| Ion and polymer dynamics of ion-containing polymers were investigated, with the majority of results obtained from application of a physical model of electrode polarization (EP) to dielectric spectroscopy data. The physical model of MacDonald, further developed by Coelho, was extended for application to tan delta (the ratio of dielectric loss to dielectric constant) as a function of frequency. The validity of this approach was confirmed by plotting the characteristic EP time as a function of thickness and comparing the actual and predicted unrelaxed dielectric constant for a poly(ethylene oxide) (PEO)-based ionomer neutralized by lithium, sodium, and cesium. Results were obtained for ion mobility and mobile ion concentration for a neat PEO-based ionomer, two (methoxyethoxy-ethoxy phosphazene) (MEEP) -based ionomers, two MEEP-based salt-doped polymers, sulfonated polystyrene (SPS) neutralized by sodium with a high sulfonation fraction, and SPS neutralized by zinc with a low sulfonation fraction. Additionally, the conductivity parameters of six plasticized forms of a neat PEO-based ionomer were characterized, but the method apparently failed to correctly evaluate bulk ionic behavior. In all cases except the SPS ionomers ion mobility follows a Vogel-Fulcher-Tammann (VFT) temperature dependence. In all cases, mobile ion concentration follows an Arrhenius temperature dependence. Fitting parameters from these two relationships yielded direct information about the state of ionic diffusion and ion pairing in each system. Combination of these two functionalities predicts a relationship for conductivity that is significantly different than the VFT relation typically used in the literature to fit conductivity. The most outstanding result was the extremely small fraction of ions found to be mobile. For ionomers it can be concluded that the primary reason for low conductivities arises from the low fraction of mobile ions.; The local and segmental dynamics of the neat and plasticized PEO-based ionomer were also studied in comparison to conductivity, with the conclusion that the glass transition temperature (a manifestation of the segmental segments) is the primary property governing conduction behavior in single-phase ionomers. Consideration of the solvent quality parameters yielded a similar result, that the plasticization effect on the glass transition is far stronger than the dielectric constant, donor number, or viscosity of the solvents. |
