Solid-State NMR and Impedance Spectroscopy Study of Spin Dynamics in Proton-Conducting Polymers: An Application of Anisotropic Relaxing Model

The ¹H–¹³C cross-polarization (CP) kinetics in poly­[2-(methacryloyloxy)­ethyltrimethylammonium chloride] (PMETAC) was studied under moderate (10 kHz) magic-angle spinning (MAS). To elucidate the role of adsorbed water in spin diffusion and proton conductivity, PMETAC was degassed under vacuum. The CP MAS results were processed by applying the anisotropic Naito and McDowell spin dynamics model, which includes the complete scheme of the rotating frame spin–lattice relaxation pathways. Some earlier studied proton-conducting and nonconducting polymers were added to the analysis in order to prove the capability of the used approach and to get more general conclusions. The spin-diffusion rate constant, which describes the damping of the coherences, was found to be strongly depending on the dipolar I–S coupling constant (D_IS). The spin diffusion, associated with the incoherent thermal equilibration with the bath, was found to be most probably independent of D_IS. It was deduced that the drying scarcely influences the spin-diffusion rates; however, it significantly (1 order of magnitude) reduces the rotating frame spin–lattice relaxation times. The drying causes the polymer hardening that reflects the changes of the local order parameters. The impedance spectroscopy was applied to study proton conductivity. The activation energies for dielectric relaxation and proton conductivity were determined, and the vehicle-type conductivity mechanism was accepted. The spin-diffusion processes occur on the microsecond scale and are one order faster than the dielectric relaxation. The possibility to determine the proton location in the H-bonded structures in powders using CP MAS technique is discussed.