Interfacial energy as an approach to designing amphipathic surfaces during photopolymerization curing

Photopolymerization induced phase separation (PIPS) is a platform capable of creating heterogeneous materials from initially miscible resin solutions, where both the reaction's governing thermodynamics and kinetics significantly influence the resulting phase composition and morphology. Here, PIPS is used to develop materials in a single photopolymerization step that are hydrophobic on one face and hydrophilic on the other. These two faces possess a water contact angle difference of 50°, bridged by a bulk-scale chemical gradient. The impact of the PIPS-triggering inert additive is investigated by increasing the loading of poly(methyl methacrylate) (PMMA) in an acrylonitrile/1,6-hexanediol diacrylate comonomer resin. The extent of phase separation in the sample network depends on this loading, with increasing PMMA corresponding to macroscale domains that are more chemically and mechanically distinct. A significant period between the onsets of phase separation and reaction deceleration, determined using in situ FT-IR, facilitates this enhanced phase segregation in PMMA-modified samples. Spatially directed domain formation can be further promoted using multiple interface types in the sample mold, here, glass and stainless steel. With multiple interface types, interfacial rearrangements to minimize surface energy during resin photopolymerization result in a hydrophobic face that is nitrile-rich and a hydrophilic face that is nitrile-poor (e.g., acrylate-rich). Using this strategy, patterned wettability on a single face can also be engineered. This study illustrates the capabilities of PIPS for complex surface design and in applications requiring stark differences in surface character without sharp interfaces.