Hydraulic Permeation-Induced Water Concentration Gradients in Ion Exchange Membranes

Abstract

Although substantial literature has detailed transport through swollen membranes, there are still conflicting reports regarding the fundamental physics of hydraulic water transport in such materials, with a long-standing debate centered on the applicability of the pore-flow and solution-diffusion mechanisms. The critical thermodynamic distinction between these models is the presence of a membrane-phase concentration gradient. For pure solvent transport, the pore-flow model presumes that a membrane-phase pressure gradient drives transport in the absence of a concentration gradient. In contrast, the solution-diffusion model proposes that a membrane-phase concentration gradient drives transport and that there is a negligible pressure gradient through the membrane. To address this topic for ion exchange membranes, this study reports measurements of water concentration profiles in pressurized films of Nafion and a commercial membrane based on sulfonated poly(styrene-co-divinylbenzene). Several films were stacked together in a custom-built permeation cell, with the feed side pressurized to between 68.9 and 137.9 bar, and the permeate side held at atmospheric conditions. At steady state, the experiment was stopped, the films were separated, and the water content of each film was measured, revealing a water concentration gradient through the stack thickness that increased with increasing feed pressure. The experimental data were in good agreement with theoretical predictions based on Fick’s law and polymer-solvent swelling theories (i.e., Flory-Huggins and Flory-Rehner). These results are consistent with the solution-diffusion model and cannot be explained by a pore-flow mechanism.