The aim of this study was to experimentally investigate the process of chloride binding and its sulfate-induced release in cementitious materials. The cementitious materials were replaced with hardened cement paste particles (HCPs) with water-to-cement ratios (w/c) of 0.35 and 0.45. A long-term immersion experiment of HCPs in 0.1 M sodium chloride solution was performed to investigate its chloride-binding capacity, and then it was immersed in sodium sulfate solutions with concentrations of 0.1 and 0.5 M to explore the release of chloride binding induced by sulfates. Silver nitrate titration and quantitative X-ray diffraction (QXRD) were used to measure the concentration of free chlorides in the solutions and the content of bound chlorides in HCPs, respectively. The results show that there is a higher chloride-binding capacity in HCPs with a w/c ratio of 0.45 compared to 0.35, and the content of chemically bound chlorides is associated with the formation and decomposition of Friedel's and Kuzel's salts in HCPs. The presence of sulfates can easily result in the release of bound chlorides in Friedel's salt, but it cannot cause a complete release of bound chlorides in Kuzel's salt. Physically bound chlorides are more easily released by sulfates than chemically bound chlorides, and a high w/c ratio or sulfate concentration can increase the release rate of bound chlorides in HCPs.
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