Microstructural studies of self-supported (1.5–10 μm) Pd/23 wt%Ag hydrogen separation membranes subjected to different heat treatments

The microstructure of self-supported 1.5–10-μm thick Pd/23 wt%Ag membranes grown by magnetron sputtering have been studied after heat treatment and hydrogen permeation tests using electron microscopy and synchrotron X-ray diffraction. After hydrogen flux stabilization and permeance measurements at 300 °C, the membranes were annealed in air at 300 °C or in N2/Ar at 300/400/450 °C for 4 days and then tested for hydrogen permeation. The permeation results show that changes in permeability depend on the treatment atmosphere and temperature, as well as membrane thickness. Air treatment at ~300 °C generally induced a positive effect on permeation in the thickness range of 1.5–10 μm. Significant microstructural changes, including grain growth, strain relief, void formation, and growth of nodules occurred in the membranes. The changes in microstructure are more severe for the thinner membranes, and may be attributed mainly to the oxidation processes at or near the surface. For samples annealed in N2/Ar, enhanced permeation was only obtained with treatment at ~450 °C for 5 and 10 μm. The changes in the microstructure generally increased with heat-treatment temperature, and decreased with membrane's thickness. The membrane with enhanced permeation was accompanied by significant grain growth, strain relief, and surface roughening. For all the membranes, the relative changes in the microstructure were substantially more prominent on the permeate surface than on the feed surface. Details of the analysis are presented and discussed.