Microstructural Investigation and On-Site Repair of Thin Pd-Ag Alloy Membranes
Yuyu Ma, Chunhua Tang, Feng Bao, Wei Shao, Tianying Xu, Hui Li, Hengyong Xu
Abstract
Pd membranes act in an important role in H2 purification and H2 production in membrane reactors. Pd-Ag alloy membranes fabricated by consecutive electroless- and electroplating process on alumina tubes exhibited good stability under stringent heating/cooling cycles at a ramp rate of 10 K/min, imitating practical fast initiation or emergency shutdown conditions. Bilayer Pd-Ag membranes can form dense and uniform alloy after thermal treatment for 24 h at 823 K under H2 atmosphere, despite a porous structure due to the development of liquid-like properties above Tamman temperature to enforce the migrativity. On the contrary, alloying under N2 atmosphere resulted in a Pd-enriched layer. This led to a lower H2 flux but superior thermal stability compared to that alloying under H2 atmosphere. The trilayer approach of electroless-plated Pd, electro-polated Ag and electroless-plated Pd is not suitable to achieve homogeneous Pd-Ag alloys, which, on the other hand, presented the occurrence of a small gap between top Pd layer and middle Ag layer, probably due to insufficient wetting during plating process. An on-site repair treatment in analogous to MOCVD (Metal-organic Chemical Vapor Deposition) process was first proposed to extend the lifetime of Pd-Ag membrane, i.e., by vaporizing, and subsequent decomposition of Ag(OOCC2F5) powders to "preferentially" block the pinholes under vacuum and at working temperature of ca. 473-673 K, which effectively reduced the N2 flux by 57.4% compared to the initial value. The H2 flux, however, declined by 16.7% due to carbon deposition on the membrane surface, which requires further investigation. This approach shows some potential for on-site repair without disassembly or cooling to room temperature.