a b s t r a c tOscillatory fluctuations of a single polymer electrolyte fuel cell appear upon operation with a dry cathode air supply and a fully humidified anode stream. Periodic transitions between a low and a high current operation point of the oscillating state are observed. The transition time of 20-25 s for the change from the low to the high operation is fast and does not depend on the operating parameters. Contrasting with this behavior, the downward transition depends strongly on the operating conditions. Impedance measurements indicate a high ionic resistance with low water content for the low current operation and a low ionic resistance of the membrane with high water content for the high current operation. An insight into the transitions is obtained by current density distributions at distinct times indicating a propagating active area with defined boundaries. The observations are in agreement with assuming a liquid water reservoir at the anode with a downward transition period depending on the operation conditions. The high current operation possesses a high electro-osmotic drag and a high permeation rate (corresponding to liquid-vapor permeation) leading to a large water flux to the cathode. Subsequently, the liquid reservoir at the anode is consumed leading to an anode drying. The system establishes a new quasi-stable operation point associated with a low current, low electro-osmotic drag coefficient, and a low water permeation (corresponding to vapor-vapor permeation). When liquid water is formed at the anode interface after some time the fast transition to the high current operation occurs. This interpretation is supported by conductive atomic force microscopy current images of the membrane showing a strong dependence of the ionic conductivity on the activation procedures with or without liquid water and also showing oscillatory behavior after the membrane is activated. Specifically, activation with liquid water yields a high conductivity with currents larger by three orders of magnitude.
Boron nitride has been deposited'by chemical vapor deposition from diborane and ammonia gas mixtures, in the form of either films or powders depending on the pressure in the reactor. IR analysis of the boron nitride deposits has been used to obtain the composition of the films. In the temperature range studied, 600-850 OC, the effect of the deposition temperature on the reaction kinetics has been interpreted by assuming a change in the relative concentration of activated species arising from diborane and ammonia molecules. This change modifies the reaction path followed in the boron nitride synthesis through the formation of different intermediate compounds: aminodiborane in the low-temperature range (<700 "C) and borazine at the higher temperatures (1775 "C). The presence of either of these intermediate compounds determines the deposition rate and the final composition of the boron nitride films.
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