The tricalcium aluminate (C3A) and sulfate content in cement influence the hydration chemistry, setting time and rheology of cement paste, mortar and concrete. Here, in situ experiments are performed to better understand the effect of gypsum on the early hydration of cubic (cub-)C3A and Na-doped orthorhombic (orth-)C3A. The isothermal calorimetry data show that the solid-phase assemblage produced by the hydration of C3A is greatly modified as a function of its crystal structure type and gypsum content, the latter of which induces non-linear changes in the heat release rate. These data are consistent with the in situ X-ray diffraction results, which show that a higher gypsum content accelerates the consumption of orth-C3A and the subsequent precipitation of ettringite, which is contrary to the cub-C3A system where gypsum retarded the hydration rate. These in situ results provide new insight into the relationship between the chemistry and early-age properties of cub- and orth-C3A hydration and corroborate the reported ex situ findings of these systems.

Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C3A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C3A polymorph and gypsum when no lime is added; orthorhombic C3A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.