W-doped Lanthanum Molybdenum Oxide/Lithium-Sodium-Potassium Carbonate Composite Membranes for Carbon Dioxide Permeation.

Single-phase tungsten-doped lanthanum molybdenum oxide (La2MoWO9) ceramic powders were synthesized using the complex polymerization technique. Porous ceramic pellets were obtained by thermally removing graphite, which served as a pore former. The porous pellets were then impregnated with molten eutectic lithium-sodium-potassium carbonates. The energy dispersive X-ray analysis and scanning electron microscopy (FEG-SEM) images of the external and fracture surfaces of the La2MoWO9-(Li,Na,K)2CO3 composite dual-phase membrane revealed the percolation of the carbonate mixture through the pores. Electrochemical impedance spectroscopy measurements conducted at temperatures below and above the melting point of the eutectic carbonate composition demonstrated the contributions of oxygen and carbonate ions to the ionic conductivity of the dual membrane. The electrical conductivity of the carbonate ions within the membrane was continuously monitored for over 1300 h with negligible degradation, implying that the membrane could be used for long-term monitoring of CO2 without aging effects. A comparison of FEG-SEM images taken before and after this endurance test suggested minimal fouling, indicating that the membrane could potentially replace similar zirconia- and ceria-based composite membranes.

Porous 8YSZ Ceramics Prepared with Alkali Halide Sacrificial Additives.

8 mol% Y2O3-stabilized ZrO2 (8YSZ) ceramics were prepared with KCl and LiF additions to obtain porous specimens with high skeletal density. Thermogravimetric and differential thermal analyses (TG/DTA) were carried out on 8YSZ and on 8YSZ mixed to 5 wt.% KCl or 5 wt.% LiF as sacrificial pore formers that were thermally removed during sintering. The melting and evaporation of the alkali halides were evaluated by differential thermal analysis. Dilatometric analysis was also carried out following the same TG/DTA temperature profile with results suggesting rearrangement of the 8YSZ particles during LiF and KCl melting. The dilatometric data of 8YSZ green pellets mixed to KCl or LiF exhibited an initial expansion up to the melting of the alkali halide, followed by shrinkage due to sintering evolution with grain growth and pore elimination. The time that the alkali halide molten phase was kept during sintering was found to be an important parameter for obtaining 8YSZ-sintered specimens with specific pore content; bulk density and open porosity could then be tuned by controlling the time the alkali halide remained liquid during sintering. Scanning electron microscopy images of the pellet fracture surfaces showed pores that contributed to increasing the electrical resistivity as evaluated by impedance spectroscopy analysis.

Design and Validation of an Experimental Setup for Evaluation of Gas Permeation in Ceramic Membranes.

An experimental setup for the evaluation of permeation of gaseous species with the possibility of simultaneously collecting electrochemical impedance spectroscopy data in disk-shaped ceramic membranes was designed and assembled. It consists of an alumina sample holder with thermocouple tips and platinum electrodes located close to both sides of the sample. Water-cooled inlet and outlet gas connections allowed for the insertion of the sample chamber into a programmable split tubular furnace. Gas permeation through a ceramic membrane can be monitored with mass flow controllers, a mass spectrometer, and an electrochemical impedance analyzer. For testing and data validation, ceramic composite membranes were prepared with the infiltration of molten eutectic compositions of alkali salts (lithium, sodium, and potassium carbonates) into porous gadolinia-doped ceria. Values of the alkali salt melting points and the permeation rates of carbon dioxide, in agreement with reported data, were successfully collected.