화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.110, No.11, 5439-5444, 2006
Water dynamics in ionomer membranes by field-cycling NMR relaxometry
The dynamic behavior of water within two types of ionomer membranes, Nafion and sulfonated polyimide, has been investigated by field-cycling nuclear magnetic relaxation. This technique, applied to materials prepared at different hydration levels, allows the proton motion on a time scale of microseconds to be probed. The NMR longitudinal relaxation rate R-1 measured over three decades of Larmor angular frequencies omega is particularly sensitive to the host-water interactions and thus well-suited to study fluid dynamics in restricted geometries. In the polyimide membranes, we have observed a strong dispersion of R-1(omega) following closely a 1/root omega law in a low-frequency range (correlation times from 0.1 to 10 us). This is indicative of a strong interaction of water with "interfacial" hydrophilic groups of the polymeric matrix (wetting situation). Variations of the relaxation rates with water uptake reveal a two-step hydration process: solvation and formation of disconnected aqueous clusters near polar groups, followed by the formation of a continuous hydrogen bond network. On the contrary, in the Nafion we observed weak variations of R-1(omega) at low frequencies. This is typical of a nonwetting behavior. At early hydration stages, R-1(omega) evolves logarithmically, suggesting a confined bidimensional diffusion of protons in the microsecond time range. Such an evolution is lost at higher swelling where a plateau related to three-dimensional diffusion is observed.