CVD of solid oxides in porous substrates for ceramic membrane modification

The deposition of yttria-doped zirconia has been experimented systematically in various types of porous ceramic substrates by a modified chemical vapor deposition (CVD) process operating in an opposing reactant geometry using water vapor and corresponding metal chloride vapors as reactants. The effects of substrate pore dimension and structure, bulk-phase reactant concentration, reactant diffusivity in substrate pores and deposition temperature are experimentally studied and explained qualitatively by a theoretical modeling analysis. The experimental and theoretical results suggest a reaction mechanism which depends on water vapor and chloride vapor concentrations. Consequently, the diffusivity, bulk-phase reactant concentration, and substrate pore dimension are important in the CVD process. Effects of deposition temperature on the deposition results and narrow deposition zone compared to the substrate thickness also suggest a Langmuir-Hinshelwood reaction mechanism involved in the CVD process with a very fast CVD reaction rate. Gas permeation data indicate that whether deposition of solid in substrate pores could result in the pore-size reduction depends strongly on the initial pore-size distribution of the substrate

Experimental studies on pore size change of porous ceramic membranes after modification

Experimental results on pore size change of a microfiltration (MF) -alumina membrane and an ultrafiltration (UF) γ-alumina membrane after modification by chemical vapor deposition (CVD) of solid oxides in the membrane pores are presented and explained using the results of a theoretical analysis. With an approx. 10-fold reduction in permeability, the average pore size of the MF membrane is found to increase after CVD modification, due to its relatively broader initial pore size distribution with a small amount of large pores and due to the particular CVD conditions (heterogeneous deposition mechanism) which give a pore narrowing rate independent of pore size. The effective pore size of the UF membrane appears to remain unchanged after modification with an approx. 50-fold reduction in permeability, as a result of the slit-shaped pores of the γ-alumina film and the particular modification conditions. The experimental and theoretical results suggest that, in order to reduce effectively the average pore size of a membrane by a modification process, the membrane should have a rather uniform pore size distribution, or the modification process should be conducted under conditions which give a pore narrowing rate proportional to the pore size

Modified CVD of nanoscale structures in and EVD of thin layers on porous ceramic membranes

Experiments on the modified chemical vapour deposition (CVD) and the electrochemical vapour deposition (EVD) of yttria-stabilized zirconia on porous substrates are reported. It is shown that, in the CVD stage, deposition occurs in a small (<20 um) region at the edge of the substrate, very likely leading to pore narrowing. This result illustrates the feasibility of the CVD technique for the modification of ceramic membranes to the (sub)nanometer scale. Film growth in the EVD stage is shown to be controlled by the inpore diffusion of the oxygen source reactant for short (<5 h) deposition times. The yttria to zirconia ratio in the deposited film is determined by the ratio present in the vapour phase. Very thin (<2 um) films can be deposited, which have a potential application in solid oxide fuel cells

Oxygen semipermeable solid oxide membrane composites prepared by electrochemical vapor deposition

Ceramic membrane composites consisting of a coarse porous -alumina or two-layer porous alumina membrane support and an oxygen semipermeable gas tight thin (0.2–5 μm) yttria stabilized zirconia (YSZ) film are prepared by the electrochemical vapor deposition (EVD) method. The minimum gas-tight thickness of the YSZ films depends strongly on the average pore size of the support on which the films are deposited by the EVD process. The oxygen permeation fluxes through such gas tight YSZ membrane composites, measured in situ on the EVD apparatus, are in the range of 3 × 10−9 to 6 × 10−8 mol/cm2-sec with an oxygen partial pressures of P′O2 (high) ≈ 3 × 10−2 atm and P″O2 (low) ≈ 10−5 atm, much larger than the literature data for thicker YSZ pellets. During the oxygen permeation experiments the rate-limiting step is found to be the bulk electrochemical transport in the grown YSZ films with a thickness smaller than 10 μm.\u

On the kinetic study of electrochemical vapour deposition

A theoretical analysis is presented which quantitatively describes the transition behavior of the kinetics of the electrochemical vapour deposition of yttria-stabilized zirconia on porous substrates. It is shown that up to a certain deposition time and corresponding film thickness the rate limiting step is oxygen diffusion through the substrate pores, giving a linear dependence of the film thickness on the deposition time. For longer deposition times, i.e. thicker films, a transition of the rate limiting step to bulk electrochemical diffusion in the film occurs, resulting in a parabolic dependence of the film thickness on the deposition time. Simulation results are presented to show the effects of the experimental conditions on this transition time

Modelling and analysis of CVD processes in porous media for ceramic composite preparation

A continuum phenomenological model is presented to describe chemical vapour deposition (CVD) of solid product inside porous substrate media for the preparation of reinforced ceramic-matrix composites [by the chemical vapour infiltration (CVI) process] and ceramic membrane composites (by a modified CVD process). The chemical reaction, intrapore diffusion, non-isobaric viscous flow and variation of substrate pore geometry during deposition are considered in the model which is readily solved by the orthogonal collocation numerical technique. Simulated deposition profiles across substrate are given to examine the effects of the reaction mechanism, reaction and diffusion rate, substrate pore dimension, deposition temperature, bulk phase reactant concentration, intrapore diffusivity of reactants and pressure drop on the deposition results of a one-dimensional isothermal forced-flow CVI process and a modified non-isobaric CVD process for ceramic composite preparation. The theoretical analysis provides a better insight of the CVD processes in porous media and is useful in explaining experimental findings and guiding the selection of optimum process conditions for the CVD preparation of ceramic composites

PROTON-CONDUCTING DENSE CERAMIC MEMBRANES FOR HYDROGEN SEPARATION

This project is aimed at preparation of thin membranes of a modified strontium ceramic material on porous substrates with improved hydrogen permeance. The research work conducted in this reporting period was focused on studying synthesis methods for preparation of thin thulium doped strontium cerate (SrCe{sub 0.95}Tm{sub 0.05}O{sub 3}, SCTm) membranes. The following two methods were studied in the past year: (1) polymeric-gel casting and (2) dry-pressing. The polymeric-gel casting method includes preparation of mixed metal oxide gel and coating of the gel on a macroporous alumina support. Micrometer thick SCTm films of the perovskite structure can be obtained by this method. However, the deposited films are not hermetic and it may require about 50 coatings in order to obtain gas-tight SCTm films by this method. Asymmetric SCTm membranes consisting of a thick macroporous SCTm support and a thin SCTm layer can be effectively prepared by the dry-pressing method. The membranes were prepared by pressing together a thick layer of coarse SCTm powder and a thin layer of finer SCTm powder, followed by calcination and sintering under proper conditions. The asymmetric SCTm membranes have desired phase structure and are hermetic. Hydrogen permeation flux through the SCT membranes is inversely proportional to the thickness of the dense layer of the asymmetric membranes. The results show a substantial improvement in hydrogen permeation flux by reducing the SCTm membrane thickness

DUAL PHASE MEMBRANE FOR HIGH TEMPERATURE CO2 SEPARATION

This project is aimed at synthesis of a new inorganic dual-phase carbonate membrane for high temperature CO{sub 2} separation. Metal-carbonate dual-phase membranes were prepared by the direct infiltration method and the synthesis conditions were optimized. The dual-phase membranes are gas-tight with helium permeance about six orders of magnitude lower than that for the metal support. Efforts were made to test seals for permeation and separation experiments for dual-phase membrane at the intermediate temperature range (about 500 C) under oxidizing atmosphere. An effective new permeation cell with a metal seal was designed, fabricated and tested. The permeation setup provided leak-free sealing for the dual-phase membranes under the desired operation conditions. Though the reliable data showing high permeance for carbon dioxide with oxygen for the prepared metal-carbonate dual phase membrane has not been measured, the research efforts in improving membrane synthesis and setting up a new permeation cell with suitable seal have made it closer for one to demonstrate good dual-phase membranes for high temperature carbon dioxide separation. Research efforts were also directed towards preparation of a new ceramic-carbonate dual-phase membrane. Porous lanthanum cobaltite (LC) perovskite type oxide ceramic support with oxidation resistance better than the metal support and high electronic conductivity (1300-1500 S/cm in 400-600 C), was prepared and studied as an alternative support for the dual-phase carbonate membranes. The LC powder was found not reactive with the carbonate at 600 C. The porous LC disks have helium permeance and pore diameter smaller than the metal support but larger than the common {alpha}-alumina support. These results show promise to use the LC support for preparation of oxidation resistant dual-phase carbonate membranes

Distributed H∞-consensus filtering in sensor networks with multiple missing measurements: The finite-horizon case

The official published version of the article can be found at the link below.This paper is concerned with a new distributed H∞-consensus filtering problem over a finite-horizon for sensor networks with multiple missing measurements. The so-called H∞-consensus performance requirement is defined to quantify bounded consensus regarding the filtering errors (agreements) over a finite-horizon. A set of random variables are utilized to model the probabilistic information missing phenomena occurring in the channels from the system to the sensors. A sufficient condition is first established in terms of a set of difference linear matrix inequalities (DLMIs) under which the expected H∞-consensus performance constraint is guaranteed. Given the measurements and estimates of the system state and its neighbors, the filter parameters are then explicitly parameterized by means of the solutions to a certain set of DLMIs that can be computed recursively. Subsequently, two kinds of robust distributed H∞-consensus filters are designed for the system with norm-bounded uncertainties and polytopic uncertainties. Finally, two numerical simulation examples are used to demonstrate the effectiveness of the proposed distributed filters design scheme.This work was supported in part by the Engineering and Physical Sciences Research Council (EPSRC) of the UK under Grant GR/S27658/01, the Royal Society of the UK, and the Alexander von Humboldt Foundation of Germany