Effect of surface water on wollastonite carbonation: Activated dissolution and mass transfer

Carbonation of non-hydraulic calcium silicate to produce cement represents a crucial strategy for mitigating carbon emissions in the cement industry. However, the dissolution rate of Ca2+ is the main constraint on the reaction kinetics. In this study, the carbonation of wollastonite (CS) was investigated, with an emphasis on the role of water in the Ca2+ dissolution process. Firstly, we investigated carbonation performance of CS and its influencing factors. Results revealed a significant impact of the water-to-solid (w-s) ratio on carbonation. In the carbonate products, we observed that the dissolution of Ca2+ adsorbed on the particle surface, referred to as “pseudocrystalline replacement”, which can serve as supplementary cementitious material. Additionally, this observation signifies the accordance of Ca2+ dissolution with the electric double layer (EDL) theory. Subsequently, we quantitatively assessed the influence of w-s ratio on carbonation using kinetic models. Based on EDL theory and the kinetic model, we categorized water film effect into three stages and determined the influence of water film thickness on the rate-determining factors of CS carbonation. This provides theoretical support for preparation of CS-based cement. Interestingly, we found that reaction rate constant varies with changes in the w-s ratio, indicating a catalytic role of water. Further analysis using density functional theory demonstrated that the free water combined with the O/Ca sites on CS to form hydroxylated surfaces, thereby decreasing and increasing the abilities of the local and neighboring sites, respectively, to absorb H2CO3. These findings provide a theoretical foundation for the curing method of low-carbon cements and offer a methodology for the preparation of supplementary cementitious materials.