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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Reinforced concrete (RC) structures may suffer from serious durability problems during long-term service. To investigate the deterioration of RC structures subjected to the dual attacks of chlorides and sulfates, this study proposes a coupled model for external sulfate attack (ESA) and its effect on chloride binding and diffusion. To account for the influence of sulfate attack on chloride binding, a reduction function is proposed. The effect of sulfate-induced damage on the chloride diffusion and chloride binding is considered through a damage function. The coupled model is validated against third-party experimental data from multiple perspectives. Some important factors such as solution concentration, immersion time, curing time and water-cement ratio, as well as how these factors affect the impact of sulfate attack on chloride transport, were elaborated. The findings may bring insights to the durability design of RC structures serving in harsh environments.@en