Fast Field-Cycling Nuclear Magnetic Resonance Relaxometry of Perfluorosulfonic Acid Ionomers and Their Perfluorosulfonyl Fluoride Precursors Membranes.

The spin-lattice relaxation rates () of fluorine nuclei in perfluorosulfonic acid (PFSA) ionomer membranes and their precursor solid perfluorosulfonyl fluoride (PFSF) were measured by fast field-cycling (FFC) NMR relaxometry. The XRD profiles of PFSA and PFSF are similar and show a characteristic peak, indicating the alignment of main chains. While the SAXS profiles of the PFSA membranes show two peaks, those of the solid PFSF lack the ionomer peak which is characteristic of hydrophilic side chains in the PFSA ionomer membranes. The Larmor frequency dependence of obeys power law and the indices are dependent on the sample and temperature. The indices of the PFSA membranes change from -1/2 to -1 along with the Larmor frequency and temperature dependence decrease, which is consistent with the generalized defect diffusion model. Estimated activation energies are in good agreement with those obtained from dynamical mechanical analysis and dielectric spectroscopy, indicating the segmental motion of the backbones as the common origin of these observations. On the other hand, the index changes to -3/4 in the case of the PFSFs, which has been predicted by the reptation model.