Modeling Dynamic Surface Tension on Surfactant-Enhanced Polydimethylsiloxane.

Surfactants are often added to aqueous solutions to induce spreading on otherwise unwettable hydrophobic surfaces. Alternatively, they can be introduced directly into solid hydrophobic materials─such as the soft elastomer, polydimethylsiloxane─to induce autonomous wetting without requiring additional surface or liquid modifications. Given the similarity between mechanisms of these two approaches, models that describe wetting by aqueous surfactant solutions should also characterize wetting on surfactant-solid systems. To investigate this theory, multiple surfactants of varying size and chemical composition were added to prepolymerized PDMS samples. After cross-linking, water droplets were placed on the surfaces at set time points, and their contact angles were recorded to track the temporal evolution of the interfacial tension. Multiple nonlinear models were fitted to this data, their parameters were analyzed, and each goodness of fit was compared. An empirical model of dynamic surface tension was found to describe the wetting process better than the single established model found in the literature. The proposed model adapted better to the longer time scales induced by slow molecular diffusivity in PDMS. Siloxane ethoxylate surfactants induced faster and more complete wetting of PDMS by water than oxyoctylphenol ethoxylates did. The generalizability of this model for characterizing nonionic surfactants of a wide range of physiochemical properties was demonstrated.