Using Indentation to Characterize Water Transport and Structure in Nafion Thin Films

Perfluorinated ionomers, specifically Nafion, are the state-of-the-art polymer used in fuel cells. For this application, Nafion is utilized in both a bulk (hundreds of microns) and confined (tens of nanometers) state. For Nafion thin films in a confined state, i.e., Nafion as thin film coatings on catalyst particles, in-plane transport may play a critical role in the movement of water and protons through this catalysis layer. In this study, water transport was measured for a series of Nafion thin film thicknesses using poroelastic relaxation indentation (PRI). Unlike traditional through-thickness diffusion measurement techniques for thin polymer films (e.g., quartz crystal microbalance), PRI can be used to probe the in-plane water transport behavior. Relative to bulk Nafion, reduced in-plane water diffusion was observed in thin film Nafion, and below approximately 1 micron, water diffusivity and Nafion film thickness exhibited a logarithmic relationship. Equilibrium swelling measurements of water saturated Nafion thin films were used in conjunction with pore network theory to develop a picture of how the molecular-scale structure of Nafion changes with confinement to nanoscale film thicknesses.