Structure, orientation, and dynamics of water-soluble ions adsorbed to basal surfaces of calcium monosulfoaluminate hydrates

Transport of water molecules and chloride ions in nanopores of hydrated cement paste (HCP) is proven to adversely affect the long-term durability of reinforced concrete structures exposed to seawater or deicing salts. The resistance against chloride attack is primarily associated with the chloride binding capacity of the main HCP constituents. Experimental tests revealed that AFm phases of HCP play a central role in binding the chloride ions. However, many aspects of AFm–solution interactions were largely unknown, especially at their interfaces. This was the motivation of the current study, in which the atomistic processes underlying the transport of water-soluble ions are investigated in detail using the classical molecular dynamics (MD) method. To this end, an aqueous layer containing various concentrations of sodium chloride solution is sandwiched between two basal surfaces of calcium monosulfoaluminate hydrate, which is the most abundant phase of AFm. The adsorption mechanisms of water molecules and diffusing ions are then characterized for inner- and outer-sphere distance ranges from the basal surfaces of monosulfoaluminate. It is found that the self-diffusion coefficient of the chloride and sodium ions present in the outer-sphere range are 83% and 47% larger than those residing in the inner-sphere range. With increasing the distance from the solid surface, an increase in the self-diffusion coefficient is captured. This increase in mobility is larger for chloride ions than sodium ions. This can be understood based on the observation that the inner- and outer-sphere complex formation are the governing adsorption mechanisms for the chloride and sodium ions, respectively.