Dynamic properties of polyelectrolyte calcium membranes.

Shashoua observed spontaneous oscillations in a polyelectrolyte membrane formed by interfacial precipitates of polyacid and polybase. We have here undertaken experimental and theoretical studies of polyglutamic acid-Ca++ membrane in order to clarify the processes involved in this dynamic behavior. We find a region of distinct hysteresis in the voltage current curve for this system. A sharp transition from a state of low membrane resistance to one of high resistance occurs at a current density different from that of inverse transition. This membrane system is modeled as a two layer structure: a negatively charged layer alpha made of ionized polyelectrolyte in series with a neutral region beta in which the polymeric ionic sites are masked by calcium ion. This structure results in a difference in the transference number for the mobile ions, causing salt accumulation at the interfacial region during a current flow in the alpha to beta direction. This altered salt concentration induces a change of polymeric conformation, which in turn affects the membrane permeability and the rate of accumulation. Based upon nonequilibrium thermodynamic flow equations, and a two-state representation of membrane macromolecular conformation, this model displays a region of hysteresis in the current range of experimental observations.