Short-Term Morphological Response of Polypropylene Membranes to Hypersaline Lithium Fluoride Solutions: A Multiscale Modeling Approach

Understanding the early-stage physical interactions between polymeric membranes and supersaturated salt solutions is crucial for advancing membrane-assisted crystallization (MCr) processes. In this study, we employed molecular dynamics (MD) simulations to investigate the short-term morphological response of an isotactic polypropylene (PP) membrane in contact with LiF solutions at different concentrations (5.8 M and 8.9 M) and temperatures (300–353 K), across multiple time points (0, 150, and 300 ns). These data were used as input for computational fluid dynamics (CFD) analysis to evaluate structural descriptors of the membrane, including tortuosity, connectivity, void fraction, anisotropy, and deviatoric anisotropy, under varying thermodynamic conditions. The results show subtle but consistent rearrangements of polymer chains upon exposure to the hypersaline environment, with a marked reduction in anisotropy and connectivity, indicating a more compact and isotropic local structure. Surface charge density analyses further suggest a temperature- and concentration-dependent modulation of chain mobility and terminal group orientation at the membrane–solution interface. Despite localized rearrangements, the membrane consistently maintains a net negative surface charge. This electrostatic feature may influence ion–membrane interactions during the crystallization process. While these non-reactive, short-timescale simulations do not capture long-term degradation or fouling mechanisms, they provide mechanistic insight into the initial physical response of PP membranes under MCr-relevant conditions. This study lays a computational foundation for future investigations bridging atomistic modeling and membrane performance in real-world applications.