CEMENT CHEMISTRY

As we know Cement is the binding material which consists of argillaceous and calcareous
materials such as shale or clay and limestone or chalk .The raw materials used in manufacture
of cement are silica , lime ,alumina and iron oxide. these oxides account for more than 90%
of the cement. These oxides interact with each other in the kiln at high temperatures to form
more complex compounds. The approximate oxide composition of ordinary Portland cement
is given in the table.

Oxide Common Name Abbreviation Approx. Amount (%)

CaO Lime C 60-67
SiO2 Silica S 17-25
Al2O3 Alumina A 3-8

Fe2O3 Iron-oxide F 0.5-6

MgO Magnesia M 0.1-4

Na2O Soda N
0.2-1.3
K2O Potassa K

SO3 Sulfuric Anhydride 1-3

These oxides present in the raw material when subjected to high clinkering temperature
combine with each other to form more complex compounds .these compounds are called
Bogue’s compound namely:

Tricalcium silicate = 3CaO·SiO2 = C3S (51%)

Dicalcium silicate = 2CaO·SiO2 = C2S (23%)

Tricalcium aluminate = 3CaO. Al2O3 = C3A (8%)

Tetracalcium aluminoferrite = 4CaO.Al2O3.Fe2O3 = C4AF(9%).

On grinding clinker various types of Portland cements can be produced. The anhydrous
cement does not bind fine and coarse aggregate. The cement acquires adhesive property only
when it is mixed with water. The chemical reactions that take place between cement and
water is referred as hydration of cement. The products formed on hydration of cement have a
good adhesive value. The cement reacts with water to form hydrated hydrated compounds of
very low solubility. The hydration of cement can be visualised in two ways. The first is
through the “solution” mechanism. In this cement compounds dissolve to produce a super
saturated solution from which different hydrated products get precipitated. The second is the
water attacks the cement compounds in the solid state converting the compounds into
hydrated products starting from the surface and preceeding towards interior of the compounds
with time. The reaction of cement is exothermic. On mixing of cement with the water a rapid
heat evolution will occur and this is due to the reaction of solution of aluminates and
sulphates which results in hard mass over a period of time. Both C3S and C2S make up
nearly 75% of the cement.it is immediate reaction when it comes in contact with the water.
The cement grains become smaller as the reaction proceeds, the hydration continues as long
as heat and moisture are available. All four bogue’s compounds along with the gypsum are
involved in the hydration reaction and small amount of water is needed for it.

Hydration of C3S

The chemical reaction of C3Swith water is

C3S +Water → C-S-H + C-H + heat

Where C-S-H is calcium silicate hydrate and C-His calcium hydrate.

C-S-H is calcium silicate hydrate constitutes 50- 60% of the solids in the paste. İt forms
continous binding. İt is amorphous and fibrous and hence it has a large surface area.

C-H calcium hydrates makes about 20% of the solids in the paste , it exists in the form of
thick , crystalline hexagonal plates and is embedded in C-S-H matrix. İts growth fill the pore
spaces.its leaching causes white patches and efflorescence.

Hardens rapidly Responsible for initial set and early strength.

Hydration of C2S

The same products are generated as same as C3S, however C2S reacts slowly and hence
generates less heat .it contributes to strength development at later stages. Hardens slowly and
its effect on strength increases occurs at ages beyond one week.

Hydration of C3A
Is is the first compound to hydrate .contributes to strength development in the first few days.
The least desirable component because of its high heat generation and its reactiveness with
soils and water containing moderate to high sulfate concentrations.

The hydration reaction produces a substance called ettringite as follows:

Effect of gypsum:

C3A + gypsum +water →ettringite + heat.

C3A + ettringite +water →monosulphoaluminate.

İf the amount of gypsum is too little , C3A will react fast and causes ‘flash set’.

If the concentration of gypsum is too much will delay setting and cause undue expansion.
ettringite is a crysttaline and needle like a structure. It is a long slender and prismatic crystal
and is stable only in the presence of the gypsum. It plays a major role in a strength
development but contributes to durability property. Monosulphoaluminate is a stable
hydration product. Hence it fills the pores and can reform ettringite in presence of sulphate
ions.

Hydration of C4AF

Lowers clinkering temperature. C4AF contributes very little to strength of concrete even
though it hydrates very rapidly. The hydration of C4AF is similar to tricalcium aluminate it
produces less heat and combines well with the gypsum .Ferrite phase has lesser role in
development of strength. The hydration products are similar to C3A. Alumina & iron oxide
occur interchangebly in the hydration products

The hydration rate has the following steps like C3S, C2S, C3A, C4AF.

The ettringite is formed first then C-H ,C-S-H . there is no change in the volume of the
cement paste as a result of the hydration .

The hydration can be summarized as :

2 C3S+6H → C-S-H +3 C-H

2 C2S+4H→ C-S-H + C-H

C3A +3CSH2 +26 H→C6AS3H32

2C3A + C6AS3H32+4H →3C4ASH12

C4AF+10H+2CH→C6AFH12.
TYPES OF CEMENT
The use of additives , changing chemical composition and use of different raw materials have
resulted in availability of many types of cements to cater the needs of construction industries
for specific purposes.

Standard Cements (ASTM):

Type I: Ordinary Portland Cement

Suitable to be used in general concrete construction when special properties are not required

Type II: Modified Portland Cement :

For use in general concreteconstruction exposed to moderate sulphate action , or where

moderate heat of hydration is required.

Type III: High Early Strength P.C:

For use when high early strength is required, It is useful for repair works, cold weather & for
early demolding.Its early strength is due to higher C3S & C3A content.

Type IV: Low Heat P.C.

For use when low heat of hydration is required.

It is used in mass-concrete and hot-weather concreting.

Type V: Sulfate Resistant P.C.

For use when high sulphate resistance is required.

Used in construction where concrete will be subjected to external sulfate attack – chemical
plants, marine & harbor structures

Type IP:

This consists of an intimate and uniform blend of Portland cement and fine pozzolona in
which pozzolona content is between 15 to 40 % of the weight of total cement.

Type IA, IIA, IIIA:

These are type I ,II or III cement in which air-entraining agent is interground where air
entrainment in concrete is desired. Only difference is adding an air-entraining agent to the
cement during manufacturing to increase freeze-thaw resistance by providing small sized air
bubbles in concrete.
There are various types of cement in use and latest revised edition of IS :456-2000 permits
use of different types of cement.

1. Ordinary Portland cement:

The indian standards has classified ordinary Portland cement into three grades to produce
diiferent grades of concrete to meet demands of construction industry.

The classification has been made on basis of compressive strength at 28days.

Grade 33, Grade 43 ,Grade 53.

The grade of concrete indicates its mortar cube compressive strength in N/mm2 at 28 days.

2. Rapid hardening cement :

It develops early strength rapidly. Rapid hardening cement develops at the age of three days ,
the same strength as is expected of ordinary Portland cement at seven days.

The rapid rate of development of strength is attributed to the higher fineness of grinding and
higher C3S and lower C2S content.

It is used in pre fabricated concrete construction .

where form work as to be removed early for re use works , road repair works, in cold weather
concrete where rapid rate of development of strength reduces the vulnerability of concrete to
frost damage.

3. Portland Pozzolan Cement:

Pozzolan: Volcanic dust found at Pozzuoli, Italy and used since Roman times as hydraulic
cement when mixed with lime. All pozzolans contain silica and siliceous or aluminous
minerals. Fly ash, slag (blast-furnace), silica fume are artificial pozzolans. Volcanic ash is
natural pozzolan.

Portland Pozzolan Cement produces less heat of hydration and offers greater resistance to the
sulfate attack than OPC . Most pozzolans do not contribute to the strength at early ages, so
strength gain of these cements is slow.

Therefore they require larger curing period, but the ultimate strength is the same as OPC.

4. High Alumina Cement (HAC):

The raw materials of HAC are limestone or chalk and bauxite. Which are interground and
calcined at 1600 0C in the kiln .

The solidified material is fragmented and ground to a fineness of 2500-3000 cm2/gr.

Its color is dark grey.High resistance to the action of sulfate waters.

 Extremely high early strength . 80% of the ultimate strength is achieved in 24 hours or even
at 6-8 hours.

5. Portland Blast-Furnace Slag Cement:

PBFSC = OPC clinker + 25-60% granulated blast-furnace slag.

Granulated blast-furnace slag is a waste product of the manufacture of iron. The amount of
iron and slag being obtained is in the same order. This cement is less reactive than OPC and
gains strength at a slower rate during first 28 days, so adequate curing is essential.

Suitable for mass concrete .Unsuitable for cold weather ,It has high sulfate resistance.

6. Masonry Cement :

Is used in mortar for brickwork. Made by intergrinding very finely ground PC, limestone and
air-entraining agent, or alternatively PC and hydrated lime, granulated slag or inert filler and
an air-entraining agent.

More plastic than OPC.Higher water retaining power which leads lower shrinkage. Due to
low strength it cannot be used for structural concrete

7. White Portland Cement (WPC): It is made from raw materials containing very little iron
oxide and manganese oxide. China clay (Kaolin) is generally used together with chalk or
limestone free from specified impurities (iron oxide, manganese oxide).

To avoid contamination by coal ash, oil is used as fuel in the kiln.

Specific gravity and strength of White Portland Cement are less than those of OPC. WPC is
used for architectural purposes.

It is not liable to cause staining, since it has a low content of soluble alkalies.

8. Low heat cement :

A low heat evolution is achieved by reducing the contents it contains lower percentage of
tricalcium aluminate and higher percentage of dicalcium silicate which reduce the amount of
heat produced.

9. Expansive Cements :

These are cements which upon hydration give product capable of expansion. Expansive
cements are used in special applications such as the prevention of water leakage. It has high
resistance to sulfate attack.

References: CONCRETE TECHNOLOGY – M S SHETTY