Investigation of Multi-Ion Transport Properties in Cement Paste Based on a Multi-Scale Phase Evolution Model

Marine concrete structures are subjected to multiple aggressive ions that react with hydration products, driving dynamic phase evolution and altering ion transport pathways. This study develops a multi-scale lattice diffusion–reaction coupled framework grounded in a microstructural evolution model, incorporating a simplified analytical correction for the electrical double layer (EDL) effect. Validation against Poisson–Boltzmann numerical solutions across a pore size range of 1.5–50 nm confirms that the mean relative errors for monovalent, divalent, and trivalent ions remain within 10%. The phase evolution of cement paste under single-ion attack was simulated, and its impact on ion transport performance under multi-ion coupled ingress was systematically investigated. Under multi-ion attack, solid phases exhibit a highly ordered spatial zonation. Chloride ions completely displace monosulfate, forming a Friedel’s salt-enriched zone. Meanwhile, directly penetrating external sulfate generates a pronounced surface ettringite peak, while sulfate released from monosulfate decomposition in the Friedel’s salt zone induces secondary ettringite precipitation deeper within the material, producing a characteristic double-step ettringite distribution. A cracking criterion based on the critical capillary pore filling fraction captures the transition from pore filling to microcracking, yielding a three-zone profile for the relative diffusion coefficient. At 500 days of exposure, crystallization-induced microcracking triggers a more than 7-fold increase in surface relative diffusivity (w/c = 0.35). Furthermore, at 250 days, once cracking initiates, low water-to-cement ratio (w/c = 0.3) matrices display a higher relative diffusivity amplification factor of approximately 9, compared to approximately 6 for high water-to-cement ratio (w/c = 0.4) matrices. The established framework provides a quantitative tool for assessing the durability of concrete structures under complex chemical attack environments.