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This is a study of morphology, water uptake, and proton conductivity of a sulfonated polystyrene-block-polyethylene (PSS-PE) copolymer equilibrated in humid air with controlled relative humidity (RH), and in liquid water. Extrapolation of the domain size, water uptake, and conductivity obtained in humid air to RH = 100% allowed for an accurate comparison between the properties of PSS-PE hydrated in saturated vapor and in liquid water. We demonstrate that extrapolations of domain size and water uptake on samples equilibrated in humid air are consistent with measurements on samples equilibrated in liquid water. Small (5%) differences in proton conductivity were found in samples equilibrated in humid air and liquid water. We argue that differences in transport coefficients in disordered heterogeneous systems, particularly small differences, present no paradox whatsoever. Schroeder's Paradox, wherein properties of polymers measured in saturated water vapor are different from those obtained in liquid water, is thus not observed in the PSS-PE sample.

Polymer electrolyte membranes with bicontinuous microphases comprising soft hydrated domains and mechanically robust hydrophobic domains are used in a wide range of electrochemical devices including fuel cells and electrolyzers. The self-assembly, water uptake, and proton conductivity of model block copolymer electrolytes with semicrystalline hydrophobic blocks were investigated. A series of sulfonated polystyrene-block-polyethylene (PSS-PE) copolymers were synthesized to probe the interplay between crystallization, morphology, hydration, and proton transport. In block copolymer systems with amorphous hydrophobic blocks, it has been shown that higher water update and proton conductivity are obtained in low molecular weight systems. However, crystallization is known to disrupt the self-assembly of low molecular weight block copolymers. We found that this disruption results in lower water uptake and proton conductivity. Increasing molecular weight results in less morphological disruption and improvement in performance. © 2014 American Chemical Society.