Effects of Thermal Treatments on Perfluorosulfonate Ionomer Membranes

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Virginia Tech

Perfluorosulfonate ionomer (PFSI) membranes were annealed at elevated temperature for various periods of time in order to investigate the morphological effects of thermal treatments. For Nafion® 117, the DSC thermograms of Na+-, Cs+- and tetramethylammonium(TMA+)-form membranes show an endothermic peak develops upon annealing at 200ºC, indicating the development of crystallinity in the membrane. For these three samples annealed under same conditions, the heat of fusion (ΠH) values of the endothermic event increases with increasing counterion size. Larger tetraalkylammonium ions, tetraethylammonium(TEA+) and tetrapropylammonium(TPA+), result in no significant peak upon annealing at 200ºC. DSC thermograms of annealed Na+-form 3M Ionomer show no peak upon annealing and DSC thermograms of annealed TMA+-form 3M Ionomer show a very small peak that develops with annealing time at high equivalent weights. Annealed TMA+-form Dow Ionomer, which has a side chain shorter than both Nafion® and 3M Ionomer and a smaller mole% of side chains at the same equivalent weight, shows a relatively high ΠH value, which might also be related to its blocky nature. These results show that the isothermal crystallization kinetics of PFSI is affected by the counterion attached to the sulfonate group, the length of side chain, the mole% of side chains and the nature of the membrane. Water uptake analysis has been performed on annealed membranes, and the result shows that water uptake decreases with increasing degree of crystallinity.

morphology, Nafion®, perfluorosulfonate ionomers, crystallinity, thermal treatment