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Interesting Facets of Surface, Interfacial, and Bulk Characteristics of Perfluorinated Ionomer Films.

Ion-containing perfluorinated polymers possess unique viscoelastic properties, excellent proton conductivity, and nanophase-segregated structure all arising from the clustering of hydrophilic sulfonic acid groups within a matrix of hydrophobic fluorocarbons. When these ionomers are confined to nanothin films, a broad swathe of structural organization imparting a rich variety of surface, interfacial, and bulk characteristics can be expected. However, our understanding of perfluorinated ionomer thin film behavior is still in a rudimentary stage, and much of the research focus to date has been on its hydration-related structure and properties pertinent to electrochemical applications. Thus, many hidden gems-their interesting surface and interfacial properties-have been overlooked. In this Invited Feature Article, which is a summary of the key contributions by the author's group, including several collaborative publications on ionomer thin films, we unravel many of these facets. In addition, the article attempts to integrate knowledge acquired from a variety of investigations of different aspects of the ionomer thin films to refine and develop a consistent picture of their structure and behavior. First, we focus on the self-assembly of ionomers and show that dispersion media and hydrophobicity/hydrophilicity of the substrate can result in partial or even no coverage of substrates, shedding light on the complexity of polymer-substrate, polymer-solvent, and polymer-polymer interactions, an insight completely obscured when the spin-coating method is adopted for film creation. We demonstrate that the same ionomer can be used to create a variety of surfaces ranging from superhydrophilic to highly hydrophobic by controlling the film thickness or through the choice of substrate material. The ultrathin, hydrophilic surfaces of self-assembled Nafion ionomer films exhibit wettability switching behavior which opens the door to creating stimuli-responsive smart surfaces. The thermoresponsive behavior of the films is discussed in the context of surface (wettability) and bulk (thermal expansion) characteristics as well as a newly discovered vibrational mode. The substrate- and film thickness-dependent thermal expansion coefficients reinforce the importance of interfacial interactions and confinement on the structure/properties of these films. They also open up the potential of tuning ionomer bulk properties via substrate chemistry. The discovery of a vibrational mode that becomes thermally activated at high temperature has provided new insights into the origins of the molecular motions responsible for the α-relaxation of the Nafion ionomer as well as the underlying reason for wettability switching. Our recent neutron reflectometry study of different ionomers varying in side-chain composition/length on a platinum substrate shows that the interfacial hydration level is correlated to the side-chain length, which opens up the possibility of the controlling the interfacial electrochemistry. Finally, a systematic analysis of factors affecting proton conduction is presented to elucidate the yet-unresolved origins of the suppressed conduction of nanothin ionomer films compared to that of the bulk membrane. By revealing these interesting yet poorly understood facets of ionomer thin films, the article aims to stimulate further scientific pursuit on this topic.