Cosmology in an accelerated universe: observations and phenomenology

En las últimas décadas la cosmología ha experimentado notables avances como consecuencia del desarrollo de nuevos experimentos que nos han abastecido con precisos datos observacionales. La calidad de estos datos ha permitido construir una imagen global del universo actual; un universo acelerado compuesto principalmente por materia oscura (23%) distinta a la materia ordinaria (5%), y energía oscura (70%), la componente del universo que contrarresta el efecto gravitatorio y explica la expansión acelerada de éste. Con la existencia de estas dos principales componentes se puede explicar la situación actual del universo y los fenómenos que tienen lugar en él. Sin embargo, su naturaleza es todavía un misterio, por lo que nos encontramos ante un largo y apasionante camino que recorrer.Es en este contexto donde se enmarca el trabajo presentado en esta tesis, cuyo principal objetivo es ir más allá y obtener algunas pistas nuevas sobre la naturaleza de la energía oscura. Las investigaciones llevadas a cabo durante esta tesis tratan de hacer frente a este sector ¿oscuro" desde varias perspectivas, combinando la teoría y el análisis de datos astronómicos.Como primer acercamiento, en el capítulo 2 se propone un nuevo modelo para unificar el sector ¿oscuro¿: materia y energía oscura. En los capítulos 3 y 4 se aborda el problema de la energía oscura desde una nueva perspectiva y se presentan unas nuevas parametrizaciones de la ecuación de estado de la energía oscura. Por último, en el capítulo 5, a través de los datos del fondo cósmico de microondas, se da un paso más allá en física de las épocas tempranas del universo, y se obtienen restricciones sobre el exceso de densidad de radiación observado. Por otra parte, se da una explicación a este fenómeno: se atribuye este exceso al fondo cósmico de ondas gravitacionales primordiales producido por las cuerdas cósmicas, bajo condiciones adiabáticas.

Soluciones solitón y aplicación a las proteínas

Podemos encontrar en la naturaleza dos tipos de ondas. Por una lado est an las ondas lineales y por otro lado las ondas no lineales. Tradicionalmente, hablamos de las ondas lineales, que son las m as familia- res, las que estamos m as acostumbrados a encontrarnos en el d a a d a, y las que llevamos estudiando desde hace mucho tiempo. Entre ellas encontramos las ondas de la luz y las del sonido, por ejemplo. Estas ondas tienen, sea cual sea su forma, velocidad, amplitud y longitud de onda constantes. Asimismo, obedecen al principio de superposici on. Por otro lado, en este trabajo, destacaremos las ondas no lineales, que son menos familiares que las anteriores comentadas, pero no por ello menos im- portantes. Este tipo de ondas son muy diferentes a las lineales, ya que en ellas la amplitud, la longitud de onda y la velocidad no son constantes. Entre los ejemplos donde las encontramos, destacamos una ola en el mar aproxi- mandose a la orilla. Vemos que la distancia entre las crestas va decreciendo, la velocidad cambia y la altura de la ola va creciendo conforme va percibien- do el fondo; llegando a un punto en el que la ola se rompe ya que la parte superior se ha adelantado demasiado a la inferior. Con respecto a esta parte de la ciencia, la Matem atica y F sica No Lineal, cabe destacar sus grandes avances en la segunda mitad del siglo XX con la Teor a de Solitones, punto en el que centraremos el tema de este trabajo. En primer lugar daremos una de nici on sencilla de solit on: los solitones son ondas no lineales que exhiben un comportamiento extremadamente inespe- rado e interesante, son ondas solitarias que se propagan sin deformarse. De ah que su nombre derive de onda solitaria

Spin-related phenomena in magnetic and spin-orbit couppled bose-einstein condensates

129 p.

Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

Estudio de señales cerebrales y aplicación a cojín elevador para discapacitados.

[ES]Estudio de obtención de señales cerebrales, creación de sensores de electroencefalograma y circuito que procesa frecuencias cerebrales para control de un prototipo de cojín elevador que ayude a personas discapacitadas a levantarse de un asiento con el fin de dar los primeros pasos en la creación de un exoesqueleto controlado cerebralmente.

Desarrollo de un prototipo de exoesqueleto básico activado con una señal cerebral.

[ES]En este documento se estudia el desarrollo de una aplicación electrónica para la ayuda a gente con movilidad reducida a través de unos sensores cerebrales que permitan el análisis de la iniciativa de la persona a realizar acciones que de otra manera no podría realizar. El concepto completo consiste en el diseño del sensor que el paciente se colocaría en la cabeza, el tratamiento de la información extraída y la actuación por medio de una solución mecánica, como un conjunto cilindro-pistón para el futuro desarrollo de un sistema de ayuda a la movilidad.

Diseño de un sistema de monitorización de estructuras de procesamiento paralelo.

[ES]Este proyecto consiste en el diseño de un sistema de monitorización de estructuras (SHM) con procesamiento paralelo. Los sistemas SHM sirven para analizar la integridad de estructuras y detectar daños en las mismas. El sistema diseñado utiliza la técnica de ondas ultrasónicas superficiales. Integra todos los circuitos electrónicos para generar y adquirir las señales. También incluye un procesador para tratar las señales y detectar los daños de la estructura. El sistema se ha diseñado para conectar varios equipos en paralelo

Estudio de las ecuaciones de Boussinesq para la modelización de tsunamis

[es]Podemos encontrar las ecuaciones de Boussinesq en la descripción de playas, rios y lagos. Estas ecuaciones estudian la dinámica de las aguas poco profundas como las ecuaciones “ Korteweg-deVries (KdV)". Sin embargo, a pesar de ser más conocidas, las ecuaciones de KdV, no son capaces de modelar olas solitarias propagándose en distintas direcciones. Entre muchas otras aplicaciones de las ecuaciones de Boussinesq destaca la de modelar olas de tsunamis. Estos tipos de olas ya son perfectamente descritos por las ecuaciones de Navier Stokes, pero todavía no existen técnicas que permitan resolverlas en un dominio tridimensional. Para ello se usan las ecuaciones de Boussinesq, pensadas como una simplificación de las ecuaciones de Navier Stokes. Los años 1871 y 1872 fueron muy importantes para el desarrollo de las ecuaciones de Boussinesq. Fue en 1871 cuando Valentin Joseph Boussinesq recibió el premio de la “Academy of Sciences”, por su trabajo dedicado a las aguas poco profundas. Ahí fue donde Boussinesq introdujo por primera vez los efectos dispersivos en las ecuaciones de Saint-Venant. Por ello, se puede decir que las ecuaciones de Boussinesq son más completas físicamente que las ecuaciones de Saint-Venant. Las ecuaciones de Boussinesq contienen una estructura hiperbólica (al igual que las ecuaciones no lineales de aguas poco profundas) combinada con derivadas de orden elevado para modelar la dispersión de la ola. Las ecuaciones de Boussinesq pueden aparecer de muchas formas distintas. Dependiendo de como hayamos escogido la variable de la velocidad podemos obtener un modelo u otro. El caso más usual es escoger la variable velocidad en un nivel del agua arbitrario. La efectividad de la ecuación de Boussinesq seleccionada variará dependiendo de la dispersión. Una buena elección de la variable velocidad puede mejorar significativamente la modelización de la propagación de ondas largas. Formalmente, como veremos en el capítulo 1, podemos transformar términos de orden elevado en términos de menor orden usando las relaciones asintóticas. Esto nos proporciona una forma elegante de mejorar las relaciones de dispersi\'on. Las ecuaciones de Boussinesq más conocidas son las que resolveremos en el capítulo 2. En dicho capítulo veremos la ecuación cúbica de Boussinesq, que sirve para describir el movimiento de ondas largas en aguas poco profundas; las ecuaciones de Boussinesq acopladas, que describen el movimiento de dos fluidos distintos en aguas poco profundas (como puede ser el caso de un barco que desprende accidentalmente aceite, el aceite va creando una capa que flota encima de la superficie del agua); la ecuación de Boussinesq estándar, que describe un gran número de fenómenos de olas dispersivas no lineales como la propagaci\ón en ambas direcciones de olas largas en la superficie de aguas poco profundas. Pero en olas de longitud de onda corta presenta una inestabilidad y la ecuación es incorrecta para el problema de Cauchy, por ello Bogolubsky propuso la ecuación de Boussinesq mejorada. Esta ecuación es la última que estudiaremos en el capítulo 2 y es una ecuación físicamente estable, correcta para el problema de Cauchy y además como veremos en el capítulo 3, apropiada para las simulaciones numéricas. Como ya indicado, en el capi tulo 1 deduciremos las ecuaciones de Boussinesq a partir de las ecuaciones físicas del flujo potencial. El objetivo principal es deducir dos modelos de ecuaciones de Boussinesq acopladas y obtener su relación de dispersión. Para llegar a ello, se usa un método de la expansión asintótica de la velocidad potencial en términos de un pequeño parámetro. De esta manera conseguimos dos modelos distintos, cada uno asociado a uno de los dos modelo de disipación que hemos establecido. Por último dado que las ecuaciones siempre vienen dadas en variables dimensionales, volveremos a la notación dimensional para analizar la relación de dispersión de las ecuaciones de Boussinesq disipativas. En el capí tulo 2 pasaremos a su resolución analítica, buscando soluciones de tipo solitón. Introduciremos el método de la tangente hiperbólica, muy útil para encontrar soluciones exactas de ecuaciones no lineales. Usaremos este método para resolver la ecuación cúbica de Boussinesq, un sistema de ecuaciones acopladas de Boussinesq, la ecuación estandar de Boussinesq y la mejorada. Los sistemas que aparecen en la aplicación del método de la tangente hiperbólica estan resueltos usando el software Mathematica y uno de ellos irá incluido en el apéndice A. En el capíulo 3 se introduce un esquema en diferencias finitas, que sirve para convertir problemas de ecuaciones diferenciales en problemas algebraicos fácilmente resolubles numéricamente. Este método nos ayudaráa estudiar la estabilidad y a resolver la ecuación mejorada de Boussinesq numéricamente en dos ejemplos distintos. En el apéndice B incluiremos el programa para la resolución numérica del primer ejemplo con el Mathematica.