CHEMISTRY OF CEMENT

-Mangala.CA 8th sem, civil 1sj01cv011

INTRODUCTION OF CEMENT: Has adhesive and cohesive properties

Capable of bonding mineral fragments

Principle constituents being: - compounds of lime - calcareous cement HYDRAULIC CEMENT
The cement having the property of setting & hardening under water By virtue of chemical reaction is called HYDRAULIC CEMENT.
CONSTITUENTS:

-Silicates -Aluminates

MANUFACTURE OF PORTLAND CEMENT:

Raw materials used-calcareous materials and argillaceous materials.

Process of manufacture-grinding the raw material, mixing and burning.

Two process of manufacture-wet and dry process.

Clay water

limestone

Wash mill

crusher

Storage basinswet grindingstorage basins

mills to make
slurry blending of slurry to correct composition

storage of corrected slurry Powdered coal or gas corrected slurry fed to rotary kiln

slurry is converted into clinker Addition of 2-3% gypsum clinker is ground in ball millcement silospacking plant

INFLUENCE OF RATE OF COOLING ON COMPRESSIVE STRENGTH:

Type of cement Cooling conditions Compressive strength in kg/sq cm 3 day Normal cement quick Moderate Slow Very slow High early strength cement quick moderate slow Very slow 99 97 97 87 102 142 102 91 7 day 153 210 193 187 188 267 210 181 28 day 259 273 239 230 293 333 292 279

CHEMICAL COMPOSITION :
Approximate oxide composition limits of ordinary Portland cement.

OXIDE
CaO SIO2 Al2O3 Fe2O3 MgO Alkalies (K2O,Na2O) SO3

% content
60-70 17-25 3.0-8.0 0.5-6.0 0.1-4.0 0.4-1.3 1-3

INDIAN STANDARD SPECIFICATION 269-1976 SPECIFIES THE FOLLOWING CHEMICAL REQUIREMENT:

Ratio of % of lime to % of silica, alumina and iron oxide;

When calculated by formula(CaO-0.7SO3)/(2.8SiO2+1.2Al2O3+0.65Fe2O3)= not greater than 1.02 and not less than 0.66

Ratio of % of alumina to that of iron oxide=not less then 0.66

Weight of insoluble residue= not more then 2% Weight of magnesia=not more then 6% Total sulphur content, calculated as sulphuric anhydride (SO3)=not more then 2.75% Total loss on ignition=not more then 5%

The oxide present in the raw materials when subjected to high clinkering temperature combine with each other to form complex compounds (BOGUES compound). The four compounds regarded as BOGUES compounds are listed in table:
Name of compound Tricalcium silicate Dicalcium silicate Tricalcium aluminate formula 3 CaO.SiO2 2CaO.SiO2 3 CaO.Al2O3 Abbreviated formula C3S C2S C3A

Tetracalcium aluminoferrite

4 C4AF CaO.Al2O3.Fe2 O3

C-CaO
S-SiO2 A-Al2O3

F-Fe2O3
H-H2O The equation for calculating the % of major compounds (as given by Bogues) are: C3S=4.07 (CaO)-7.60 (SiO2)-6.72 (Al2O3)-1.43 (FE2O3)-2.85 (SO3)

C2S=2.87 (SiO2)-0.754 (3CaO.SiO2)

C3A=2.65 (Al2O3)-1.69 (Fe2O3) C4AF=3.04 (Fe2O3)

The oxide composition and the corresponding calculated compound composition is shown in table below: Oxide composition % Calculated compound composition using Bogues equation
C3S C2S C3A

CaO SiO2 Al2O3

63 20 6

54.1 16.6 10.8

Fe2O3
MgO SO3

3
1.5 2

C4AF

9.1

HYDRATION OF CEMENT:
Anhydrous cement compounds when mixed with water, react with each other to form hydrated compounds Two ways of hydration-through solution and solid state Reaction of cement with water is exothermic-heat of hydration

Pattern of liberation of heat from setting cement is given in the next slide.

Heat liberation from a setting cement

Fig below shows the rate of hydration of pure compounds:

CALCIUM SILICATE HYDRATES:

During the course of reaction of C3S or C2S with water, silicate hydrate and calcium hydroxide are formed. The following are the equation showing the reaction of C3S and C2S with water 2 (3 CaO.SiO2)+6H2O3 CaO.2SiO2 .3H2O+3Ca(OH)2 Similarly, 2C2S + 4H C3S2H3 + Ca(OH)2

C3S reacts with water and producers more heat of hydration.

C2S hydrates slowly and responsible for later strength of concrete.

Figure shows the development of strength of pure compounds.

CALCIUM ALUMINATE HYDRATES

Due to the hydration of C3A, a calcium aluminate system CaO-Al2O3-H2O is formed. Hydrated aluminates do not contribute anything to the strength of the paste.

On hydration, C4AF is believed to form a system of the form CaO-Fe2O3-H2O (this compound is most stable).
CaO.SiO2.H2O of hydration is called tobermorite gel.

STRUCTURE OF HYDRATED CEMENT

To understand the behavior of concrete, it is necessary to acquaint ourselves with the structure of hydrated hardened cement paste.
Two phases: 1) paste phase 2) aggregate phase

Figure shows the composition of cement paste at different stages of hydration:

Figure (a) and (b) shows the structure of hydrated cement paste:

WATER REQUIREMENTS FOR HYDRATION

C3S requires 24% of water by weight of cement and C2S requires 21%. This 23% of water of C3S combines with cement and is called as bound water. A certain quantity of water is imbibed within the gel pores and is called gel water. It has been further estimated that about 15% by rate of cement is required to fill up the gel pores. Therefore 38% of water by weight of cement is required for the complete chemical reaction and to occupy the space within gel pores.

The diagrammatic representation of progress of hydration is shown in the figure below:

CURING OF CONCRETE
Concrete derives its strength by hydration of cement particles. Water/cement ratio of about 0.38 would be required to hydrate all the particles of cement and also to occupy the spacing gel pores. Water used in the concrete evaporates and water available in the concrete will not be sufficient for effective hydration to take place especially in the top layer. Curing is described as keeping the concrete moist and warm enough so that the hydration of cement ca continue under a favorable temperature

CURING METHODS
Curing methods maybe divided into 4 categories: a) Water curing satisfies all requirements of curing.

b) Membrane curing it is a method of maintaining a satisfactory state of wetness in the body of concrete to promote continuous hydration when W/C ratio is not less than 0.5.
c) Application of heat subjecting the concrete to higher temperature and maintaining the required wetness can be achieved by steam curing. d) Miscellaneous methods of curing by using calcium chloride as a surface coating.

WHEN TO START CURING AND HOW LONG TO CURE

Concrete should not be allowed to dry fast in any situation. Concrete cured for a long time will show superior strength and develop other good properties. However curing for a long time will entail cost.

Curing period cannot be prescribed definitely, it varies for different structures, situation and atmospheric temperature.
For general guidance-concrete must be cured for 7 days.

On the other hand for low heat cement curing should be extended to 21 days.