Humidity-Driven Interfacial Restructuring of Lubricating Films in Phosphate Ester Ionic Liquids: Aromatic vs. Aliphatic Cation Effects

This study investigates the interfacial behavior of four phosphate ester ionic liquids (ILs) with contrasting cation hydrophobicity under humid environments. Through tribological tests, surface analysis, and molecular dynamics simulations, we reveal how moisture absorption governs lubricant film organization at metal interfaces. Aromatic ILs (imidazolium/pyridinium cations) exhibit significant degradation in lubrication after moisture exposure, with friction coefficients increasing by 0.03–0.05 and wear volumes scaling with humidity. This deterioration arises from competitive water–cation adsorption, where hydrogen bonding disrupts Fe-cation coordination bonds and destabilizes the protective film. In contrast, aliphatic ILs (tetraalkylammonium/phosphonium cations) maintain robust tribological performance. Their alkyl chains spatially confine water to outer adsorption layers (>17 Å from the surface), preserving a stable core lubricating film (~14 Å thick). Molecular dynamics simulations confirm that water co-adsorbs with aromatic cations (RDF peak: 2.5 Å), weakening interfacial interactions, while aliphatic ILs minimize cation–water affinity (RDF peak: 4 Å). These findings establish cation hydrophobicity as a critical design parameter for humidity-resistant lubricants, providing fundamental insights into water-mediated interfacial phenomena in complex fluid systems.