Evolution of pore size distribution and average pore size of porous ceramic membranes during modification by counter-diffusion chemical vapor deposition

The modification of porous ceramic membranes by counter-diffusion chemical vapor deposition (CVD) is studied theoretically and experimentally. Numerical simulations of the evolution of the membrane permeance, average pore size and pore size distribution as a function of extent of modification are presented and compared with experimental data. It is found that the change of the average pore size of the membranes after modification strongly depends on the initial pore size distribution of the membrane, CVD reaction kinetics and characterization method. Experimental data suggest that CVD of zirconia (and yttria) inside porous ceramic membranes by reaction of zirconium (and yttrium) chlorides with steam/air at elevated temperatures proceeds by quasi-zero reaction kinetics with respect to the oxidant, typical of non-stoichiometric supply of the reactants from opposite sides of the membrane. Under such conditions, CVD modification may result in a modest increase of the average pore size of coarse-pore ceramic membranes as suggested by numerical calculations and experimental data.