Cementitious materials exposed to marine and saline environments are commonly threatened by a combined attack of sulfate and chloride ions. This study developed a numerical framework to investigate two combined coupling mechanisms of 1) coupled solid-liquid chemical reactions for competitive chloride-sulfate attack and 2) electrostatic multi-ion coupling effect on reactive-transport mechanisms. Various chemical reactions including sulfate attack with anhydrous calcium aluminates, secondary precipitation of expansive minerals, competitive binding, and calcium leaching have been quantified. The electrostatic potential caused by multi-ions coupling was solved according to constitutive electrochemical laws. After model validation, the chemical coupling mechanisms for solid-liquid reactions during competitive chloride-sulfate binding were investigated. On this foundation, the influence of electrostatic multi-ionic coupling effects on ionic transport and its interaction with chemical coupling were disclosed. It was found that neglecting multi-ions coupling effect would result in an underestimated chemical coupling strength in competitive chloride-sulfate binding.

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A coupled numerical approach is used to evaluate the influence of pore connectivity and microcracks on leaching kinetics in fully saturated cement paste. The unique advantage of the numerical model is the ability to construct and evaluate a material with controlled properties, which is very difficult under experimental conditions. Our analysis is based on two virtual microstructures, which are different in terms of pore connectivity but the same in terms of porosity and the amount of solid phases. Numerical fracturing was performed on these microstructures. The non-fractured and fractured microstructures were both subjected to chemical leaching. Results show that despite very different material physical properties, for example, pore connectivity and effective diffusivity, the leaching kinetics remain the same as long as the amount of soluble phases, i.e., buffering capacity, is the same. The leaching kinetics also remains the same in the presence of microcracks.@en