31Jul13

31Jul13

Kinetics of cement hydration

The progress of cement hydration depends on: 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
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Factors affecting the kinetics of hydration

The phase composition of cement The amount and form of gypsum in the cement Fineness of cement w/c of mix Curing conditions Hydration temperature Presence of chemical admixtures
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Several theories proposed

Dormant period

Stages in Cement Hydration

3. Acceleration stage (3 12 hours after mixing): Nucleation and growth of C-S-H (often termed as the second-stage CSH) and CH occurs. C2S also starts hydrating substantially. Ca2+ concentration in the liquid phase declines as CH starts precipitating. SO42- concentration starts to decline with increasing AFt formation, and adsorption of SO42on C-S-H.
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Formation of an impermeable hydrate layer (CSH) on the surface of the C3S particle precludes the further dissolution of C3S. The hydrate layer has a lower C/S ratio compared to C3S. As a result Ca2+ is released into the liquid phase (which contains OH-), and a silica rich layer forms on the surface of the C3S particle. This electrical double layer thus formed prevents any reaction to form CSH by impeding the passage of ions. Liquid phase gets supersaturated with respect to CH. As a result CH starts precipitating and this stops the further dissolution of C3S.

End of the dormant period can come about in many ways:

The barrier can weaken due to ageing. Diffusion of ions can occur across the barrier by osmosis. A gradual weakening of the electrical double layer may occur. Nucleation of CH can get slowed down when the nuclei 5 start approaching their critical size.

Stages in Cement Hydration

1. Pre-induction period (first few minutes):
Rapid dissolution of ionic species (alkali sulphates contribute K+, Na+, and SO42-; CaSO4 dissolves until saturation, contributing Ca2+ and SO42-) C3A dissolves, and reacts with SO4 to form ettringite (AFt), which forms a surface barrier. C4AF also reacts to form AFt.
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Stages in Cement Hydration

2. Induction (dormant) period (first few hours):
Formation of electrical double layer, and the precipitation of Calcium hydroxide (CH) leads to the dormant period

Stages in Cement Hydration

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 ettringite to Monosulphate.
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Evolution of hydration (Normal Setting)

C-S-H forms on the surface of dissolving C3S. C/S of CS-H is lesser than of C3S, thus an increase of the Ca2+ concentration in the liquid phase occurs. Only very small % of C2S reacts at this stage. 3

The concentration of SO42- remains constant as the amount consumed due to AFt formation is balanced by the amount dissolved from gypsum.

Young et al. 1998

IndianInstituteofTechnologyBombay

IndianInstituteofTechnologyBombay

31Jul13

Evolution of hydration products

Some more points on Hydration mechanism

In the first few minutes, about 2 10 % of C3S hydrates, and a significant fraction is consumed within 28 days. On the other hand, 5 25% of C3A reacts in the first few minutes of hydration. With an increase in the amount of SO3, the C3S reaction becomes faster. However, beyond a limit, SO3 can start causing retardation. 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.

Taylor, 1968

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Heat evolution during cement hydration

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IndianInstituteofTechnologyBombay