High Interfacial Adsorption/Low Solubility of Light Gases on Pristine Nano-Thin Molten Polyethylene Films

Classical Molecular Dynamics simulations were used to investigate the interfacial adsorption of ethane on ultrathin molten polyethylene films. We investigated the interfacial adsorption of supercritical ethane on ultrathin molten polyethylene films at various temperatures (298.15 - 448.15 K) and pressures (0.28 - 13.17 MPa). Ethane was found to accumulate preferentially at the film's interfaces rather than dissolving into the film's core. The ultra-thin, metastable films, studied at their mechanical stability limit, are composed of two overlapping interfaces. The films show some fractions of interfacial chains transiently desorbing from the film surface and entering the gas phase, which facilitates the accumulation of ethane at the interfaces. At 373.15 K and pressures between 0.29 and 9.65 MPa, the combined film interfaces adsorb between 4.8 and 8.6 times more ethane than the amount solubilized in the central, bulk region of the film. Interfacial tension decreases exponentially with increasing gas pressure. Interfacial tension is primarily governed by inter-chain interactions at the interface. Minor contributions arise from the vibrational dynamics of polyethylene chain fractions that transiently desorb from the film surface. Furthermore, the solubility of ethane in the film's bulk region exhibits a temperature-dependent inversion: at 298.15 K, the ethane density in the film's center slightly exceeds that of the bulk gas, but this trend reverses at 373.15 K and becomes more pronounced as the temperature increases. This indicates a potential solubility transition temperature between 298.15 and 373.15 K.