A comprehensive study was carried out involving electroless plating (ELP) synthesis and permeation characterization of a series of Pd and Pd/Ag membranes supported on alpha-Al2O3 hollow fibers. A multi-fiber ELP apparatus with film thickness monitoring quantified Pd and Ag deposition rates over a range of conditions. The Pd deposition rate exhibited a maximum while the Ag growth rate demonstrated autocatalytic behavior and was enhanced by Pd. Electron micrographs reveal the grain size and morphology are sensitive functions of the plating temperature. Three membrane types synthesized by ambient temperature ELP were of high quality determined by permeation measurements (H-2 flux, pure component and mixture separation factors) over a range of temperature, pressure, and time on stream: Pd (13 mu m)/alpha-Al2O3, Pd-(12 wt.%)Ag (11 mu m)/alpha-Al2O3, and Pd (5 mu m)/alpha-Al2O3/alpha-Al2O3. Initial binary separation factors of 1000-10,000 were obtained with the low temperature ELP. The permselectivity for the Pd membrane decreased to 100 after 300 h of temperature and pressure cycling. The Pd/Ag alloy membrane exhibited high permselectivity for extended operation with the separation factor (alpha) decreasing from an initial value of 970 to 650 after 300 h with the H-2 flux sustained at 0.5 mol/m(2)s at 550 degrees C for a transmembrane pressure gradient (Delta p(H2)) of similar to 4 x 10(5) Pa. The thinner composite Pd/gamma-Al2O3/alpha-Al2O3 exhibited high initial flux and permselectivity (0.5 mol/m(2)s, alpha similar to 1000 at 350 degrees C, Delta p(H2) similar to 4 x 10(5) Pa) with reduced non-selective transport compared to the Pd/alpha-Al2O3 fiber. A phenomenological model was used to quantify the contribution of non-selective Knudsen diffusion and convective transport. (c) 2006 Elsevier B.V. All rights reserved.