The spectroscopic and thermal properties of swollen Nafion membranes in methanol aqueous mixtures were investigated to understand the behavior of commercial electrolytes in the presence of polar solvents. Several differences were observed in the absorption processes depending on the composition of the solvent. Deconvolution methods were applied to study specific contributions of solvents and polymer groups based on Fourier transform infrared spectroscopy and thermogravimetric analysis. The results evidence compositional effects on the interactions between solvents and Nafion. A major influence of the nonpolar domains (hydrophobic regions) in the absorption of methanol together with a reduction of the interactions with sulfonate groups was observed. Such changes are accompanied by a modification of the cluster morphology of the equilibrated membranes evaluated by differential scanning calorimetry. These findings can be useful to improve the knowledge on Nafion's microstructure in the presence of polar solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
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