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 7 day 28
day
Normal cement quick 99 153 259
Moderate 97 210 273
Slow 97 193 239
Very slow 87 187 230
High early strength quick 102 188 293
cement moderate 142 267 333
slow 102 210 292
Very slow 91 181 279
CHEMICAL COMPOSITION :
Approximate oxide composition limits of ordinary Portland
cement.

OXIDE % content
CaO 60-70
SIO2 17-25
Al2O3 3.0-8.0
Fe2O3 0.5-6.0
MgO 0.1-4.0
Alkalies 0.4-1.3
(K2O,Na2O)
SO3 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 formula Abbreviated formula

Tricalcium silicate 3 CaO.SiO2 C3S

Dicalcium silicate 2CaO.SiO2 C2S
Tricalcium aluminate 3 CaO.Al2O3 C3A

Tetracalcium 4 C4AF
aluminoferrite 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 % Calculated %
composition compound
composition
using Bogues
equation
CaO 63 C3S 54.1

SiO2 20 C2S 16.6

Al2O3 6 C3A 10.8

Fe2O3 3 C4AF 9.1

MgO 1.5

SO3 2
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.