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This paper investigates the mechanical stability and critical thickness of free-standing, ultrathin molten polyethylene films using Molecular Dynamics simulations. By comparing the “interfacial drying” and “film stretching” methodologies, this research establishes that both methods consistently identify a stability threshold where continuous films transition into fibrillar and void structures known as “crazes”. A key finding is that films at extremely reduced thicknesses exhibit an anisotropic pressure profile in their core—characterized by a positive normal pressure—which serves as a manifestation of positive disjoining pressure and a precursor to film transformation. Consequently, the study proposes a more rigorous stability criterion based on mechanical isotropy, which yields higher critical thickness values (approximately 6.5 nm at 373.15 K and 9.3 nm at 673.15 K) than those previously estimated from short-term (100 ns) visual observations. Ultimately, the work concludes that maintaining a negative disjoining pressure is fundamental to the structural integrity of these polymeric nanomaterials.

Classical Molecular Dynamics simulations were used to investigate 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 MPa 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 of the film decreases exponentially with increasing gas pressure of ethane and 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 K and 373.15 K.