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Abstract

Chemical degradation and stability of perfluorosulfonic acid (PFSA) ionomers against radical attack were investigated by an (ex situ) Fenton test. Solid-state and solution NMR as well as ATR-FTIR studies were performed on the samples before and after the Fenton reaction. By changing the concentration of the Fenton's solution it is found that the metallic catalyst (Fe(2+)) is a critical factor which may affect the solid-state NMR results. After adjusting the experimental conditions, i.e., by reducing the Fe(2+) concentration, it was possible to detect by solid-state (19)F NMR spectroscopy the structural changes of the perfluorosulfonic acid ionomers during the ex situ Fenton test. A comparative study was made on the degradation of Nation and Hyflon Ion membranes which differ in the length of the side chains. It is shown that the Hyflon Ion membrane with shorter side chains is more stable against side chain attack, most probably because of the absence of an additional tertiary carbon in the side chain. At the same time, there is evidence for enhanced main chain degradation in membranes with unprotected backbone chain ends. (C) 2010 Elsevier B.V. All rights reserved.