Influence of silica fume addition and content on the early hydration of calcium aluminate cement – The role of soluble silicon

Hydration of a commercial white calcium aluminate cement (CAC) at 23 °C was modified by silica fume (SF) addition in varying amounts. The process was followed by heat flow calorimetry, quantitative in-situ XRD analysis and Gillmore needle experiments supplemented by pore solution analysis, thermodynamic modelling, and ¹H-TD-NMR measurements. Lower SF/cement ratios accelerate the hydration of CAC. Higher ratios trigger an intermediate heat flow event, which is correlated to increased setting rates. This intermediate event (IE) initiates an induction period of constant duration, which appears later with increasing SF/cement ratios. Results show the IE is caused by an initially hindered CA dissolution, in which dissolved silicon provided by SF plays a crucial role. Increasing the [Si] concentration in the pore solution leads to a further retardation of the IE and eventually prevents the entire hydration reaction if a critical amount is reached. A detailed model explaining the observed behavior is proposed.