Calcite,vaterite and aragonite forming on cement hydration from liquid and gaseous phase

Cement hydration products were studied as influenced by the hydration conditions (hydration time in liquid phase; relative humidity, RH, in gaseous phase). The formation of calcium hydroxide (portlandite, P) and its transformation to calcium carbonates is mainly discussed here. More hydration products, including P, were formed in liquid phase (paste) than in water vapor (powder), due to the higher availability of water molecules. Full hydration was observed only in the paste hydrated for 6 month, otherwise the P content, estimated from its water escape, DM(400-800°C), increased after storage in water vapor of the prehydrated paste. All the three polymorphs of CaCO₃ (calcite, vaterite and aragonite) were found on prolonged contact with air of the hydrated powder (XRD, HRTEM). Their content was dependent on sequence of RH conditions on hydration: higher after water retention, WR, on lowering RH=1.0→0.95→0.5, than after water sorption, WS, on increasing RH in the inverse order. It increased also on wetting and drying, both of hydrated powder and paste. Ca was found to accumulate on the micro-surfaces of WR samples (SEM, TEM), whereas more Al was observed on WS samples and the crystallinity of hydration products was here higher (ED). Dissolution-diffusion-recrystallization was possible: small Al-ions concentrated at one end and the bigger Ca ions - at the other end of some needles (TEM). At 400-500°C the P in cement transforms in air into CaCO₃, which decomposes at 600-700°C. Thus the sensitivity to carbonation was estimated from ΔM(600-800°C). This value was similar in pastes hydrated for 1 month and in powder (WR). It was lower in powder WS and much lower in the paste (6 months). It increased pronouncedly when the prehydrated paste was stored in water vapor in WS. The nanocrystals of portlandite, vaterite and aragonite, embedded in the amorphous matrix, were observed by HRTEM in the hydrated powder. They may contribute to the cement strength. This revised version was published online in July 2006 with corrections to the Cover Date.