Sodium chloride diffusion in sulfonated polymers for membrane applications

Sodium chloride permeability and sorption measurements were used to calculate average salt diffusion coefficients for charged, sulfonated polymers of interest for membrane applications. A sulfonated polysulfone random copolymer and two phase-separated, sulfonated styrenic pentablock copolymers were considered, and data for these materials were compared with those for an uncharged cross-linked poly(ethylene glycol diacrylate) hydrogel. The average salt diffusion coefficients reported for the block copolymers are apparent salt diffusion coefficients because the values have not been adjusted for the polymer's phase separated morphology. The sodium chloride permeability of the uncharged hydrogel decreases by about 16% as upstream salt concentration increases from 0.01 to 1molL^-1. This salt permeability change results from a decrease in the salt diffusion coefficient with increasing salt concentration because the polymer's water content decreases as salt concentration increases (i.e., osmotic de-swelling). This decrease in salt diffusion coefficient is consistent with free volume theory, wherein a decrease in water content leads to a decrease in free volume, thereby decreasing the salt diffusion coefficient and, in turn, salt permeability. In contrast, the sodium chloride permeability of the charged polymers increases by more than an order of magnitude as upstream salt concentration increases from 0.01 to 1molL^-1. This salt permeability increase is due to increases in both mobile salt sorption and diffusion coefficients with increasing salt concentration, despite the fact that water content (and, therefore, free volume) in the polymer decreases as salt concentration increases. Thus, the increase in salt diffusion coefficient with increasing salt concentration in the charged polymers results from factors (which are currently poorly understood) other than simply water uptake or free volume.