Thin Dense Membranes Research Articles

Fabrication of BSCF-based mixed ionic-electronic conducting membrane by electrophoretic deposition for oxygen separation application

Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), which exhibits a high mixed oxide ionic-electronic conduction, was used for the fabrication of an oxygen separation membrane. An asymmetric structure, which was a thin and dense BSCF membrane layer supported on a porous BSCF substrate, was fabricated by the electrophoretic deposition method (EPD). Porous BSCF supports were prepared by the uniaxial pressing method using a powder mixture with BSCF and starch as the pore-forming agent (0–50 wt.%). The sintering behaviors of the porous support and the thin layer were separately characterized by dilatometry to determine the co-fired temperature at which cracking did not occur. A crack-free and thin dense membrane layer, which had about a 15 μm thickness and >95% relative density, was obtained after optimizing the processes of EPD and sintering. The dense/porous interface was well-bonded and the oxygen permeation flux was 2.5 ml (STP) min−1 cm-2 at 850 °C.

High-Performance Microchanneled Asymmetric Gd(0.1)Ce(0.9)O(1.95-δ)-La(0.6)Sr(0.4)FeO(3-δ)-Based Membranes for Oxygen Separation.

A microchanneled asymmetric dual phase composite membrane of 70 vol % Gd(0.1)Ce(0.9)O(1.95-δ)-30 vol % La(0.6)Sr(0.4)FeO(3-δ) (CGO-LSF) was fabricated by a "one step" phase-inversion tape casting. The sample consists of a thin dense membrane (100 μm) and a porous substrate including "finger-like" microchannels. The oxygen permeation flux through the membrane with and without catalytic surface layers was investigated under a variety of oxygen partial pressure gradients. At 900 °C, the oxygen permeation flux of the bare membrane was 1.6 (STP) ml cm(-2) min(-1) for the air/He-case and 10.10 (STP) ml cm(-2) min(-1) for the air/CO-case. Oxygen flux measurements as well as electrical conductivity relaxation show that the oxygen flux through the bare membrane without catalyst is limited by the oxygen surface exchange. The surface exchange can be enhanced by introduction of catalyst on the membrane surface. An increase of the oxygen flux of ∼1.49 (STP) mL cm(-2) min(-1) at 900 °C was observed when catalyst is added for the air/He-case. Mass transfer polarization through the finger-like support was confirmed to be negligible, which benefits the overall performance. A stable flux of 7.00 (STP) ml cm(-2) min(-1) was observed between air/CO/CO2 over 200 h at 850 °C. Partial surface decomposition was observed on the permeate side exposed to CO, in line with predictions from thermodynamic calculations. In a mixture of CO, CO2, H2, and H2O at similar oxygen activity the material will according to the calculation not decompose. The microchanneled asymmetric CGO-LSF membranes show high oxygen permeability and chemical stability under a range of technologically relevant oxygen potential gradients.

Strength degradation and failure limits of dense and porous ceramic membrane materials

Abstract Thin dense membrane layers, mechanically supported by porous substrates, are considered as the most efficient designs for oxygen supply units used in Oxy-fuel processes and membrane reactors. Based on the favorable permeation properties and chemical stability, several materials were suggested as promising membrane and substrate materials: Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3− δ , La 0.6− x Sr 0.4 Co 0.2 Fe 0.8 O 3− δ ( x = 0, 0.02) and Ce 0.9 Gd 0.1 O 1.95− δ . Although membranes operate at elevated temperatures, the ends of tubes in certain three-end concepts remain almost at room temperature. The current work concentrates on the failure potential of these membrane parts, where in a complex device also the highest residual stresses should arise due to differences in thermal expansion. In particular, sensitivity of the materials to subcritical crack growth was assessed since the long-term reliability of the component does not only depend on its initial strength, but also on strength degradation effects. The results were subsequently used as a basis for a strength–probability–time lifetime prediction.

Sintering process optimization for multi-layer CGO membranes by in situ techniques

Abstract The sintering of asymmetric CGO bi-layers (thin dense membrane on a porous support; Ce 0.9 Gd 0.1 O 1.95− δ = CGO) with Co 3 O 4 as sintering additive has been optimized by combination of two in situ techniques. Optical dilatometry revealed that bi-layer shape and microstructure are dramatically changing in a narrow temperature range of less than 100 °C. Below 1030 °C, a higher densification rate in the dense membrane layer than in the porous support leads to concave shape, whereas the densification rate of the support is dominant above 1030 °C, leading to convex shape. A flat bi-layer could be prepared at 1030 °C, when shrinkage rates were similar. In situ van der Pauw measurements on tape cast layers during sintering allowed following the conductivity during sintering. A strong increase in conductivity and in activation energy E a for conduction was observed between 900 and 1030 °C indicating an activation of the reactive sintering process and phase transformation of cobalt oxide.

Dense/Porous Asymmetric-Structured Oxygen Permeable Membranes Based on La0.6Ca0.4CoO3Perovskite-Type Oxide

To achieve high-efficiency oxygen permeation using mixed (ionic and electronic) conducting perovskite-type oxides, we examined asymmetric-structured membranes of La0.6Ca0.4CoO3 in which a thin dense membrane was deposited on a porous support. The La0.6Ca0.4CoO3 porous support was fabricated using irregular-shaped precursor particles prepared through an oxalate method. The fabricated support had good gas permeability and thermal stability, showing sufficient properties as a support for dense thin membranes. A dense membrane of 10 μm thickness was successfully formed on the porous support by coating a La0.6Ca0.4CoO3 slurry and subsequent densification by sintering. The deposited thin membrane was gastight and free from clacks, as revealed by gas permeation tests and SEM observations. The asymmetric membrane exhibited a high oxygen permeability of 1.66 cm3 (STP, standard temperature and pressure) min−1 cm−2 at 930 °C, which was four times higher than that of a typical sintered-disk type membrane with 1200 μm thickness, demonstrating its feasibility as a high-performance oxygen separation membrane.