Tape-tether design for de-orbiting from given altitude and inclination

The product of the tether-to-satellite mass ratio and the probability of tether cuts by small debris must be small to make electrodynamic bare tethers a competitive and useful de-orbiting technology. In the case of a circular orbit and assuming a model for the debris population, the product can be written as a function that just depends on the initial orbit parameters (altitude and inclination) and the tether geometry. This formula, which does not contain the time explicitly and ignores the details of the tether dynamics during the de-orbiting, is used to find design rules for the tape dimensions and the orbit parameter ranges where tethers dominate other de-orbiting technologies like rockets, electrical propulsion, and sails.

Statistical distributions obtained from the compression of monodisperse, soft and frictionless particles

The cyclic compression of several granular systems has been simulated with a molecular dynamics code. All the samples consisted of bidimensional, soft, frictionless and equal-sized particles that were initially arranged according to a squared lattice and were compressed by randomly generated irregular walls. The compression protocols can be described by some control variables (volume or external force acting on the walls) and by some dimensionless factors, that relate stiffness, density, diameter, damping ratio and water surface tension to the external forces, displacements and periods. Each protocol, that is associated to a dynamic process, results in an arrangement with its own macroscopic features: volume (or packing ratio), coordination number, and stress; and the differences between packings can be highly significant. The statistical distribution of the force-moment state of the particles (i.e. the equivalent average stress multiplied by the volume) is analyzed. In spite of the lack of a theoretical framework based on statistical mechanics specific for these protocols, it is shown how the obtained distributions of mean and relative deviatoric force-moment are. Then it is discussed on the nature of these distributions and on their relation to specific protocols.

Comportamiento frente a la durabilidad de morteros de reparación de cemento modificados con polímeros

El auge que ha surgido en los últimos años por la reparación de edificios y estructuras construidas con hormigón ha llevado al desarrollo de morteros de reparación cada vez más tecnológicos. En el desarrollo de estos morteros por parte de los fabricantes, surge la disyuntiva en el uso de los polímeros en sus formulaciones, por no encontrarse justificado en ocasiones el trinomio prestaciones/precio/aplicación. En esta tesis se ha realizado un estudio exhaustivo para la justificación de la utilización de estos morteros como morteros de reparación estructural como respuesta a la demanda actual disponiéndolo en tres partes: En la primera parte se realizó un estudio del arte de los morteros y sus constituyentes. El uso de los morteros se remonta a la antigüedad, utilizándose como componentes yeso y cal fundamentalmente. Los griegos y romanos desarrollaron el concepto de morteros de cal, introduciendo componentes como las puzolanas, cales hidraúlicas y áridos de polvo de mármol dando origen a morteros muy parecidos a los hormigones actuales. En la edad media y renacimiento se perdió la tecnología desarrollada por los romanos debido al extenso uso de la piedra en las construcciones civiles, defensivas y religiosas. Hubo que esperar hasta el siglo XIX para que J. Aspdin descubriese el actual cemento como el principal compuesto hidraúlico. Por último y ya en el siglo XX con la aparición de moléculas tales como estireno, melanina, cloruro de vinilo y poliésteres se comenzó a desarrollar la industria de los polímeros que se añadieron a los morteros dando lugar a los “composites”. El uso de polímeros en matrices cementantes dotan al mortero de propiedades tales como: adherencia, flexibilidad y trabajabilidad, como ya se tiene constancia desde los años 30 con el uso de caucho naturales. En la actualidad el uso de polímeros de síntesis (polivinialacetato, estireno-butadieno, viniacrílico y resinas epoxi) hacen que principalmente el mortero tenga mayor resistencia al ataque del agua y por lo tanto aumente su durabilidad ya que se minimizan todas las reacciones de deterioro (hielo, humedad, ataque biológico,…). En el presente estudio el polímero que se utilizó fue en estado polvo: polímero redispersable. Estos polímeros están encapsulados y cuando se ponen en contacto con el agua se liberan de la cápsula formando de nuevo el gel. En los morteros de reparación el único compuesto hidraúlico que hay es el cemento y es el principal constituyente hoy en día de los materiales de construcción. El cemento se obtiene por molienda conjunta de Clínker y yeso. El Clínker se obtiene por cocción de una mezcla de arcillas y calizas hasta una temperatura de 1450-1500º C por reacción en estado fundente. Para esta reacción se deben premachacar y homogeneizar las materias primas extraídas de la cantera. Son dosificadas en el horno con unas proporciones tales que cumplan con unas relación de óxidos tales que permitan formar las fases anhidras del Clínker C3S, C2S, C3A y C4AF. De la hidratación de las fases se obtiene el gel CSH que es el que proporciona al cemento de sus propiedades. Existe una norma (UNE-EN 197-1) que establece la composición, especificaciones y tipos de cementos que se fabrican en España. La tendencia actual en la fabricación del cemento pasa por el uso de cementos con mayores contenidos de adiciones (cal, puzolana, cenizas volantes, humo de sílice,…) con el objeto de obtener cementos más sostenibles. Otros componentes que influyen en las características de los morteros son: - Áridos. En el desarrollo de los morteros se suelen usar naturales, bien calizos o silícicos. Hacen la función de relleno y de cohesionantes de la matriz cementante. Deben ser inertes - Aditivos. Son aquellos componentes del mortero que son dosificados en una proporción menor al 5%. Los más usados son los superplastificantes por su acción de reductores de agua que revierte en una mayor durabilidad del mortero. Una vez analizada la composición de los morteros, la mejora tecnológica de los mismos está orientada al aumento de la durabilidad de su vida en obra. La durabilidad se define como la capacidad que éste tiene de resistir a la acción del ambiente, ataques químicos, físicos, biológicos o cualquier proceso que tienda a su destrucción. Estos procesos dependen de factores tales como la porosidad del hormigón y de la exposición al ambiente. En cuanto a la porosidad hay que tener en cuenta la distribución de macroporos, mesoporos y microporos de la estructura del hormigón, ya que no todos son susceptibles de que se produzca el transporte de agentes deteriorantes, provocando tensiones internas en las paredes de los mismos y destruyendo la matriz cementante Por otro lado los procesos de deterioro están relacionados con la acción del agua bien como agente directo o como vehículo de transporte del agente deteriorante. Un ambiente que resulta muy agresivo para los hormigones es el marino. En este caso los procesos de deterioro están relacionados con la presencia de cloruros y de sulfatos tanto en el agua de mar como en la atmosfera que en combinación con el CO2 y O2 forman la sal de Friedel. El deterioro de las estructuras en ambientes marinos se produce por la debilitación de la matriz cementante y posterior corrosión de las armaduras que provocan un aumento de volumen en el interior y rotura de la matriz cementante por tensiones capilares. Otras reacciones que pueden producir estos efectos son árido-álcali y difusión de iones cloruro. La durabilidad de un hormigón también depende del tipo de cemento y su composición química (cementos con altos contenidos de adición son más resistentes), relación agua/cemento y contenido de cemento. La Norma UNE-EN 1504 que consta de 10 partes, define los productos para la protección y reparación de estructuras de hormigón, el control de calidad de los productos, propiedades físico-químicas y durables que deben cumplir. En esta Norma se referencian otras 65 normas que ofrecen los métodos de ensayo para la evaluación de los sistemas de reparación. En la segunda parte de esta Tesis se hizo un diseño de experimentos con diferentes morteros poliméricos (con concentraciones de polímero entre 0 y 25%), tomando como referencia un mortero control sin polímero, y se estudiaron sus propiedades físico-químicas, mecánicas y durables. Para mortero con baja proporción de polímero se recurre a sistemas monocomponentes y para concentraciones altas bicomponentes en la que el polímero está en dispersión acuosa. Las propiedades mecánicas medidas fueron: resistencia a compresión, resistencia a flexión, módulo de elasticidad, adherencia por tracción directa y expansión-retracción, todas ellas bajo normas UNE. Como ensayos de caracterización de la durabilidad: absorción capilar, resistencia a carbonatación y adherencia a tracción después de ciclos hielo-deshielo. El objeto de este estudio es seleccionar el mortero con mejor resultado general para posteriormente hacer una comparativa entre un mortero con polímero (cantidad optimizada) y un mortero sin polímero. Para seleccionar esa cantidad óptima de polímero a usar se han tenido en cuenta los siguientes criterios: el mortero debe tener una clasificación R4 en cuanto a prestaciones mecánicas al igual que para evaluar sus propiedades durables frente a los ciclos realizados, siempre teniendo en cuenta que la adición de polímero no puede ser elevada para hacer el mortero competitivo. De este estudio se obtuvieron las siguientes conclusiones generales: - Un mortero normalizado no cumple con propiedades para ser clasificado como R3 o R4. - Sin necesidad de polímero se puede obtener un mortero que cumpliría con R4 para gran parte de las características medidas - Es necesario usar relaciones a:c< 0.5 para conseguir morteros R4, - La adición de polímero mejora siempre la adherencia, abrasión, absorción capilar y resistencia a carbonatación - Las diferentes proporciones de polímero usadas siempre suponen una mejora tecnológica en propiedades mecánicas y de durabilidad. - El polímero no influye sobre la expansión y retracción del mortero. - La adherencia se mejora notablemente con el uso del polímero. - La presencia de polímero en los morteros mejoran las propiedades relacionadas con la acción del agua, por aumento del poder cementante y por lo tanto de la cohesión. El poder cementante disminuye la porosidad. Como consecuencia final de este estudio se determinó que la cantidad óptima de polímero para la segunda parte del estudio es 2.0-3.5%. La tercera parte consistió en el estudio comparativo de dos morteros: uno sin polímero (mortero A) y otro con la cantidad optimizada de polímero, concluida en la parte anterior (mortero B). Una vez definido el porcentaje de polímeros que mejor se adapta a los resultados, se plantea un nuevo esqueleto granular mejorado, tomando una nueva dosificación de tamaños de áridos, tanto para el mortero de referencia, como para el mortero con polímeros, y se procede a realizar los ensayos para su caracterización física, microestructural y de durabilidad, realizándose, además de los ensayos de la parte 1, mediciones de las propiedades microestructurales que se estudiaron a través de las técnicas de porosimetría de mercurio y microscopia electrónica de barrido (SEM); así como propiedades del mortero en estado fresco (consistencia, contenido de aire ocluido y tiempo final de fraguado). El uso del polímero frente a la no incorporación en la formulación del mortero, proporcionó al mismo de las siguientes ventajas: - Respecto a sus propiedades en estado fresco: El mortero B presentó mayor consistencia y menor cantidad de aire ocluido lo cual hace un mortero más trabajable y más dúctil al igual que más resistente porque al endurecer dejará menos huecos en su estructura interna y aumentará su durabilidad. Al tener también mayor tiempo de fraguado, pero no excesivo permite que la manejabilidad para puesta en obra sea mayor, - Respecto a sus propiedades mecánicas: Destacar la mejora en la adherencia. Es una de las principales propiedades que confiere el polímero a los morteros. Esta mayor adherencia revierte en una mejora de la adherencia al soporte, minimización de las posibles reacciones en la interfase hormigón-mortero y por lo tanto un aumento en la durabilidad de la reparación ejecutada con el mortero y por consecuencia del hormigón. - Respecto a propiedades microestructurales: la porosidad del mortero con polímero es menor y menor tamaño de poro critico susceptible de ser atacado por agentes externos causantes de deterioro. De los datos obtenidos por SEM no se observaron grandes diferencias - En cuanto a abrasión y absorción capilar el mortero B presentó mejor comportamiento como consecuencia de su menor porosidad y su estructura microscópica. - Por último el comportamiento frente al ataque de sulfatos y agua de mar, así como al frente de carbonatación, fue más resistente en el mortero con polímero por su menor permeabilidad y su menor porosidad. Para completar el estudio de esta tesis, y debido a la gran importancia que están tomando en la actualidad factores como la sostenibilidad se ha realizado un análisis de ciclo de vida de los dos morteros objeto de estudio de la segunda parte experimental.In recent years, the extended use of repair materials for buildings and structures made the development of repair mortars more and more technical. In the development of these mortars by producers, the use of polymers in the formulations is a key point, because sometimes this use is not justified when looking to the performance/price/application as a whole. This thesis is an exhaustive study to justify the use of these mortars as a response to the current growing demand for structural repair. The thesis is classified in three parts:The first part is the study of the state of the art of mortars and their constituents.In ancient times, widely used mortars were based on lime and gypsum. The Greeks and Romans developed the concept of lime mortars, introducing components such as pozzolans, hydraulic limes and marble dust as aggregates, giving very similar concrete mortars to the ones used currently. In the middle Age and Renaissance, the technology developed by the Romans was lost, due to the extensive use of stone in the civil, religious and defensive constructions. It was not until the 19th century, when J. Aspdin discovered the current cement as the main hydraulic compound. Finally in the 20th century, with the appearance of molecules such as styrene, melanin, vinyl chloride and polyester, the industry began to develop polymers which were added to the binder to form special "composites".The use of polymers in cementitious matrixes give properties to the mortar such as adhesion, Currently, the result of the polymer synthesis (polivynilacetate, styrene-butadiene, vynilacrylic and epoxy resins) is that mortars have increased resistance to water attack and therefore, they increase their durability since all reactions of deterioration are minimised (ice, humidity, biological attack,...). In the present study the polymer used was redispersible polymer powder. These polymers are encapsulated and when in contact with water, they are released from the capsule forming a gel.In the repair mortars, the only hydraulic compound is the cement and nowadays, this is the main constituent of building materials. The current trend is centered in the use of higher contents of additions (lime, pozzolana, fly ash, silica, silica fume...) in order to obtain more sustainable cements. Once the composition of mortars is analyzed, the technological improvement is centred in increasing the durability of the working life. Durability is defined as the ability to resist the action of the environment, chemical, physical, and biological attacks or any process that tends to its destruction. These processes depend on factors such as the concrete porosity and the environmental exposure. In terms of porosity, it be considered, the distribution of Macropores and mesopores and pores of the concrete structure, since not all of them are capable of causing the transportation of damaging agents, causing internal stresses on the same walls and destroying the cementing matrix.In general, deterioration processes are related to the action of water, either as direct agent or as a transport vehicle. Concrete durability also depends on the type of cement and its chemical composition (cement with high addition amounts are more resistant), water/cement ratio and cement content. The standard UNE-EN 1504 consists of 10 parts and defines the products for the protection and repair of concrete, the quality control of products, physical-chemical properties and durability. Other 65 standards that provide the test methods for the evaluation of repair systems are referenced in this standard. In the second part of this thesis there is a design of experiments with different polymer mortars (with concentrations of polymer between 0 and 25%), taking a control mortar without polymer as a reference and its physico-chemical, mechanical and durable properties were studied. For mortars with low proportion of polymer, 1 component systems are used (powder polymer) and for high polymer concentrations, water dispersion polymers are used. The mechanical properties measured were: compressive strength, flexural strength, modulus of elasticity, adhesion by direct traction and expansion-shrinkage, all of them under standards UNE. As a characterization of the durability, following tests are carried out: capillary absorption, resistance to carbonation and pull out adhesion after freeze-thaw cycles. The target of this study is to select the best mortar to make a comparison between mortars with polymer (optimized amount) and mortars without polymer. To select the optimum amount of polymer the following criteria have been considered: the mortar must have a classification R4 in terms of mechanical performance as well as in durability properties against the performed cycles, always bearing in mind that the addition of polymer cannot be too high to make the mortar competitive in price. The following general conclusions were obtained from this study: - A standard mortar does not fulfill the properties to be classified as R3 or R4 - Without polymer, a mortar may fulfill R4 for most of the measured characteristics. - It is necessary to use relations w/c ratio < 0.5 to get R4 mortars - The addition of polymer always improves adhesion, abrasion, capillary absorption and carbonation resistance - The different proportions of polymer used always improve the mechanical properties and durability. - The polymer has no influence on the expansion and shrinkage of the mortar - Adhesion is improved significantly with the use of polymer. - The presence of polymer in mortars improves the properties related to the action of the water, by the increase of the cement power and therefore the cohesion. The cementitious properties decrease the porosity. As final result of this study, it was determined that the optimum amount of polymer for the second part of the study is 2.0 - 3.5%. The third part is the comparative study between two mortars: one without polymer (A mortar) and another with the optimized amount of polymer, completed in the previous part (mortar B). Once the percentage of polymer is defined, a new granular skeleton is defined, with a new dosing of aggregate sizes, for both the reference mortar, the mortar with polymers, and the tests for physical, microstructural characterization and durability, are performed, as well as trials of part 1, measurements of the microstructural properties that were studied by scanning electron microscopy (SEM) and mercury porosimetry techniques; as well as properties of the mortar in fresh State (consistency, content of entrained air and final setting time). The use of polymer versus non polymer mortar, provided the following advantages: - In fresh state: mortar with polymer presented higher consistency and least amount of entrained air, which makes a mortar more workable and more ductile as well as more resistant because hardening will leave fewer gaps in its internal structure and increase its durability. Also allow it allows a better workability because of the longer (not excessive) setting time. - Regarding the mechanical properties: improvement in adhesion. It is one of the main properties which give the polymer to mortars. This higher adhesion results in an improvement of adhesion to the substrate, minimization of possible reactions at the concrete-mortar interface and therefore an increase in the durability of the repair carried out with mortar and concrete. - Respect to microstructural properties: the porosity of mortar with polymer is less and with smaller pore size, critical to be attacked by external agents causing deterioration. No major differences were observed from the data obtained by SEM - In terms of abrasion and capillary absorption, polymer mortar presented better performance as a result of its lower porosity and its microscopic structure. - Finally behavior against attack by sulfates and seawater, as well as to carbonation, was better in the mortar with polymer because of its lower permeability and its lower porosity. To complete the study, due to the great importance of sustainability for future market facts, the life cycle of the two mortars studied was analysed.

Analysis of the static and dynamic behaviour of hydraulic fills

En la actualidad existe un gran conocimiento en la caracterización de rellenos hidráulicos, tanto en su caracterización estática, como dinámica. Sin embargo, son escasos en la literatura estudios más generales y globales de estos materiales, muy relacionados con sus usos y principales problemáticas en obras portuarias y mineras. Los procedimientos semi‐empíricos para la evaluación del efecto silo en las celdas de cajones portuarios, así como para el potencial de licuefacción de estos suelos durantes cargas instantáneas y terremotos, se basan en estudios donde la influencia de los parámetros que los rigen no se conocen en gran medida, dando lugar a resultados con considerable dispersión. Este es el caso, por ejemplo, de los daños notificados por el grupo de investigación del Puerto de Barcelona, la rotura de los cajones portuarios en el Puerto de Barcelona en 2007. Por estos motivos y otros, se ha decidido desarrollar un análisis para la evaluación de estos problemas mediante la propuesta de una metodología teórico‐numérica y empírica. El enfoque teórico‐numérico desarrollado en el presente estudio se centra en la determinación del marco teórico y las herramientas numéricas capaces de solventar los retos que presentan estos problemas. La complejidad del problema procede de varios aspectos fundamentales: el comportamiento no lineal de los suelos poco confinados o flojos en procesos de consolidación por preso propio; su alto potencial de licuefacción; la caracterización hidromecánica de los contactos entre estructuras y suelo (camino preferencial para el flujo de agua y consolidación lateral); el punto de partida de los problemas con un estado de tensiones efectivas prácticamente nulo. En cuanto al enfoque experimental, se ha propuesto una metodología de laboratorio muy sencilla para la caracterización hidromecánica del suelo y las interfaces, sin la necesidad de usar complejos aparatos de laboratorio o procedimientos excesivamente complicados. Este trabajo incluye por tanto un breve repaso a los aspectos relacionados con la ejecución de los rellenos hidráulicos, sus usos principales y los fenómenos relacionados, con el fin de establecer un punto de partida para el presente estudio. Este repaso abarca desde la evolución de las ecuaciones de consolidación tradicionales (Terzaghi, 1943), (Gibson, English & Hussey, 1967) y las metodologías de cálculo (Townsend & McVay, 1990) (Fredlund, Donaldson and Gitirana, 2009) hasta las contribuciones en relación al efecto silo (Ranssen, 1985) (Ravenet, 1977) y sobre el fenómeno de la licuefacción (Casagrande, 1936) (Castro, 1969) (Been & Jefferies, 1985) (Pastor & Zienkiewicz, 1986). Con motivo de este estudio se ha desarrollado exclusivamente un código basado en el método de los elementos finitos (MEF) empleando el programa MATLAB. Para ello, se ha esablecido un marco teórico (Biot, 1941) (Zienkiewicz & Shiomi, 1984) (Segura & Caron, 2004) y numérico (Zienkiewicz & Taylor, 1989) (Huerta & Rodríguez, 1992) (Segura & Carol, 2008) para resolver problemas de consolidación multidimensional con condiciones de contorno friccionales, y los correspondientes modelos constitutivos (Pastor & Zienkiewicz, 1986) (Fiu & Liu, 2011). Asimismo, se ha desarrollado una metodología experimental a través de una serie de ensayos de laboratorio para la calibración de los modelos constitutivos y de la caracterización de parámetros índice y de flujo (Castro, 1969) (Bahda 1997) (Been & Jefferies, 2006). Para ello se han empleado arenas de Hostun como material (relleno hidráulico) de referencia. Como principal aportación se incluyen una serie de nuevos ensayos de corte directo para la caracterización hidromecánica de la interfaz suelo – estructura de hormigón, para diferentes tipos de encofrados y rugosidades. Finalmente, se han diseñado una serie de algoritmos específicos para la resolución del set de ecuaciones diferenciales de gobierno que definen este problema. Estos algoritmos son de gran importancia en este problema para tratar el procesamiento transitorio de la consolidación de los rellenos hidráulicos, y de otros efectos relacionados con su implementación en celdas de cajones, como el efecto silo y la licuefacciones autoinducida. Para ello, se ha establecido un modelo 2D axisimétrico, con formulación acoplada u‐p para elementos continuos y elementos interfaz (de espesor cero), que tratan de simular las condiciones de estos rellenos hidráulicos cuando se colocan en las celdas portuarias. Este caso de estudio hace referencia clara a materiales granulares en estado inicial muy suelto y con escasas tensiones efectivas, es decir, con prácticamente todas las sobrepresiones ocasionadas por el proceso de autoconsolidación (por peso propio). Por todo ello se requiere de algoritmos numéricos específicos, así como de modelos constitutivos particulares, para los elementos del continuo y para los elementos interfaz. En el caso de la simulación de diferentes procedimientos de puesta en obra de los rellenos se ha requerido la modificacion de los algoritmos empleados para poder así representar numéricamente la puesta en obra de estos materiales, además de poder realizar una comparativa de los resultados para los distintos procedimientos. La constante actualización de los parámetros del suelo, hace también de este algoritmo una potente herramienta que permite establecer un interesante juego de perfiles de variables, tales como la densidad, el índice de huecos, la fracción de sólidos, el exceso de presiones, y tensiones y deformaciones. En definitiva, el modelo otorga un mejor entendimiento del efecto silo, término comúnmente usado para definir el fenómeno transitorio del gradiente de presiones laterales en las estructuras de contención en forma de silo. Finalmente se incluyen una serie de comparativas entre los resultados del modelo y de diferentes estudios de la literatura técnica, tanto para el fenómeno de las consolidaciones por preso propio (Fredlund, Donaldson & Gitirana, 2009) como para el estudio del efecto silo (Puertos del Estado, 2006, EuroCódigo (2006), Japan Tech, Stands. (2009), etc.). Para concluir, se propone el diseño de un prototipo de columna de decantación con paredes friccionales, como principal propuesta de futura línea de investigación. Wide research is nowadays available on the characterization of hydraulic fills in terms of either static or dynamic behavior. However, reported comprehensive analyses of these soils when meant for port or mining works are scarce. Moreover, the semi‐empirical procedures for assessing the silo effect on cells in floating caissons, and the liquefaction potential of these soils during sudden loads or earthquakes are based on studies where the underlying influence parameters are not well known, yielding results with significant scatter. This is the case, for instance, of hazards reported by the Barcelona Liquefaction working group, with the failure of harbor walls in 2007. By virtue of this, a complex approach has been undertaken to evaluate the problem by a proposal of numerical and laboratory methodology. Within a theoretical and numerical scope, the study is focused on the numerical tools capable to face the different challenges of this problem. The complexity is manifold; the highly non‐linear behavior of consolidating soft soils; their potentially liquefactable nature, the significance of the hydromechanics of the soil‐structure contact, the discontinuities as preferential paths for water flow, setting “negligible” effective stresses as initial conditions. Within an experimental scope, a straightforward laboratory methodology is introduced for the hydromechanical characterization of the soil and the interface without the need of complex laboratory devices or cumbersome procedures. Therefore, this study includes a brief overview of the hydraulic filling execution, main uses (land reclamation, filled cells, tailing dams, etc.) and the underlying phenomena (self‐weight consolidation, silo effect, liquefaction, etc.). It comprises from the evolution of the traditional consolidation equations (Terzaghi, 1943), (Gibson, English, & Hussey, 1967) and solving methodologies (Townsend & McVay, 1990) (Fredlund, Donaldson and Gitirana, 2009) to the contributions in terms of silo effect (Ranssen, 1895) (Ravenet, 1977) and liquefaction phenomena (Casagrande, 1936) (Castro, 1969) (Been & Jefferies, 1985) (Pastor & Zienkiewicz, 1986). The novelty of the study lies on the development of a Finite Element Method (FEM) code, exclusively formulated for this problem. Subsequently, a theoretical (Biot, 1941) (Zienkiewicz and Shiomi, 1984) (Segura and Carol, 2004) and numerical approach (Zienkiewicz and Taylor, 1989) (Huerta, A. & Rodriguez, A., 1992) (Segura, J.M. & Carol, I., 2008) is introduced for multidimensional consolidation problems with frictional contacts and the corresponding constitutive models (Pastor & Zienkiewicz, 1986) (Fu & Liu, 2011). An experimental methodology is presented for the laboratory test and material characterization (Castro 1969) (Bahda 1997) (Been & Jefferies 2006) using Hostun sands as reference hydraulic fill. A series of singular interaction shear tests for the interface calibration is included. Finally, a specific model algorithm for the solution of the set of differential equations governing the problem is presented. The process of consolidation and settlements involves a comprehensive simulation of the transient process of decantation and the build‐up of the silo effect in cells and certain phenomena related to self‐compaction and liquefaction. For this, an implementation of a 2D axi‐syimmetric coupled model with continuum and interface elements, aimed at simulating conditions and self‐weight consolidation of hydraulic fills once placed into floating caisson cells or close to retaining structures. This basically concerns a loose granular soil with a negligible initial effective stress level at the onset of the process. The implementation requires a specific numerical algorithm as well as specific constitutive models for both the continuum and the interface elements. The simulation of implementation procedures for the fills has required the modification of the algorithm so that a numerical representation of these procedures is carried out. A comparison of the results for the different procedures is interesting for the global analysis. Furthermore, the continuous updating of the model provides an insightful logging of variable profiles such as density, void ratio and solid fraction profiles, total and excess pore pressure, stresses and strains. This will lead to a better understanding of complex phenomena such as the transient gradient in lateral pressures due to silo effect in saturated soils. Interesting model and literature comparisons for the self‐weight consolidation (Fredlund, Donaldson, & Gitirana, 2009) and the silo effect results (Puertos del Estado (2006), EuroCode (2006), Japan Tech, Stands. (2009)). This study closes with the design of a decantation column prototype with frictional walls as the main future line of research.

Selected topics in the Hydrodynamics of floating offshore wind turbines: heave damping and second order surge motions

La Energía eléctrica producida mediante tecnología eólica flotante es uno de los recursos más prometedores para reducir la dependencia de energía proveniente de combustibles fósiles. Esta tecnología es de especial interés en países como España, donde la plataforma continental es estrecha y existen pocas áreas para el desarrollo de estructuras fijas. Entre los diferentes conceptos flotantes, esta tesis se ha ocupado de la tipología semisumergible. Estas plataformas pueden experimentar movimientos resonantes en largada y arfada. En largada, dado que el periodo de resonancia es largo estos puede ser inducidos por efectos de segundo orden de deriva lenta que pueden tener una influencia muy significativa en las cargas en los fondeos. En arfada las fuerzas de primer orden pueden inducir grandes movimientos y por tanto la correcta determinación del amortiguamiento es esencial para la analizar la operatividad de la plataforma. Esta tesis ha investigado estos dos efectos, para ello se ha usado como caso base el diseño de una plataforma desarrollada en el proyecto Europeo Hiprwind. La plataforma se compone de 3 columnas cilíndricas unidas mediante montantes estructurales horizontales y diagonales, Los cilindros proporcionan flotabilidad y momentos adrizante. A la base de cada columna se le ha añadido un gran “Heave Plate” o placa de cierre. El diseño es similar a otros diseños previos (Windfloat). Se ha fabricado un modelo a escala de una de las columnas para el estudio detallado del amortiguamiento mediante oscilaciones forzadas. Las dimensiones del modelo (1m diámetro en la placa de cierre) lo hacen, de los conocidos por el candidato, el mayor para el que se han publicado datos. El diseño del cilindro se ha realizado de tal manera que permite la fijación de placas de cierre planas o con refuerzo, ambos modelos se han fabricado y analizado. El modelo con refuerzos es una reproducción exacta del diseño a escala real incluyendo detalles distintivos del mismo, siendo el más importante la placa vertical perimetral. Los ensayos de oscilaciones forzadas se han realizado para un rango de frecuencias, tanto para el disco plano como el reforzado. Se han medido las fuerzas durante los ensayos y se han calculado los coeficientes de amortiguamiento y de masa añadida. Estos coeficientes son necesarios para el cálculo del fondeo mediante simulaciones en el dominio del tiempo. Los coeficientes calculados se han comparado con la literatura existente, con cálculos potenciales y por ultimo con cálculos CFD. Para disponer de información relevante para el diseño estructural de la plataforma se han medido y analizado experimentalmente las presiones en la parte superior e inferior de cada placa de cierre. Para la correcta estimación numérica de las fuerzas de deriva lenta en la plataforma se ha realizado una campaña experimental que incluye ensayos con modelo cautivo de la plataforma completa en olas bicromaticas. Pese a que estos experimentos no reproducen un escenario de oleaje realista, los mismos permiten una verificación del modelo numérico mediante la comparación de fuerzas medidas en el modelo físico y el numérico. Como resultados de esta tesis podemos enumerar las siguientes conclusiones. 1. El amortiguamiento y la masa añadida muestran una pequeña dependencia con la frecuencia pero una gran dependencia con la amplitud del movimiento. siendo coherente con investigaciones existentes. 2. Las medidas con la placa de cierre reforzada con cierre vertical en el borde, muestra un amortiguamiento significativamente menor comparada con la placa plana. Esto implica que para ensayos de canal es necesario incluir estos detalles en el modelo. 3. La masa añadida no muestra grandes variaciones comparando placa plana y placa con refuerzos. 4. Un coeficiente de amortiguamiento del 6% del crítico se puede considerar conservador para el cálculo en el dominio de la frecuencia. Este amortiguamiento es equivalente a un coeficiente de “drag” de 4 en elementos de Morison cuadráticos en las placas de cierre usadas en simulaciones en el dominio del tiempo. 5. Se han encontrado discrepancias en algunos valores de masa añadida y amortiguamiento de la placa plana al comparar con datos publicados. Se han propuesto algunas explicaciones basadas en las diferencias en la relación de espesores, en la distancia a la superficie libre y también relacionadas con efectos de escala. 6. La presión en la placa con refuerzos son similares a las de la placa plana, excepto en la zona del borde donde la placa con refuerzo vertical induce una gran diferencias de presiones entre la cara superior e inferior. 7. La máxima diferencia de presión escala coherentemente con la fuerza equivalente a la aceleración de la masa añadida distribuida sobre la placa. 8. Las masas añadidas calculadas con el código potencial (WADAM) no son suficientemente precisas, Este software no contempla el modelado de placas de pequeño espesor con dipolos, la poca precisión de los resultados aumenta la importancia de este tipo de elementos al realizar simulaciones con códigos potenciales para este tipo de plataformas que incluyen elementos de poco espesor. 9. Respecto al código CFD (Ansys CFX) la precisión de los cálculos es razonable para la placa plana, esta precisión disminuye para la placa con refuerzo vertical en el borde, como era de esperar dado la mayor complejidad del flujo. 10. Respecto al segundo orden, los resultados, en general, muestran que, aunque la tendencia en las fuerzas de segundo orden se captura bien con los códigos numéricos, se observan algunas reducciones en comparación con los datos experimentales. Las diferencias entre simulaciones y datos experimentales son mayores al usar la aproximación de Newman, que usa únicamente resultados de primer orden para el cálculo de las fuerzas de deriva media. 11. Es importante remarcar que las tendencias observadas en los resultados con modelo fijo cambiarn cuando el modelo este libre, el impacto que los errores en las estimaciones de fuerzas segundo orden tienen en el sistema de fondeo dependen de las condiciones ambientales que imponen las cargas ultimas en dichas líneas. En cualquier caso los resultados que se han obtenido en esta investigación confirman que es necesaria y deseable una detallada investigación de los métodos usados en la estimación de las fuerzas no lineales en las turbinas flotantes para que pueda servir de guía en futuros diseños de estos sistemas. Finalmente, el candidato espera que esta investigación pueda beneficiar a la industria eólica offshore en mejorar el diseño hidrodinámico del concepto semisumergible. ABSTRACT Electrical power obtained from floating offshore wind turbines is one of the promising resources which can reduce the fossil fuel energy consumption and cover worldwide energy demands. The concept is the most competitive in countries, such as Spain, where the continental shelf is narrow and does not provide space for fixed structures. Among the different floating structures concepts, this thesis has dealt with the semisubmersible one. Platforms of this kind may experience resonant motions both in surge and heave directions. In surge, since the platform natural period is long, such resonance can be excited with second order slow drift forces and may have substantial influence on mooring loads. In heave, first order forces can induce significant motion, whose damping is a crucial factor for the platform downtime. These two topics have been investigated in this thesis. To this aim, a design developed during HiPRWind EU project, has been selected as reference case study. The platform is composed of three cylindrical legs, linked together by a set of structural braces. The cylinders provide buoyancy and restoring forces and moments. Large circular heave plates have been attached to their bases. The design is similar to other documented in literature (e.g. Windfloat), which implies outcomes could have a general value. A large scale model of one of the legs has been built in order to study heave damping through forced oscillations. The final dimensions of the specimen (one meter diameter discs) make it, to the candidate’s knowledge, the largest for which data has been published. The model design allows for the fitting of either a plain solid heave plate or a flapped reinforced one; both have been built. The latter is a model scale reproduction of the prototype heave plate and includes some distinctive features, the most important being the inclusion of a vertical flap on its perimeter. The forced oscillation tests have been conducted for a range of frequencies and amplitudes, with both the solid plain model and the vertical flap one. Forces have been measured, from which added mass and damping coefficients have been obtained. These are necessary to accurately compute time-domain simulations of mooring design. The coefficients have been compared with literature, and potential flow and CFD predictions. In order to provide information for the structural design of the platform, pressure measurements on the top and bottom side of the heave discs have been recorded and pressure differences analyzed. In addition, in order to conduct a detailed investigation on the numerical estimations of the slow-drift forces of the HiPRWind platform, an experimental campaign involving captive (fixed) model tests of a model of the whole platform in bichromatic waves has been carried out. Although not reproducing the more realistic scenario, these tests allowed a preliminary verification of the numerical model based directly on the forces measured on the structure. The following outcomes can be enumerated: 1. Damping and added mass coefficients show, on one hand, a small dependence with frequency and, on the other hand, a large dependence with the motion amplitude, which is coherent with previously published research. 2. Measurements with the prototype plate, equipped with the vertical flap, show that damping drops significantly when comparing this to the plain one. This implies that, for tank tests of the whole floater and turbine, the prototype plate, equipped with the flap, should be incorporated to the model. 3. Added mass values do not suffer large alterations when comparing the plain plate and the one equipped with a vertical flap. 4. A conservative damping coefficient equal to 6% of the critical damping can be considered adequate for the prototype heave plate for frequency domain analysis. A corresponding drag coefficient equal to 4.0 can be used in time domain simulations to define Morison elements. 5. When comparing to published data, some discrepancies in added mass and damping coefficients for the solid plain plate have been found. Explanations have been suggested, focusing mainly on differences in thickness ratio and distance to the free surface, and eventual scale effects. 6. Pressures on the plate equipped with the vertical flap are similar in magnitude to those of the plain plate, even though substantial differences are present close to the edge, where the flap induces a larger pressure difference in the reinforced case. 7. The maximum pressure difference scales coherently with the force equivalent to the acceleration of the added mass, distributed over the disc surface. 8. Added mass coefficient values predicted with the potential solver (WADAM) are not accurate enough. The used solver does not contemplate modeling thin plates with doublets. The relatively low accuracy of the results highlights the importance of these elements when performing potential flow simulations of offshore platforms which include thin plates. 9. For the full CFD solver (Ansys CFX), the accuracy of the computations is found reasonable for the plain plate. Such accuracy diminishes for the disc equipped with a vertical flap, an expected result considering the greater complexity of the flow. 10. In regards to second order effects, in general, the results showed that, although the main trend in the behavior of the second-order forces is well captured by the numerical predictions, some under prediction of the experimental values is visible. The gap between experimental and numerical results is more pronounced when Newman’s approximation is considered, making use exclusively of the mean drift forces calculated in the first-order solution. 11. It should be observed that the trends observed in the fixed model test may change when the body is free to float, and the impact that eventual errors in the estimation of the second-order forces may have on the mooring system depends on the characteristics of the sea conditions that will ultimately impose the maximum loads on the mooring lines. Nevertheless, the preliminary results obtained in this research do confirm that a more detailed investigation of the methods adopted for the estimation of the nonlinear wave forces on the FOWT would be welcome and may provide some further guidance for the design of such systems. As a final remark, the candidate hopes this research can benefit the offshore wind industry in improving the hydrodynamic design of the semi-submersible concept.

Co-simulation Methodologies for Hybrid and Electric Vehicle Dynamics

In recent decades, full electric and hybrid electric vehicles have emerged as an alternative to conventional cars due to a range of factors, including environmental and economic aspects. These vehicles are the result of considerable efforts to seek ways of reducing the use of fossil fuel for vehicle propulsion. Sophisticated technologies such as hybrid and electric powertrains require careful study and optimization. Mathematical models play a key role at this point. Currently, many advanced mathematical analysis tools, as well as computer applications have been built for vehicle simulation purposes. Given the great interest of hybrid and electric powertrains, along with the increasing importance of reliable computer-based models, the author decided to integrate both aspects in the research purpose of this work. Furthermore, this is one of the first final degree projects held at the ETSII (Higher Technical School of Industrial Engineers) that covers the study of hybrid and electric propulsion systems. The present project is based on MBS3D 2.0, a specialized software for the dynamic simulation of multibody systems developed at the UPM Institute of Automobile Research (INSIA). Automobiles are a clear example of complex multibody systems, which are present in nearly every field of engineering. The work presented here benefits from the availability of MBS3D software. This program has proven to be a very efficient tool, with a highly developed underlying mathematical formulation. On this basis, the focus of this project is the extension of MBS3D features in order to be able to perform dynamic simulations of hybrid and electric vehicle models. This requires the joint simulation of the mechanical model of the vehicle, together with the model of the hybrid or electric powertrain. These sub-models belong to completely different physical domains. In fact the powertrain consists of energy storage systems, electrical machines and power electronics, connected to purely mechanical components (wheels, suspension, transmission, clutch…). The challenge today is to create a global vehicle model that is valid for computer simulation. Therefore, the main goal of this project is to apply co-simulation methodologies to a comprehensive model of an electric vehicle, where sub-models from different areas of engineering are coupled. The created electric vehicle (EV) model consists of a separately excited DC electric motor, a Li-ion battery pack, a DC/DC chopper converter and a multibody vehicle model. Co-simulation techniques allow car designers to simulate complex vehicle architectures and behaviors, which are usually difficult to implement in a real environment due to safety and/or economic reasons. In addition, multi-domain computational models help to detect the effects of different driving patterns and parameters and improve the models in a fast and effective way. Automotive designers can greatly benefit from a multidisciplinary approach of new hybrid and electric vehicles. In this case, the global electric vehicle model includes an electrical subsystem and a mechanical subsystem. The electrical subsystem consists of three basic components: electric motor, battery pack and power converter. A modular representation is used for building the dynamic model of the vehicle drivetrain. This means that every component of the drivetrain (submodule) is modeled separately and has its own general dynamic model, with clearly defined inputs and outputs. Then, all the particular submodules are assembled according to the drivetrain configuration and, in this way, the power flow across the components is completely determined. Dynamic models of electrical components are often based on equivalent circuits, where Kirchhoff’s voltage and current laws are applied to draw the algebraic and differential equations. Here, Randles circuit is used for dynamic modeling of the battery and the electric motor is modeled through the analysis of the equivalent circuit of a separately excited DC motor, where the power converter is included. The mechanical subsystem is defined by MBS3D equations. These equations consider the position, velocity and acceleration of all the bodies comprising the vehicle multibody system. MBS3D 2.0 is entirely written in MATLAB and the structure of the program has been thoroughly studied and understood by the author. MBS3D software is adapted according to the requirements of the applied co-simulation method. Some of the core functions are modified, such as integrator and graphics, and several auxiliary functions are added in order to compute the mathematical model of the electrical components. By coupling and co-simulating both subsystems, it is possible to evaluate the dynamic interaction among all the components of the drivetrain. ‘Tight-coupling’ method is used to cosimulate the sub-models. This approach integrates all subsystems simultaneously and the results of the integration are exchanged by function-call. This means that the integration is done jointly for the mechanical and the electrical subsystem, under a single integrator and then, the speed of integration is determined by the slower subsystem. Simulations are then used to show the performance of the developed EV model. However, this project focuses more on the validation of the computational and mathematical tool for electric and hybrid vehicle simulation. For this purpose, a detailed study and comparison of different integrators within the MATLAB environment is done. Consequently, the main efforts are directed towards the implementation of co-simulation techniques in MBS3D software. In this regard, it is not intended to create an extremely precise EV model in terms of real vehicle performance, although an acceptable level of accuracy is achieved. The gap between the EV model and the real system is filled, in a way, by introducing the gas and brake pedals input, which reflects the actual driver behavior. This input is included directly in the differential equations of the model, and determines the amount of current provided to the electric motor. For a separately excited DC motor, the rotor current is proportional to the traction torque delivered to the car wheels. Therefore, as it occurs in the case of real vehicle models, the propulsion torque in the mathematical model is controlled through acceleration and brake pedal commands. The designed transmission system also includes a reduction gear that adapts the torque coming for the motor drive and transfers it. The main contribution of this project is, therefore, the implementation of a new calculation path for the wheel torques, based on performance characteristics and outputs of the electric powertrain model. Originally, the wheel traction and braking torques were input to MBS3D through a vector directly computed by the user in a MATLAB script. Now, they are calculated as a function of the motor current which, in turn, depends on the current provided by the battery pack across the DC/DC chopper converter. The motor and battery currents and voltages are the solutions of the electrical ODE (Ordinary Differential Equation) system coupled to the multibody system. Simultaneously, the outputs of MBS3D model are the position, velocity and acceleration of the vehicle at all times. The motor shaft speed is computed from the output vehicle speed considering the wheel radius, the gear reduction ratio and the transmission efficiency. This motor shaft speed, somehow available from MBS3D model, is then introduced in the differential equations corresponding to the electrical subsystem. In this way, MBS3D and the electrical powertrain model are interconnected and both subsystems exchange values resulting as expected with tight-coupling approach.When programming mathematical models of complex systems, code optimization is a key step in the process. A way to improve the overall performance of the integration, making use of C/C++ as an alternative programming language, is described and implemented. Although this entails a higher computational burden, it leads to important advantages regarding cosimulation speed and stability. In order to do this, it is necessary to integrate MATLAB with another integrated development environment (IDE), where C/C++ code can be generated and executed. In this project, C/C++ files are programmed in Microsoft Visual Studio and the interface between both IDEs is created by building C/C++ MEX file functions. These programs contain functions or subroutines that can be dynamically linked and executed from MATLAB. This process achieves reductions in simulation time up to two orders of magnitude. The tests performed with different integrators, also reveal the stiff character of the differential equations corresponding to the electrical subsystem, and allow the improvement of the cosimulation process. When varying the parameters of the integration and/or the initial conditions of the problem, the solutions of the system of equations show better dynamic response and stability, depending on the integrator used. Several integrators, with variable and non-variable step-size, and for stiff and non-stiff problems are applied to the coupled ODE system. Then, the results are analyzed, compared and discussed. From all the above, the project can be divided into four main parts: 1. Creation of the equation-based electric vehicle model; 2. Programming, simulation and adjustment of the electric vehicle model; 3. Application of co-simulation methodologies to MBS3D and the electric powertrain subsystem; and 4. Code optimization and study of different integrators. Additionally, in order to deeply understand the context of the project, the first chapters include an introduction to basic vehicle dynamics, current classification of hybrid and electric vehicles and an explanation of the involved technologies such as brake energy regeneration, electric and non-electric propulsion systems for EVs and HEVs (hybrid electric vehicles) and their control strategies. Later, the problem of dynamic modeling of hybrid and electric vehicles is discussed. The integrated development environment and the simulation tool are also briefly described. The core chapters include an explanation of the major co-simulation methodologies and how they have been programmed and applied to the electric powertrain model together with the multibody system dynamic model. Finally, the last chapters summarize the main results and conclusions of the project and propose further research topics. In conclusion, co-simulation methodologies are applicable within the integrated development environments MATLAB and Visual Studio, and the simulation tool MBS3D 2.0, where equation-based models of multidisciplinary subsystems, consisting of mechanical and electrical components, are coupled and integrated in a very efficient way.

Estimate of the total volume of Svalbard glaciers, and their potential contribution to sea-level rise, using new regionally based scaling relationships

We present a set of new volume scaling relationships specific to Svalbard glaciers, derived from a sample of 60 volume–area pairs. Glacier volumes are computed from ground-penetrating radar (GPR)-retrieved ice thickness measurements, which have been compiled from different sources for this study. The most precise scaling models, in terms of lowest cross-validation errors, are obtained using a multivariate approach where, in addition to glacier area, glacier length and elevation range are also used as predictors. Using this multivariate scaling approach, together with the Randolph Glacier Inventory V3.2 for Svalbard and Jan Mayen, we obtain a regional volume estimate of 6700 ± 835 km3, or 17 ± 2 mm of sea-level equivalent (SLE). This result lies in the mid- to low range of recently published estimates, which show values as varied as 13 and 24 mm SLE. We assess the sensitivity of the scaling exponents to glacier characteristics such as size, aspect ratio and average slope, and find that the volume of steep-slope and cirque-type glaciers is not very sensitive to changes in glacier area.

Arachidonate lipoxygenases as essential regulators of cell survival and apoptosis.

Arachidonic acid (AA) metabolites derived from both cyclooxygenase (COX) and lipoxygenase (LOX) pathways transduce a variety of signals related to cell growth. Here, we report that the AA LOX pathway also functions as a critical regulator of cell survival and apoptosis. Rat Walker 256 (W256) carcinosarcoma cells express 12-LOX and synthesize 12(S)- and 15(S)-hydroxyeicosatetraenoic acids as their major LOX metabolites. W256 cells transfected with 12-LOX-specific antisense oligonucleotide or antisense oligonucleotides directed to conserved regions of LOXs underwent time- and dose-dependent apoptosis. Likewise, treatment of W256 cells with various LOX but not COX inhibitors induced apoptotic cell death, which could be partially inhibited by exogenous 12(S)- or 15(S)-hydroxyeicosatetraenoic acids. The W256 cell apoptosis induced by antisense oligos and LOX inhibitors was followed by a rapid downregulation of bcl-2 protein, a dramatic decrease in the bcl-2/bax ratio, and could be suppressed by bcl-2 overexpression. In contrast, p53, which is wild type in W256 cells, did not undergo alterations during apoptosis induction. The results suggest that the LOX pathway plays an important physiological role in regulating apoptosis.

Bioenergetic scaling: metabolic design and body-size constraints in mammals.

The cytosolic phosphorylation ratio ([ATP]/[ADP][P(i)]) in the mammalian heart was found to be inversely related to body mass with an exponent of -0.30 (r = 0.999). This exponent is similar to -0.25 calculated for the mass-specific O2 consumption. The inverse of cytosolic free [ADP], the Gibbs energy of ATP hydrolysis (delta G'ATP), and the efficiency of ATP production (energy captured in forming 3 mol of ATP per cycle along the mitochondrial respiratory chain from NADH to 1/2 O2) were all found to scale with body mass with a negative exponent. On the basis of scaling of the phosphorylation ratio and free cytosolic [ADP], we propose that the myocardium and other tissues of small mammals represent a metabolic system with a higher driving potential (a higher delta G'ATP from the higher [ATP]/[ADP][P(i)]) and a higher kinetic gain [(delta V/Vmax)/delta [ADP]] where small changes in free [ADP] produce large changes in steady-state rates of O2 consumption. From the inverse relationship between mitochondrial efficiency and body size we calculate that tissues of small mammals are more efficient than those of large mammals in converting energy from the oxidation of foodstuffs to the bond energy of ATP. A higher efficiency also indicates that mitochondrial electron transport is not the major site for higher heat production in small mammals. We further propose that the lower limit of about 2 g for adult endotherm body size (bumblebee-bat, Estrucan shrew, and hummingbird) may be set by the thermodynamics of the electron transport chain. The upper limit for body size (100,000-kg adult blue whale) may relate to a minimum delta G'ATP of approximately 55 kJ/mol for a cytoplasmic phosphorylation ratio of 12,000 M-1.

Extração de oleuropeína de folhas de oliva com solvente hidroalcoólico e efeito dos extratos sobre a estabilidade oxidativa de óleos vegetais

A oleuropeína é o composto fenólico mais abundante presente nas folhas da oliveira, sendo que muitos estudos vêm demonstrando que este composto apresenta importantes propriedades antimicrobiana, antioxidante, anti-inflamatória, entre outras, surgindo o interesse em estudos de métodos para sua extração e aplicação em produtos na área alimentícia, cosmética e farmacêutica. O objetivo deste estudo foi a extração da oleuropeína à partir de folhas de oliva, utilizando solvente não tóxico, para posterior aplicação dos extratos em óleos vegetais a fim de se verificar seu efeito sobre a estabilidade oxidativa dos mesmos. O solvente selecionado para o estudo foi uma mistura de etanol e água (70:30, em massa, condição obtida através de um trabalho prévio), na presença de 1 % de ácido acético. Em uma primeira etapa, foram realizados experimentos de extração utilizando-se as técnicas de maceração (tipo I) e ultrassom (tipo II), em diferentes condições de temperatura (20, 30, 40, 50 e 60°C). Em uma segunda etapa, através de experimentos com maceração à temperatura ambiente, estudou-se o efeito da razão folhas:solvente (1:8, 1:6 e 1:3) e a influência da presença de ácido acético sobre o processo de extração (tipo III). Por fim, realizando-se a maceração na presença de ácido acético, temperatura ambiente e proporção folhas: solvente igual a 1:3, realizaram-se extrações sequenciadas a partir de uma mesma matéria-prima (tipo IV). Os resultados desses experimentos foram expressos em rendimento de oleuropeína (RO), teor de oleuropeína nos extratos (TO) e rendimento global (RG). Analisando-se os experimentos I e II, verificou-se que a temperatura não exerceu influência significativa sobre as respostas RO, TO e RG. Além disso, verificou-se que os valores das respostas para os experimentos com a maceração foram um pouco maiores do que os valores obtidos para as extrações com o auxílio do ultrassom. Nos experimentos tipo III, em linhas gerais, observou-se a influência positiva da presença do ácido acético sobre as respostas estudadas. Verificou-se também que, na presença de ácido, o aumento da quantidade de solvente na extração conduz ao aumento de RO e RG, e à diminuição de TO. Através do experimento tipo IV, constatou-se que mesmo após quatro extrações sequenciadas, ainda não foi possível esgotar a oleuropeína da matéria-prima. Após a obtenção de todos os extratos hidroalcoólicos, selecionou-se um contendo aproximadamente 19 % de oleuropeína para o estudo da estabilidade oxidativa em óleos vegetais (oliva e girassol) utilizando o método Rancimat. A presença de extrato aumentou em 3 horas o tempo de indução do azeite de oliva extra-virgem, e em 2 horas o tempo de indução do azeite de oliva comum. Os óleos de girassol bruto e refinado não apresentaram melhora na estabilidade oxidativa quando adicionados dos extratos. Foram realizados também testes de estabilidade oxidativa através da adição direta de folhas de oliva em pó nos azeites de oliva extra-virgem e comum. Para o azeite extra-virgem, a adição das folhas não proporcionou melhora da estabilidade oxidativa, porém para o azeite comum, houve um aumento de mais de 2 horas no tempo de indução.Os resultados apresentados neste trabalho demonstraram que é possível obter extratos contendo teores significativos de oleuropeína utilizando-se um solvente renovável. Além disso, constatou-se que os mesmos podem ser utilizados como um antioxidante natural em azeite de oliva, melhorando sua estabilidade oxidativa.

Bioactive compounds and physical and chemical characteristics of mini tomatoes: influence of postharvest treatments

Tomatoes are among the most cultivated and used vegetables in the world. They are very succeptible to post harvest losses due to high perishability, therefore the use of postharvest treatments may contribute to conservation of this fruit, however the treatments might affect significantly physico-chemical, sensory and nutritional characteristics of tomatoes. Given the perishability of tomato and the economic importance of small tomato fruits, the purpose of the present study was to determine the effect of gamma radiation, carnauba coating and 1-MCP treatments on tomato fruit quality during storage. The study may be divided into two parts. In the first, mini tomatoes cv. Sweet Grape were harvested at breaker stage, divided into 4 grous and treated with gamma radiation (0.6 kGy), carnauba coating (1 L 1000 kg-1) and 1-MCP (500 nL L-1) and then stored at 25±2°C for 30 days with a control group of tomatoes. In the seconnd part, tomatoes harvested at light-red stage were submitted to the same treatments and storage period. Every 6 days tomatoes were evaluated for color modifications, fruit firmness, souble and total pectin (only for light-red tomatoes), mass loss, titratable acidity (TA), soluble solids (SS), SS/TA ratio, carotenoids profile, formation of lycopene isomers, total phenolic compounds, ascorbic acid and antioxidant capacity. For tomatoes harvested at breaker stage and submitted to the treatments the results showed mass loss was delaying mainly by carnauba wax, and to a lesser extend by 1-MCP. Fruit firmness were better retained for 1-MCP treated fruits and carnauba treatment showed a transient effect in preserving fruit firmness. SS/TA of tomatoes treated with gamma radiation and carnauba presented no differences from control values, and were lower with the application of 1-MCP. Color was negatively affected by 1-MCP and earlier changed (6th day) when gamma radiation was applied. In relation to bioactive compounds of tomatoes harvest at breaker stage, results indicated gamma radiation and 1-MCP decreased the final content of lycopene and produced more (Z)-isomers of lycopene. Gamma radiation also induced a decreased in ?-carotene and an increased in phenolic compounds by the end of storage period. 1-MCP treatment promoted a slow down increase in ascorbic acid content during storage. Antioxidant capacity of the hydrophilic fraction was not dramatically affected by treatments and the lipophilic fraction was lower, especially for 1-MCP fruits. In addition, contents of ?-carotene, lycopene, (Z)-isomers of lycopene, ascorbic acid and antioxidant capacity increased during the period of storage while contents of lutein and phenolic compounds tended to decrease. Regarding tomatoes harvest at light-red stage, the most effective treatments for delaying fruit firmness and mass loss was carnauba and 1-MCP, while gamma radiation was the treatment with higher mass loss and the less fruit firmness, which could be associated with the higher solubilization of pectins promoted by radiation treatment. Color (L* and Hue) was mainly affected by 1-MCP treatment which delayed color development, however, by the end of storage, the values were not different from the other treatments. SS/TA ratio was lower for fruits treated with 1-MCP and TA was not so dramatically affected by treatments. Furthermore, mini tomatoes harvested at light-red stage, demonstrated irradiation induced changes in the final content of lycopene, increasing it, and formed less (13Z)-lycopene, while 1-MCP and carnauba coating slow down the increase in lycopene and slown down the decrease of ascorbic acid and phenolic compounds. Antioxidant capacity of lipophilic fraction was not affected by treatments and the hydrophilic fraction was lower for irradiated fruits only on day 0 as well as phenolic compounds. In the other days, no differences among treatments were observed for hydrophilic antioxidant capacity. Considering the results, the best combination of SS and TA and fruit preservation for mini tomatoes harvest at breaker stage was promoted by carnauba coating, which seems to be the treatment that causes fewer changes in bioactive compounds of breaker tomatoes. However, when mini tomatoes were harvested at light-red stage, SS/TA ratio and color were better and, to preserve the quality of these fruits, besides carnauba coating, 1-MCP also could be indicated

Comparative analysis of the relationship between anterior and posterior corneal shape analyzed by Scheimpflug photography in normal and keratoconus eyes

Background To analyze and compare the relationship between anterior and posterior corneal shape evaluated by a tomographic system combining the Scheimpflug photography and Placido-disc in keratoconus and normal healthy eyes, as well as to evaluate its potential diagnostic value. Methods Comparative case series including a sample of 161 eyes of 161 subjects with ages ranging from 7 to 66 years and divided into two groups: normal group including 100 healthy eyes of 100 subjects, and keratoconus group including 61 keratoconus eyes of 61 patients. All eyes received a comprehensive ophthalmologic examination including an anterior segment analysis with the Sirius system (CSO). Antero-posterior ratios for corneal curvature (k ratio) and shape factor (p ratio) were calculated. Logistic regression analysis was used to evaluate if some antero–posterior ratios combined with other clinical parameters were predictors of the presence of keratoconus. Results No statistically significant differences between groups were found in the antero–posterior k ratios for 3-, 5- and 7-mm diameter corneal areas (p ≥ 0.09). The antero–posterior p ratio for 4.5- and 8-mm diameter corneal areas was significantly higher in the normal group than in the keratoconus group (p < 0.01). The k ratio for 3, 5, and 7 mm was significantly higher in the keratoconus grade IV subgroup than in the normal group (p < 0.01). Furthermore, significant differences were found in the p ratio between the normal group and the keratoconus grade II subgroup (p ≤ 0.01). Finally, the logistic regression analysis identified as significant independent predictors of the presence of keratoconus (p < 0.01) the 8-mm anterior shape factor, the anterior chamber depth, and the minimal corneal thickness. Conclusions The antero-posterior k and p ratios are parameters with poor prediction ability for keratoconus, in spite of the trend to the presence of more prolate posterior corneal surfaces compared to the anterior in keratoconus eyes.

1,2-Functionalized Imidazoles as Palladium Ligands: An Efficient and Robust Catalytic System for the Fluorine-Free Hiyama Reaction

A variety of hydroxy- and amino-functionalized imidazoles were prepared from 1-methyl- and 1-(diethoxymethyl)imidazole by means of isoprene-mediated lithiation followed by reaction with an electrophile. These compounds in combination with palladium acetate were screened as catalyst systems for the Hiyama reaction under fluorine-free conditions using microwave irradiation. The systematic study of the catalytic system showed 1-methyl-2-aminoalkylimidazole derivative L1 to be the best ligand, which was employed under solvent-free conditions with a 1:2 Pd/ligand ratio and TBAB (20 mol-%) as additive. The study has revealed an interaction between the Pd/ligand ratio and the amount of TBAB. The established catalytic system presented a certain degree of robustness, and it has been successfully employed in the coupling of a range of aryl bromides and chlorides with different aryl siloxanes. Furthermore, both reagents were employed in an equimolecular amount, without an excess of organosilane.

Very high methane uptake on activated carbons prepared from mesophase pitch: A compromise between microporosity and bulk density

Two petroleum residues were pyrolyzed under two different conditions to obtain pitches with low or high mesophase content. The effect of the KOH: precursor ratio and the activation temperature on the packing density and porous texture of the carbons have been studied and optimized. Activated carbons combining high micropore volume (>1 cm3/g) and high packing density (0.7 g/cm3) have been successfully prepared. Regarding excess methane adsorption capacities, the best results (160 cm3 (STP)/cm3 at 25 °C and 3.5 MPa) were obtained using the pitch with the higher content of the more organized mesophase, activated at relatively low temperature (700 °C), with a medium KOH: precursor ratio (3:1). Some of the activated carbons exhibit enhanced adsorption capacity at high pressure, giving values as high as 175 cm3 (STP)/cm3 at 25 °C and 5 MPa and 200 cm3 (STP)/cm3 at 25 °C and 10 MPa (the same amount as in an empty cylinder but at half of the pressure), indicating a contribution of large micropores and narrow mesopores to adsorption at high pressure. The density of methane in pores between 1 and 2.5 nm at pressure up to 10 MPa was estimated to understand their contribution to the total adsorption capacity.

Fatores de risco para a progressão da gamapatia monoclonal de significado indeterminado para mieloma múltiplo

Trabalho Final do Curso de Mestrado Integrado em Medicina, Faculdade de Medicina, Universidade de Lisboa, 2014