Nafion Swelling in Salt Solutions in a Finite Sized Cell: Curious Phenomena Dependent on Sample Preparation Protocol

When a membrane of Nafion swells in water, polymer fibers "unwind" into the adjoining liquid. They extend to a maximum of about ~300 μm. We explore features of Nafion nanostructure in several electrolyte solutions that occur when the swelling is constrained to a cell of size less than a distance of 300 μm. The constraint forces the polymer fibers to abut against the cell windows. The strongly amphiphilic character of the polymer leads to a shear stress field and the expulsion of water from the complex swollen fiber mixture. An air cavity is formed. It is known that Nafion membrane swelling is highly sensitive to small changes in ion concentration and exposure to shaking. Here we probe such changes further by studying the dynamics of the collapse of the induced cavity. Deionized water and aqueous salt solutions were investigated with Fourier IR spectrometry. The characteristic times of collapse differ for water and for the salt solutions. The dynamics of the cavity collapse differs for solutions prepared by via different dilution protocols. These results are surprising. They may have implications for the standardization of pharmaceutical preparation processes.