Kerbala University 2nd Class

Engineering College Concrete Technology

Civil Engineering Department Asst. Lect. Laith M-Ridha

Hydration of cement
It is the reaction (series of chemical reactions) of cement with water to form the binding material.
In other words, in the presence of water, the silicates (C3S and C2S) and aluminates (C3A and C4AF)
form products of hydration which in time produce a firm and hard mass - the hydrated cement paste.

There are two ways in which compounds of the type present in cement can react with water. In the
first, a direct addition of some molecules of water takes place, this being a true reaction of
hydration. The second type of reaction with water is hydrolysis, in which its nature can be illustrated
using the C3S hydration equation

3CaO.SiO2 + H2O Ca(OH)2 + xCaO.ySiO2.aq. (calcium silicate hydrate)

2 C3S +6 H 3Ca(OH)2 + C3S2H3

The reaction of C3S with water continue even when the solution is saturated with lime and the resulted
amounts of lime precipitate in crystals form Ca(OH)2.

Calcium silicate hydrate remains stable when it is in contact with the solution saturated with
lime.

Calcium silicate hydrate hydrolyzed when being in water - some of lime form, and the process
continues until the water saturate with lime.

If the calcium silicate hydrate remains in contact with water it will leave the hardened compound
only as hydrated silica due to the hydrolysis of all of the lime.

The rates of the chemical reactions of the main compounds are different:

Aluminates

- React with the water in the beginning

-Affect the route of the chemical reactions at early periods of hydration.

Silicates
- Affect the later stage reactions.

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 Kerbala University 2nd Class
Engineering College Concrete Technology
Civil Engineering Department Asst. Lect. Laith M-Ridha

The main hydrates of the hydration process are:

- Calcium silicates hydrate, including hydrated products of C3S (not pure)

named as Alite, and C2S (not pure) named as Belite.

-Tricalcium aluminate hydrate

- C4AF hydrates to tricalcium aluminate hydrate and calcium ferrite CaO.Fe2O3

in amorphous form.

Since calcium silicates (C3S and C2S) - are the main cement compounds (occupies about 75% of
cement weight) - they are responsible for the final strength of the hardened cement paste.

With time:

- The rate of hydration decreases continuously.

- The size of unhydrated cement particles decrease. For instance, after 28 days
in contact with water, grains of cement have been found to have hydrated to a
depth of only 4 (im, and 8 (im after a year.
This is due to:
1) Accumulation of hydration products around the unhydrated cement grains
which lead to prevent water from channeling to them.

2) Reduction of the amount of water either due to chemical reaction or

evaporation.

3) Reduction of the amount of cement due to reaction.

The progress of hydration of cement can be determined by different means:
- The measurement of the amount of Ca(OH)2 in the paste resulted from the
hydration of the silicates.
2C3S + 6H C3S2H3 + 3 Ca(OH)2
2 C2S + 4H C3S2H3 + Ca(OH)2
- The heat evolved by hydration.
- The specific gravity of the paste.
- The amount of chemically combined water.
- The amount of unhydrated cement present (using X-ray quantitative analysis).
- Also indirectly from the strength of the hydrated paste.

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 Kerbala University 2nd Class
Engineering College Concrete Technology
Civil Engineering Department Asst. Lect. Laith M-Ridha

Tricalcium aluminate hydrate and the action of gypsum

The amount of C3A present in most cement is comparatively small but its behavior and structural
relationship with the other phases in cement make it of interest. The tricalcium aluminate hydrate
forms a prismatic dark interstitial material in the form of flat plates individually surrounded by the
calcium silicate hydrate.
The reaction of pure C3A with water is very violent with evolution of large amount of heat, forming
calcium aluminates hydrate in the form of leaf hexagonal crystals. In Portland cement, this reaction
leads to immediate stiffening known as "flash setting".
Gypsum, added to the clinker through grinding process cause delaying the reaction of C3A with water
by its reaction with C3A to form insoluble calcium sulfoaluminate (3CaO.Al2O3.3CaSO.30-32H2O) -
ettringite -around C3A particles, which permits enough time for the hydration of C3S that its reaction is
slower than C3A and permits the occurring of natural setting. But eventually tricalcium aluminate
hydrate is formed, although this is preceded by a metastable 3CaO.Al2O3. CaSO.12H2O, produced at
the expense of the original high-sulfate calcium sulfoaluminate. The reaction of gypsum with C3A
continues until one of them exhausted, while C3S continue in hydration.

- If C3A exhausted before gypsum

The surplus gypsum expand become an agent assist the disruption and
deterioration of cement paste.
-If gypsum exhausted before C3A
The remaining C3A begins in hydration:
C3A + 6H C3AH6
C3AH6 is stable -cubical crystals- with high sulfate resistance.
Calcium aluminate hydrate - Be at many forms before transforming to the stable state (C3AH6). It is
probably forming hexagonal crystals (C4AH8, C4AH C4AH12) before the cubical crystals. When the
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hexagonal crystals expose to sulfates (inside concrete from sand or external from soil or ground water)
— react with it forming calcium sulfoaluminate with increase in volume, depending on the amount
of remaining aluminates and the concentration of sulfates — crack and deteriorate of the hardened
concrete.
The transformation of calcium aluminates hydrate from the metastable hexagonal form to the stable
cubical form is accompanied with - change in the density and size of the crystals - leading to decrease
in the late ages strength of the cement paste due to:
- lose the adhesion and cohesion in the microstructure
-increase the porosity of the hardened cement paste.
The presence of C3A in cement is undesirable: it contributes little to the strength of cement except at
early ages (1-3 days) and, when hardened cement paste is attacked by sulfates, expansion due to the
formation of calcium sulfoaluminate from C3A may result in a disruption of the hardened paste.
But it is useful in the cement industry - work as flux material - reduce the temperature needed to form
the clinker. Also it facilitates the combination of lime with silica.

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 Kerbala University 2nd Class
Engineering College Concrete Technology
Civil Engineering Department Asst. Lect. Laith M-Ridha

C4AF compound
Gypsum reacts with C4AF to form calcium sulfoaluminates and calcium sulfoferrite.
C4AF - work as flux material and also it accelerates the hydration of silicates.
Using the optimum percentage of gypsum is very important because:
- It regulates the speed of the chemical reactions in the early ages.
- Prevent the local concentration of the hydration products.
The necessary gypsum content increase with the increase of:
- C3A content in the cement.
- Alkalis content in the cement.
- Fineness of cement. Iraqi specification No. 5 limits the maximum gypsum
content (expressed as the mass of SO3 present) to be not more than 2.5% when C3A < 7% and 3%
when C3A >7%.
The gel formed after the completion of hydration of the two compounds is — C3S2H3 - Tobermorite.

C3S and C2S - require approximately the same amount of water for hydration, but C3S produces more
than twice as much Ca(OH)2 as is formed by the hydration of C2S, as shown in the equations below:

For C3S hydration

2 C3S+ 6H C3S2H3 + 3Ca(OH)2
The corresponding masses involved are:
100 +24 75 +49
For C2S hydration
2 C2S+ 4H C3S2H3 + Ca(OH)2
The corresponding masses involved are:
100 +21 99 +22

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Kerbala University 2nd Class
Engineering College Concrete Technology
Civil Engineering Department Asst. Lect. Laith M-Ridha

Fig.1 Development of Strength of Pure Compounds

Fig.2 Rate of Hydration of Pure Compunds

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