Microstructure water diffusion

Kreuer et al. [25] investigated the membrane properties, including water sorption, transport (proton conductivity, electro-osmotic water drag and water diffusion), microstructure and viscoelasticity of the short-side-chain (SSC) perfluorosulfonic acid ionomers (PFSA, Dow 840 and Dow 1150) with different lEC-values. The data were compared to those for Nafion 117, and the implications for using such ionomers as separator materials in direct methanol and hydrogen fuel cells discussed. Tire major advantages of PFSA membranes were seen to be (i) a high proton conductivity. 

Polymeric ion exchange membranes are a particular class of these ion-containing polymers. We have been interested in understanding their microstructure in order to explain membrane characteristics such as permselectivity, ionic conductivity, and water diffusion. 

In principle, we can distinguish (for surfactant self-assemblies in general) between a microstructure in which either oil or water forms discrete domains (droplets, micelles) and one in which both form domains that extend over macroscopic distances (Fig. 7a). It appears that there are few techniques that can distinguish between the two principal cases uni- and bicontinuous. The first technique to prove bicontinuity was self-diffusion studies in which oil and water diffusion were monitored over macroscopic distances [35]. It appears that for most surfactant systems, microemulsions can be found where both oil and water diffusion are uninhibited and are only moderately reduced compared to the neat liquids. Quantitative agreement between experimental self-diffusion behavior and Scriven s suggestion of zero mean curvature surfactant monolayers has been demonstrated [36]. Independent experimental proof of bicontinuity has been obtained by cryo-electron microscopy, and neutron diffraction by contrast variation has demonstrated a low mean curvature surfactant film under balanced conditions. The bicontinuous microemulsion structure (Fig. 7b) has attracted considerable interest and has stimulated theoretical work strongly. 

Sefa-Dedeh, S. Stanley, D.W. (1979). The Relationship of Microstructure of Cowpeas to Water Absorption and Dehulling Properties. Cereal Chemistry, Vol.56, No.4, pp. 379-386. Seyhan-Gurtas, F. Ak, M.M. Evranuz, E.O. (2001). Water Diffusion Coefficients of Selected Legumes Grown in Turkey as Affected by Temperature and Variety. Turkish Journal of Agriculture and Forestry, Vol.25, pp. 297-304. 

The amorphous orientation is considered a very important parameter of the microstructure of the fiber. It has a quantitative and qualitative effect on the fiber de-formability when mechanical forces are involved. It significantly influences the fatigue strength and sorptive properties (water, dyes), as well as transport phenomena inside the fiber (migration of electric charge carriers, diffusion of liquid). The importance of the amorphous phase makes its quantification essential. Indirect and direct methods currently are used for the quantitative assessment of the amorphous phase. 

The last, and less extensively studied field variable driving percolation effects is chemical potential. Salinity was examined in the seminal NMR self-diffusion paper of Clarkson et al. [12] as a component in brine, toluene, and SDS (sodium dodecylsulfate) microemulsions. Decreasing levels of salinity were found to be sufficient to drive the microemulsion microstructure from water-in-oil to irregular bicontinuous to oil-in-water. This paper was... 

Self-diffusion data [37] derived from NMR PGSE measurements for decane, water, and AOT are illustrated in Fig. 3. The self-diffusion of decane decreases gradually as a decreases from 1.0 to 0.3. The magnitude of decane self-diffusion suggests that the microstructure remains substantially continuous in decane over this composition range. Both water and AOT diffusion initially decrease as a decreases. One can readily see that in this... 

While the order parameters derived from the self-diffusion data provide quantitative estimates of the distribution of water among the competing chemical equilibria for the various pseudophase microstructures, the onset of electrical percolation, the onset of water self-diffusion increase, and the onset of surfactant self-diffusion increase provide experimental markers of the continuous transitions discussed here. The formation of irregular bicontinuous microstructures of low mean curvature occurs after the onset of conductivity increase and coincides with the onset of increase in surfactant self-diffusion. This onset of surfactant diffusion increase is not observed in the acrylamide-driven percolation. This combination of conductivity and self-diffusion yields the possibility of mapping pseudophase transitions within isotropic microemulsions domains. 

A. Bazylak, D. Sinton, Z. S. Liu, and N. Djilali. Effect of compression on liquid water transport and microstructure of PEMFC gas diffusion layers. Journal of... 

While D issuing from these experiments is not strictly the diffusion coefficient of water per se, but rather that of H throughout the ensemble of environments in the hydration microstructure, these authors rationalized that it could in fact be identified with D at both high and low water contents. It should be appreciated that self-diffusion coefficients measured in this way reflect fundamental hopping events on a molecular scale. 

---