RELAXATION AND CHARGE-TRANSPORT IN MIXTURES OF ZWITTERIONIC POLYMERS AND INORGANIC SALTS

Dielectric spectroscopy is employed to analyze the molecular dynamics and the charge transport in mixtures of zwitterionic polymers of the type poly(3-[N-(omega-methacryloyloxyalkyl)-N, N-dimethylammonio]propanesulfonate) with sodium iodide in the frequency range of 10(2) Hz-10(7) Hz and in the temperature range of 110 K-400 K. The amount of inorganic salt added varies from 0-200 mol-% relative to the number of zwitterionic groups present in the polymer, contributing strongly to the conductivity. One relaxation process is observed whose relaxation rate depends strongly on the length of the aliphatic spacer between the polymethacrylate main chain and the zwitterionic group. Exhibiting an Arrhenius-like temperature dependence with activation energy E(A) = 47 kJ/mol, this relaxation process is assigned to fluctuation of the quaternary ammonium groups in the side chains. At higher temperatures, the dielectric properties and the conductivity are primarily dominated by the mobile inorganic ions: conductivity strongly depends on the salt concentration, showing a pronounced electrode polarization effect. The frequency and salt concentration dependences of the conductivity can be quantitatively described as hopping of charge carriers being subject to spatially randomly varying energy barriers. For the low-frequency regime and for the critical frequency marking the onset of the conductivity's dispersion, the Barton-Nakajima-Namikawa (BNN) relationship is fulfilled.