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Cement Chemistry
Cement Chemistry
Fresh
Concrete
Hardened
Concrete
Dimensio
nal
Stability
Durability
The initial burst is followed by a slowdown of the heat evolution rate. The
rate does not become negative or zero at any stage, implying that
although slowly, the reactions do continue. This is termed as the
‘dormant’ or the ‘induction’ period. This period is followed by the main
peak of cement hydration, which is associated with the rapid dissolution
of C3S to form CSH and CH, and formation of ettringite (AFt) from C3A.
A slowdown of the hydration process beyond the main peak leads to lower
rates of heat evolution. A broader peak is associated with the conversion
of ettringite to monosulphate (AFm).
The latest calorimeters can also detect an extra endothermic peak in the
beginning that corresponds with the dissolution of potassium sulphate
(when it is present in the cement).
It is difficult to obtain the correct relationship between heat evolution and
temperature unless the system is perfectly insulated. Another problem is
the dependence on the water to cement ratio. Water has a much higher
specific heat than cement, thus when more water is present, a higher
degree of heat will be required to increase the temperature of the system.
Cement contains highly soluble alkali oxides (Na2O and K2O). The
dissolution of these compounds is responsible for the high alkalinity (pH
12 – 13) of the pore solution. Thus, the hydration of cement actually takes
place in the pore solution, and not in water.
Dormant Period
Various theories have been proposed for the existence of the dormant
period. As stated earlier, the rate of heat evolution during this stage is
low. The slowdown of the hydration process has been explained using the
following ideas:
The end of the dormant period can come about in many ways:
C4AF produces similar hydration products as C3A, with the Al3+ being
partly replaced by Fe3+. The final hydration product depends on the
availability of lime in the system. In the presence of gypsum, C4AF
produces an iron-substituted ettringite. Higher the ratio C4AF/C3A, lower
is the conversion of ettringite to monosulphate.
• Rate of dissolution of the involved phases (in the initial stages), and at
later stages,
• Rate of nucleation and crystal growth of hydrates
• Rate of diffusion of water and dissolved ions through the hydrated
materials already formed
The factors affecting the kinetics of hydration are:
• Rapid dissolution of ionic species (alkali sulphates contribute K+, Na+, and
SO42-; CaSO4 dissolves until saturation, contributing Ca2+ and SO42-)
• C-S-H forms on the surface of dissolving C3S. C/S of C-S-H is lesser than of
C3S, thus an increase of the Ca2+ concentration in the liquid phase occurs.
Formation of electrical double layer, and the precipitation of CH leads to
the dormant period.
• C3A dissolves, and reacts with SO42- to form AFt, which forms a surface
barrier. C4AF also reacts to form AFt.
• Only very small % of C2S reacts at this stage.
4. Post-acceleration period:
• Slow down due to decline in non-reacted material, and because the
process becomes diffusion controlled.
• The contribution of C2S increases steadily, leading to a decline in the rate
of formation of CH.
• Consumption of SO42- leads to a conversion of AFt to AFm.
The hydration of C2S is a slow process, and does not pick up for many
hours. On the other hand, 5 – 25% of C3A reacts in the first few minutes
of hydration. The initial reactivity depends on the quantity and quality of
alkalis present (K+ increases reactivity, while Na+ decreases it).The
reactivity of C4AF is dependent on the A/F of the cement.
The method of grinding cement may also influence the hydration kinetics.
Cements ground in high pressure roller mills set faster than in ball mills,
because of higher reactivity of C3A and C3S phases, and a lowered rate of
decomposition of CaSO4.
1. Capillary water: Present in voids larger than 50 Ao. Further classified into:
(a) free water, the removal of which does not cause any shrinkage strains,
and (b) water held by capillary tension in small pores, which causes
shrinkage strains on drying.
2. Adsorbed water: Water adsorbed on the surface of hydration products,
primarily C-S-H. Water can be physically adsorbed in many layers, but the
drying of farther surfaces can occur at about 30 % relative humidity. Drying
of this water is responsible for a lot of shrinkage.
3. Interlayer water: Water held in between layers of C-S-H. The drying of this
water leads to a lot of shrinkage due to the collapse of the C-S-H structure.
4. Bound water: This is chemically bound to the hydration product, and can
only be removed on ignition. Also called ‘non-evaporable’ water.
Using the above data, some sample calculations are provided below.
That means there are 4.2 ml of empty capillary pores. If this cement paste
gets any external moisture (for example, from curing) more cement will
hydrate and fill up this space.
Figure 9 depicts the relative sizes of pores in concrete. At one end of the
scale are entrapped air voids, while on the lower extreme are the
interparticle spaces between sheets of CSH.
Supersulphated cement
This cement contains 32 – 45% Al2O3, about 15% iron oxides, and 5%
SiO2, with the remainder composed of CaO. The primary phase present is
Calcium Aluminate, or CA. This cement is produced by sintering a
mixture of aluminous (typically bauxite) and calcareous components, and
grinding to a fine powder. A complete fusion of all the compounds occurs
in the kiln itself, and thus this cement is also called ‘Ciment fondu’ in
French.
The setting time of this cement is similar to PC. The initial strength gain
is much faster than PC. For hydration at ambient temperatures, the
strength is due to the filling up of pore spaces by the metastable hydration
products such as CAH10 and C2AH8. There is a decline in strength when
the temperature increases and a conversion to C3AH6 occurs. This
conversion can also occur as a result of ageing. The loss in strength due to
conversion is a result of an increase in the porosity of the system. The long
term strength is due to C3AH6 and AH3. Apart from strength, the
durability of the cement is also compromised due to this conversion.
CAH10 is inert with respect to sulphates, but C3AH6 can react with
SO42- in the presence of lime to form ettringite. The increase in porosity
also increases the permeability of the system. The degree of strength loss
is dependent on the w/c of the system. At higher w/c, the strength loss is
greater.