Novel Inductor‐less Conversion Strategy Based on Multiphase Transformer‐Coupled Converters: Analysis, Design and Applications

There are many the requirements that modern power converters should fulfill. Most of the applications where these converters are used, demand smaller converters with high efficiency, improved power density and a fast dynamic response. For instance, loads like microprocessors demand aggressive current steps with very high slew rates (100A/mus and higher); besides, during these load steps, the supply voltage of the microprocessor should be kept within tight limits in order to ensure its correct performance. The accomplishment of these requirements is not an easy task; complex solutions like advanced topologies - such as multiphase converters- as well as advanced control strategies are often needed. Besides, it is also necessary to operate the converter at high switching frequencies and to use capacitors with high capacitance and low ESR. Improving the dynamic response of power converters does not rely only on the control strategy but also the power topology should be suited to enable a fast dynamic response. Moreover, in later years, a fast dynamic response does not only mean accomplishing fast load steps but output voltage steps are gaining importance as well. At least, two applications that require fast voltage changes can be named: Low power microprocessors. In these devices, the voltage supply is changed according to the workload and the operating frequency of the microprocessor is changed at the same time. An important reduction in voltage dependent losses can be achieved with such changes. This technique is known as Dynamic Voltage Scaling (DVS). Another application where important energy savings can be achieved by means of changing the supply voltage are Radio Frequency Power Amplifiers. For example, RF architectures based on ‘Envelope Tracking’ and ‘Envelope Elimination and Restoration’ techniques can take advantage of voltage supply modulation and accomplish important energy savings in the power amplifier. However, in order to achieve these efficiency improvements, a power converter with high efficiency and high enough bandwidth (hundreds of kHz or even tens of MHz) is necessary in order to ensure an adequate supply voltage. The main objective of this Thesis is to improve the dynamic response of DC-DC converters from the point of view of the power topology. And the term dynamic response refers both to the load steps and the voltage steps; it is also interesting to modulate the output voltage of the converter with a specific bandwidth. In order to accomplish this, the question of what is it that limits the dynamic response of power converters should be answered. Analyzing this question leads to the conclusion that the dynamic response is limited by the power topology and specifically, by the filter inductance of the converter which is found in series between the input and the output of the converter. The series inductance is the one that determines the gain of the converter and provides the regulation capability. Although the energy stored in the filter inductance enables the regulation and the capability of filtering the output voltage, it imposes a limitation which is the concern of this Thesis. The series inductance stores energy and prevents the current from changing in a fast way, limiting the slew rate of the current through this inductor. Different solutions are proposed in the literature in order to reduce the limit imposed by the filter inductor. Many publications proposing new topologies and improvements to known topologies can be found in the literature. Also, complex control strategies are proposed with the objective of improving the dynamic response in power converters. In the proposed topologies, the energy stored in the series inductor is reduced; examples of these topologies are Multiphase converters, Buck converter operating at very high frequency or adding a low impedance path in parallel with the series inductance. Control techniques proposed in the literature, focus on adjusting the output voltage as fast as allowed by the power stage; examples of these control techniques are: hysteresis control, V 2 control, and minimum time control. In some of the proposed topologies, a reduction in the value of the series inductance is achieved and with this, the energy stored in this magnetic element is reduced; less stored energy means a faster dynamic response. However, in some cases (as in the high frequency Buck converter), the dynamic response is improved at the cost of worsening the efficiency. In this Thesis, a drastic solution is proposed: to completely eliminate the series inductance of the converter. This is a more radical solution when compared to those proposed in the literature. If the series inductance is eliminated, the regulation capability of the converter is limited which can make it difficult to use the topology in one-converter solutions; however, this topology is suitable for power architectures where the energy conversion is done by more than one converter. When the series inductor is eliminated from the converter, the current slew rate is no longer limited and it can be said that the dynamic response of the converter is independent from the switching frequency. This is the main advantage of eliminating the series inductor. The main objective, is to propose an energy conversion strategy that is done without series inductance. Without series inductance, no energy is stored between the input and the output of the converter and the dynamic response would be instantaneous if all the devices were ideal. If the energy transfer from the input to the output of the converter is done instantaneously when a load step occurs, conceptually it would not be necessary to store energy at the output of the converter (no output capacitor COUT would be needed) and if the input source is ideal, the input capacitor CIN would not be necessary. This last feature (no CIN with ideal VIN) is common to all power converters. However, when the concept is actually implemented, parasitic inductances such as leakage inductance of the transformer and the parasitic inductance of the PCB, cannot be avoided because they are inherent to the implementation of the converter. These parasitic elements do not affect significantly to the proposed concept. In this Thesis, it is proposed to operate the converter without series inductance in order to improve the dynamic response of the converter; however, on the other side, the continuous regulation capability of the converter is lost. It is said continuous because, as it will be explained throughout the Thesis, it is indeed possible to achieve discrete regulation; a converter without filter inductance and without energy stored in the magnetic element, is capable to achieve a limited number of output voltages. The changes between these output voltage levels are achieved in a fast way. The proposed energy conversion strategy is implemented by means of a multiphase converter where the coupling of the phases is done by discrete two-winding transformers instead of coupledinductors since transformers are, ideally, no energy storing elements. This idea is the main contribution of this Thesis. The feasibility of this energy conversion strategy is first analyzed and then verified by simulation and by the implementation of experimental prototypes. Once the strategy is proved valid, different options to implement the magnetic structure are analyzed. Three different discrete transformer arrangements are studied and implemented. A converter based on this energy conversion strategy would be designed with a different approach than the one used to design classic converters since an additional design degree of freedom is available. The switching frequency can be chosen according to the design specifications without penalizing the dynamic response or the efficiency. Low operating frequencies can be chosen in order to favor the efficiency; on the other hand, high operating frequencies (MHz) can be chosen in order to favor the size of the converter. For this reason, a particular design procedure is proposed for the ‘inductorless’ conversion strategy. Finally, applications where the features of the proposed conversion strategy (high efficiency with fast dynamic response) are advantageus, are proposed. For example, in two-stage power architectures where a high efficiency converter is needed as the first stage and there is a second stage that provides the fine regulation. Another example are RF power amplifiers where the voltage is modulated following an envelope reference in order to save power; in this application, a high efficiency converter, capable of achieving fast voltage steps is required. The main contributions of this Thesis are the following: The proposal of a conversion strategy that is done, ideally, without storing energy in the magnetic element. The validation and the implementation of the proposed energy conversion strategy. The study of different magnetic structures based on discrete transformers for the implementation of the proposed energy conversion strategy. To elaborate and validate a design procedure. To identify and validate applications for the proposed energy conversion strategy. It is important to remark that this work is done in collaboration with Intel. The particular features of the proposed conversion strategy enable the possibility of solving the problems related to microprocessor powering in a different way. For example, the high efficiency achieved with the proposed conversion strategy enables it as a good candidate to be used for power conditioning, as a first stage in a two-stage power architecture for powering microprocessors.

Aplicaciones de interés forestal de las imágenes obtenidas con el sensor Multi-angle Imaging SpectroRadiometer (MISR)

Las aplicaciones de la teledetección al seguimiento de lo que ocurre en la superficie terrestre se han ido multiplicando y afinando con el lanzamiento de nuevos sensores por parte de las diferentes agencias espaciales. La necesidad de tener información actualizada cada poco tiempo y espacialmente homogénea, ha provocado el desarrollo de nuevos programas como el Earth Observing System (EOS) de la National Aeronautics and Space Administration (NASA). Uno de los sensores que incorpora el buque insignia de ese programa, el satélite TERRA, es el Multi-angle Imaging SpectroRadiometer (MISR), diseñado para capturar información multiangular de la superficie terrestre. Ya desde los años 1970, se conocía que la reflectancia de las diversas ocupaciones y usos del suelo variaba en función del ángulo de observación y de iluminación, es decir, que eran anisotrópicas. Tal variación estaba además relacionada con la estructura tridimensional de tales ocupaciones, por lo que se podía aprovechar tal relación para obtener información de esa estructura, más allá de la que pudiera proporcionar la información meramente espectral. El sensor MISR incorpora 9 cámaras a diferentes ángulos para capturar 9 imágenes casi simultáneas del mismo punto, lo que permite estimar con relativa fiabilidad la respuesta anisotrópica de la superficie terrestre. Varios trabajos han demostrado que se pueden estimar variables relacionadas con la estructura de la vegetación con la información que proporciona MISR. En esta Tesis se ha realizado una primera aplicación a la Península Ibérica, para comprobar su utilidad a la hora de estimar variables de interés forestal. En un primer paso se ha analizado la variabilidad temporal que se produce en los datos, debido a los cambios en la geometría de captación, es decir, debido a la posición relativa de sensores y fuente de iluminación, que en este caso es el Sol. Se ha comprobado cómo la anisotropía es mayor desde finales de otoño hasta principios de primavera debido a que la posición del Sol es más cercana al plano de los sensores. También se ha comprobado que los valores máximo y mínimo se van desplazando temporalmente entre el centro y el extremo angular. En la caracterización multiangular de ocupaciones del suelo de CORINE Land Cover que se ha realizado, se puede observar cómo la forma predominante en las imágenes con el Sol más alto es convexa con un máximo en la cámara más cercana a la fuente de iluminación. Sin embargo, cuando el Sol se encuentra mucho más bajo, ese máximo es muy externo. Por otra parte, los datos obtenidos en verano son mucho más variables para cada ocupación que los de noviembre, posiblemente debido al aumento proporcional de las zonas en sombra. Para comprobar si la información multiangular tiene algún efecto en la obtención de imágenes clasificadas según ocupación y usos del suelo, se han realizado una serie de clasificaciones variando la información utilizada, desde sólo multiespectral, a multiangular y multiespectral. Los resultados muestran que, mientras para las clasificaciones más genéricas la información multiangular proporciona los peores resultados, a medida que se amplían el número de clases a obtener tal información mejora a lo obtenido únicamente con información multiespectral. Por otra parte, se ha realizado una estimación de variables cuantitativas como la fracción de cabida cubierta (Fcc) y la altura de la vegetación a partir de información proporcionada por MISR a diferentes resoluciones. En el valle de Alcudia (Ciudad Real) se ha estimado la fracción de cabida cubierta del arbolado para un píxel de 275 m utilizando redes neuronales. Los resultados muestran que utilizar información multiespectral y multiangular puede mejorar casi un 20% las estimaciones realizadas sólo con datos multiespectrales. Además, las relaciones obtenidas llegan al 0,7 de R con errores inferiores a un 10% en Fcc, siendo éstos mucho mejores que los obtenidos con el producto elaborado a partir de datos multiespectrales del sensor Moderate Resolution Imaging Spectroradiometer (MODIS), también a bordo de Terra, para la misma variable. Por último, se ha estimado la fracción de cabida cubierta y la altura efectiva de la vegetación para 700.000 ha de la provincia de Murcia, con una resolución de 1.100 m. Los resultados muestran la relación existente entre los datos espectrales y los multiangulares, obteniéndose coeficientes de Spearman del orden de 0,8 en el caso de la fracción de cabida cubierta de la vegetación, y de 0,4 en el caso de la altura efectiva. Las estimaciones de ambas variables con redes neuronales y diversas combinaciones de datos, arrojan resultados con R superiores a 0,85 para el caso del grado de cubierta vegetal, y 0,6 para la altura efectiva. Los parámetros multiangulares proporcionados en los productos elaborados con MISR a 1.100 m, no obtienen buenos resultados por sí mismos pero producen cierta mejora al incorporarlos a la información espectral. Los errores cuadráticos medios obtenidos son inferiores a 0,016 para la Fcc de la vegetación en tanto por uno, y 0,7 m para la altura efectiva de la misma. Regresiones geográficamente ponderadas muestran además que localmente se pueden obtener mejores resultados aún mejores, especialmente cuando hay una mayor variabilidad espacial de las variables estimadas. En resumen, la utilización de los datos proporcionados por MISR ofrece una prometedora vía de mejora de resultados en la media-baja resolución, tanto para la clasificación de imágenes como para la obtención de variables cuantitativas de la estructura de la vegetación. ABSTRACT Applications of remote sensing for monitoring what is happening on the land surface have been multiplied and refined with the launch of new sensors by different Space Agencies. The need of having up to date and spatially homogeneous data, has led to the development of new programs such as the Earth Observing System (EOS) of the National Aeronautics and Space Administration (NASA). One of the sensors incorporating the flagship of that program, the TERRA satellite, is Multi-angle Imaging Spectroradiometer (MISR), designed to capture the multi-angle information of the Earth's surface. Since the 1970s, it was known that the reflectance of various land covers and land uses varied depending on the viewing and ilumination angles, so they are anisotropic. Such variation was also related to the three dimensional structure of such covers, so that one could take advantage of such a relationship to obtain information from that structure, beyond which spectral information could provide. The MISR sensor incorporates 9 cameras at different angles to capture 9 almost simultaneous images of the same point, allowing relatively reliable estimates of the anisotropic response of the Earth's surface. Several studies have shown that we can estimate variables related to the vegetation structure with the information provided by this sensor, so this thesis has made an initial application to the Iberian Peninsula, to check their usefulness in estimating forest variables of interest. In a first step we analyzed the temporal variability that occurs in the data, due to the changes in the acquisition geometry, i.e. the relative position of sensor and light source, which in this case is the Sun. It has been found that the anisotropy is greater from late fall through early spring due to the Sun's position closer to the plane of the sensors. It was also found that the maximum and minimum values are displaced temporarily between the center and the ends. In characterizing CORINE Land Covers that has been done, one could see how the predominant form in the images with the highest sun is convex with a maximum in the camera closer to the light source. However, when the sun is much lower, the maximum is external. Moreover, the data obtained for each land cover are much more variable in summer that in November, possibly due to the proportional increase in shadow areas. To check whether the information has any effect on multi-angle imaging classification of land cover and land use, a series of classifications have been produced changing the data used, from only multispectrally, to multi-angle and multispectral. The results show that while for the most generic classifications multi-angle information is the worst, as there are extended the number of classes to obtain such information it improves the results. On the other hand, an estimate was made of quantitative variables such as canopy cover and vegetation height using information provided by MISR at different resolutions. In the valley of Alcudia (Ciudad Real), we estimated the canopy cover of trees for a pixel of 275 m by using neural networks. The results showed that using multispectral and multiangle information can improve by almost 20% the estimates that only used multispectral data. Furthermore, the relationships obtained reached an R coefficient of 0.7 with errors below 10% in canopy cover, which is much better result than the one obtained using data from the Moderate Resolution Imaging Spectroradiometer (MODIS), also onboard Terra, for the same variable. Finally we estimated the canopy cover and the effective height of the vegetation for 700,000 hectares in the province of Murcia, with a spatial resolution of 1,100 m. The results show a relationship between the spectral and the multi-angle data, and provide estimates of the canopy cover with a Spearman’s coefficient of 0.8 in the case of the vegetation canopy cover, and 0.4 in the case of the effective height. The estimates of both variables using neural networks and various combinations of data, yield results with an R coefficient greater than 0.85 for the case of the canopy cover, and 0.6 for the effective height. Multi-angle parameters provided in the products made from MISR at 1,100 m pixel size, did not produce good results from themselves but improved the results when included to the spectral information. The mean square errors were less than 0.016 for the canopy cover, and 0.7 m for the effective height. Geographically weighted regressions also showed that locally we can have even better results, especially when there is high spatial variability of estimated variables. In summary, the use of the data provided by MISR offers a promising way of improving remote sensing performance in the low-medium spatial resolution, both for image classification and for the estimation of quantitative variables of the vegetation structure.

Propuesta metodológica de aplicación sectorial de Análisis de Ciclo de Vida (ACV) para la evaluación ambiental de la edificación en España

La aplicación de criterios de sostenibilidad ha de entenderse como el procedimiento esencial para la necesaria reconversión del sector de la construcción, que movilizando el 10% de la economía mundial, representa más de la tercera parte del consumo mundial de recursos, en torno al 30-40% del consumo energético y emisiones de gases de efecto invernadero, 30-40% de la generación de residuos y el 12% de todo el gasto en agua dulce del planeta. La presente investigación se enmarca en una estrategia general de promover la evaluación de la sostenibilidad en la edificación en el contexto español, dando un primer paso centrado en la evaluación del comportamiento ambiental. El hilo conductor de la investigación parte de la necesidad de establecer un marco teórico de sostenibilidad, que permita clarificar conceptos y definir criterios de valoración adecuados. Como siguiente paso, la investigación se dirige a la revisión del panorama internacional de normativa e instrumentos voluntarios, con el objetivo de clarificar el difuso panorama que caracteriza a la sostenibilidad en el sector de la edificación en la actualidad y enmarcar la investigación en un contexto de políticas y programaciones ya existentes. El objetivo principal reside en el planteamiento de una metodología de evaluación de los aspectos o impactos ambientales asociados al ciclo de vida de la edificación, aplicable al contexto español, como una de las tres dimensiones que constituyen los pilares básicos de la sostenibilidad. Los ámbitos de evaluación de los aspectos sociales y económicos, para los que no existe actualmente un grado de definición metodológico suficientemente congruente, son adicionalmente examinados, de cara a ofrecer una visión holística de la evaluación. Previo al desarrollo de la propuesta, se aborda, en primer lugar, la descripción de las características básicas y limitaciones de la metodología de Análisis de Ciclo de Vida (ACV), para posteriormente proceder a profundizar en el estado del arte de aplicación de ACV a la edificación, realizando una revisión crítica de los trabajos de investigación que han sido desarrollados en los últimos años. Esta revisión permite extraer conclusiones sobre su grado de coherencia con el futuro entorno normativo e identificar dos necesidades prioritarias de actuación: -La necesidad de armonización, dadas las fuertes inconsistencias metodológicas detectadas, que imposibilitan la comparación de los resultados obtenidos en los trabajos de evaluación. -La necesidad de simplificación, dada la complejidad inherente a la evaluación, de modo que, manteniendo el máximo rigor, sea viable su aplicación práctica en el contexto español. A raíz de la participación en los trabajos de desarrollo normativo a nivel europeo, se ha adquirido una visión crítica sobre las implicaciones metodológicas de la normativa en definición, que permite identificar la hoja de ruta que marcará el escenario europeo en los próximos años. La definición de la propuesta metodológica integra los principios generales de aplicación de ACV con el protocolo metodológico establecido en la norma europea, considerando adicionalmente las referencias normativas de las prácticas constructivas en el contexto español. En el planteamiento de la propuesta se han analizado las posibles simplificaciones aplicables, con el objetivo de hacer viable su implementación, centrando los esfuerzos en la sistematización del concepto de equivalente funcional, el establecimiento de recomendaciones sobre el tipo de datos en función de su disponibilidad y la revisión crítica de los modelos de cálculo de los impactos ambientales. Las implicaciones metodológicas de la propuesta se describen a través de una serie de casos de estudio, que ilustran su viabilidad y las características básicas de aplicación. Finalmente, se realiza un recorrido por los aspectos que han sido identificados como prioritarios en la conformación del escenario de perspectivas futuras, líneas de investigación y líneas de acción. Abstract Sustainability criteria application must be understood as the essential procedure for the necessary restructuring of the construction sector, which mobilizes 10% of the world economy, accounting for more than one third of the consumption of the world's resources, around 30 - 40% of energy consumption and emissions of greenhouse gases, 30-40% of waste generation and 12% of all the fresh water use in the world. This research is in line with an overall strategy to promote the sustainability assessment of building in the Spanish context, taking a first step focused on the environmental performance assessment. The thread of the present research sets out from the need to establish a theoretical framework of sustainability which clarifies concepts and defines appropriate endpoints. As a next step, the research focuses on the review of the international panorama regulations and voluntary instruments, with the aim of clarifying the fuzzy picture that characterizes sustainability in the building sector at present while framing the research in the context of existing policies and programming. The main objective lies in the approach of a methodology for the assessment of the environmental impacts associated with the life cycle of building, applicable to the Spanish context, as one of the three dimensions that constitute the pillars of sustainability. The areas of assessment of social and economic issues, for which there is currently a degree of methodological definition consistent enough, are further examined, in order to provide a holistic view of the assessment. The description of the basic features and limitations of the methodology of Life Cycle Assessment (LCA) are previously addressed, later proceeding to deepen the state of the art of LCA applied to the building sector, conducting a critical review of the research works that have been developed in recent years. This review allows to establish conclusions about the degree of consistency with the future regulatory environment and to identify two priority needs for action: - The need for harmonization, given the strong methodological inconsistencies detected that prevent the comparison of results obtained in assessment works. - The need for simplification, given the inherent complexity of the assessment, so that, while maintaining the utmost rigor, make the practical application feasible in the Spanish context. The participation in the work of policy development at European level has helped to achieve a critical view of the methodological implications of the rules under debate, identifying the roadmap that will mark the European scene in the coming years. The definition of the proposed methodology integrates the general principles of LCA methodology with the protocol established in the European standard, also considering the regulatory standards to construction practices in the Spanish context. In the proposed approach, possible simplifications applicable have been analyzed, in order to make its implementation possible, focusing efforts in systematizing the functional equivalent concept, establishing recommendations on the type of data based on their availability and critical review of the calculation models of environmental impacts. The methodological implications of the proposal are described through a series of case studies, which illustrate the feasibility and the basic characteristics of its application. Finally, the main aspects related to future prospects, research lines and lines of action that have been identified as priorities are outlined.

Desarrollo de nuevos tratamientos térmicos para aleaciones avanzadas de interés aeroespacial

La corrosión bajo tensiones (SCC) es un problema de gran importancia en las aleaciones de aluminio de máxima resistencia (serie Al-Zn-Mg-Cu). La utilización de tratamientos térmicos sobremadurados, en particular el T73, ha conseguido prácticamente eliminar la susceptibilidad a corrosión bajo tensiones en dichas aleaciones pero a costa de reducir su resistencia mecánica. Desde entonces se ha tratado de optimizar simultáneamente ambos comportamientos, encontrándose para ello diversos inconvenientes entre los que destacan: la dificultad de medir experimentalmente el crecimiento de grieta por SCC, y el desconocimiento de las causas y el mecanismo por el cual se produce la SCC. Los objetivos de esta Tesis son mejorar el sistema de medición de grietas y profundizar en el conocimiento de la SCC, con el fin de obtener tratamientos térmicos que aúnen un óptimo comportamiento tanto en SCC como mecánico en las aleaciones de aluminio de máxima resistencia utilizadas en aeronáutica. Para conseguir los objetivos anteriormente descritos se han realizado unos cuarenta tratamientos térmicos diferentes, de los cuales la gran mayoría son nuevos, para profundizar en el conocimiento de la influencia de la microestructura (fundamentalmente, de los precipitados coherentes) en el comportamiento de las aleaciones Al-Zn-Mg-Cu, y estudiar la viabilidad de nuevos tratamientos apoyados en el conocimiento adquirido. Con el fin de obtener unos resultados aplicables a productos o semiproductos de aplicación aeronáutica, los tratamientos térmicos se han realizado a trozos grandes de una plancha de 30 mm de espesor de la aleación de aluminio 7475, muy utilizada en las estructuras aeronáuticas. Asimismo con el objeto de conseguir una mayor fiabilidad de los resultados obtenidos se han utilizado, normalmente, tres probetas de cada tratamiento para los diferentes ensayos realizados. Para la caracterización de dichos tratamientos se han utilizado diversas técnicas: medida de dureza y conductividad eléctrica, ensayos de tracción, calorimetría diferencial de barrido (DSC), metalografía, fractografía, microscopia electrónica de transmisión (MET) y de barrido (MEB), y ensayos de crecimiento de grieta en probeta DCB, que a su vez han permitido hacer una estimación del comportamiento en tenacidad del material. Las principales conclusiones del estudio realizado se pueden resumir en las siguientes: Se han diseñado y desarrollado nuevos métodos de medición de grieta basados en el empleo de la técnica de ultrasonidos, que permiten medir el crecimiento de grieta por corrosión bajo tensiones con la precisión y fiabilidad necesarias para valorar adecuadamente la susceptibilidad a corrosión bajo tensiones. La mejora de medida de la posición del frente de grieta ha dado lugar, entre otras cosas, a la definición de un nuevo ensayo a iniciación en probetas preagrietadas. Asimismo, se ha deducido una nueva ecuación que permite calcular el factor de intensidad de tensiones existente en punta de grieta en probetas DCB teniendo en cuenta la influencia de la desviación del plano de crecimiento de la grieta del plano medio de la probeta. Este aspecto ha sido determinante para poder explicar los resultados experimentales obtenidos ya que el crecimiento de la grieta por un plano paralelo al plano medio de la probeta DCB pero alejado de él reduce notablemente el factor de intensidades de tensiones que actúa en punta de grieta y modifica las condiciones reales del ensayo. Por otro lado, se han identificado los diferentes constituyentes de la microestructura de precipitación de todos los tratamientos térmicos estudiados y, en especial, se ha conseguido constatar (mediante MET y DSC) la existencia de zonas de Guinier-Preston del tipo GP(II) en la microestructura de numerosos tratamientos térmicos (no descrita en la bibliografía para las aleaciones del tipo de la estudiada) lo que ha permitido establecer una nueva interpretación de la evolución de la microestructura en los diferentes tratamientos. Al hilo de lo anterior, se han definido nuevas secuencias de precipitación para este tipo de aleaciones, que han permitido entender mejor la constitución de la microestructura y su relación con las propiedades en los diferentes tratamientos térmicos estudiados. De igual manera, se ha explicado el papel de los diferentes microconstituyentes en diversas propiedades mecánicas (propiedades a tracción, dureza y tenacidad KIa); en particular, el estudio realizado de la relación de la microestructura con la tenacidad KIa es inédito. Por otra parte, se ha correlacionado el comportamiento en corrosión bajo tensiones, tanto en la etapa de incubación de grieta como en la de propagación, con las características medidas de los diferentes constituyentes microestructurales de los tratamientos térmicos ensayados, tanto de interior como de límite de grano, habiéndose obtenido que la microestructura de interior de grano tiene una mayor influencia en el comportamiento en corrosión bajo tensiones que la de límite de grano. De forma especial, se ha establecido la importancia capital, y muy negativa, de la presencia en la microestructura de zonas de Guinier-Preston en el crecimiento de la grieta por corrosión bajo tensiones. Finalmente, como consecuencia de todo lo anterior, se ha propuesto un nuevo mecanismo por el que se produce la corrosión bajo tensiones en este tipo de aleaciones de aluminio, y que de forma muy resumida se puede concretar lo siguiente: la acumulación de hidrógeno (formado, básicamente, por un proceso corrosivo de disolución anódica) delante de la zonas GP (en especial, de las zonas GP(I)) próximas a la zona libre de precipitados que se desarrolla alrededor del límite de grano provoca enfragilización local y causa el rápido crecimiento de grieta característico de algunos tratamientos térmicos de este tipo de aleaciones. ABSTRACT The stress corrosion cracking (SCC) is a major problem in the aluminum alloys of high resistance (series Al-Zn-Mg-Cu). The use of overaged heat treatments, particularly T73 has achieved virtually eliminate the susceptibility to stress corrosion cracking in such alloys but at the expense of reducing its mechanical strength. Since then we have tried to simultaneously optimize both behaviors, several drawbacks found for it among them: the difficulty of measuring experimentally the SCC crack growth, and ignorance of the causes and the mechanism by which SCC occurs. The objectives of this thesis are to improve the measurement system of cracks and deeper understanding of the SCC, in order to obtain heat treatments that combine optimum performance in both SCC and maximum mechanical strength in aluminum alloys used in aerospace To achieve the above objectives have been made about forty different heat treatments, of which the vast majority are new, to deepen the understanding of the influence of microstructure (mainly of coherent precipitates) in the behavior of the alloys Al -Zn-Mg-Cu, and study the feasibility of new treatments supported by the knowledge gained. To obtain results for products or semi-finished aircraft application, heat treatments were performed at a large pieces plate 30 mm thick aluminum alloy 7475, widely used in aeronautical structures. Also in order to achieve greater reliability of the results obtained have been used, normally, three specimens of each treatment for various tests. For the characterization of these treatments have been used several techniques: measurement of hardness and electrical conductivity, tensile testing, differential scanning calorimetry (DSC), metallography, fractography, transmission (TEM) and scanning (SEM) electron microscopy, and crack growth tests on DCB specimen, which in turn have allowed to estimate the behavior of the material in fracture toughness. The main conclusions of the study can be summarized as follows: We have designed and developed new methods for measuring crack based on the use of the ultrasound technique, for measuring the growth of stress corrosion cracks with the accuracy and reliability needed to adequately assess the susceptibility to stress corrosion. Improved position measurement of the crack front has resulted, among other things, the definition of a new initiation essay in pre cracked specimens. Also, it has been inferred a new equation to calculate the stress intensity factor in crack tip existing in DCB specimens considering the influence of the deviation of the plane of the crack growth of the medium plane of the specimen. This has been crucial to explain the experimental results obtained since the crack growth by a plane parallel to the medium plane of the DCB specimen but away from it greatly reduces the stress intensity factor acting on the crack tip and modifies the actual conditions of the essay. Furthermore, we have identified the various constituents of the precipitation microstructure of all heat treatments studied and, in particular note has been achieved (by TEM and DSC) the existence of the type GP (II) of Guinier-Preston zones in the microstructure of several heat treatments (not described in the literature for alloys of the type studied) making it possible to establish a new interpretation of the evolution of the microstructure in the different treatments. In line with the above, we have defined new precipitation sequences for these alloys, which have allowed a better understanding of the formation of the microstructure in relation to the properties of different heat treatments studied. Similarly, explained the role of different microconstituents in various mechanical properties (tensile properties, hardness and toughness KIa), in particular, the study of the relationship between the tenacity KIa microstructure is unpublished. Moreover, has been correlated to the stress corrosion behavior, both in the incubation step as the crack propagation, with the measured characteristics of the various microstructural constituents heat treatments tested, both interior and boundary grain, having obtained the internal microstructure of grain has a greater influence on the stress corrosion cracking behavior in the grain boundary. In a special way, has established the importance, and very negative, the presence in the microstructure of Guinier-Preston zones in crack growth by stress corrosion. Finally, following the above, we have proposed a new mechanism by which stress corrosion cracking occurs in this type of aluminum alloy, and, very briefly, one can specify the following: the accumulation of hydrogen (formed basically by a corrosive process of anodic dissolution) in front of the GP zones (especially the GP (I) zones) near the precipitates free zone that develops around grain boundary causes local embrittlement which characterizes rapid crack growth of some heat treatments such alloys.

Aplicación de documentos de identificación electrónica a un esquema de voto telemático a escala paneuropea, seguro, auditable y verificable.

En este trabajo de tesis se propone un esquema de votación telemática, de carácter paneuropeo y transnacional, que es capaz de satisfacer las más altas exigencias en materia de seguridad. Este enfoque transnacional supone una importante novedad que obliga a identificar a los ciudadanos más allá de las fronteras de su país, exigencia que se traduce en la necesidad de que todos los ciudadanos europeos dispongan de una identidad digital y en que ésta sea reconocida más allá de las fronteras de su país de origen. Bajo estas premisas, la propuesta recogida en esta tesis se aborda desde dos vertientes complementarias: por una parte, el diseño de un esquema de votación capaz de conquistar la confianza de gobiernos y ciudadanos europeos y, por otra, la búsqueda de una respuesta al problema de interoperabilidad de Sistemas de Gestión de Identidad (IDMs), en consonancia con los trabajos que actualmente realiza la UE para la integración de los servicios proporcionados por las Administraciones Públicas de los distintos países europeos. El punto de partida de este trabajo ha sido la identificación de los requisitos que determinan el adecuado funcionamiento de un sistema de votación telemática para, a partir de ellos,proponer un conjunto de elementos y criterios que permitan, por una parte, establecer comparaciones entre distintos sistemas telemáticos de votación y, por otra, evaluar la idoneidad del sistema propuesto. A continuación se han tomado las más recientes y significativas experiencias de votación telemática llevadas a cabo por diferentes países en la automatización de sus procesos electorales, analizándolas en profundidad para demostrar que, incluso en los sistemas más recientes, todavía subsisten importantes deficiencias relativas a la seguridad. Asimismo, se ha constatado que un sector importante de la población se muestra receloso y, a menudo, cuestiona la validez de los resultados publicados. Por tanto, un sistema que aspire a ganarse la confianza de ciudadanos y gobernantes no sólo debe operar correctamente, trasladando los procesos tradicionales de votación al contexto telemático, sino que debe proporcionar mecanismos adicionales que permitan superar los temores que inspira el nuevo sistema de votación. Conforme a este principio, el enfoque de esta tesis, se orienta, en primer lugar, hacia la creación de pruebas irrefutables, entendibles y auditables a lo largo de todo el proceso de votación, que permitan demostrar con certeza y ante todos los actores implicados en el proceso (gobierno, partidos políticos, votantes, Mesa Electoral, interventores, Junta Electoral,jueces, etc.) que los resultados publicados son fidedignos y que no se han violado los principios de anonimato y de “una persona, un voto”. Bajo este planteamiento, la solución recogida en esta tesis no sólo prevé mecanismos para minimizar el riesgo de compra de votos, sino que además incorpora mecanismos de seguridad robustos que permitirán no sólo detectar posibles intentos de manipulación del sistema, sino también identificar cuál ha sido el agente responsable. De forma adicional, esta tesis va más allá y traslada el escenario de votación a un ámbito paneuropeo donde aparecen nuevos problemas. En efecto, en la actualidad uno de los principales retos a los que se enfrentan las votaciones de carácter transnacional es sin duda la falta de procedimientos rigurosos y dinámicos para la actualización sincronizada de los censos de votantes de los distintos países que evite la presencia de errores que redunden en la incapacidad de controlar que una persona emita más de un voto, o que se vea impedido del todo a ejercer su derecho. Este reconocimiento de la identidad transnacional requiere la interoperabilidad entre los IDMs de los distintos países europeos. Para dar solución a este problema, esta tesis se apoya en las propuestas emergentes en el seno de la UE, que previsiblemente se consolidarán en los próximos años, tanto en materia de identidad digital (con la puesta en marcha de la Tarjeta de Ciudadano Europeo) como con el despliegue de una infraestructura de gestión de identidad que haga posible la interoperabilidad de los IDMs de los distintos estados miembros. A partir de ellas, en esta tesis se propone una infraestructura telemática que facilita la interoperabilidad de los sistemas de gestión de los censos de los distintos estados europeos en los que se lleve a cabo conjuntamente la votación. El resultado es un sistema versátil, seguro, totalmente robusto, fiable y auditable que puede ser aplicado en elecciones paneuropeas y que contempla la actualización dinámica del censo como una parte crítica del proceso de votación. ABSTRACT: This Ph. D. dissertation proposes a pan‐European and transnational system of telematic voting that is capable of meeting the strictest security standards. This transnational approach is a significant innovation that entails identifying citizens beyond the borders of their own country,thus requiring that all European citizens must have a digital identity that is recognized beyond the borders of their country of origin. Based on these premises, the proposal in this thesis is analyzed in two mutually‐reinforcing ways: first, a voting system is designed that is capable of winning the confidence of European governments and citizens and, second, a solution is conceived for the problem of interoperability of Identity Management Systems (IDMs) that is consistent with work being carried out by the EU to integrate the services provided by the public administrations of different European countries. The starting point of this paper is to identify the requirements for the adequate functioning of a telematic voting system and then to propose a set of elements and criteria that will allow for making comparisons between different such telematic voting systems for the purpose of evaluating the suitability of the proposed system. Then, this thesis provides an in‐depth analysis of most recent significant experiences in telematic voting carried out by different countries with the aim of automating electoral processes, and shows that even the most recent systems have significant shortcomings in the realm of security. Further, a significant portion of the population has shown itself to be wary,and they often question the validity of the published results. Therefore, a system that aspires to win the trust of citizens and leaders must not only operate correctly by transferring traditional voting processes into a telematic environment, but must also provide additional mechanisms that can overcome the fears aroused by the new voting system. Hence, this thesis focuses, first, on creating irrefutable, comprehensible and auditable proof throughout the voting process that can demonstrate to all actors in the process – the government, political parties, voters, polling station workers, electoral officials, judges, etc. ‐that the published results are accurate and that the principles of anonymity and one person,one vote, have not been violated. Accordingly, the solution in this thesis includes mechanisms to minimize the risk of vote buying, in addition to robust security mechanisms that can not only detect possible attempts to manipulate the system, but also identify the responsible party. Additionally, this thesis goes one step further and moves the voting scenario to a pan‐European scale, in which new problems appear. Indeed, one of the major challenges at present for transnational voting processes is the lack of rigorous and dynamic procedures for synchronized updating of different countries’ voter rolls, free from errors that may make the system unable to keep an individual from either casting more than one vote, or from losing the effective exercise of the right to vote. This recognition of transnational identity requires interoperability between the IDMs of different European countries. To solve the problem, this thesis relies on proposals emerging within the EU that are expected to take shape in the coming years, both in digital identity – with the launch of the European Citizen Card – and in the deployment of an identity management infrastructure that will enable interoperability of the IDMs of different member states. Based on these, the thesis proposes a telematic infrastructure that will achieve interoperability of the census management systems of European states in which voting processes are jointly carried out. The result is a versatile, secure, totally robust, reliable and auditable system that can be applied in pan‐European election, and that includes dynamic updating of the voter rolls as a critical part of the voting process.

Conexión con la meseta desde el Ebro medio de las vías romanas como base de la malla territorial de España

No tenemos conocimiento de ninguna red de caminos prerromanos que sirvieran como base de una posible malla territorial de España. Sin embargo, una sociedad prerromana sin caminos, por muy fragmentada y aislada que fuera, es algo improbable y mucho menos en la Edad del Hierro. Por eso en época prerromana existían infinidad de caminos, muchos de los cuales hoy han desaparecido y otros han sobrevivido, casi siempre con sus recorridos mejorados. Los pueblos prerromanos aprovecharon vías naturales de comunicación (ríos, vados, valles, puertos naturales, llanuras, etc.) para tender sus caminos. En sus orígenes no siguieron pautas concretas, si no que los caminos se originaban por el tránsito (de personas, ganados, mercancías, etc.) de un lugar a otro. De este modo la red viaria prerromana era caótica y anárquica: todo camino tenía numerosos ramales y variantes, según las necesidades. Pendientes excesivas, anchuras variables, etc., en decir eran vías espontáneas, surgidas sin ninguna planificación aparente. Los recorridos en general eran cortos, aunque algunas investigaciones actuales están demostrando que algunas de las cañadas ganaderas más importantes, como la Galiana, y de largo recorrido, eran de origen prerromano. En el caso de la península Ibérica, y más concretamente en el caso de la Meseta, el territorio estaba fragmentado en diversos pueblos y tribus, agrupados según criterios étnicos y culturales y con contactos con los pueblos próximos que motivan la preponderancia de caminos de recorrido cortos. Solo la necesidad de llevar los rebaños (de cabras y ovejas sobre todo) desde las serranías en verano a las llanuras en invierno, motivaría viajes más largos en los que algunas cañadas ganaderas jugarían un papel más importante. Con la llegada de los romanaos, se implantó en Hispania una densa red viaria, cuya construcción se prolongó durante toda la dominación romana, siendo reparadas muchas calzadas y vías en varias ocasiones. En época romana la red caminera era variada y estaba constituida por “las calzadas” que comunicaban puntos importantes, eran muy transitadas, de ahí que la administración romana las mantuviera siempre en buen estado, para asegurar el intercambio comercial entre zonas distintas, cobro de impuestos, etc. “Los caminos de tierra (viae terrenae)” que además de las calzadas, que podemos asemejar a las actuales carreteras de primer y segundo orden, constituían la infinidad de caminos locales y comarcales. Los trazados se realizaron unos en época romana, y otros muchos apoyándose en los caminos de la época prerromana, éstas vías no se realizaban buscando el recorrido más corto entre dos puntos, ni tampoco el más cómodo y con un firme estructural de menor importancia que en las calzadas. Tampoco estaban hechos para un tipo concreto de transporte, por lo que nos encontraríamos algunos que por su anchura permitían el paso de carros, y otros que sólo permitirían el paso a pie, a caballo o en burro. Solían ser, como hemos indicado, caminos de tierra con acabados en zahorras y recorridos en su mayor parte cortos y medianos. Dentro de la malla territorial de España las calzadas constituirían las denominadas “viae publicae” que constituían la red principal y esqueleto vertebrador de Hispania. Los caminos de tierra constituirían los denominados “actus” caminos de carácter regional que configuraban la mayor parte de la red. Muchas de las “viae publicae” y de los “actus” tendrían su origen en las “viae militares” que habrían sido los primeros construidos, apoyándose en muchas ocasiones en los caminos prerromanos, por los romanos para realizar la conquista de Hispania y que luego con la Paz romana habrían tenido otro tipo de uso. Dentro de estas “viae militares” tuvieron una importancia relevancia aquellas que se utilizaron en la conquista de la Celtiberia, culminada con la caída de Numantia. Dentro de ellas tuvo una importancia fundamental la vía romana del río Alhama, objeto de esta Tesis, que facilitaría el desplazamiento de los ejércitos romanos desde Graccurris, primera ciudad romana fundada en el Ebro medio, hasta Numantia. Desde la época Augusta, la vía romana del río Alhama, pasaría a formar parte de los denominados “actus” formando parte de la malla territorial de la Península Ibérica como vía de comunicación entre la Meseta y el Ebro Medio. We do not have knowledge of any network of ways prerromanos that were serving as base of a possible territorial mesh of Spain. Nevertheless, a company prerromana without ways, for very fragmented and isolated that was, is something improbable and great less in the Age of the Iron. Because of it in epoch prerromana existed infinity of ways, many of which today have disappeared and others have survived, almost always with his improved tours. The people prerromanos took advantage of natural routes of communication (rivers, fords, valleys, natural ports, plains, etc.) to stretch his ways. In his origins concrete guidelines did not continue, if not that the ways were originating for the traffic (of persons, cattle, goods, etc.) to and from. Thus the network viaria prerromana was chaotic and anarchic: all way had numerous branches and variants, according to the needs. Excessive slopes, variable widths, etc., in saying were spontaneous routes arisen without no apparent planning. The tours in general were short, though some current investigations are demonstrating that some of the most important cattle glens, as the Galiana, and of crossed length, were of origin prerromano. In case of the Iberian Peninsula, and more concretely in case of the Plateau, the territory was fragmented in diverse peoples and tribes, grouped according to ethnic and cultural criteria and with contacts with the near peoples that motivate the prevalence of short ways of tour. Only the need to take the flocks (of goats and sheeps especially) from the mountainous countries in summer to the plains in winter, would motivate longer trips in which some cattle glens would play a more important paper. With the arrival of the romanos, a dense network was implanted in Roman Spain viaria, whose construction extended during the whole Roman domination, being repaired many causeways and routes in several occasions. In Roman epoch the pertaining to roads network was changed and constituted by " the causeways " that were communicating important points, they were very travelled, of there that the Roman administration was supporting always in good condition, to assure the commercial exchange between different zones, collection of taxes, etc. "The dirt tracks (viae terrenae)" that besides the causeways, which we can make alike to the current roads of the first and second order, were constituting the infinity of local and regional ways. The tracings were realized some in Roman epoch, and great others resting on the ways of the epoch prerromana, these routes were not realized looking for the most short tour neither between points, two nor neither most comfortable and with a structural road surface of minor importance that in the causeways. They were not also done for a concrete type of transport, for what some of us would think that for his width they were allowing the step of cars, and others that only would allow the step afoot, astride or in donkey. They were in the habit of being, since we have indicated, dirt tracks with ended in zahorras and tours in his most short and medium. Inside the territorial mesh of Spain the causeways would constitute the called ones "viae publicae" that constituted the principal network and skeleton vertebrador of Roman Spain. The dirt tracks would constitute the "actus” called ways of regional character that were forming most of the network. Many of "viae publicae" and of the "actus" they would have his origin in " viae military" that would have been the first ones constructed, resting on many occasions on the ways prerromanos, for the Romans to realize the conquest of Roman Spain and that then with the Roman Peace they would have had another type of use. Inside these "viae military" had an importance relevancy those that were in use in the conquest of the Celtiberia, reached with Numantia's fall. Inside them a fundamental importance had the Roman route of the river Alhama, object of this Thesis, which would facilitate the displacement of the Roman armies from Graccurris, the first Roman city been founded on the average Ebro, up to Numantia. From the August epoch, the Roman route of the river Alhama, would happen to form a part of the "actus” forming a part of the territorial mesh of the Iberian Peninsula as road link between the Plateau and the Average Ebro.

Effectiveness of AFLPs and retrotransposon-based markers for the identification of portuguese grapevine cultivars and clones

Grapevine germplasm, including 38 of the main Portuguese cultivars and three foreign cultivars, Pinot Noir, Pinot Blanc and Chasselas, used as a reference, and 37 true-to-type clones from the Alvarinho, Arinto, Loureiro, Moscatel Galego Branco, Trajadura and Vinhão cultivars were studied using AFLP and three retrotransposon-based molecular techniques, IRAP, REMAP and SSAP. To study the retrotransposon-based polymorphisms, 18 primers based on the LTR sequences of Tvv1, Gret1 and Vine-1 were used. In the analysis of 41 cultivars, 517 IRAP, REMAP, AFLP and SSAP fragments were obtained, 83% of which were polymorphic. For IRAP, only the Tvv1Fa primer amplified DNA fragments. In the REMAP analysis, the Tvv1Fa-Ms14 primer combination only produced polymorphic bands, and the Vine-1 primers produced mainly ISSR fragments. The highest number of polymorphic fragments was found for AFLP. Both AFLP and SSAP showed a greater capacity for identifying clones, resulting in 15 and 9 clones identified, respectively. Together, all of the techniques allowed for the identification of 54% of the studied clones, which is an important step in solving one of the challenges that viticulture currently faces.

Integrated robust airline schedule development

In air transportation, airline profitability is influenced by the airline's ability to build flight schedules. In order to generate operational schedules, airlines engage in a complex decision-making process, referred to as airline schedule planning. Up to now, the generation of flight schedules has been separated and optimized sequentially. The schedule design has been traditionally decomposed into two sequential steps. The frequency planning and the timetable development. The purpose of the second problem of schedule development, fleet assignment, is to assign available aircraft types to flight legs such that seating capacity on an assigned aircraft matches closely with flight demand and such that costs are minimized. Our work integrates these planning phases into one single model in order to produce more economical solutions and create fewer incompatibilities between the decisions. We propose an integrated robust approach for the schedule development step. We design the timetable ensuring that enough time is available to perform passengers’ flight connections, making the system robust avoiding misconnected passengers. An application of the model for a simplified IBERIA network is shown.

Estudios de especiación de arsénico y acumulación de metales en muestras de interés medioambiental : Arsenic speciation and metal accumulation studies in environmental samples

Se ha estudiado la determinación de especies de arsénico y de contenidos totales de arsénico y metales pesados, específicamente cadmio, cromo, cobre, níquel, plomo y cinc, en muestras de interés medioambiental por su elevada capacidad acumuladora de metales, concretamente algas marinas comestibles y plantas terrestres procedentes de suelos contaminados por la actividad minera. La determinación de contenidos totales se ha llevado a cabo mediante espectrometría de emisión atómica con plasma de acoplamiento inductivo (ICP‐AES), así como por espectrometría de fluorescencia atómica con generación de hidruros (HG‐AFS), para bajos contenidos de arsénico. Las muestras fueron mineralizadas en medio ácido y calentamiento en horno de microondas. Los métodos fueron validados a través de su aplicación a materiales de referencia de matriz similar a la de las muestras, certificados en contenidos totales de los elementos seleccionados. Los resultados obtenidos mostraron su elevada capacidad de bioabsorción, especialmente en relación a los elevados contenidos de arsénico encontrados en algunas especies de algas pardas (Phaeophytas). En las plantas, se calcularon los factores de translocación, acumulación y biodisponibilidad de los elementos estudiados, permitiendo identificar a la especie Corrigiola telephiifolia como posible acumuladora de plomo e hiperacumuladora de arsénico. La determinación de especies de arsénico hidrosolubles en las muestras objeto de estudio, se llevó a cabo por cromatografía líquida de alta eficacia (HPLC) acoplado a ICP‐AES, HG‐ICP‐AES y HG‐AFS, incluyendo una etapa previa de foto‐oxidación. Los métodos desarrollados, mediante intercambio aniónico y catiónico, permitieron la diferenciación de hasta once especies de arsénico. Para el análisis de las muestras, fue necesaria la optimización de métodos de extracción, seleccionándose la extracción asistida por microondas (MAE) con agua desionizada. Asimismo, se realizaron estudios de estabilidad de arsénico total y de las especies hidrosolubles presentes en las algas, tanto sobre la muestra sólida como en sus extractos acuosos, evaluando las condiciones de almacenamiento adecuadas. En el caso de las plantas, la aplicación del diseño factorial de experimentos permitió optimizar el método de extracción y diferenciar entre las especies de arsénico presentes en forma de iones sencillos de mayor movilidad y el arsénico más fuertemente enlazado a componentes estructurales. Los resultados obtenidos permitieron identificar la presencia de arseniato (As(V)) y arsenito (As(III)) en las plantas, así como de ácido monometilarsónico (MMA) y óxido de trimetilarsina (TMAO) en algunas especies. En la mayoría de las algas se encontraron especies tóxicas, tanto mayoritarias (arseniato) como minoritarias (ácido dimetilarsínico (DMA)), así como hasta cuatro arsenoazúcares. Los resultados obtenidos y su estudio a través de la legislación vigente, mostraron la necesidad de desarrollar una reglamentación específica para el control de este tipo de alimentos. La determinación de especies de arsénico liposolubles en las muestras de algas se llevó a cabo mediante HPLC, en modo fase inversa, acoplado a espectrometría de masas con plasma de acoplamiento inductivo (ICP‐MS) y con ionización por electrospray (ESI‐MS), permitiendo la elucidación estructural de estos compuestos a través de la determinación de sus masas moleculares. Para ello, fue necesaria la puesta a punto de métodos extracción y purificación de los extractos. La metodología desarrollada permitió identificar hasta catorce especies de arsénico liposolubles en las algas, tres de ellas correspondientes a hidrocarburos que contienen arsénico, y once a arsenofosfolípidos, además de dos especies desconocidas. Las masas moleculares de las especies identificadas fueron confirmadas mediante cromatografía de gases acoplada a espectrometría de masas (GC‐MS) y espectrometría de masas de alta resolución (HR‐MS). ABSTRACT The determination of arsenic species and total arsenic and heavy metal contents (cadmium, chromium, cooper, nickel, lead and zinc) in environmental samples, with high metal accumulator capacity, has been studied. The samples studied were edible marine algae and terrestrial plants from soils polluted by mining activities. The determination of total element contents was performed by inductively coupled plasma atomic emission spectrometry (ICP‐AES), as well as by hydride generation atomic fluorescence spectrometry (HG‐AFS) for low arsenic contents. The samples studied were digested in an acidic medium by heating in a microwave oven. The digestion methods were validated against reference materials, with matrix similar to sample matrix and certified in total contents of the elements studied. The results showed the high biosorption capacity of the samples studied, especially regarding the high arsenic contents in some species of brown algae (Phaeophyta division). In terrestrial plants, the translocation, accumulation and bioavailability factors of the elements studied were calculated. Thus, the plant species Corrigiola telephiifolia was identified as possible lead accumulator and arsenic hyperaccumulator. The determination of water‐soluble arsenic species in the samples studied was carried out by high performance liquid chromatography (HPLC) coupled to ICP‐AES, HG‐ICP‐AES and HG‐AFS, including a prior photo‐oxidation step. The chromatographic methods developed, by anion and cation exchange, allowed us to differentiate up to eleven arsenic species. The sample analysis required the optimization of extraction methods, choosing the microwave assisted extraction (MAE) with deionized water. On the other hand, the stability of total arsenic and water‐soluble arsenic species in algae, both in the solid samples and in the water extracts, was studied, assessing the suitable storage conditions. In the case of plant samples, the application of a multivariate experimental design allowed us to optimize the extraction method and differentiate between the arsenic species present as simple ions of higher mobility and the arsenic more strongly bound to structural components. The presence of arsenite (As(III)) and arsenate (As(V)) was identified in plant samples, as well as monomethylarsonic acid (MMA) and trimethylarsine oxide (TMAO) in some cases. Regarding algae, toxic arsenic species were found in most of them, both As(V) and dimethylarsinic acid (DMA), as well as up to four arsenosugars. These results were discussed according to the current legislation, showing the need to develop specific regulations to control this kind of food products. The determination of lipid‐soluble arsenic species in alga samples was performed by reversed‐phase HPLC coupled to inductively coupled plasma and electrospray mass spectrometry (ICP‐MS and ESI‐MS), in order to establish the structure of these compounds by determining the corresponding molecular masses. For this purpose, it was necessary to develop an extraction method, as well as a clean‐up method of the extracts. The method developed permitted the identification of fourteen lipid‐soluble arsenic compounds in algae, corresponding to three arsenic‐hydrocarbons and eleven arsenosugarphospholipids, as well as two unknown compounds. Accurate mass measurements of the identified compounds were performed by gas chromatography coupled to mass spectrometry (GC‐MS) and high resolution mass spectrometry (HR‐MS).

Coupled model of initiation and propagation of corrosion in reinforced concrete

Corrosion of reinforcing steel in concrete due to chloride ingress is one of the main causes of the deterioration of reinforced concrete structures. Structures most affected by such a corrosion are marine zone buildings and structures exposed to de-icing salts like highways and bridges. Such process is accompanied by an increase in volume of the corrosión products on the rebarsconcrete interface. Depending on the level of oxidation, iron can expand as much as six times its original volume. This increase in volume exerts tensile stresses in the surrounding concrete which result in cracking and spalling of the concrete cover if the concrete tensile strength is exceeded. The mechanism by which steel embedded in concrete corrodes in presence of chloride is the local breakdown of the passive layer formed in the highly alkaline condition of the concrete. It is assumed that corrosion initiates when a critical chloride content reaches the rebar surface. The mathematical formulation idealized the corrosion sequence as a two-stage process: an initiation stage, during which chloride ions penetrate to the reinforcing steel surface and depassivate it, and a propagation stage, in which active corrosion takes place until cracking of the concrete cover has occurred. The aim of this research is to develop computer tools to evaluate the duration of the service life of reinforced concrete structures, considering both the initiation and propagation periods. Such tools must offer a friendly interface to facilitate its use by the researchers even though their background is not in numerical simulation. For the evaluation of the initiation period different tools have been developed: Program TavProbabilidade: provides means to carry out a probability analysis of a chloride ingress model. Such a tool is necessary due to the lack of data and general uncertainties associated with the phenomenon of the chloride diffusion. It differs from the deterministic approach because it computes not just a chloride profile at a certain age, but a range of chloride profiles for each probability or occurrence. Program TavProbabilidade_Fiabilidade: carries out reliability analyses of the initiation period. It takes into account the critical value of the chloride concentration on the steel that causes breakdown of the passive layer and the beginning of the propagation stage. It differs from the deterministic analysis in that it does not predict if the corrosion is going to begin or not, but to quantifies the probability of corrosion initiation. Program TavDif_1D: was created to do a one dimension deterministic analysis of the chloride diffusion process by the finite element method (FEM) which numerically solves Fick’second Law. Despite of the different FEM solver already developed in one dimension, the decision to create a new code (TavDif_1D) was taken because of the need to have a solver with friendly interface for pre- and post-process according to the need of IETCC. An innovative tool was also developed with a systematic method devised to compare the ability of the different 1D models to predict the actual evolution of chloride ingress based on experimental measurements, and also to quantify the degree of agreement of the models with each others. For the evaluation of the entire service life of the structure: a computer program has been developed using finite elements method to do the coupling of both service life periods: initiation and propagation. The program for 2D (TavDif_2D) allows the complementary use of two external programs in a unique friendly interface: • GMSH - an finite element mesh generator and post-processing viewer • OOFEM – a finite element solver. This program (TavDif_2D) is responsible to decide in each time step when and where to start applying the boundary conditions of fracture mechanics module in function of the amount of chloride concentration and corrosion parameters (Icorr, etc). This program is also responsible to verify the presence and the degree of fracture in each element to send the Information of diffusion coefficient variation with the crack width. • GMSH - an finite element mesh generator and post-processing viewer • OOFEM – a finite element solver. The advantages of the FEM with the interface provided by the tool are: • the flexibility to input the data such as material property and boundary conditions as time dependent function. • the flexibility to predict the chloride concentration profile for different geometries. • the possibility to couple chloride diffusion (initiation stage) with chemical and mechanical behavior (propagation stage). The OOFEM code had to be modified to accept temperature, humidity and the time dependent values for the material properties, which is necessary to adequately describe the environmental variations. A 3-D simulation has been performed to simulate the behavior of the beam on both, action of the external load and the internal load caused by the corrosion products, using elements of imbedded fracture in order to plot the curve of the deflection of the central region of the beam versus the external load to compare with the experimental data.

Beitrag zur Entwicklung der Querschnittsgestaltung im Verbundbrückenbau

Die grafische Darstellung des Verbundquerschnittes mit einer oberen Betonplatte und einem darunter liegenden Stahlträger war seit seiner Vorstellung in den 1950er Jahren ein Symbol, das weit über die Theorie hinausging und weite Verbreitung in der Praxis des Verbundbrückenbaus fand. Seit den 1970er bzw. 1980er Jahren hat dieses Bild – bedingt durch neue und freiere Formen, Beton und Stahl miteinander zu kombinieren – seine Symbolhaftigkeit verloren. In Deutschland und Spanien wurde der Doppelverbund mit unten liegenden Betonplatten in Bereichen mit negativen Momenten eingeführt, in Frankreich werden Stahlträger auch in vorgespannten Betonquerschnitten eingebettet. Beide Ansätze haben dazu beigetragen, dass in der Gegenwart die Materialien Stahl und Beton im Verbundbau frei miteinander kombiniert werden können. On the development of sections in composite bridges. A comprehensive theory of composite construction was established in Germany by Sattler in 1953. The theoretical image of the composite section with a superior concrete slab and a lower metallic structure was shaped in addition to the analytical resolution. Theory and graphical representation were going to be known together in Europe. This figure was repeated in all theoretical and academic publications, so becoming an authentic icon of the composite section. Its translation to the bridge deck in flexion was obvious: the superior slab defines the tread platform, while the metallic structure was left off-hook at the bottom. Nevertheless, in continuous decks the section is not optimal at all in zones of negative bending moments. But the overcoming of the graphical representation of the theory did not happen immediately. It was produced after a process in which several European countries played an active role and where different mechanisms of technological transference were developed. One approach to this overcoming is the “double composite action”, with a lower concrete slab in areas of a negative bending moment. The first accomplishments, a bridge in Orasje built in 1968 with 134 m span, as well as the publications of the system proposed by Fabrizio de Miranda in 1971 did not extend nor had continuity. Spanish bridges by Fernández Ordoñez and Martínez Calzón used double composite action for the first time in 1979. The German team of Leonhard, Andrä und partners, has used it since the end of the 1980's to solve bridges of great span. Once the technology has been well known thanks to the ASCE International Congress and the Spanish International Meetings organised by the “Colegio de Ingenieros de Caminos”, double composite action has been integrated well into the structural vocabulary everywhere. In France the approach was different. What Michel Virlogeux calls “double floor composite section” was reached as an evolution of prestressed concrete bridges. In an experimental process widely known, the external prestressing allows weight reduction by diminishing the thickness of the concrete webs. The following step, in the 1980's, was the substitution of the webs by metallic elements: stiffened plates, trusses or folded plates. A direct result of this development is the Brass de la Plaine Bridge in the Reunion Island in 2001 with 280 m span. Both approaches have contributed to a freedom of design in composite construction in steel and concrete today.

Engineering metal precipitate size distributions to enhance gettering in multicrystalline silicon

The extraction of metal impurities during phosphorus diffusion gettering (PDG) is one of the crucial process steps when fabricating high-efficiency solar cells using low-cost, lower-purity silicon wafers. In this work, we show that for a given metal concentration, the size and density of metal silicide precipitates strongly influences the gettering efficacy. Different precipitate size distributions can be already found in silicon wafers grown by different techniques. In our experiment, however, the as-grown distribution of precipitated metals in multicrystalline Si sister wafers is engineered through different annealing treatments in order to control for the concentration and distribution of other defects. A high density of small precipitates is formed during a homogenization step, and a lower density of larger precipitates is formed during extended annealing at 740º C. After PDG, homogenized samples show a decreased interstitial iron concentration compared to as-grown and ripened samples, in agreement with simulations.

Proyecto de viabilidad de una planta de tratamiento para mineral de estaño y tántalo

El proyecto tiene como objeto definir la viabilidad de explotación de un importante yacimiento de Estaño y Tántalo que se encuentra en una formación geológica de base pegmatítica situada en el norte de España. En base a las reservas calculadas, se define la capacidad de tratamiento de la planta de procesamiento del mineral para un periodo de explotación de 10 años. Como primer paso se estudian los ensayos de caracterización y concentración realizados en laboratorio a partir de muestras de mano representativas del mineral así como otros en planta piloto llevados a cabo anteriormente. Una vez definida la recuperación del Estaño y Tántalo se procede al diseño conceptual del proceso. Posteriormente se desarrolla un diseño e ingeniería preliminar más aproximados, a partir de los cuales se evalúan los costes de equipos y operacionales que, en base a los retornos por la venta de los concentrados, permitirán calcular la rentabilidad del proyecto y riesgos de la inversión. ABSTRACT The purpose of this project is to define the feasibility of mining a major deposit of tin and tantalum found in a pegmatite formation in northern Spain. Based on the estimated reserves, the operating capacity for mining and mineral processing plant was defined for a period of 10 years. As a first step for the development, a research program for characterization and concentration of the ore, were performed in the laboratory based on representative samples from the deposit. In addition, previous pilot plant results were also taken into account. Once determined the recovery of tin and tantalum, the conceptual design process was defined. As a second step, it was developed a preliminary design and engineering, from which the capital and operating costs were estimated .By means of the calculated returns from the sale of concentrates, the profitability of the project and investment risks were finally assessed

Tratamiento consistente de restricciones e impacto en dinámica de sistemas multicuerpo

Esta tesis está enmarcada en el estudio de diferentes procedimientos numéricos para resolver la dinámica de un sistema multicuerpo sometido a restricciones e impacto, que puede estar compuesto por sólidos rígidos y deformables conectados entre sí por diversos tipos de uniones. Dentro de los métodos numéricos analizados se presta un especial interés a los métodos consistentes, los cuales tienen por objetivo que la energía calculada en cada paso de tiempo, para un sistema mecánico, tenga una evolución coherente con el comportamiento teórico de la energía. En otras palabras, un método consistente mantiene constante la energía total en un problema conservativo, y en presencia de fuerzas disipativas proporciona un decremento positivo de la energía total. En esta línea se desarrolla un algoritmo numérico consistente con la energía total para resolver las ecuaciones de la dinámica de un sistema multicuerpo. Como parte de este algoritmo se formulan energéticamente consistentes las restricciones y el contacto empleando multiplicadores de Lagrange, penalización y Lagrange aumentado. Se propone también un método para el contacto con sólidos rígidos representados mediante superficies implícitas, basado en una restricción regularizada que se adaptada adecuadamente para el cumplimiento exacto de la restricción de contacto y para ser consistente con la conservación de la energía total. En este contexto se estudian dos enfoques: uno para el contacto elástico puro (sin deformación) formulado con penalización y Lagrange aumentado; y otro basado en un modelo constitutivo para el contacto con penetración. En el segundo enfoque se usa un potencial de penalización que, en ausencia de componentes disipativas, restaura la energía almacenada en el contacto y disipa energía de forma consistente con el modelo continuo cuando las componentes de amortiguamiento y fricción son consideradas. This thesis focuses on the study of several numerical procedures used to solve the dynamics of a multibody system subjected to constraints and impact. The system may be composed by rigid and deformable bodies connected by different types of joints. Within this framework, special attention is paid to consistent methods, which preserve the theoretical behavior of the energy at each time step. In other words, a consistent method keeps the total energy constant in a conservative problem, and provides a positive decrease in the total energy when dissipative forces are present. A numerical algorithm has been developed for solving the dynamical equations of multibody systems, which is energetically consistent. Energetic consistency in contacts and constraints is formulated using Lagrange multipliers, penalty and augmented Lagrange methods. A contact methodology is proposed for rigid bodies with a boundary represented by implicit surfaces. The method is based on a suitable regularized constraint formulation, adapted both to fulfill exactly the contact constraint, and to be consistent with the conservation of the total energy. In this context two different approaches are studied: the first applied to pure elastic contact (without deformation), formulated with penalty and augmented Lagrange; and a second one based on a constitutive model for contact with penetration. In this second approach, a penalty potential is used in the constitutive model, that restores the energy stored in the contact when no dissipative effects are present. On the other hand, the energy is dissipated consistently with the continuous model when friction and damping are considered.

Techniques to accelerate convergence of stress-controlled molecular dynamics simulations of dislocation motion

Dislocation mobility —the relation between applied stress and dislocation velocity—is an important property to model the mechanical behavior of structural materials. These mobilities reflect the interaction between the dislocation core and the host lattice and, thus, atomistic resolution is required to capture its details. Because the mobility function is multiparametric, its computation is often highly demanding in terms of computational requirements. Optimizing how tractions are applied can be greatly advantageous in accelerating convergence and reducing the overall computational cost of the simulations. In this paper we perform molecular dynamics simulations of ½ 〈1 1 1〉 screw dislocation motion in tungsten using step and linear time functions for applying external stress. We find that linear functions over time scales of the order of 10–20 ps reduce fluctuations and speed up convergence to the steady-state velocity value by up to a factor of two.