GdBaCo2O5+x layered perovskite as an intermediate temperature solid oxide fuel cell cathode

GdBaCo2O5+x (GBCO) was evaluated as a cathode for intermediate-temperature solid oxide fuel cells. A porous layer of GBCO was deposited on an anode-supported fuel cell consisting of a 15m thick electrolyte of yttria-stabilized zirconia (YSZ) prepared by dense screen-printing anda Ni–YSZ cermet as an anode (Ni–YSZ/YSZ/GBCO). Values of power density of 150 mW cm−2 at 700◦C and ca. 250 mW cm−2 at 800◦C are reported for this standard configuration using 5% of H2 in nitrogen as fuel. An intermediate porous layer of YSZ was introduced between the electrolyte and the cathode improving the performance of the cell. Values for power density of 300 mW cm−2 at 700◦C and ca. 500 mW cm−2 at 800◦C in this configuration were achieved.

Strong solutions for stochastic porous media equations with jumps

We prove global well-posedness in the strong sense for stochastic generalized porous media equations driven by locally square integrable martingales with stationary independent increments.

Statistical similarity between the compression of a porous material and earthquakes

It has been long stated that there are profound analogies between fracture experiments and earthquakes; however, few works attempt a complete characterization of the parallelisms between these so separate phenomena. We study the Acoustic Emission events produced during the compression of Vycor (SiO&sub&2&/sub&). The Gutenberg-Richter law, the modified Omori's law, and the law of aftershock productivity hold for a minimum of 5 decades, are independent of the compression rate, and keep stationary for all the duration of the experiments. The waiting-time distribution fulfills a unified scaling law with a power-law exponent close to 2.45 for long times, which is explained in terms of the temporal variations of the activity rate.

Solubilization of decane into gemini surfactant with a modified Jeffamine backbone: Design of hierarchical porous silica

Herein, we have investigated the solubilization of decane into a novel nonionic gemini surfactant, myristoyl-end capped Jeffamine, synthesized from a polyoxyalkyleneamine (ED900). Starting from this system, porous silica materials have been prepared. Performing the hydrothermal treatment at low temperature, a slight increase of the mesopore diameter is observed in the presence of decane. Increasing the temperature of the hydrothermal treatment, no swelling effect of decane is detected. By contrast, the pore diameter decreases but better mesopore homogeneity and a larger wall thickness are obtained. At high decane concentration the new myristoyl-end capped Jeffamine/decane/water system forms oil-in-water emulsions, which are used as template for the formation of hierarchical porous silica materials.

Preparació, estudi estructural i aplicabilitat de derivats de Poli-(4R)-hidroxi-L-prolina a la separació d’enantiòmers per tècniques cromatogràfiques o relacionades

La separació d’enantiòmers (isòmers òptics) és molt important en molts diversos camps, com les síntesis quirals, biologia, i en el camp de la farmacologia especialment. És per això, que es fa necessari de disposar de tècniques i mètodes analítics ràpids, fiables i sensibles per a la separació d’enantiòmers. La present tesi s’emmarca en el camp de la separació d’enantiòmers, concretament en la preparació de fases estacionàries quirals per al seu ús en cromatografia liquida. En aquest sentit, s’ha desenvolupat la síntesi i caracterització de molècules polimèriques quirals derivades de l’aminoàcid L-prolina que incorporades en matrius de gel de sílice poden constituïr columnes quirals per a la separació d’enantiòmers per cromatografia liquida. S’han estudiat les característiques enantioselectives d’aquests nous materials en la separació de molècules quirals, trobant-se ésser satisfactòriament enantioselectius. L’interès que suscita l’obtenció d’enantiòmers a gran escala fa que la recerca s’orienti a la recerca de materials amb elevada capacitat de càrrega, és a dir, que puguin donar lloc a la separació d’elevades quantitats d’enantiòmers. Amb aquesta finalitat s’han dut a terme assaigs de capacitat de càrrega, que han posat de manifest la possible aplicació d’aquests materials a la separació preparativa d’enantiòmers. També s’ha parat especial atenció a l’estudi de les característiques de la matriu de gel de sílice, assajant-se altres materials de sílice més porosos i que permeten així treballar amb fluxos més elevats tot reduint-ne el temps d’anàlisi i els costos associats a la separació preparativa d’enantiòmers. L'estudi conformacional d'aquests nous selectors també ha estat contemplat per tal d'explicar l'enantioselectivitat específica que s'observa en certs dissolvents orgànics en els qual es duu a terme la separació dels enantiòmers.

A mixed finite element method for nonlinear diffusion equations

We propose a mixed finite element method for a class of nonlinear diffusion equations, which is based on their interpretation as gradient flows in optimal transportation metrics. We introduce an appropriate linearization of the optimal transport problem, which leads to a mixed symmetric formulation. This formulation preserves the maximum principle in case of the semi-discrete scheme as well as the fully discrete scheme for a certain class of problems. In addition solutions of the mixed formulation maintain exponential convergence in the relative entropy towards the steady state in case of a nonlinear Fokker-Planck equation with uniformly convex potential. We demonstrate the behavior of the proposed scheme with 2D simulations of the porous medium equations and blow-up questions in the Patlak-Keller-Segel model.

Obtenció de matrius poroses d'àcid polilàctic (PDLLA) mitjançant fluids comprimits per a ús en regeneració tissular

En aquest treball es pretén obtenir material porós de PDLLA, amb ús potencial com a bastida en enginyeria tissular, mitjançant l’ús de freó R-134a com a fluid escumant. Per aquest motiu, s’ha realitzat un estudi on es valoren diferents variables com la temperatura de procés, la pressió de treball i l’ús de N2 en la despressurització que poden modificar la microestructura final de la bastida.

Elaboració de membranes de fibra buida modificades amb nanopartícules metàl·liques per aplicacions catalítiques

Investigación producida a partir de una estancia en la Université Paul Sabatier, Toulouse III - CNRS, entre 2007 y 2009. Durante los últimos años la investigación centrada en nuevos materiales de tamaño nanoscòpico (nanopartículas, quantum dots, nanotubos de carbono,...) ha experimentado un crecimiento considerable debido a las especiales propiedades de los "nanoobjetos" con respecto a magnetismo, catálisis, conductividad eléctrica, etc ... Sin embargo, hoy en día todavía existen pocas aplicaciones de las nanopartículas en temas medioambientales. Uno de los motivos de esta situación es la posible toxicidad de los nanoobjetos, pero existe también una dificultad tecnológica dado que las nanopartículas tienden a agregarse y es muy difícil manipularlas sin que pierdan sus propiedades especiales. Así, aunque la preparación de materiales catalíticos nanoestructurados es muy interesante, es necesario definir nuevas estrategias para prepararlos. Este proyecto de investigación tiene como objetivo principal la preparación de nuevas membranas catalíticas con nanopartículas metálicas en el interior para aplicaciones de tratamiento de agua. La innovación principal de este proyecto consiste en que las nanopartículas no son introducidas en la matriz polimérica una vez preformadas sino que se hacen crecer en el interior de la matriz polimérica mediante una síntesis intermatricial. El único requisito es que la matriz polimérica contenga grupos funcionales capaces de interaccionar con los precursores de las nanopartículas. Una vez finalizado el proyecto se puede afirmar que se han logrado parte de los objetivos planteados inicialmente. Concreamente ha quedado demostrado que se pueden sintetizar nanopartículas metálicas de metales nobles (platino y paladio) en membranas de fibra hueca de micro- y ultrafiltración siguiendo dos metodologías diferentes: modificación fotoquímica de polímeros y deposición de multicapas de polielectrolitos. Los nuevos materiales son efectivos en la catálisis de reducción de un compuesto modelo (4-nitrofenol con borohidruro de sodio) y, en general, los resultados han sido satisfactorios. Sin embargo, se ha puesto de manifiesto que el uso de un reactivo que genera hidrógeno gas en contacto con la solución acuosa dificulta enormemente la implementación de la reacción catalítica al ser el medio de la membrana una matriz porosa. Así, como conclusión principal se puede decir que se han encontrado las limitaciones de esta aproximación y se sugieren dos posibilidades de continuidad: la utilización de las membranas sintetizadas en contactores gas-líquido o bien el estudio y optimización del sistema de membrana en configuración de membranas planas, un objetivo más asequible dada su menor complejidad. Esta investigación se ha realizado en el seno del “Laboratoire de Génie Chimique” de Toulouse y del Departamento de Química de la Michigan State University y ha sido posible gracias a un proyecto financiado por la “Agence National pour la Recherce” y al programa PERMEANT entre el CNRS y la NSF.

Estudio comparado de la génesis de espeleotemas silíceos en granitoides de climas semiáridos y templados húmedos

Silica speleothems take differenr forms such as cylindrical stems growing from either the floor or the ceiling in granitic caves. Mineralogically they are opal-A and accumulate in successive layers with a whiskery druse tip formed by gypsum crystals. Initially they are porous but progressively become infilled by opal precipitation. This results in formation of solid speleothems. their size is only a few millimetres long. Bacterial activity accelerate quartz dissolution

Pressure-dependent scaling scenarios in experiments of spontaneous imbibition

The scaling properties of the rough liquid-air interface formed in the spontaneous imbibition of a viscous liquid by a model porous medium are found to be very sensitive to the magnitude of the pressure difference applied at the liquid inlet. Interface fluctuations change from obeying intrinsic anomalous scaling at large negative pressure differences, to being super-rough with the same dynamic exponent z¿3 at less negative pressure differences, to finally obeying ordinary Family-Vicsek scaling with z¿2 at large positive pressure differences. This rich scenario reflects the relative importance on different length scales of capillary and permeability disorder, and the role of surface tension and viscous pressure in damping interface fluctuations.

Influence of disorder strength on phase-field models of interfacial growth

We study the influence of disorder strength on the interface roughening process in a phase-field model with locally conserved dynamics. We consider two cases where the mobility coefficient multiplying the locally conserved current is either constant throughout the system (the two-sided model) or becomes zero in the phase into which the interface advances (one-sided model). In the limit of weak disorder, both models are completely equivalent and can reproduce the physical process of a fluid diffusively invading a porous media, where super-rough scaling of the interface fluctuations occurs. On the other hand, increasing disorder causes the scaling properties to change to intrinsic anomalous scaling. In the limit of strong disorder this behavior prevails for the one-sided model, whereas for the two-sided case, nucleation of domains in front of the invading front are observed.

Plasma-enhanced chemical vapor deposition of boron nitride thin films from B2H6-H2-NH3 and B2H6-N2 gas mixtures

Highly transparent and stoichiometric boron nitride (BN) films were deposited on both electrodes (anode and cathode) of a radio-frequency parallel-plate plasma reactor by the glow discharge decomposition of two gas mixtures: B2H6-H2-NH3 and B2H6-N2. The chemical, optical, and structural properties of the films, as well as their stability under long exposition to humid atmosphere, were analyzed by x-ray photoelectron, infrared, and Raman spectroscopies; scanning and transmission electron microscopies; and optical transmittance spectrophotometry. It was found that the BN films grown on the anode using the B2H6-H2-NH3 mixture were smooth, dense, adhered well to substrates, and had a textured hexagonal structure with the basal planes perpendicular to the film surface. These films were chemically stable to moisture, even after an exposition period of two years. In contrast, the films grown on the anode from the B2H6-N2 mixture showed tensile stress failure and were very unstable in the presence of moisture. However, the films grown on the cathode from B2H6-H2-NH3 gases suffered from compressive stress failure on exposure to air; whereas with B2H6-N2 gases, adherent and stable cathodic BN films were obtained with the same crystallographic texture as anodic films prepared from the B2H6-H2-NH3 mixture. These results are discussed in terms of the origin of film stress, the effects of ion bombardment on the growing films, and the surface chemical effects of hydrogen atoms present in the gas discharge.

Mineralization of the recalcitrant oxalic and oxamic acids by electrochemical advanced oxidation processes using a boron-doped diamond anode

Oxalic and oxamic acids are the ultimate and more persistent by-products of the degradation of N-aromatics by electrochemical advanced oxidation processes (EAOPs). In this paper, the kinetics and oxidative paths of these acids have been studied for several EAOPs using a boron-doped diamond (BDD) anode and a stainless steel or an air-diffusion cathode. Anodic oxidation (AO-BDD) in the presence of Fe2+ (AO-BDD-Fe2+) and under UVA irradiation (AO-BDD-Fe2+-UVA), along with electro-Fenton (EF-BDD), was tested. The oxidation of both acids and their iron complexes on BDD was clarified by cyclic voltammetry. AO-BDD allowed the overall mineralization of oxalic acid, but oxamic acid was removed much more slowly. Each acid underwent a similar decay in AO-BDD-Fe2+ and EFBDD, as expected if its iron complexes were not attacked by hydroxyl radicals in the bulk. The faster and total mineralization of both acids was achieved in AO-BDD-Fe2+-UVA due to the high photoactivity of their Fe(III) complexes that were continuously regenerated by oxidation of their Fe(II) complexes. Oxamic acid always released a larger proportion of NH4 + than NO3- ion, as well as volatile NOx species. Both acids were independently oxidized at the anode in AO-BDD, but in AO-BDD-Fe2+-UVA oxamic acid was more slowlydegraded as its content decreased, without significant effect on oxalic acid decay. The increase in current density enhanced the oxidation power of the latter method, with loss of efficiency. High Fe2+ contents inhibited the oxidation of Fe(II) complexes by the competitive oxidation of Fe2+ to Fe3+. Low current densities and Fe2+ contents are preferable to remove more efficiently these acids by the most potent AO-BDD-Fe2+-UVA method.

Role of structural saturation and geometry in the luminescence of silicon-based nanostructured materials

The structural saturation and stability, the energy gap, and the density of states of a series of small, silicon-based clusters have been studied by means of the PM3 and some ab initio (HF/6-31G* and 6-311++G**, CIS/6-31G* and MP2/6-31G*) calculations. It is shown that in order to maintain a stable nanometric and tetrahedral silicon crystallite and remove the gap states, the saturation atom or species such as H, F, Cl, OH, O, or N is necessary, and that both the cluster size and the surface species affect the energetic distribution of the density of states. This research suggests that the visible luminescence in the silicon-based nanostructured material essentially arises from the nanometric and crystalline silicon domains but is affected and protected by the surface species, and we have thus linked most of the proposed mechanisms of luminescence for the porous silicon, e.g., the quantum confinement effect due to the cluster size and the effect of Si-based surface complexes.

Experimental investigation of the initial regime in fingering electrodeposition: Dispersion relation and velocity measurements.

Recently a fingering morphology, resembling the hydrodynamic Saffman-Taylor instability, was identified in the quasi-two-dimensional electrodeposition of copper. We present here measurements of the dispersion relation of the growing front. The instability is accompanied by gravity-driven convection rolls at the electrodes, which are examined using particle image velocimetry. While at the anode the theory presented by Chazalviel et al. [J. Electroanal. Chem. 407, 61 (1996)] describes the convection roll, the flow field at the cathode is more complicated because of the growing deposit. In particular, the analysis of the orientation of the velocity vectors reveals some lag of the development of the convection roll compared to the finger envelope.