Influence of the Ca/Si ratio of the C–S–H phase on the interaction with sulfate ions and its impact on the ettringite crystallization pressure

The effect of the Ca/Si ratio of the calcium–silicate–hydrate (C–S–H) phase on the interaction with sulfate ions is investigated for C–S–H phases (Ca/Si = 0.83, 1.25, 1.50) and mortar samples of blended Portland cements. It is shown that leaching of calcium from C–S–H and portlandite affects the composition of the pore solution and contributes to the developing crystallization pressure of ettringite. Sulfate profiles show that sulfate binding before cracking is similar for different Ca/Si ratios whereas the highest expansion rates are observed for the mortars with the highest Ca/Si ratios. After leaching in sulfate solutions, the C–S–H samples have been characterized by ²⁹Si MAS NMR, thermogravimetric analysis, and elemental solution analysis. Generally, the exposure to sulfate solutions results in decalcification of the C–S–H, which increases with decreasing Ca/Si ratio. The data are in good agreement with thermodynamic modeling, indicating that equilibrium is almost achieved in the leached systems. Finally, the expansion of mortar samples exposed to sulfate solutions was much less at lower Ca/Si ratios of the cement blends. This reduced expansion can be related to the decrease of the supersaturation of the pore solution with respect to ettringite at lower Ca/Si ratios of the C–S–H and in the absence of portlandite.