Three methods of estimating H20 contents of geologic glasses are compared: (1) ion microprobe analysis (secondary ion mass spectrometry), (2) Fourier-transform infrared spectroscopy (FTIR), and (3) electron microprobe analysis using the Na decay-curve method. Each analytical method has its own advantages under certain conditions, depending on the relative importance of analytical accuracy, precision, sensitivity, spatial resolution, and convenience, and each is capable of providing reasonably accurate estimates of the H20, or total volatile, content of geologic glasses. The accuracy of ion microprobe analyses depends critically on the availability of well-characterized hydrous standard glasses. Precision is often better than 0,2 wt% (10). The method provides good spatial resolution (-15 #m) and the capability to determine simultaneously the abundance of other volatile species of interest (e.g., F, B). FTIR spectroscopy provides excellent analytical sensitivity (-10 ppm), accuracy and precision «0.1 wt%), and the capability to determine the abundance of H20 and C02 species (H20, OH-, C02' eOj-) in analyzed glasses, although the spatial resolution (> 25-35 #m) is not as good as that of the ion microprobe. The main advantages of the estimation of H20 contents of hydrous glasses using the electron microprobe are excellent spatial resolution (-10 #m) and analytical convenience. The disadvantages are that accuracy and precision (>0.5 wt%) are not as good as those associated with the other methods, but, for certain applications, these uncertainties may be acceptable for the estimation of H20 contents of H20-rich (> 1 wt%) samples.
The radiation grafting method is of interest for the preparation of ion-exchange membranes for electrochemical and other applications. Typically styrene is used in this method because the grafted polystyrene can be readily modi®ed to introduce a variety of functionalities. The grafting of poly(ethylene-alt-tetra¯uoroethylene), or ETFE, ®lms with styrene by the pre-irradiation method has been investigated and compared to that of poly(tetra¯uorethylene-co-hexa¯uoropropylene), or FEP, and poly(vinylidene ¯uoride), or PVDF. The in¯uence of base polymer ®lm properties such as ®lm thickness, extent of orientation, and molar mass on the grafting behavior of ETFE ®lms is reported. Film orientation was found to often have a dominant in¯uence either directly, as in the case of monoaxially oriented ®lms, or indirectly, as a result of the ®lm extrusion process. In addition, the effects of the irradiation type and atmosphere and grafting temperature on the grafting behavior of one ETFE ®lm type were examined in more detail.
Membrane electrode assemblies (MEAs) based on radiation‐grafted proton exchange membranes developed at PSI have shown encouraging performance in the past in hydrogen and methanol fuelled polymer electrolyte fuel cells. In this study, the effect of the pre‐treatment of crosslinked radiation‐grafted FEP membranes prior to lamination with the electrodes on the performance of the MEAs was investigated. Two approaches were assessed separately and in combination: (1) the impregnation of the radiation‐grafted membranes with solubilised Nafion®, and (2) the use of a swollen vs. dry membrane. It is found that the combination of coating the membrane with Nafion® ionomer and hot‐pressing the MEA with the membrane in the wet state produce the best single cell performance. In the second part of the study, the durability of an MEA, based on a radiation‐grafted FEP membrane, was investigated. The performance was stable for 4,000 h at a cell temperature of 80 °C. Then, a notable degradation of the membrane, as well as the electrode material, started to occur as a consequence of either controlled or uncontrolled start‐stop cycles of the cell. It is assumed that particular conditions, to which the cell is subjected during such an event, strongly accelerate materials degradation, which leads to the premature failure of the MEA.
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