0.4 Hydration of portland cement

The addition of water to dry cement powder results in a thin cement slurry that can be easily manipulated and cast into different shapes. In time, the slurry sets and develops strength through a series of hydration reactions. Hydration of cement is not linear through time, it proceeds very slowly at first, allowing the thin mixture to be properly placed before hardening. The chemical reactions that cause the delay in hardening are not completely understood; however, they are critical to developing a rational methodology for the control of cement setting.

Tri- and di-calcium silicates

The tri- and di-calcium silicates (C3S and C2S, respectively) comprise over 80% by weight of most cement. It is known that C3S is the most important phase in cement for strength development during the first month, while C2S reacts much more slowly, and contributes to the long-term strength of the cement. Both the silicate phases react with water as shown below to form calcium hydroxide and a rigid calcium-silicate hydrate gel, C–S–H, [link] and [link] .

The detailed structure of C–S–H is not completely known, however it is generally agreed upon that it consists of condensed silicate tetrahedra sharing oxygen atoms with a central, calcium hydroxide-like CaO ₂ layer. Calcium hydroxide consists of hexagonal layers of octahedrally coordinated calcium atoms and tetrahedrally coordinated oxygen atoms. Taylor has proposed that the structure is most similar to either Tobermorite or Jennite, both of which share a skeletal silicate chain [link] .

Although the precise mechanism of C3S hydration is unclear, the kinetics of hydration is well known. The hydration of the calcium silicates proceeds via four distinct phases as shown in [link] . The first 15-20 minutes, termed the pre-induction period ( [link] a), is marked by rapid heat evolution. During this period calcium and hydroxyl ions are released into the solution. The next, and perhaps most important, phase is the induction period ( [link] b), which is characterized by very slow reactivity. During this phase, calcium oxide continues to dissolve producing a pH near 12.5. The chemical reactions that cause the induction period are not precisely known; however, it is clear that some form of an activation barrier must be overcome before hydration can continue. It has been suggested that in pure C3S, the induction period may be the length of time it takes for C–S–H to begin nucleation, which may be linked to the amount of time required for calcium ions to become supersaturated in solution. Alternatively, the induction period may be caused by the development of a small amount of an impermeable calcium-silicon-hydrate (C–S–H) gel at the surface of the particles, which slows down the migration of water to the inorganic oxides. The initial Ca/Si ratio at the surface of the particles is near 3. As calcium ions dissolve out of this C–S–H gel, the Ca/Si ratio in the gel becomes 0.8-1.5. This change in Ca/Si ratio corresponds to a change in gel permeability, and may indicate an entirely new mechanism for C–S–H formation. As the initial C–S–H gel is transformed into the more permeable layer, hydration continues and the induction period gives way to the third phase of hydration, the acceleratory period ( [link] c).