Small‐angle scattering studies of nafion membranes

Abstract

The physical structure of Nafion membranes has been investigated by small‐angle neutron scattering (SANS) and small‐angle x‐ray scattering (SAXS). Samples in the acid form may exhibit two scattering peaks. The first, observed by SANS at an angle corresponding to a Bragg spacing of 180 Å, is shown to arise from structures in crystalline regions. A second peak at larger scattering angles is shown to arise from ion‐containing regions which may be swollen with water. Salt‐form samples made by soaking the acid form in an aqueous salt solution can also exhibit the same two scattering signals. But in amorphous salt‐form samples produced by quenching from the melt the first peak is absent. This permits a more accurate study of the second peak by SAXS, which shows that the second scattering component is present as a maximum over a wide range of water contents but is absent in a sample dried at 200°C. The position of the peak shifts to lower scattering angles (or larger spacings) at higher water contents. Possible structural models that might give rise to the maximum are discussed. A calculation of the SAX invariant is made and results are consistent with a phase separation of a large fraction of the water.