Calcium sulfoaluminate cement (CSA) is a type of low-CO₂ binder which has been widely applied in the production of concrete. To investigate the protection capability offered by CSA to keep steel from corrosion, the pore solution chemistry of CSA on steel passivation was investigated in this study. The pore solution of CSA pastes, extracted by an ex situ leaching method, was studied and compared with ordinary Portland cement (OPC). The results show that the alkalinity of the CSA pore solution is not only much lower than that of OPC, but also that a new type of ion, Al(OH)₄⁻, and high concentration of SO₄²⁻ were detected in the liquid phase of CSA. Based on pore solution chemistry analysis, a simulated pore solution (SPS) system was designed to assess the comprehensive impact of alkalinity and ion composition, featured as properties of CSA, on steel passivation. The results of the corrosion potential evolution highlight the importance of alkalinity in passivation. SO₄²⁻ can cause depassivation when there is not enough hydroxyl, but Al(OH)₄⁻ is able to maintain the alkalinity of the system, enhancing the stability of the passive film.

In response to rising CO₂ emissions in the cement industry and the growing demand for durable offshore engineering materials, calcium sulphoaluminate (CSA) cement concrete, known for its lower carbon footprint and enhanced corrosion resistance compared to Ordinary Portland Cement (OPC), is increasingly important. However, the chloride transport behavior of CSA concrete in both laboratory and marine environments remains underexplored and controversial. Accordingly, the chloride ion transport behaviors and mechanisms of CSA concrete in laboratory-accelerated drying-wetting cyclic environments using NaCl solution and seawater, as well as in marine tidal environments, were characterized using the rapid chloride test (RCT), X-ray diffraction (XRD), mercury infiltration porosimetry (MIP), and thermogravimetric analysis (TGA). The results reveal that CSA concrete accumulates more chloride ions in NaCl solution than in seawater, with concentrations 2–3.5 times higher at the same water–cement ratio. Microscopic analysis indicates that calcium and sulfate ions present in seawater facilitate the regeneration of ettringite, thereby increasing the density of the surface pore structure. The hydration and repair mechanisms of CSA concrete under laboratory conditions closely resemble those in marine tidal conditions when exposed to seawater. Additionally, this study found that lower chloride ion concentrations and pH levels inhibit the formation of Friedel’s salt. Therefore, laboratory experiments with seawater can effectively simulate CSA concrete’s chloride transport properties in marine tidal environments, whereas NaCl solution does not accurately reflect actual marine conditions.