Lanthanum tungstate membranes for H-2 extraction and CO2 utilization: Fabrication strategies based on sequential tape casting and plasma-spray physical vapor deposition

[EN] In the context of energy conversion efficiency and decreasing greenhouse gas emissions from power generation and energy-intensive industries, membrane technologies for H-2 extraction and CO2 capture and utilization become pronouncedly important. Mixed protonic-electronic conducting ceramic membranes are hence attractive for the pre-combustion integrated gasification combined cycle, specifically in the water gas shift and H-2 separation process, and also for designing catalytic membrane reactors. This work presents the fabrication, microstructure and functional properties of Lanthanum tungstates (La28-xW4+xO54+delta, LaWO) asymmetric membranes supported on porous ceramic and porous metallic substrates fabricated by means of the sequential tape casting route and plasma spray-physical vapor deposition (PS-PVD). Pure LaWO and W site substituted LaWO were employed as membrane materials due to the promising combination of properties: appreciable mixed protonic-electronic conductivity at intermediate temperatures and reducing atmospheres, good sinterability and noticeable chemical stability under harsh operating conditions. As substrate materials porous LaWO (non-substituted), MgO and Crofer22APU stainless steel were used to support various LaWO membrane layers. The effect of fabrication parameters and material combinations on the assemblies' microstructure, LaWO phase formation and gas tightness of the functional layers was explored along with the related fabrication challenges for shaping LaWO layers with sufficient quality for further practical application. The two different fabrication strategies used in the present work allow for preparing all-ceramic and ceramic-metallic assemblies with LaWO membrane layers with thicknesses between 25 and 60 mu m and H-2 flux of ca. 0.4 ml/min cm(2) measured at 825 degrees C in 50 vol% H-2 in He dry feed and humid Ar sweep configuration. Such a performance is an exceptional achievement for the LaWO based H-2 separation membranes and it is well comparable with the H-2 flux reported for other newly developed dual phase cer-cer and cer-met membranes.ProtOMem Project under the BMBF grant 03SF0537 is gratefully acknowledged. Furthermore, the authors thank Ralf Laufs for his assistance in operating the PS-PVD facility. Dr. A. 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Cu and Gd co-doped BaCeO3 proton conductors: Experimental vs SEM image algorithmic-segmentation results

Segmentation algorithms for the quantitative description of the surface microstructure and the evaluation of the grain-boundary conductivity of ceramic materials surface using SEM microphotographs analysis was developed and applied in the present work for first time in barium cerate based solid solutions. To this purpose novel polycrystalline ceramic materials based on Cu and Gd co-doped BaCeO3 proton conductors exhibiting high proton conductivity have been prepared and characterized. The influence of copper oxide as a dopant on the microstructure and the electrical properties of BaCe0.9-xGd0.1CuxO3-delta (0 <= x <= 0.1) have been examined in detail. It is shown that the dependence of the electrical conductivity is correlated with the average oxide grain diameter variation in air at various temperatures. Moreover, it was found that the algorithmic segmentation evaluation results are in good agreement with the experimental ones, verifying the considerable contribution of the grain-boundary conductivity to the electrical transport of Cu and Gd co-doped BaCeO3 proton conductors. (C) 2014 Elsevier Ltd. All rights reserved

Mo-Substituted Lanthanum Tungstate La_{28–<i>y</i>}W_4+<i>y</i>O_54+δ: A Competitive Mixed Electron–Proton Conductor for Gas Separation Membrane Applications

Molybdenum substituted lanthanum tungstate, La_{28–<i>y</i>}(W_1–<i>x</i>Mo_<i>x</i>)_4+<i>y</i>O_54+δ (<i>x</i> = 0–1, <i>y</i> = 0.923), was investigated seeking for an enhancement of the n-type electronic conductivity for its use as a mixed electron–proton conductor in hydrogen gas separation membrane applications. The materials were synthesized by the freeze-drying precursor method, and they were single phase after firing between 1300 and 1500 °C for <i>x</i> ≤ 0.8. The crystal structure changed from cubic (<i>x</i> ≤ 0.4) to rhombohedral (<i>x</i> ≥ 0.6) with increasing the molybdenum content. Transmission electron microscopy (TEM) investigations revealed an ordering of the oxygen vacancies with increasing Mo-content, giving rise to superstructure domains. The dependency of the conductivity with the oxygen and water partial pressure showed that these materials are good mixed electron–proton conductors under wet reducing conditions for <i>x</i> ≤ 0.4. The conductivity of the materials with <i>x</i> ≥ 0.6 was dominated by electrons, and they are expected to be less chemically stable due to the lower redox stability of Mo⁶⁺. The total conductivities in humidified H₂ were 0.016 S/cm for <i>x</i> = 0.2 and 0.043 S/cm for <i>x</i> = 0.4 at 900 °C, and they were stable under these conditions for more than 60 h. The ambipolar proton–electron conductivity was estimated to be ∼1.6 × 10^–3 S/cm for <i>x</i> = 0.4 at temperatures as low as 600 °C, which makes this family of materials very interesting and competitive candidates for applications such as hydrogen gas separation membranes at lower temperatures than state-of-the-art materials