14 resultados para atropisomers, dynamic NMR, maleimides, circular dichroism, DFT calculations

em Universidad Politécnica de Madrid


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Los terremotos constituyen una de las más importantes fuentes productoras de cargas dinámicas que actúan sobre las estructuras y sus cimentaciones. Cuando se produce un terremoto la energía liberada genera movimientos del terreno en forma de ondas sísmicas que pueden provocar asientos en las cimentaciones de los edificios, empujes sobre los muros de contención, vuelco de las estructuras y el suelo puede licuar perdiendo su capacidad de soporte. Los efectos de los terremotos en estructuras constituyen unos de los aspectos que involucran por su condición de interacción sueloestructura, disciplinas diversas como el Análisis Estructural, la Mecánica de Suelo y la Ingeniería Sísmica. Uno de los aspectos que han sido poco estudiados en el cálculo de estructuras sometidas a la acciones de los terremotos son los efectos del comportamiento no lineal del suelo y de los movimientos que pueden producirse bajo la acción de cargas sísmicas, tales como posibles despegues y deslizamientos. En esta Tesis se estudian primero los empujes sísmicos y posibles deslizamientos de muros de contención y se comparan las predicciones de distintos tipos de cálculos: métodos pseudo-estáticos como el de Mononobe-Okabe (1929) con la contribución de Whitman-Liao (1985), y formulaciones analíticas como la desarrollada por Veletsos y Younan (1994). En segundo lugar se estudia el efecto del comportamiento no lineal del terreno en las rigideces de una losa de cimentación superficial y circular, como la correspondiente a la chimenea de una Central Térmica o al edificio del reactor de una Central Nuclear, considerando su variación con frecuencia y con el nivel de cargas. Finalmente se estudian los posibles deslizamientos y separación de las losas de estas dos estructuras bajo la acción de terremotos, siguiendo la formulación propuesta por Wolf (1988). Para estos estudios se han desarrollado una serie de programas específicos (MUROSIS, VELETSOS, INTESES y SEPARSE) cuyos listados y detalles se incluyen en los Apéndices. En el capítulo 6 se incluyen las conclusiones resultantes de estos estudios y recomendaciones para futuras investigaciones. ABSTRACT Earthquakes constitute one of the most important sources of dynamic loads that acting on structures and foundations. When an earthquake occurs the liberated energy generates seismic waves that can give rise to structural vibrations, settlements of the foundations of buildings, pressures on retaining walls, and possible sliding, uplifting or even overturning of structures. The soil can also liquefy losing its capacity of support The study of the effects of earthquakes on structures involve the use of diverse disciplines such as Structural Analysis, Soil Mechanics and Earthquake Engineering. Some aspects that have been the subject of limited research in relation to the behavior of structures subjected to earthquakes are the effects of nonlinear soil behavior and geometric nonlinearities such as sliding and uplifting of foundations. This Thesis starts with the study of the seismic pressures and potential displacements of retaining walls comparing the predictions of two types of formulations and assessing their range of applicability and limitations: pseudo-static methods as proposed by Mononobe-Okabe (1929), with the contribution of Whitman-Liao (1985), and analytical formulations as the one developed by Veletsos and Younan (1994) for rigid walls. The Thesis deals next with the effects of nonlinear soil behavior on the dynamic stiffness of circular mat foundations like the chimney of a Thermal Power Station or the reactor building of a Nuclear Power Plant, as a function of frequency and level of forces. Finally the seismic response of these two structures accounting for the potential sliding and uplifting of the foundation under a given earthquake are studied, following an approach suggested by Wolf (1988). In order to carry out these studies a number of special purposes computer programs were developed (MUROSIS, VELETSOS, INTESES and SEPARSE). The listing and details of these programs are included in the appendices. The conclusions derived from these studies and recommendations for future work are presented in Chapter 6.

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Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

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Nowadays, treatment of food allergy only considered the avoidance of the specific food. However, the possibility of cross-reactivity makes this practice not very effective. Immunotherapy may exhibit as a good alternative to food allergy treatment. The use of hypoallergenic molecules with reduced IgE binding capacity but with ability to stimulate the immune system is a promising tool which could be developed for immunotherapy. In this study, three mutants of Pru p 3, the principal allergen of peach, were produced based on the described mimotope and T cell epitopes, by changing the specific residues to alanine, named as Pru p 3.01, Pru p 3.02, and Pru p 3.03. Pru p 3.01 showed very similar allergenic activity as the wild type by in vitro assays. However, Pru p 3.02 and Pru p 3.03 presented reduced IgE binding with respect to the native form, by in vitro, ex vivo, and in vivo assays. In addition, Pru p 3.03 had affected the IgG4 binding capacity and presented a random circular dichroism, which was reflected in the nonrecognition by specific antibodies anti-Pru p 3. Nevertheless, both Pru p 3.02 and Pru p 3.03 maintained the binding to IgG1 and their ability to activate T lymphocytes. Thus, Pru p 3.02 and Pru p 3.03 could be good candidates for potential immunotherapy in peach-allergic patients.

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A boundary element approach for time harmonic axisymmetric problems using the complete space point load fundamental solution is presented. The fundamental solution is integrated numerically along the azimuthal co-ordinate of each axisymmetric element. To increase the accuracy of the numerical integration a simple co-ordinate transformation is proposed. The approach is applied to the computation of the dynamic stiffness functions of rigid circular foundations on layered viscoelastic soils. Three different sites are considered: a uniform half-space, a soil layer on a half-space, and a soil consisting of four horizontal layers and a compliant half-space. The numerical results obtained by the proposed approach for surface circular foundations are very close to corresponding published results obtained by different procedures.

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The traditional ballast track structures are still being used in high speed railways lines with success, however technical problems or performance features have led to non-ballast track solution in some cases. A considerable maintenance work is needed for ballasted tracks due to the track deterioration. Therefore it is very important to understand the mechanism of track deterioration and to predict the track settlement or track irregularity growth rate in order to reduce track maintenance costs and enable new track structures to be designed. The objective of this work is to develop the most adequate and efficient models for calculation of dynamic traffic load effects on railways track infrastructure, and then evaluate the dynamic effect on the ballast track settlement, using a ballast track settlement prediction model, which consists of the vehicle/track dynamic model previously selected and a track settlement law. The calculations are based on dynamic finite element models with direct time integration, contact between wheel and rail and interaction with railway cars. A initial irregularity profile is used in the prediction model. The track settlement law is considered to be a function of number of loading cycles and the magnitude of the loading, which represents the long-term behavior of ballast settlement. The results obtained include the track irregularity growth and the contact force in the final interaction of numerical simulation

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This paper reports the studies carried out to develop and calibrate the optimal models for the objectives of this work. In particular, quarter bogie model for vehicle, rail-wheel contact with Lagrangian multiplier method, 2D spatial discretization were selected as the optimal decisions. Furthermore, the 3D model of coupled vehicle-track also has been developed to contrast the results obtained in the 2D model. The calculations were carried out in the time domain and envelopes of relevant results were obtained for several track profiles and speed ranges. Distributed elevation irregularities were generated based on power spectral density (PSD) distributions. The results obtained include the wheel-rail contact forces, forces transmitted to the bogie by primary suspension. The latter loads are relevant for the purpose of evaluating the performance of the infrastructure

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Tin disulfide SnS2 was recently proposed as a high efficiency solar cell precursor [1]. The aim of this work is a deep study of the structural disposition of the most important polytipes of this layered material, not only describing the electronic correlation but also the interatomic Van der Waals interactions that is present between the layers. The two recent implementations to take Van der Waals interactions into account in the VASP code are the self-consistent Dion et al. [2] functional optimized for solids by Michaelides et al [3] and the Grimme [4] dispersion correction that is applied after each autoconsistent PBE electronic calculation. In this work these two methods are compared with DFT PBE functional. The results we will presented at this Conference, demonstrates the enhancement of the geometric parameters by the use of the Van der Waals interactions in agreement with the experimental values.

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Screw dislocations in bcc metals display non-planar cores at zero temperature which result in high lattice friction and thermally-activated strain rate behavior. In bcc W, electronic structure molecular statics calculations reveal a compact, non-degenerate core with an associated Peierls stress between 1.7 and 2.8 GPa. However, a full picture of the dynamic behavior of dislocations can only be gained by using more efficient atomistic simulations based on semiempirical interatomic potentials. In this paper we assess the suitability of five different potentials in terms of static properties relevant to screw dislocations in pure W. Moreover, we perform molecular dynamics simulations of stress-assisted glide using all five potentials to study the dynamic behavior of screw dislocations under shear stress. Dislocations are seen to display thermally-activated motion in most of the applied stress range, with a gradual transition to a viscous damping regime at high stresses. We find that one potential predicts a core transformation from compact to dissociated at finite temperature that affects the energetics of kink-pair production and impacts the mechanism of motion. We conclude that a modified embedded-atom potential achieves the best compromise in terms of static and dynamic screw dislocation properties, although at an expense of about ten-fold compared to central potentials.

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In this work, the influence of the surrounding fluid on the dynamic characteristics of almost circular plates is investigated. First the natural frequencies and normal modes for the plates in vacuum are calculated by a perturbation procedure. The method is applied for the case of elliptical plates with a low value of eccentricity. The results are compared with other available methods for this type of plates with good agreement. Next, the effect of the fluid is considered. The normal modes of the plate in vacuum are used as a base to express the vibration mode of the coupled plate-fluid system. By applying the Hankel transformation the nondimensional added virtual mass 2 increment (NAVMI) are calculated for elliptical plates. Results of the NAVMI factors and the effect of the fluid on the natural frequencies are given and it is shown that when the eccentricity of the plate is reduced to zero (circular plate) the known results of the natural frequencies for circular plates surrounded by liquid are recovered.

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In this paper a dynamic analysis of transnational shells is presented. The general linear shell theory is used in conjunction with additional shallow and curved plate approximations. In order to apply some type of extended Levy solution, the shell is assumed to be limited by a rectangular plan form, with two opposite edges simply supported (gable boundary conditions). First, the shells free vibrations are studied in the usual way, obtaining for each Fourier term the natural frequencies as solutions of a transcendental equation. However, solving these equations arises enormous computational difficulties. This paper deals specifically with this problem, trying to reduce its dimension by a discretization procedure. In the shell dynamic characteristics, namely the mass. The shell mass is lumped along a family of coordinate lines. Therefore, the natural frequencies for each harmonic term can be found from the solution of a typical matrix eigenvalues problem and standard numerical techniques can be applied. The shell response to forced vibrations, particularly to earthquake excitation, can be determined by using conventional procedure either in the time or in the frequency domain. Finally, extending the above procedure, any system of translational shells under dynamic loading can be studied. Then, by using matrix methods, a general computer program is written and applied to some illustrative examples. Numerical results has been obtained in two cases: circular cylindrical shell and box girder bridge.

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El gran desarrollo experimentado por la alta velocidad en los principales países de la Unión Europea, en los últimos 30 años, hace que este campo haya sido y aún sea uno de los principales referentes en lo que a investigación se refiere. Por otra parte, la aparición del concepto super − alta velocidad hace que la investigación en el campo de la ingeniería ferroviaria siga adquiriendo importancia en los principales centros de investigación de los países en los que se desea implantar este modo de transporte, o en los que habiendo sido ya implantado, se pretenda mejorar. Las premisas de eficacia, eficiencia, seguridad y confort, que este medio de transporte tiene como razón de ser pueden verse comprometidas por diversos factores. Las zonas de transición, definidas en la ingeniería ferroviaria como aquellas secciones en las que se produce un cambio en las condiciones de soporte de la vía, pueden afectar al normal comportamiento para el que fue diseñada la infraestructura, comprometiendo seriamente los estándares de eficiencia en el tiempo de viaje, confort de los pasajeros y aumentando considerablemente los costes de mantenimiento de la vía, si no se toman las medidas oportunas. En esta tesis se realiza un estudio detallado de la zonas de transición, concretamente de aquellas en las que existe una cambio en la rigidez vertical de la vía debido a la presencia de un marco hidráulico. Para realizar dicho estudio se lleva a cabo un análisis numérico de interacción entre el vehículo y la estructura, con un modelo bidimensional de elemento finitos, calibrado experimentalmente, en estado de tensión plana. En este análisis se tiene en cuenta el efecto de las irregularidades de la vía y el comportamiento mecánico de la interfaz suelo-estructura, con el objetivo de reproducir de la forma más real posible el efecto de interacción entre el vehículo, la vía y la estructura. Otros efectos como la influencia de la velocidad del tren y los asientos diferenciales, debidos a deformaciones por consolidación de los terraplenes a ambos lados el marco hidráulico, son también analizados en este trabajo. En esta tesis, los cálculos de interacción se han llevado a cabo en dos fases diferentes. En la primera, se ha considerado una interacción sencilla debida al paso de un bogie de un tren Eurostar. Los cálculos derivados de esta fase se han denominado cálculos a corto plazo. En la segunda, se ha realizado un análisis considerando múltiples pasos de bogie del tren Eurostar, conformando un análisis de degradación en el que se tiene en cuenta, en cada ciclo, la deformación de la capa de balasto. Los cálculos derivados de esta fase, son denominados en el texto como cálculos a largo plazo. Los resultados analizados muestran que la utilización de los denominados elementos de contacto es fundamental cuando se desea estudiar la influencia de asientos diferenciales, especialmente en transiciones terraplén-estructura en las que la cuña de cimentación no llega hasta la base de cimentación de la estructura. Por otra parte, tener en cuenta los asientos del terraplén, es sumamente importante, cuando se desea realizar un análisis de degradación de la vía ya que su influencia en la interacción entre el vehículo y la vía es muy elevada, especialmente para valores altos de velocidad del tren. En cuanto a la influencia de las irregularidades de la vía, en los cálculos efectuados, se revela que su importancia es muy notable, siendo su influencia muy destacada cuanto mayor sea la velocidad del tren. En este punto cabe destacar la diferencia de resultados derivada de la consideración de perfiles de irregularidades de distinta naturaleza. Los resultados provenientes de considerar perfiles artificiales son en general muy elevados, siendo estos más apropiados para realizar estudios de otra índole, como por ejemplo de seguridad al descarrilamiento. Los resultados provenientes de perfiles reales, dados por diferentes Administradores ferroviarios, presentan resultados menos elevados y más propios del problema analizar. Su influencia en la interacción dinámica entre el vehículo y la vía es muy importante, especialmente para velocidades elevadas del tren. Además el fenómeno de degradación conocido como danza de traviesas, asociado a zonas de transición, es muy susceptible a la consideración de irregularidades de la vía, tal y como se desprende de los cálculos efectuados a largo plazo. The major development experienced by high speed in the main countries of the European Union, in the last 30 years, makes railway research one of the main references in the research field. It should also be mentioned that the emergence of the concept superhigh − speed makes research in the field of Railway Engineering continues to gain importance in major research centers in the countries in which this mode of transportation is already implemented or planned to be implemented. The characteristics that this transport has as rationale such as: effectiveness, efficiency, safety and comfort, may be compromised by several factors. The transition zones are defined in railway engineering as a region in which there is an abrupt change of track stiffness. This stiffness variation can affect the normal behavior for which the infrastructure has been designed, seriously compromising efficiency standards in the travel time, passenger comfort and significantly increasing the costs of track maintenance, if appropriate measures are not taken. In this thesis a detailed study of the transition zones has been performed, particularly of those in which there is a change in vertical stiffness of the track due to the presence of a reinforced concrete culvert. To perform such a study a numerical interaction analysis between the vehicle, the track and the structure has been developed. With this purpose a two-dimensional finite element model, experimentally calibrated, in a state of plane stress, has been used. The implemented numerical models have considered the effects of track irregularities and mechanical behavior of soil-structure interface, with the objective of reproducing as accurately as possible the dynamic interaction between the vehicle the track and the structure. Other effects such as the influence of train speed and differential settlement, due to secondary consolidation of the embankments on both sides of culvert, have also been analyzed. In this work, the interaction analysis has been carried out in two different phases. In the first part a simple interaction due to the passage of a bogie of a Eurostar train has been considered. Calculations derived from this phase have been named short-term analysis. In the second part, a multi-load assessment considering an Eurostar train bogie moving along the transition zone, has been performed. The objective here is to simulate a degradation process in which vertical deformation of the ballast layer was considered. Calculations derived from this phase have been named long-term analysis. The analyzed results show that the use of so-called contact elements is essential when one wants to analyze the influence of differential settlements, especially in embankment-structure transitions in which the wedge-shaped backfill does not reach the foundation base of the structure. Moreover, considering embankment settlement is extremely important when it is desired to perform an analysis of track degradation. In these cases the influence on the interaction behaviour between the vehicle and the track is very high, especially for higher values of speed train. Regarding the influence of the track irregularities, this study has proven that the track’s dynamic response is heavily influenced by the irregularity profile and that this influence is more important for higher train velocities. It should also be noted that the difference in results derived from consideration of irregularities profiles of different nature. The results coming from artificial profiles are generally very high, these might be more appropriate in order to study other effects, such as derailment safety. Results from real profiles, given by the monitoring works of different rail Managers, are softer and they fit better to the context of this thesis. The influence of irregularity profiles on the dynamic interaction between the train and the track is very important, especially for high-speeds of the train. Furthermore, the degradation phenomenon known as hanging sleepers, associated with transition zones, is very susceptible to the consideration of track irregularities, as it can be concluded from the long-term analysis.

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La fusión nuclear es, hoy en día, una alternativa energética a la que la comunidad internacional dedica mucho esfuerzo. El objetivo es el de generar entre diez y cincuenta veces más energía que la que consume mediante reacciones de fusión que se producirán en una mezcla de deuterio (D) y tritio (T) en forma de plasma a doscientos millones de grados centígrados. En los futuros reactores nucleares de fusión será necesario producir el tritio utilizado como combustible en el propio reactor termonuclear. Este hecho supone dar un paso más que las actuales máquinas experimentales dedicadas fundamentalmente al estudio de la física del plasma. Así pues, el tritio, en un reactor de fusión, se produce en sus envolturas regeneradoras cuya misión fundamental es la de blindaje neutrónico, producir y recuperar tritio (fuel para la reacción DT del plasma) y por último convertir la energía de los neutrones en calor. Existen diferentes conceptos de envolturas que pueden ser sólidas o líquidas. Las primeras se basan en cerámicas de litio (Li2O, Li4SiO4, Li2TiO3, Li2ZrO3) y multiplicadores neutrónicos de Be, necesarios para conseguir la cantidad adecuada de tritio. Los segundos se basan en el uso de metales líquidos o sales fundidas (Li, LiPb, FLIBE, FLINABE) con multiplicadores neutrónicos de Be o el propio Pb en el caso de LiPb. Los materiales estructurales pasan por aceros ferrítico-martensíticos de baja activación, aleaciones de vanadio o incluso SiCf/SiC. Cada uno de los diferentes conceptos de envoltura tendrá una problemática asociada que se estudiará en el reactor experimental ITER (del inglés, “International Thermonuclear Experimental Reactor”). Sin embargo, ITER no puede responder las cuestiones asociadas al daño de materiales y el efecto de la radiación neutrónica en las diferentes funciones de las envolturas regeneradoras. Como referencia, la primera pared de un reactor de fusión de 4000MW recibiría 30 dpa/año (valores para Fe-56) mientras que en ITER se conseguirían <10 dpa en toda su vida útil. Esta tesis se encuadra en el acuerdo bilateral entre Europa y Japón denominado “Broader Approach Agreement “(BA) (2007-2017) en el cual España juega un papel destacable. Estos proyectos, complementarios con ITER, son el acelerador para pruebas de materiales IFMIF (del inglés, “International Fusion Materials Irradiation Facility”) y el dispositivo de fusión JT-60SA. Así, los efectos de la irradiación de materiales en materiales candidatos para reactores de fusión se estudiarán en IFMIF. El objetivo de esta tesis es el diseño de un módulo de IFMIF para irradiación de envolturas regeneradoras basadas en metales líquidos para reactores de fusión. El módulo se llamará LBVM (del inglés, “Liquid Breeder Validation Module”). La propuesta surge de la necesidad de irradiar materiales funcionales para envolturas regeneradoras líquidas para reactores de fusión debido a que el diseño conceptual de IFMIF no contaba con esta utilidad. Con objeto de analizar la viabilidad de la presente propuesta, se han realizado cálculos neutrónicos para evaluar la idoneidad de llevar a cabo experimentos relacionados con envolturas líquidas en IFMIF. Así, se han considerado diferentes candidatos a materiales funcionales de envolturas regeneradoras: Fe (base de los materiales estructurales), SiC (material candidato para los FCI´s (del inglés, “Flow Channel Inserts”) en una envoltura regeneradora líquida, SiO2 (candidato para recubrimientos antipermeación), CaO (candidato para recubrimientos aislantes), Al2O3 (candidato para recubrimientos antipermeación y aislantes) y AlN (material candidato para recubrimientos aislantes). En cada uno de estos materiales se han calculado los parámetros de irradiación más significativos (dpa, H/dpa y He/dpa) en diferentes posiciones de IFMIF. Estos valores se han comparado con los esperados en la primera pared y en la zona regeneradora de tritio de un reactor de fusión. Para ello se ha elegido un reactor tipo HCLL (del inglés, “Helium Cooled Lithium Lead”) por tratarse de uno de los más prometedores. Además, los valores también se han comparado con los que se obtendrían en un reactor rápido de fisión puesto que la mayoría de las irradiaciones actuales se hacen en reactores de este tipo. Como conclusión al análisis de viabilidad, se puede decir que los materiales funcionales para mantos regeneradores líquidos podrían probarse en la zona de medio flujo de IFMIF donde se obtendrían ratios de H/dpa y He/dpa muy parecidos a los esperados en las zonas más irradiadas de un reactor de fusión. Además, con el objetivo de ajustar todavía más los valores, se propone el uso de un moderador de W (a considerar en algunas campañas de irradiación solamente debido a que su uso hace que los valores de dpa totales disminuyan). Los valores obtenidos para un reactor de fisión refuerzan la idea de la necesidad del LBVM, ya que los valores obtenidos de H/dpa y He/dpa son muy inferiores a los esperados en fusión y, por lo tanto, no representativos. Una vez demostrada la idoneidad de IFMIF para irradiar envolturas regeneradoras líquidas, y del estudio de la problemática asociada a las envolturas líquidas, también incluida en esta tesis, se proponen tres tipos de experimentos diferentes como base de diseño del LBVM. Éstos se orientan en las necesidades de un reactor tipo HCLL aunque a lo largo de la tesis se discute la aplicabilidad para otros reactores e incluso se proponen experimentos adicionales. Así, la capacidad experimental del módulo estaría centrada en el estudio del comportamiento de litio plomo, permeación de tritio, corrosión y compatibilidad de materiales. Para cada uno de los experimentos se propone un esquema experimental, se definen las condiciones necesarias en el módulo y la instrumentación requerida para controlar y diagnosticar las cápsulas experimentales. Para llevar a cabo los experimentos propuestos se propone el LBVM, ubicado en la zona de medio flujo de IFMIF, en su celda caliente, y con capacidad para 16 cápsulas experimentales. Cada cápsula (24-22 mm de diámetro y 80 mm de altura) contendrá la aleación eutéctica LiPb (hasta 50 mm de la altura de la cápsula) en contacto con diferentes muestras de materiales. Ésta irá soportada en el interior de tubos de acero por los que circulará un gas de purga (He), necesario para arrastrar el tritio generado en el eutéctico y permeado a través de las paredes de las cápsulas (continuamente, durante irradiación). Estos tubos, a su vez, se instalarán en una carcasa también de acero que proporcionará soporte y refrigeración tanto a los tubos como a sus cápsulas experimentales interiores. El módulo, en su conjunto, permitirá la extracción de las señales experimentales y el gas de purga. Así, a través de la estación de medida de tritio y el sistema de control, se obtendrán los datos experimentales para su análisis y extracción de conclusiones experimentales. Además del análisis de datos experimentales, algunas de estas señales tendrán una función de seguridad y por tanto jugarán un papel primordial en la operación del módulo. Para el correcto funcionamiento de las cápsulas y poder controlar su temperatura, cada cápsula se equipará con un calentador eléctrico y por tanto el módulo requerirá también ser conectado a la alimentación eléctrica. El diseño del módulo y su lógica de operación se describe en detalle en esta tesis. La justificación técnica de cada una de las partes que componen el módulo se ha realizado con soporte de cálculos de transporte de tritio, termohidráulicos y mecánicos. Una de las principales conclusiones de los cálculos de transporte de tritio es que es perfectamente viable medir el tritio permeado en las cápsulas mediante cámaras de ionización y contadores proporcionales comerciales, con sensibilidades en el orden de 10-9 Bq/m3. Los resultados son aplicables a todos los experimentos, incluso si son cápsulas a bajas temperaturas o si llevan recubrimientos antipermeación. Desde un punto de vista de seguridad, el conocimiento de la cantidad de tritio que está siendo transportada con el gas de purga puede ser usado para detectar de ciertos problemas que puedan estar sucediendo en el módulo como por ejemplo, la rotura de una cápsula. Además, es necesario conocer el balance de tritio de la instalación. Las pérdidas esperadas el refrigerante y la celda caliente de IFMIF se pueden considerar despreciables para condiciones normales de funcionamiento. Los cálculos termohidráulicos se han realizado con el objetivo de optimizar el diseño de las cápsulas experimentales y el LBVM de manera que se pueda cumplir el principal requisito del módulo que es llevar a cabo los experimentos a temperaturas comprendidas entre 300-550ºC. Para ello, se ha dimensionado la refrigeración necesaria del módulo y evaluado la geometría de las cápsulas, tubos experimentales y la zona experimental del contenedor. Como consecuencia de los análisis realizados, se han elegido cápsulas y tubos cilíndricos instalados en compartimentos cilíndricos debido a su buen comportamiento mecánico (las tensiones debidas a la presión de los fluidos se ven reducidas significativamente con una geometría cilíndrica en lugar de prismática) y térmico (uniformidad de temperatura en las paredes de los tubos y cápsulas). Se han obtenido campos de presión, temperatura y velocidad en diferentes zonas críticas del módulo concluyendo que la presente propuesta es factible. Cabe destacar que el uso de códigos fluidodinámicos (e.g. ANSYS-CFX, utilizado en esta tesis) para el diseño de cápsulas experimentales de IFMIF no es directo. La razón de ello es que los modelos de turbulencia tienden a subestimar la temperatura de pared en mini canales de helio sometidos a altos flujos de calor debido al cambio de las propiedades del fluido cerca de la pared. Los diferentes modelos de turbulencia presentes en dicho código han tenido que ser estudiados con detalle y validados con resultados experimentales. El modelo SST (del inglés, “Shear Stress Transport Model”) para turbulencia en transición ha sido identificado como adecuado para simular el comportamiento del helio de refrigeración y la temperatura en las paredes de las cápsulas experimentales. Con la geometría propuesta y los valores principales de refrigeración y purga definidos, se ha analizado el comportamiento mecánico de cada uno de los tubos experimentales que contendrá el módulo. Los resultados de tensiones obtenidos, han sido comparados con los valores máximos recomendados en códigos de diseño estructural como el SDC-IC (del inglés, “Structural Design Criteria for ITER Components”) para así evaluar el grado de protección contra el colapso plástico. La conclusión del estudio muestra que la propuesta es mecánicamente robusta. El LBVM implica el uso de metales líquidos y la generación de tritio además del riesgo asociado a la activación neutrónica. Por ello, se han estudiado los riesgos asociados al uso de metales líquidos y el tritio. Además, se ha incluido una evaluación preliminar de los riesgos radiológicos asociados a la activación de materiales y el calor residual en el módulo después de la irradiación así como un escenario de pérdida de refrigerante. Los riesgos asociados al módulo de naturaleza convencional están asociados al manejo de metales líquidos cuyas reacciones con aire o agua se asocian con emisión de aerosoles y probabilidad de fuego. De entre los riesgos nucleares destacan la generación de gases radiactivos como el tritio u otros radioisótopos volátiles como el Po-210. No se espera que el módulo suponga un impacto medioambiental asociado a posibles escapes. Sin embargo, es necesario un manejo adecuado tanto de las cápsulas experimentales como del módulo contenedor así como de las líneas de purga durante operación. Después de un día de después de la parada, tras un año de irradiación, tendremos una dosis de contacto de 7000 Sv/h en la zona experimental del contenedor, 2300 Sv/h en la cápsula y 25 Sv/h en el LiPb. El uso por lo tanto de manipulación remota está previsto para el manejo del módulo irradiado. Por último, en esta tesis se ha estudiado también las posibilidades existentes para la fabricación del módulo. De entre las técnicas propuestas, destacan la electroerosión, soldaduras por haz de electrones o por soldadura láser. Las bases para el diseño final del LBVM han sido pues establecidas en el marco de este trabajo y han sido incluidas en el diseño intermedio de IFMIF, que será desarrollado en el futuro, como parte del diseño final de la instalación IFMIF. ABSTRACT Nuclear fusion is, today, an alternative energy source to which the international community devotes a great effort. The goal is to generate 10 to 50 times more energy than the input power by means of fusion reactions that occur in deuterium (D) and tritium (T) plasma at two hundred million degrees Celsius. In the future commercial reactors it will be necessary to breed the tritium used as fuel in situ, by the reactor itself. This constitutes a step further from current experimental machines dedicated mainly to the study of the plasma physics. Therefore, tritium, in fusion reactors, will be produced in the so-called breeder blankets whose primary mission is to provide neutron shielding, produce and recover tritium and convert the neutron energy into heat. There are different concepts of breeding blankets that can be separated into two main categories: solids or liquids. The former are based on ceramics containing lithium as Li2O , Li4SiO4 , Li2TiO3 , Li2ZrO3 and Be, used as a neutron multiplier, required to achieve the required amount of tritium. The liquid concepts are based on molten salts or liquid metals as pure Li, LiPb, FLIBE or FLINABE. These blankets use, as neutron multipliers, Be or Pb (in the case of the concepts based on LiPb). Proposed structural materials comprise various options, always with low activation characteristics, as low activation ferritic-martensitic steels, vanadium alloys or even SiCf/SiC. Each concept of breeding blanket has specific challenges that will be studied in the experimental reactor ITER (International Thermonuclear Experimental Reactor). However, ITER cannot answer questions associated to material damage and the effect of neutron radiation in the different breeding blankets functions and performance. As a reference, the first wall of a fusion reactor of 4000 MW will receive about 30 dpa / year (values for Fe-56) , while values expected in ITER would be <10 dpa in its entire lifetime. Consequently, the irradiation effects on candidate materials for fusion reactors will be studied in IFMIF (International Fusion Material Irradiation Facility). This thesis fits in the framework of the bilateral agreement among Europe and Japan which is called “Broader Approach Agreement “(BA) (2007-2017) where Spain plays a key role. These projects, complementary to ITER, are mainly IFMIF and the fusion facility JT-60SA. The purpose of this thesis is the design of an irradiation module to test candidate materials for breeding blankets in IFMIF, the so-called Liquid Breeder Validation Module (LBVM). This proposal is born from the fact that this option was not considered in the conceptual design of the facility. As a first step, in order to study the feasibility of this proposal, neutronic calculations have been performed to estimate irradiation parameters in different materials foreseen for liquid breeding blankets. Various functional materials were considered: Fe (base of structural materials), SiC (candidate material for flow channel inserts, SiO2 (candidate for antipermeation coatings), CaO (candidate for insulating coatings), Al2O3 (candidate for antipermeation and insulating coatings) and AlN (candidate for insulation coating material). For each material, the most significant irradiation parameters have been calculated (dpa, H/dpa and He/dpa) in different positions of IFMIF. These values were compared to those expected in the first wall and breeding zone of a fusion reactor. For this exercise, a HCLL (Helium Cooled Lithium Lead) type was selected as it is one of the most promising options. In addition, estimated values were also compared with those obtained in a fast fission reactor since most of existing irradiations have been made in these installations. The main conclusion of this study is that the medium flux area of IFMIF offers a good irradiation environment to irradiate functional materials for liquid breeding blankets. The obtained ratios of H/dpa and He/dpa are very similar to those expected in the most irradiated areas of a fusion reactor. Moreover, with the aim of bringing the values further close, the use of a W moderator is proposed to be used only in some experimental campaigns (as obviously, the total amount of dpa decreases). The values of ratios obtained for a fission reactor, much lower than in a fusion reactor, reinforce the need of LBVM for IFMIF. Having demonstrated the suitability of IFMIF to irradiate functional materials for liquid breeding blankets, and an analysis of the main problems associated to each type of liquid breeding blanket, also presented in this thesis, three different experiments are proposed as basis for the design of the LBVM. These experiments are dedicated to the needs of a blanket HCLL type although the applicability of the module for other blankets is also discussed. Therefore, the experimental capability of the module is focused on the study of the behavior of the eutectic alloy LiPb, tritium permeation, corrosion and material compatibility. For each of the experiments proposed an experimental scheme is given explaining the different module conditions and defining the required instrumentation to control and monitor the experimental capsules. In order to carry out the proposed experiments, the LBVM is proposed, located in the medium flux area of the IFMIF hot cell, with capability of up to 16 experimental capsules. Each capsule (24-22 mm of diameter, 80 mm high) will contain the eutectic allow LiPb (up to 50 mm of capsule high) in contact with different material specimens. They will be supported inside rigs or steel pipes. Helium will be used as purge gas, to sweep the tritium generated in the eutectic and permeated through the capsule walls (continuously, during irradiation). These tubes, will be installed in a steel container providing support and cooling for the tubes and hence the inner experimental capsules. The experimental data will consist of on line monitoring signals and the analysis of purge gas by the tritium measurement station. In addition to the experimental signals, the module will produce signals having a safety function and therefore playing a major role in the operation of the module. For an adequate operation of the capsules and to control its temperature, each capsule will be equipped with an electrical heater so the module will to be connected to an electrical power supply. The technical justification behind the dimensioning of each of these parts forming the module is presented supported by tritium transport calculations, thermalhydraulic and structural analysis. One of the main conclusions of the tritium transport calculations is that the measure of the permeated tritium is perfectly achievable by commercial ionization chambers and proportional counters with sensitivity of 10-9 Bq/m3. The results are applicable to all experiments, even to low temperature capsules or to the ones using antipermeation coatings. From a safety point of view, the knowledge of the amount of tritium being swept by the purge gas is a clear indicator of certain problems that may be occurring in the module such a capsule rupture. In addition, the tritium balance in the installation should be known. Losses of purge gas permeated into the refrigerant and the hot cell itself through the container have been assessed concluding that they are negligible for normal operation. Thermal hydraulic calculations were performed in order to optimize the design of experimental capsules and LBVM to fulfill one of the main requirements of the module: to perform experiments at uniform temperatures between 300-550ºC. The necessary cooling of the module and the geometry of the capsules, rigs and testing area of the container were dimensioned. As a result of the analyses, cylindrical capsules and rigs in cylindrical compartments were selected because of their good mechanical behavior (stresses due to fluid pressure are reduced significantly with a cylindrical shape rather than prismatic) and thermal (temperature uniformity in the walls of the tubes and capsules). Fields of pressure, temperature and velocity in different critical areas of the module were obtained concluding that the proposal is feasible. It is important to mention that the use of fluid dynamic codes as ANSYS-CFX (used in this thesis) for designing experimental capsules for IFMIF is not direct. The reason for this is that, under strongly heated helium mini channels, turbulence models tend to underestimate the wall temperature because of the change of helium properties near the wall. Therefore, the different code turbulence models had to be studied in detail and validated against experimental results. ANSYS-CFX SST (Shear Stress Transport Model) for transitional turbulence model has been identified among many others as the suitable one for modeling the cooling helium and the temperature on the walls of experimental capsules. Once the geometry and the main purge and cooling parameters have been defined, the mechanical behavior of each experimental tube or rig including capsules is analyzed. Resulting stresses are compared with the maximum values recommended by applicable structural design codes such as the SDC- IC (Structural Design Criteria for ITER Components) in order to assess the degree of protection against plastic collapse. The conclusion shows that the proposal is mechanically robust. The LBVM involves the use of liquid metals, tritium and the risk associated with neutron activation. The risks related with the handling of liquid metals and tritium are studied in this thesis. In addition, the radiological risks associated with the activation of materials in the module and the residual heat after irradiation are evaluated, including a scenario of loss of coolant. Among the identified conventional risks associated with the module highlights the handling of liquid metals which reactions with water or air are accompanied by the emission of aerosols and fire probability. Regarding the nuclear risks, the generation of radioactive gases such as tritium or volatile radioisotopes such as Po-210 is the main hazard to be considered. An environmental impact associated to possible releases is not expected. Nevertheless, an appropriate handling of capsules, experimental tubes, and container including purge lines is required. After one day after shutdown and one year of irradiation, the experimental area of the module will present a contact dose rate of about 7000 Sv/h, 2300 Sv/h in the experimental capsules and 25 Sv/h in the LiPb. Therefore, the use of remote handling is envisaged for the irradiated module. Finally, the different possibilities for the module manufacturing have been studied. Among the proposed techniques highlights the electro discharge machining, brazing, electron beam welding or laser welding. The bases for the final design of the LBVM have been included in the framework of the this work and included in the intermediate design report of IFMIF which will be developed in future, as part of the IFMIF facility final design.

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Esta investigación se enmarca dentro del proyecto MODIFICA (modelo predictivo - Edificios - Isla de Calor Urbano), financiado por el Programa de I + D + i Orientada a los Retos de la sociedad 'Retos Investigación' de 2013. Está dirigido a desarrollar un modelo predictivo de eficiencia energética para viviendas, bajo el efecto de isla de calor urbano (AUS) con el fin de ponerla en práctica en la evaluación de la demanda de energía real y el consumo en las viviendas. A pesar de los grandes avances que se han logrado durante los últimos años en el rendimiento energético de edificios, los archivos de tiempo utilizados en la construcción de simulaciones de energía se derivan generalmente de estaciones meteorológicas situadas en las afueras de la ciudad. Por lo tanto, el efecto de la Isla de Calor Urbano (ICU) no se considera en estos cálculos, lo que implica una importante falta de precisión. Centrado en explorar cómo incluir los fenómenos ICU, el presente trabajo recopila y analiza la dinámica por hora de la temperatura en diferentes lugares dentro de la ciudad de Madrid. Abstract This research is framed within the project MODIFICA (Predictive model - Buildings - Urban Heat Island), funded by Programa de I+D+i orientada a los retos de la sociedad 'Retos Investigación' 2013. It is aimed at developing a predictive model for dwelling energy performance under the Urban Heat Island (UHI) effect in order to implement it in the evaluation of real energy demand and consumption in dwellings. Despite great advances on building energy performance have been achieved during the last years, weather files used in building energy simulations are usually derived from weather stations placed in the outskirts of the city. Hence, Urban Heat Island (UHI) effect is not considered in this calculations, which implies an important lack of accuracy. Focused on exploring how to include the UHI phenomena, the present paper compiles and analyses the hourly dynamics of temperature in different locations within the city of Madrid.

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When a structure vibrates immersed in a fluid it is known that the dynamic properties of the system are modified. The surrounding fluid will, in general, contribute to the inertia, the rigidity and the damping coefficient of the coupled fluid-structure system. For light structures, like spacecraft antennas, even when the fluid is air the contribution to the dynamic properties can be important. For not so light structures the ratio of the equivalent fluid/structure mass and rigidity can be very small and the fluid contribution could be neglected. For the ratio of equivalent fluid/structure damping both terms are of the same order and therefore the fluid contribution must be studied. The working life of the spacecraft structure would be on space and so without any surrounding fluid. The response of a spacecraft structure on its operational life would be attenuated by the structural damping alone but when the structure is dynamically tested on the earth the dynamic modal test is performed with the fluid surrounding it. The results thus are contaminated by the effects of the fluid. If the damping added by the fluid is of the same order as the structural damping the response of the structure in space can be quite different to the response predicted on earth. It is therefore desirable to have a method able to determine the amount of damping induced by the fluid and that should be subtracted of the total damping measured on the modal vibration test. In this work, a method for the determination of the effect of the surrounding fluid on the dynamic characteristics of a circular plate has been developed. The plate is assumed to vibrate harmonically with the vacuum modes and the generalized forces matrix due to the fluid is thus computed. For a compressible fluid this matrix is formed by complex numbers including terms of inertia, rigidity and damping. The matrix due to the fluid loading is determined by a boundary element method (BEM). The BEM used is of circular rings on the plate surface so the number of elements to obtain an accurate result is very low. The natural frequencies of the system are computed by an iteration procedure one by one and also the damping fluid contribution. Comparisons of the present method with various experimental data and other theories show the efficiency and accuracy of the method for any support condition of the plate.