Fabrication of Pd/Pd-Alloy Films by Surfactant Induced Electroless Plating for Hydrogen Separation from Advanced Coal Gasification Processes

Abstract

Dense Pd, Pd-Cu and Pd-Ag composite membranes on microporous stainless steel substrate (MPSS) were fabricated by a novel electroless plating (EP) process. In the conventional Pd-EP process, the oxidation-reduction reactions between Pd-complex and hydrazine result in an evolution of NH{sub 3} and N{sub 2} gas bubbles. When adhered to the substrate surface and in the pores, these gas bubbles hinder uniform Pd-film deposition which results in dendrite growth leading to poor film formation. This problem was addressed by introducing cationic surfactant in the electroless plating process known as surfactant induced electroless plating (SIEP). The unique features of this innovation provide control of Pd-deposition rate, and Pd-grain size distribution. The surfactant molecules play an important role in the EP process by tailoring grain size and the process of agglomeration by removing tiny gas bubbles through adsorption at the gas-liquid interface. As a result surfactant can tailor a nanocrystalline Pd, Cu and Ag deposition in the film resulting in reduced membrane film thickness. Also, it produces a uniform, agglomerated film structure. The Pd-Cu and Pd-Ag membranes on MPSS support were fabricated by sequential deposition using SIEP method. The pre- and post-annealing characterizations of these membranes (Pd, Pd-Cu and Pd-Ag on MPSS substrate) were carried out by SEM, EDX, XRD, and AFM studies. The SEM images show significant improvement of the membrane surface morphology, in terms of metal grain structures and grain agglomeration compared to the membranes fabricated by conventional EP process. The SEM images and helium gas-tightness studies indicate that dense and thinner films of Pd, Pd-Cu and Pd-Ag membranes can be produced with shorter deposition time using surfactant. H{sub 2} Flux through the membranes fabricated by SIEP shows large improvement compared to those by CEP with comparable permselectivity. Pd-MPSS composite membrane was subjected to test for long term performance and thermal cycling (573 - 723 - 573 K) at 15 psi pressure drop for 1200 hours. Pd membranes showed excellent hydrogen permeability and thermal stability during the operational period. Under thermal cycling (573 K - 873 K - 573 K), Pd-Cu-MPSS membrane was stable and retained hydrogen permeation characteristics for over three months of operation. From this limited study, we conclude that SIEP is viable method for fabrication of defect-free, robust Pd-alloy membranes for high-temperature H{sub 2}-separation applications.