Confinement-Driven Increase in Ionomer Thin-Film Modulus

Ion-conductive polymers, or ionomers, are critical materials for a wide range of electrochemical technologies. For optimizing the complex heterogeneous structures in which they occur, there is a need to elucidate the governing structure–property relationships, especially at nanoscale dimensions where interfacial interactions dominate the overall materials response due to confinement effects. It is widely acknowledged that polymer physical behavior can be drastically altered from the bulk when under confinement and the literature is replete with examples thereof. However, there is a deficit in the understanding of ionomers when confined to the nanoscale, although it is apparent from literature that confinement can influence ionomer properties. Herein we show that as one particular ionomer, Nafion, is confined to thin films, there is a drastic increase in the modulus over the bulk value, and we demonstrate that this stiffening can explain previously observed deviations in materials properties such as water transport and uptake upon confinement. Moreover, we provide insight into the underlying confinement-induced stiffening through the application of a simple theoretical framework based on self-consistent micromechanics. This framework can be applied to other polymer systems and assumes that as the polymer is confined the mechanical response becomes dominated by the modulus of individual polymer chains.