HARDENING OF PORTLAND CEMENT

AND
HEAT OF HYDRATION
By:
M.MuthuKavitha
I M.Sc Chemistry
Hardening of Portland Cement :
◦Cement when mixed with water forms a plastic
mass called Cement paste.
◦During Hydration reactions , gel and crystalline
products are formed.
◦The inter-locking of the crystals binds the inert
particles of the aggregates into a compact rock
like material.
◦This process of solidification comprises of:
1. Setting
2. Hardening
Setting is defined as stiffening of the original plastic
mass due to initial gel formation.
Hardening is development of strength, due to
crystallization.
◦Due to the gradual progress of crystallization
in the interior mass of cement, Hardening
starts after setting.

◦ The strength developed by cement paste at

any time depends upon the amount of gel
formed and the extent of Crystallization.
◦The setting and hardening of cement is due
to the formation of interlocking crystals
reinforced by rigid gels formed by hydration
and hydrolysis of the constitutional
compounds.
o Reactions involved in setting and Hardening of
Cement:
Initial setting of cement is mainly due to the
hydration of tricalcium aluminate because it’s reaction
is complete within 7 days.

3 CaO.Al2 O3 + 6 H2 O 3CaO.Al 2 O 3 .6H 2 O +

880KJ/Kg
◦ 4CaO.Al 2O 3 .Fe 2O 3 +7H 2 O 3CaO.Al 2 O 3 .6H 2O +
CaO.Fe 2O3 .6H2O +420KJ/Kg
Dicalcium silicate undergoes hydrolysis and forms
tobermonite gel which has high surface area and very
high adhesive property. Hence it contributes to Initial
setting.
2(2 CaO.SiO 2 ) +4H 2 O 3CaO.SiO 2 .6H 2 O Ca(OH) 2 +
250 KJ/Kg
◦Final setting and Hardening of Cement is mainly
due to the formation of tobermonite gel and
crystallization of calcium hydroxide and hydrated
tricalcium aluminate 3CaO.Al 2 O 3 . 6H 2 O .
Heat of Hydration of cement :
◦ Hydration of cement is an exothermic reaction
so there is a rise in temperature.
◦The heat is evolved during the first 7 days of
hardening. The compounds responsible for the
evolution of heat are tricalciumaluminate,tricalcium
silicate, tetracalcium alumino ferrite and dicalcium
silicate in the descending order.
HEAT OF HYDRATION OF BOGUE COMPOUNDS

BOGUE COMPOUNDS HEAT OF HYDRATION

(KJ/Kg)
C3A 880

C3S 500

C4AS 420

C2S 250
◦The heat evolved is used in the setting of cement.
◦The process of setting or hardening is partly
chemical and physical changes.
◦The chemical changes involves hydrolysis of
various constituents with accompanying heat
changes.
◦Physical change is the gel formation followed
by separation of crystalline products.
◦By the hydration of cement the following two
steps of reaction takes place
1. Hydrolysis:
When water is added to cement, hydrolysis of
Calcium silicate takes place. Calcium silicate
decomposes into Calcium silicate of lower basicity
and produces Calcium oxide which also forms
Calcium hydroxide with water.
2. Hydration:
Silicate and aluminates take up water of hydration
In fact, in addition to hydrolysis, tricalcium
Silicate undergoes hydration and the two process
are collectively responsible for the setting of cement
in early stages.
◦Dicalcium aluminate undergoes hydration in
the following manner :
◦Other hydration reactions
4 CaO.Al 2O 3 .Fe 2O 3 3 CaO. Al 2O 3 .6H2 O
+ CaO.Fe 2O3

The various hydrated compounds now undergo stage

wise crystallization to form a mass of interlaced
crystals accounted for the hardening of cement.
THANK YOU