HYDRATION OF

CEMENT
 CONTENTS
1. Bogue’s Compounds
2. Properties of the Bogue’s compounds
3. Hydration of the cement
4. Hydration of the individual cement
compounds
1. Hydration of C3S
1. Stages of hydration of C3S
2. Controlling the hydration of
C3S
3. Effect of Temperature on C3S
Hydration
2. Hydration of C2S
3. Hydration of C3A
1. Reactions involved in
hydration of C3A
1.1 BOGUE’S
COMPOUND
 Oxide present in the raw materials interact with
one another in the kiln at high temperature to
form more complex compounds.
 The identification of the major compound is largely
based in the work of R.H.Bogue and others and so

it is often reffered as ‘Bogue’s
TABLE :1 compounds’ or
‘Bogue’s composition’.
BOGUE’S
COMPOUNDS
Name of compound Formulae Abbreviation
Tricalcium silicate 3 Cao.SiO2 C3S
Dicalcium silicate 2 Cao.SiO2 C2S
Tricalcium aluminate 3Cao.Al2O3 C3A
Tetracalcium 4 Cao.Al2O3.Fe2O3 C4AF
aluminoferrite
BOGUE’S
COMPOUND (CONT.)
TABLE : 2
BOGUE’S
COMPOUNDS
Bogue’s compound Percentage by mass in cement
C3S 30-50
C2S 20-45
C3A 8-12
C4AF 6-10
1.2 Properties of the Bogue’s
compounds
 1. - It is responsible for early strength.
C3S : - First 7 days strength is due to C3S.
- It produces more heat of hydration
- A cement with more C3S content is better for cold weather
concreting.
 2.
C2S : - The hydration of C2S Starts after 7 days. Hence it gives
strength after 7 days.
- C2S hydrates and hardens slowly and provides much of the
ultimate strength.
 3. - It is responsible for the later strength of the concrete.
C3A : - It produces less heat of hydration.
- The reaction of C3A with water is very fast.
- It may lead to an immediate stiffening of paste, and it is called
Flash Set.
 4. C4AF : - C4AF hydrates rapidly.
- To prevent this flash set, 2-3% Gypsum is added at a time of
- It does not contribute to strength
grinding cement clinker.
Properties of the Bogue’s compounds
(cont.)
TABLE : 3
CHARACTERISTICS OF HYDRATION OF
CEMENT COMPOUND
NAME REACTION TIME STREN SETTING TIME HEAT
GTH EVALUATION
DEVELOP
MENT
C3S Medium High Low High

C2S Slow Low or High Low Low

C3A Fast Low High Very High

C4AF Medium Low Medium Medium

1.3 Hydration of the
cement
 Chemical reaction of the cement when it is mix with
water is called as Hydration of cement.
 Hydration is the collective term describing the chemical
and physical processes that
takes place between cement and water.
 During the hydration process silicates and alluminates are
produced and results into the hard mass and this hard mass is
called hydrated cement. This process is exothermic process.
 Hydration process continuous still the heat and moisture are
available in the cement.
 Hydration of cement is very important as it is responsible for
setting and hardening
of concrete.
1.4 Hydration of individual cement
compound

 1.4.1 : Hydration
of C3S
 2C3S + 6H = C3S2H3 +
tri
3CH + Heat C-S-H C-H
calcium water (50-60% (20% solid in
silicate Solid in cement

 cement
C-S-H (calcium-silicate-hydrate) paste)
is the principle hydration
product. paste)

 The formulae C3S2H3 for C-S-H is only approximate

because the composition of C-S-H is actually variable over
a quite a wide range.
 C-S-H is poorly crystalline material which forms
extremely small particles in the size range of colloidal
matter (<1 micro meter).
 C-H is the crystalline material with a fixed composition.
Hydration of C3S
(cont.)
(1) C- (2)
S-H C-H
- 1.4.1.1 Stages of hydration of
- There are some important stages of the C3S
C3S :-
hydration, as described by the following calorimetric
curve (i.e. time versus rate of heat evaluation curve)
Stages of
hydration of C3S
(Cont.)
 Stage-1 :- corresponds to a period of rapid
evolution of heat, which ceases within about 15 min.
 Stage-2 :- corresponds to a dormant period which lasts for
several hours during which the hydration is almost at halt.
This is the reason why the concrete remains in plastic state
for several hours.
 Stage-3 :- corresponds to acceleration period
starting at the end of dormant period and lasting till the
rate of heat evolution reaches a maximum value. By this
time (4 to 8 h) final set has been passed and early hardening
has begun.
 Stage-4 :- corresponds to deceleration period during
which the rate of heat
evolution reduces from its maximum value to a very low steady
state rate(stage-5).
- 1.4.1.2 Controlling the Hydration
of C3S :-
 (1) Chemical control:- The hydrolysis of the
C3S (i.e., the chemical reaction between C3S and
water) which results into release of calcium ions
and hydroxide ions from the surface of the C3S
grains, forming C- S-H and CH through
crystallization of ions and increasing the pH to over
12 within a few minutes, is called as chemical
control.
-The chemical control (i.e. the hydrolysis of C3S)
slows down quickly but continues throughout the
dormant period.
-During the dormant period, the
increase in Ca++ and OH-
concentrations continues slowly.
Controlling the Hydration of C3S
(cont.)
 (2) Nucleation Control :- When the Ca++ and OH-
concentrations reach a critical value, the hydration
products (C-S-H and CH) start to crystallize from
solution and the hydrolysis of C3S again proceeds
rapidly.
-This whole process of attenuation of critical
concentrations of Ca++ and OH- corresponding to
which the nuclei of the C-S-H and CH crystals starts
forming giving way to the further hydrolysis of C3S is
termed as nucleation control.
- Chemical and Physical Processes Controlling C3S
Hydration.
 (3) Diffusion Control :- The hydration process is said
to be under diffusion control when the coating over the
C3S grains, formed by layers of C-S-H, put a barrier
- 1.4.1.3 Effect of temperature on C3S
Hydration
- The hydration of C3S is sensitive to temperature (i.e. there
is increase in the rate of hydration with increase in
temperature) but only when the reaction is chemically
controlled (e.g. stage 3).
- Once hydration is completely diffusion-controlled in stage 5, it
is much less temperature- sensitive, although the diffusion
coefficient of the hydrate barrier varies with temperature.
- The overall effect of temperature on the hydration of C3S is
shown in the
figure.
1.4.2 Hydration of
C2S
 C2 S hydrates in a similar manner as that
of C3S
2C2S
dicalci water
+ C-S-H
4H -
Calciu
um  C3S2H3 +m
silicat CH Hydro
 But the
e hydration of C2S is much xideslower than C3S
because it is a less reactive compound than C3S. This is
the reason why C2S does not contribute to initial
strength
 Due to very low amount of heat liberated on the
hydration of C2S, it is not easy to measure the low
heat experimentally and therefore calorimetric curve
for C2S hydration is hardly plotted.
1.4.3 Hydration of
C3A
 In Portland cement the hydration of C3A involves
reactions mostly with sulfate ions which are supplied by
the dissolution of gypsum added during the
manufacturing of cement
 1.4.3.1 Reactions involved in the hydration of
C3A :-
1. The
C3 primary
+ initial reaction
3CsH2 26H of C3A, when ample
C6As3H
amount
A ofgypsum
+ is present,
- is as follows:
32
tri- gypsum water Ettringite

- calcium
The above reaction is exothermic
-Ettringite (i.e. "calcium sulfoaluminate hydrate") is
the alumin
name given to anaturally occurring mineral of the
sameatecomposition.
Reactions involved in the
hydration of C3A
-Ettringite is a stable (cont.)
hydration product only while there
is an ample supply of sulphate available
-The formation of ettringite slows down the hydration of
C3A by creating a diffusion barrier around unhydrated C3A
particles, analogous to the behavior of C-S-H during the
hydration of silicates
2. If all the sulphate is consumed before the C3A has
completely hydrated, then ettringite becomes
unstable and transforms calcium sulphoalluminate
hydrate containing less sulphate through following
reaction :
C3A + C6As3H32 + 4H -
3C4AsH32
- The second product 3C4AsH32 is simply called as
“monosulphoaluminate”
Reactions involved in the
hydration of C3A
- The diffusion barriEr created(cont.)
by the formation of ettringite
is broken down during the conversation of ettringite
into monosulphoaluminate and C3A is allow to reacts rapidly
again.
3.When monosulphoaluminates brought into contact with a new
source of sulfate ions (e.g. external source of sulfate ions),
thenettringite can be reformed, as follows:
C4AsH12 + 2CsH2 + 16H -
C6As3H32
- This potential for reforming ettringite is the basis for
sulfate attack of Portland cements when exposed to an
external supply of sulfate ions.
4. If gypsum is not added in the cement, the hydration of C3A
can lead to flash set due to the rapid formation of calcium
aluminate hydrates (C-A-H) :
C3A + 21H - C4AH13
+ C2AH8
Reactions involved in the
hydration of C3A (cont.)
5. When quite a small amounts of gypsum are present, there
may still be
unhydrated C3A present when all of the ettringite has been
converted to monosulfoaluminate. In such cases, the
monosulphoaluminate reacts with the unhydrated C3A
forming the monosulphoaluminate solid solution
[C3A(CsCH)H12] :
C4AsH12 + C3A + CH + 12H 
C3A(CsCH)H12
 1.4.3.2 Formation of the hydration products
from C3A :- It is
depending upon the sulfate/C3A molar ratio, is presented in
the following table :
1.4.3.3 Hydration curve for
C3A
 The calorimetric for
hydrating C3A,
which looks
qualitatively much
like the curve for
C3S.
 The first heat peak is
completed in 10 to 15
min and then the rate of
heat evolution has been
reduced to a very lower
value due to the
formation of the
ettringite barrier. The
heat of hydration
remains at low value till
Hydration curve for C3A
(Cont.)
 The more gypsum
there is in cement,
the longer the
ettringite will
remain stable
 In most cements
ettringite remains in
stable condition for a
period of 12 to 36
hours.
 The rate of heat
evolution starts
increasing with start
of ettringite
conversion to mono-
1.4.4 Hydration of
C4 AF
 C4AF forms the same sequence of hydration products
as doesC3A, with or without gypsum

 The
C4 reactions
+ 3CsH2 are+slower
 and involve less
C6(A,F)s3H32 + heat

 C4AF
AF 21Hnever hydrates
(A,F)H3
rapidly enough to cause
flash
C4 set,
+ andgypsum retards
7H C4AF hydrationeven
3C4(A,F)sH12
more C6(A,F)s3H32
drastically than itdoes + (A,F)H3
C3A
AF +

With increase in iron content in C4AF, hydration of

C4AFbecomes slower

 practical experience has shown that cements
low in C3A andhigh in C4AF are resistant to
sulfate attack

 This means that the formation of ettringite