10 HYDRATION OF PORTLAND CEMENT Portland cement sets and hardens due to exothermic hydration reac- tions. Hydration products include colloidal gels and sub-micron crys- tals. The crystals may be fibres, needles and plates which form an interlocking microstructure that can be observed with the aid of a scan- ning electron microscope (SEM). Both chemical and physical processes are, therefore, involved with the two standard explanations of cement setting and strength development being Le Chatelier’s interlocking crystal theory and Michaelis's colloidal gel theory (Benstead; WC; 8/1991, pg 21: Chen & Odler; Cem and Conc Res; Vol 22; 1992, pg 1130) The reactivity of cement phases with water are in the order aluminate > alite > ferrite > belite. CsA is the most soluble of the major compounds and appears to dominate early hydration. Aluminate and, particularly, silicate hydration reactions are extremely complex and many undoubt- edly contribute to setting and strength gain of cement (see Lea’s Chemistry of Cement and Concrete; Arnold, 4th Ed; 1998, pg 241). Cement hydration can be approximately divided into four stages: Initial Stage - Within seconds of contact with water, alkali sulphates dissolve and within minutes, calcium sulphate reaches saturation. Dissolved aluminate and sulphate react to form ettringite (CGsA.3CaSO,.32H20) which is precipitated, normally on the surface of cement particles. Alite dissolves slightly and forms a calcium silicate hydrate gel (C-S-H) on the surface of alite particles. These hydration product coatings block further reaction and initiate a dormant period. This initial period is characterised by heat release. The rate of dissolu- tion of sulphate relative to aluminate is critical to prevent early stiffen- ing, of cement paste. A deficiency of sulphate in solution leads to uncontrolled hydration of C3A to CyA.14H20 and CA.8H;0 which crystallise to cause flash set. An excess of soluble sulphate leads to pre- cipitation of gypsum, syngenite, or ettringite in pore solution causing flash or false set. Cement Plant Operations Handbook * 157 i 4 =] > — [e) = (2) 1 sc o =) er = P= = =] (@) iu = mm = vam]Induction or Dormant Stage - This stage lasts 1 to 3 hours while the hydration of all clinker phases progresses slowly. In the early stages, Ca®* in pore solution reaches super-saturation with respect to Ca(OH)2, and nucleation and growth of both C-S-H and Ca(OH). begin. At this stage of structure development, thin shells of C-S-H and a few ettringite rods develop around clinker particles. The subsequent decrease in the concentration of Ca* in solution and the rupture of coatings trigger renewed acceleration of alite dissolution and heat release. The continu- ous deposition of C-S-H, Ca(OH): and other hydration products causes bridging between particles and reduces paste porosity. This signals the onset of setting. Acceleration Stage - This stage begins with initial set and continues with rapid hydration of alite into C-S-H and Ca(OH)2. These reactions are accompanied by intense heat release which reaches a peak approx- imately 12 hours into hydration. More ettringite is formed as gypsum is depleted and the ettringite subsequently dissolves and reacts with Al(OH):- to form monosulfoaluminate (C3A.CaSOx.12H20). Depending upon the relative amounts of gypsum and aluminate, monosulfoalumi- nate formation may be completed before or after the peak of alite hydra- tion. Final set is reached before peak heat release from alite hydration. Deceleration Stage - This spans many days and is characterised by low heat evolution and a decreased overall rate of reaction as the reacting, species become used up and diffusion slows with decreasing porosity. Belite becomes the primary hydrating phase. C-S-H is believed to undergo polycondensation of the SiOs tetrahedral chains with progres- sively increasing strength It has been observed that setting is largely independent of CsA concen- tration and it is now believed that both setting and strength develop- ment are largely caused by hydration of CsS to tobermorite, a C-S-H gel of variable composition Hydration of cement typically involves combined water of about 22% relative to clinker weight. Given that a normal water:cement ratio in concrete is 0.4-0.5, it is clear that excess water must be used for worka- bility and that this excess water causes strength loss. The relative con- tributions to strength development are shown in the following diagram. 158 * Cement Plant Operations HandbookCompressive Strength (ka/em2) 500 gS 250 os Cah AE x 0 Time (days) Figure 10.1: Strength Gain of Cement Compounds Pozzolanic activity is the result of the reaction of soluble SiO» from the pozzolan with CaO in solution. As free CaO will always be present in solutions in contact with hydrated cement, pozzolanic reactions provide ‘self-curing’ of cracks in pozzolanic concrete. oe Cement Plant Operations Handbook ¢ 159 = a =] 5 = © Pa o "TI a") oO | =| = Pd = =] @) Ua = m = =|