Thermal Transitions in Perfluorosulfonated Ionomer Thin-Films

Thin perfluorosulfonated ion-conducting polymers (PFSI ionomers) in energy-conversion devices have limitations in functionality attributed to confinement-driven and surface-dependent interactions. This study highlights the effects of confinement and interface-dependent interactions of PFSI thin-films by exploring thin-film thermal transition temperature (TT). Change in TT in polymers is an indicator for chain relaxation and mobility with implications on properties like gas transport. This work demonstrates an increase in TT with decreasing PFSI film thickness in acid (H+) form (from 70 to 130 °C for 400 to 10 nm, respectively). In metal cation (M+) exchanged PFSI, TT remained constant with thickness. Results point to an interplay between increased chain mobility at the free surface and hindered motion near the rigid substrate interface, which is amplified upon further confinement. This balance is additionally impacted by ionomer intermolecular forces, as strong electrostatic networks within the PFSI–M+ matrix raises TT above the mainly hydrogen-bonded PFSI–H+ ionomer