A kinetic Monte Carlo study of the C3S dissolution mechanism

Abstract

Understanding the mechanism that controls cement hydration and its stages is a long-standing challenge. Over a decade ago, the mineral dissolution theory was adopted from geochemistry to explain the hydration rate evolution of alite. The theory is not fully accepted by the community and deserves further investigation. In this work, we apply Kinetic Monte Carlo (KMC) simulations with the mineral dissolution theory as a conceptual framework to investigate and discuss alite dissolution. We build a Kossel crystal model system and parameterize the dissolution activation energies and frequencies based on experimental data. The resulting KMC model is capable of reproducing the dissolution rate and activation energies as a function of the dissolution free energy. The simulations indicate that mineral dissolution theory easily explains the induction and acceleration stages due to a continuous increase of the reactive area as the etch pits open. However, the deceleration stage is hardly reconcilable with the mechanism suggested in the literature, i.e. dislocation coalescence. Still, within the mineral dissolution theory umbrella, we propose and discuss an alternative mechanism based on dislocation exhaustion.