Molecular Dynamics Investigation of Nanoscale Hydrophobicity of Polymer Surfaces: What Makes Water Wet?


The wettability of a polymer surface--related to its hydrophobicity or tendency to repel water--can be crucial for determining its utility, such as for a coating or a purification membrane. While wettability is commonly associated with the macroscopic measurement of a contact angle between surface, water, and air, the molecular physics that underlie these macroscopic observations are not fully known, and anticipating relative behavior of different polymers is challenging. To address this gap in molecular-level understanding, we use molecular dynamics simulations to investigate and contrast interactions of water with six chemically distinct polymers: polytetrafluoroethylene, polyethylene, polyvinyl chloride, poly(methyl methacrylate), Nylon 66, and polyvinyl alcohol. We show that several prospective quantitative metrics for hydrophobicity agree well with experimental contact angles. Moreover, the behavior of water in proximity to these polymer surfaces can be distinguished with analysis of interfacial water dynamics, extent of hydrogen bonding, and molecular orientation--even when macroscopic measures of hydrophobicity are similar. The predominant factor dictating wettability is found to be the extent of hydrogen-bonding between polymer and water, but the precise manifestation of hydrogen-bonding and its impact on surface-water structure varies. In the absence of hydrogen-bonding, other molecular interactions and polymer mechanics control hydrophobic ordering. These results provide new insights into how polymer chemistry specifically impacts water-polymer interactions and translates to surface hydrophobicity. Such factors may facilitate the design or processing of polymer surfaces to achieve targeted wetting behavior, and presented analyses can be useful in studying the interfacial physics of other systems.

Version notes

Updated text and references. Reorganization of some methods. Inclusion of additional supporting calculations and analysis.


Supplementary material

Supporting Information
Supporting information including description of preparation of polymer surfaces, the calculation of contact angle, summary of simulated hydrophobicity metrics for all polymer surfaces, discussion of system heterogeneity on excess chemical potential, complexity of fitting autocorrelation functions, examination of PE surfaces, overview of computational costs of hydrophobicity metrics.