The morphology of Nafion (EW = 1000, Na+ form) in dilute solvents is investigated using small angle neutron scattering (SANS) and 19F NMR. SANS modeling indicates three types of particle morphology: (i) a well-defined cylindrical dispersion in glycerol and in ethylene glycol with different degrees of solvent penetration; (ii) a less-defined, highly solvated large particle (>200 nm) in water/isopropanol mixtures; and (iii) a random-coil conformation (true solution behavior) in N-methylpyrrolidone. These distinct morphological characteristics of Nafion are consistent with the main and side chain mobilities measured by 19F NMR.

The free solution electrophoretic mobilities of poly(styrenesulfonate), ss-DNA, and duplex DNA are measured by capillary electrophoresis across a range of ionic strengths and, for poly(styrenesulfonate) and ss-DNA, across a range of chain lengths. The data are then compared with mobilities reported in the literature and predicted by theory. For ionic strengths below 0.1 M, the capillary method is more accurate and rapid than previous techniques; it also provides a distribution of mobility values for polyelectrolyte mixtures. A maximum of the free solution mobility with respect to chain length is discovered in the oligomer range for both poly(styrenesulfonate) and ss-DNA; lowering ionic strength accentuates this unexplained phenomenon. In the large chain limit, where the mobility is independent of chain length, the ionic strength dependences of mobility for all three polymers are remarkably similar. These dependences can only be explained by models that incorporate nonlinear electrostatic effects into the description of the counterion cloud. The Manning model (with relaxation correction) best approximates the dependence of mobility on ionic strength.

The gelation behavior of Nafion dispersions was investigated using small-angle neutron scattering to better understand the mechanical toughness of dispersion-cast Nafion membranes. Three types of gelation were observed, depending on dispersing fluids: (i) homogeneous, thermally reversible gelation that was present in most aprotic polar dispersing fluids; (ii) inhomogeneous, thermally irreversible gelation as films, found in alcohols; and (iii) inhomogeneous, thermally irreversible gelation which precipitates in water/monohydric alcohol mixtures. The mechanical toughness of dispersion-cast Nafion membranes depends on the dispersing fluid, varying by more than 4 orders of magnitude. Excellent correlation between the critical gelation concentration and mechanical toughness was demonstrated with the Nafion membranes cast at 140 °C. Additional thermal effects among Nafion membranes cast at 190 °C were qualitatively related to the boiling point of dispersing fluids. Little correlation between mechanical toughness and percent crystalline area of Nafion was observed, suggesting that the origin of mechanical toughness of dispersion-cast Nafion membranes is due to chain entanglements rather than crystallinity. The correlation between critical gelation concentration and mechanical toughness is a new way of predicting mechanical behavior in dispersion-cast polymer systems in which both polymer-dispersing fluid and polymer–polymer interactions play a significant role in the formation of polymer chain entanglements.

A major, unprecedented improvement in the durability of polymer electrolyte membrane fuel cells is obtained by tuning the properties of the interface between the catalyst and the ionomer by choosing the appropriate dispersing medium. While a fuel cell cathode prepared from aqueous dispersion showed 90 mV loss at 0.8 A cm(-2) after 30,000 potential cycles (0.6-1.0 V), a fuel cell cathode prepared from glycerol dispersion exhibited only 20 mV loss after 70,000 cycles. This minimum performance loss occurs even though there was an over 80% reduction of electrochemical surface area of the Pt catalyst. These findings indicate that a proper understanding and control of the catalyst-water-ionomer (three-phase) interfaces is even more important for maintaining fuel cell durability in typical electrodes than catalyst agglomeration, and this opens up a novel path for tailoring the functional properties of electrified interfaces.