Compositionally graded YSZ–NiO composites by surface laser melting

El pdf del artículo es la versión post-print.Laser surface melting has been applied to near eutectic NiO–YSZ sintered ceramics. The objective is to generate a functional gradient composite material with graded microstructure and composition. At low solidification rates the resultant material has a graded composition, with a severe NiO segregation towards the surface. A thick NiO layer whose thickness depends on the travelling speed is formed. Below this layer the microstructure is eutectic like with composition varying with depth. In contact with the ceramic, excess YSZ coming from the hypereutectic composition forms an almost continuous YSZ layer. The thickness of both segregated layers, NiO and YSZ can be controlled by traverse speed. Thickness decreases as travelling speed increases until a limiting travelling rate of 110 mm/h, at which no more segregation is found. Possible causes to explain the relevant NiO segregation towards the surface are discussed.Financial support from the Ministerio de Educación y Ciencia of Spain and the CE program FEDER under grant MAT2006-13005-C03-01 is gratefully acknowledged.Peer Reviewe

Anode supported microtubular solid oxide fuel cells running on methane

Trabajo presentado al "III Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries" celebrado en Zaragoza (España) del 27 al 30 de Junio de 2011.We would like to thank grants MAT2009-14324-C0.2-01 and CIT-120000-2007-50 financed by the Spanish Government and Feder program of the European Community for funding project. M. A. Laguna-Bercero would also like to thank the JAEprogram (CSIC) for financial support.Peer Reviewe

Directionally solidified Al2O3-Yb3Al5O12 eutectics for selective emitters

Al2O3-Yb3Al5O12 eutectic rods were directionally solidified using the laser floating zone method at rates between 25 and 750 mm/h. The microstructure consisted of an interpenetrated network of both eutectic phases for all the growth rates. The size of the phases was strongly dependent on the growth rate, the eutectic interspacing decreasing from 4.5 µm at the lowest growth rate to 600 nm at 750 mm/h. The optical transmission of the sample with coarser microstructure was measured and compared with that of an Yb3Al5O12 single crystal grown "ad hoc" using the same method. The apparent "oscillator strength" of the single 2F7/2¿2F5/2 Yb3+ absorption band was larger in the eutectic sample than in the single crystal, which was attributed to the increase in the light path caused by multiple refractions at the eutectic interphases. The thermal emission of the eutectic rod was studied between 1000 °C and 1500 °C. An intense and relatively narrow emission band at about 1 µm corresponding to the 2F5/2¿2F7/2 Yb3+ electronic transition was observed in the whole temperature range. The intensity of the band increased with the temperature up to about 1300 °C. At higher temperatures a saturation of the selective emission was observed which was attributed to the competition between the increase in the thermal population of the excited state and the enhancement of the non-radiative de-excitation channels with the temperature

Procedimiento de preparación y materiales conformados basados en compuestos eutécticos binarios o ternarios de circonia

Referencia OEPM: P9600891.-- Fecha de solicitud: 19/04/1996.-- Titular: Consejo Superior de Investigaciones Científicas (CSIC).Procedimiento de preparación y materiales conformados basados en compuestos eutécticos binarios o ternarios de circonia. La presente invención está relacionada con la preparación de materiales con estructuras eutécticas micrométricas basados en mezclas de óxidos, conformados con dimensiones mili y submilimétricas mediante fusión zonal por láser con diferentes sistemas ópticos de focalización y control de los haces de los láseres. Su utilización es en el sector de la producción y conservación de energía, como elementos calefactores, refractarios, cátodos para plasmas de aire, electrodos, en componentes para celdas de combustión, microsensores de gas oxígeno, etc.Peer reviewe

Laser-assisted surface melting of Al2O3-YSZ eutectic ceramics

[ES] Se presenta un procedimiento para la densificación y/o texturado superficial de cerámicas de Al2O3-YSZ (circona estabilizada con itria) con composición eutéctica mediante fusión zonal asistida por láser. Haciendo un barrido con la radiación proveniente de un láser de potencia sobre piezas cerámicas conseguimos modificar la microestructura y densificar completatmente la capa superficial, con un espesor que va de 30 a 1000 μm. Por ejemplo, con línea estrecha de láser de diodo, fluencia de 1.23 kW/cm2 y velocidades de barrido de 0.14 mm/s, solidificamos capas de 560 μm. El resultado es una superficie de baja rugosidad y no porosa. La microestructura de la muestra es fina debido a su composición eutéctica. La interfase sólido-líquido en el proceso de crecimiento determina la orientación de la microestructura. Se estudia la forma de esta interfase tanto en cortes transversales como longitudinales, lo que permite analizar el efecto que sobre la microestructura tiene la superposición de barridos, que es una alternativa para tratar superficies extensas. Macroscópicamente la frontera entre barridos contiguos es suave. Sin embargo, su microestructura presenta discontinuidad en el espaciado entre las fases debido a la evolución microestructural en la región no fundida sometida a altas temperaturas y a la nucleación preferencial de Al2O3 al comenzar el crecimiento cristalino. Se analizan distintas posibilidades para disminuir el choque térmico inherente al proceso y que conduce a la formación de grietas paralelas a la dirección de procesado y de delaminación. Se observa una mejora importante cuando se precalienta la pieza a tratar, de modo que es posible procesar superficies de cerámicas eutécticas 99% densas.[EN] A procedure for surface densification and/or texturing of Al2O3-YSZ (yttria stabilised zirconia) ceramics with eutectic composition by means of laser surface melting is presented. By scanning a high-power laser beam on a ceramic surface, we achieve a textured and fully dense surface layer from 30 to 1000 microns thick. For example, using a thin diode laser line with fluence 1.23 kW/cm2 and 0.14 mm/s scan rate, the solidified layer has 560 μm depth. We get a low roughness and dense surface. The microstructure is fine (micron size) due to the eutectic composition. The orientation of the microstructure is determined by the shape of the solid-liquid interface in the solidification process. We study the shape of this interface in transverse and longitudinal cross-sections in single as well as overlapping scans, which are required to process large surfaces. From the macroscopic point of view, the transition between adjacent scans is smooth. However, the microstructure presents discontinuity in the interphase spacing due to microstructural evolution in the heat affected region as well as the nucleation of an Al2O3 layer at the beginning of the crystal growth. The thermal shock inherent to the procedure generates cracks longitudinal and transverse to the scanning direction, as well as delaminating cracks. We analyse different possibilities to reduce this thermal shock. The best results are obtained by preheating the substrate, allowing us to process surfaces of Al2O3-YSZ eutectic ceramics 99% dense.Financiación del Ministerio de Ciencia y Tecnología a través de los proyectos MAT2000-1495 y MAT2000-1533-C03-02.Peer reviewe

Fabrication and microstructure of self-supporting thin ceramic electrolytes prepared by laser machining

Self-supporting thin Yttria Stabilized Zirconia (YSZ) ceramics electrolytes have been prepared by laser machining. They are carved from a sintered YSZ plate to shape a 20 µm thick and 8 mm in diameter central region, surrounded by an unprocessed 150 µm thick supporting zone. Scanning Electron Microscopy (SEM) and Electron BackScattering Diffraction (EBSD) studies confirmed that the strains produced by the laser processing are small and limited to only one or two layers of YSZ grains (~5 µm). SEM and Transmission Electron Microscopy (TEM) have been also used to characterize the surface of the membrane. It is corrugated and coated with YSZ nanoparticles as a result of the laser plasma deposition. Electrochemical characterization by Impedance Spectroscopy (EIS) showed that this surface morphology improves the electrical performance of the membrane slightly but clearly, reducing the cathode polarization resistance by about 5% in the 650-850 ºC range.This study was funded by the MAT2012-30763 project, which is financed by the Spanish Government (Ministerio de Economía y Competitividad) and the Feder program of the European Union.Peer Reviewe

Interacting plasmon and phonon polaritons in aligned nano- and microwires

The availability of macroscopic, nearly periodic structures known as eutectics opens a new path for controlling light at wavelength scales determined by the geometrical parameters of these materials and the intrinsic properties of their component phases. Here, we analyze the optical waveguiding properties of eutectic mixtures of alkali halides, formed by close-packed arrangements of aligned cylindrical inclusions. The wavelengths of phonon polaritons in these constituents are conveniently situated in the infrared and are slightly larger than the diameter and separation of the inclusions, typically consisting on single-crystal wires down to submicrometer diameter. We first discuss the gap mode and the guiding properties of metallic cylindrical waveguides in the visible and near-infrared, and in particular we investigate the transition between cylinder touching and non-touching regimes. Then, we demonstrate that these properties can be extended to the mid infrared by means of phonon polaritons. Finally, we analyze the guiding properties of an actual eutectic. For typical eutectic dimensions, we conclude that crosstalk between neighboring cylindrical wires is small, thus providing a promising platform for signal propagation and image analysis in the mid infrared

Infiltrated cathode materials for microtubular solid oxide fuel cells

Trabajo presentado a la: "European Hydrogen Energy Conference" celebrada en Sevilla (España) del 12 al 14 de marzo de 2014.Microtubular Solid Oxide Fuel Cells (MT-SOFC) have recently attracted much interest as they are more resistant to thermal cycling, and they present shorter start-up/shut-down times and higher volumetric power densities in comparison with the traditional planar geometry. Standard NiO-YSZ (yttria stabilized zirconia) tubes used in our laboratory are fabricated by either extrusion or cold isostatic pressing (CIP) of NiO, YSZ and pore former powders, followed by spray coating or dipcoating of the YSZ electrolyte. Both components are then co-sintered at 1400 ºC. Typical oxygen electrodes such as LSCF (lanthanum strontium cobalt ferrite) or LSM (lanthanum strontium manganite) are deposited by dip-coating and sintered at 1150 ºC. Thermo-mechanical matching of cell components, catalyser coarsening and quality of interfaces are important issues in cell fabrication. Fabrication of electrodes by infiltration may contribute to reduce some of these problems as the cathode sintering stage is no longer needed. In this case we fabricate the oxygen electrode by infiltration of different cathode materials into a porous YSZ structure. One of the advantages of this fabrication method is an increased of TPB (triple-phase boundary) length compared with the standard cathode due to the smallest size of the dispersed catalyser particles having a higher surface area. In addition, since no sintering process of the cathode is needed the formation of nonconducting secondary phases such as non-conducting zirconates, and also the coarsening of the catalyser during sintering is eliminated. In the present work, results about infiltrated LSM cathodes using different LSM concentrations will be shown. The j-V (current density-voltage) measurements showed an increase of near 20% in terms of power density: 700 mW cm-2 at 0.7V and 850 ºC for a standard cell and 720 and 825 mW cm-2 at 0.7V and 850 ºC for similar tubular cells but with non-optimised and optimised LSM infiltrated cathodes, respectively. In addition, we will also present results on Nd2NiO4+δ cathodes infiltrated into porous yttria stabilized zirconia (YSZ). In order to obtain nickelate single phase, calcination times and temperatures of the salt precursors will be discussed. Anode supported microtubular cells using this cathode showed power densities of about 760 mW cm-2 at 800 ºC and a voltage as high as 0.8 V. No degradation was detected after 24 hours under current load, assuring reasonable stability of the cell. Preliminary solid oxide electrolysis cell (SOEC) results showed slightly better performances in comparison with SOFC operation. It is believed that infiltration of nickelate salt precursors followed by calcination proposed in this work avoids high temperature sintering of the nickelate phase with the electrolyte and as a consequence, prevents their reaction. For this reason, infiltrated nickelates are very attractive for their use as intermediate temperature (IT) SOFC cathodes.Peer Reviewe

pTINCR microprotein promotes epithelial differentiation and suppresses tumor growth through CDC42 SUMOylation and activation

The human transcriptome contains thousands of small open reading frames (sORFs) that encode microproteins whose functions remain largely unexplored. Here, we show that TINCR lncRNA encodes pTINCR, an evolutionary conserved ubiquitin-like protein (UBL) expressed in many epithelia and upregulated upon differentiation and under cellular stress. By gain- and loss-of-function studies, we demonstrate that pTINCR is a key inducer of epithelial differentiation in vitro and in vivo. Interestingly, low expression of TINCR associates with worse prognosis in several epithelial cancers, and pTINCR overexpression reduces malignancy in patient-derived xenografts. At the molecular level, pTINCR binds to SUMO through its SUMO interacting motif (SIM) and to CDC42, a Rho-GTPase critical for actin cytoskeleton remodeling and epithelial differentiation. Moreover, pTINCR increases CDC42 SUMOylation and promotes its activation, triggering a pro-differentiation cascade. Our findings suggest that the microproteome is a source of new regulators of cell identity relevant for cancer.Acknowledgements: The authors thank VHIO Proteomics, Molecular Oncology and Genomics Core Facilities for technical assistance. We are grateful to Manuel Serrano for providing several reagents, advice and critical discussion on the manuscript. We also thank Alonso García and Raquel Pérez for their help in processing and analyzing digital images, Gemma Serra and Sandra Peiró for their assistance with subcellular fractionation and immunoprecipitation experiments, Sara Arce and Joaquín Mateo for providing several reagents during the development of critical experiments of this manuscript, and Juan Angel Recio for his help with the cSCC cohort. We are immensely grateful to all the members of the Abad lab for generating the know-how for the identification of novel sORFs, for the critical reading on the manuscript and in general for their constant support to this project. Work in the Abad lab is supported by VHIO, Fero Foundation, La Caixa Foundation, Asociación Española Contra el Cancer (AECC), La Mutua Foundation and by grants from the Spanish Ministry of Science and Innovation (SAF2015-69413-R; RTI2018-102046-B-I00). M.A. was recipient of a Ramón y Cajal contract from the Spanish Ministry of Science and Innovation (RYC-2013-14747). O.B. is recipient of a FPIAGAUR fellowship from Generalitat de Catalunya. We also acknowledge funding from grant PGC2018-094091-B-I00 from the Spanish Government