium silicate hydrate takes the form of extremely small inter-locking crystals, which grow
out slowly from the cement, grains to occupy previously water-filled spaces. The calcium silicate
hydrate is responsible for strength in hardened concrete and also for its susceptible to moisture. It
is described as a 'gel'
The Calcium Hydroxide is equally important. Its crystals partly dissolve when moisture is present
in concrete, to form an alkaline solution, which gives protection against corrosion to any metal
present. Reinforced concrete therefore, depends on this alkalinity for its durability and it is
unfortunate that Ca (OH) 2 at the surface of concrete is converted to CaCO3 by atmospheric action,
thereby becoming neutralized and ceasing to be protective to steel. To be durable, the steel must
be placed beneath this surface layer.

ALUMINATES:
C3A reacts vigorously with water leading to immediate stiffening of the paste as flash set, though
little strength is produced. Gypsum is added to prevent flash set from occurring - an intermediate
compound, calcium sulphoaluminate (ettringite) is formed initially but then as more C3A dissolves
calcium aluminate monosuiphate hydrate is formed. There should be sufficient gypsum for the
completion of this reaction. If gypsum becomes exhausted the remaining C3A may react quickly
producing a sudden heat emission some hours after mixing.
The monosulphate will revert to ettringite if the concentration of sulphates in solution rises as in
sulphates attack, causing expansion and disruption of the hardened cement.
C4AF makes little contribution to setting or strength but acts as a flux in the kiln and is responsible
for the grey color of cements.

1.4 HARDENING OF PORTLAND CEMENT

Hardening or gain of strength of cement is brought about through a process called HYDRATION.
In the process minute interlocking fibrous crystals are formed which bind the complete matrix
together.
In the process, the C3S hydrates rapidly. The C3S is therefore responsible for most of the strength
achieved during the first 28 days. After this period the C2S hydrates more quickly and the late gain
in strength is due to this.

The proportions of C3S and C2S in the cement partly control the rate of gain of strength. In addition
to that the rate of gain of strength is also affected by the temperature and fineness of the cement
particles. Thus the higher the temperature the greater the rate of hardening, everything else being
constant. Also the finer the cement is ground the greater will be the strength at a given age.
The rate of hydration therefore depends on:
• The relative properties of silicate and aluminate compounds.
• The ambient conditions (particularly temperature and moisture)
The time taken by the main constituents of cement to attain 80 per cent hydration is as follows:
CHEMICAL COMPOUND TIME (days)
C3 S 10
C2 S 100
C3 A 6
C4AF 50

1.5 SETTING
Hardening or strength is a property of the finished solidified concrete or mortar. Setting, however,
takes place after mixing and before the material had gained any load-bearing strength. Setting
starts shortly after water is added to cement whiles hardening start when setting is completed.
There are two stages in setting. First, the initial stiffening of the mix. The final settings are when
an impression on the green concrete is hardly possible.

Setting is caused by two processes:

• the hydration of the C3A and
• the evaporation of H2O
Both processes take water away from the mix. The viscosity of the mix increases as water is taken
away, The C3A present hydrates so rapidly that setting could be noticed after two or three minutes.
To prevent this quick setting of cement, about 5 per cent calcium sulphate (gypsum) is added.
As the tricalcium aluminate starts to hydrates a new compound is formed by combining with
gypsum, which shows up further hydration.
Setting, therefore, can be defined as a loss of workability or ‘flowability’ of the cement paste.

1.6 HEAT OF HYDRATION

During hydration heat is produced. Thus the chemical reaction is EXOTHERMIC. Considerable
heat is produced in the early stages of hydration because of the initial rapid reaction. Since concrete
has a fairly low thermal conductivity excessive heat may lead to cracking due to contraction on
cooling.
On the other hard heat of hydration can be useful during cold weather concreting. The heat of
hydration is expressed as joules per grams. The factors affecting the rate of hydration have a similar
effect on the liberation of heat. The heat associated with the hydration of each of the principal
compounds of cement is very different and as such cements having different compositions also
have different heat characteristics. The table below shows the Heat of hydration of the main
chemical compounds of Portland cement.

CHEMICAL COMPOUNDS HEAT OF HYDRATION (J/g)

C3 S 502
C2 S 251
C3 A 837
C4AF 419

1.7 CALCINATION OF LIMESTONE

Building limes are mainly obtained by burning limestone or chalk. This process is known as
CALCINATION. The calcination of a pure chalk or limestone (CaCO3) gives the follow reaction:

Calcium Carbonate + Heat Quicklime + Carbon dioxide (gas)

Ca CO3 + Heat CaO + CO2

Sometimes magnesium Carbonate is also present giving the reaction:

Magnesium Carbonate + Heat Magnesia + Carbon dioxide (gas)
Mg CO3 + Heat MgO + CO2

The finished lime, which contains more than 5 per cent of magnesium oxide, is classified as a
MAGNESIAN LIME. Most of these are from dolomitic limestone and have more than 30% of
magnesium oxide. Where no materials other than the CaCO3 and MgCO3 are present, the lime is
free to combine with water to form HYDRATED LIME. This process is known as SLAKING.
During slaking the lime under goes a vigorous reaction, generating great heat. The material then
undergoes considerable expansion.

Quicklime + water Hydrated lime

CaO + H2 O Ca(OH) 2

Similarly
Magnesia + water Hydrated lime
MgO + H2 O Mg(OH) 2
All limes must be fully slaked before used in building work, otherwise they will be liable to slake
at a later date, and cause instability by expansion.
Whereas the conversion of calcium carbonate (CaCO3) by calcinations takes place at a temperature
of about 900°C, the corresponding temperature in the case of magnesium carbonate (MgCO3) is
much lower, about 500°C. It, therefore, mean that if both carbonates are present the magnesium
oxide is likely to be over burnt. Such over burnt material will not hydrate readily and the slaking
must be carefully controlled.