Comportamiento mecánico de nuevas aleaciones de wolframio en función de la temperatura

La presente memoria de tesis tiene como objetivo principal la caracterización mecánica en función de la temperatura de nueve aleaciones de wolframio con contenidos diferentes en titanio, vanadio, itria y lantana. Las aleaciones estudiadas son las siguientes: W-0.5%Y2O3, W-2%Ti, W-2% Ti-0.5% Y2O3, W-4% Ti-0.5% Y2O3, W-2%V, W- 2%Vmix, W-4%V, W-1%La2O3 and W-4%V-1%La2O3. Todos ellos, además del wolframio puro se fabrican mediante compresión isostática en caliente (HIP) y son suministradas por la Universidad Carlos III de Madrid. La investigación se desarrolla a través de un estudio sistemático basado en ensayos físicos y mecánicos, así como el análisis post mortem de las muestras ensayadas. Para realizar dicha caracterización mecánica se aplican diferentes ensayos mecánicos, la mayoría de ellos realizados en el intervalo de temperatura de 25 a 1000 º C. Los ensayos de caracterización que se llevan a cabo son: • Densidad • Dureza Vicker • Módulo de elasticidad y su evolución con la temperatura • Límite elástico o resistencia a la flexión máxima, y su evolución con la temperatura • Resistencia a la fractura y su comportamiento con la temperatura. • Análisis microestructural • Análisis fractográfico • Análisis de la relación microestructura-comportamiento macroscópico. El estudio comienza con una introducción acerca de los sistemas en los que estos materiales son candidatos para su aplicación, para comprender las condiciones a las que los materiales serán expuestos. En este caso, el componente que determina las condiciones es el Divertor del reactor de energía de fusión por confinamiento magnético. Parece obvio que su uso en los componentes del reactor de fusión, más exactamente como materiales de cara al plasma (Plasma Facing Components o PFC), hace que estas aleaciones trabajen bajo condiciones de irradiación de neutrones. Además, el hecho de que sean materiales nuevos hace necesario un estudio previo de las características básicas que garantice los requisitos mínimos antes de realizar un estudio más complejo. Esto constituye la principal motivación de la presente investigación. La actual crisis energética ha llevado a aunar esfuerzos en el desarrollo de nuevos materiales, técnicas y dispositivos para la aplicación en la industria de la energía nuclear. El desarrollo de las técnicas de producción de aleaciones de wolframio, con un punto de fusión muy alto, requiere el uso de precursores de sinterizado para lograr densificaciones más altas y por lo tanto mejores propiedades mecánicas. Este es el propósito de la adición de titanio y vanadio en estas aleaciones. Sin embargo, uno de los principales problemas de la utilización de wolframio como material estructural es su alta temperatura de transición dúctil-frágil. Esta temperatura es característica de materiales metálicos con estructura cúbica centrada en el cuerpo y depende de varios factores metalúrgicos. El proceso de recristalización aumenta esta temperatura de transición. Los PFC tienen temperaturas muy altas de servicio, lo que facilita la recristalización del metal. Con el fin de retrasar este proceso, se dispersan partículas insolubles en el material permitiendo temperaturas de servicio más altas. Hasta ahora se ha utilizado óxidos de torio, lantano e itrio como partículas dispersas. Para entender cómo los contenidos en algunos elementos y partículas de óxido afectan a las propiedades de wolframio se estudian las aleaciones binarias de wolframio en comparación con el wolframio puro. A su vez estas aleaciones binarias se utilizan como material de referencia para entender el comportamiento de las aleaciones ternarias. Dada la estrecha relación entre las propiedades del material, la estructura y proceso de fabricación, el estudio se completa con un análisis fractográfico y micrográfico. El análisis fractográfico puede mostrar los mecanismos que están implicados en el proceso de fractura del material. Por otro lado, el estudio micrográfico ayudará a entender este comportamiento a través de la identificación de las posibles fases presentes. La medida del tamaño de grano es una parte de la caracterización microestructural. En esta investigación, la medida del tamaño de grano se llevó a cabo por ataque químico selectivo para revelar el límite de grano en las muestras preparadas. Posteriormente las micrografías fueron sometidas a tratamiento y análisis de imágenes. El documento termina con una discusión de los resultados y la compilación de las conclusiones más importantes que se alcanzan después del estudio. Actualmente, el desarrollo de nuevos materiales para aplicación en los componentes de cara al plasma continúa. El estudio de estos materiales ayudará a completar una base de datos de características que permita hacer una selección de ellos más fiable. The main goal of this dissertation is the mechanical characterization as a function of temperature of nine tungsten alloys containing different amounts of titanium, vanadium and yttrium and lanthanum oxide. The alloys under study were the following ones: W-0.5%Y2O3, W-2%Ti, W-2% Ti-0.5% Y2O3, W-4% Ti-0.5% Y2O3, W-2%V, W- 2%Vmix, W-4%V, W-1%La2O3 and W-4%V-1%La2O3. All of them, besides pure tungsten, were manufactured using a Hot Isostatic Pressing (HIP) process and they were supplied by the Universidad Carlos III de Madrid. The research was carried out through a systematic study based on physical and mechanical tests as well as the post mortem analysis of tested samples. Diverse mechanical tests were applied to perform this characterization; most of them were conducted at temperatures in the range 25-1000 ºC. The following characterization tests were performed: • Density • Vickers hardness • Elastic modulus • Yield strength or ultimate bending strength, and their evolution with temperature • Fracture toughness and its temperature behavior • Microstructural analysis • Fractographical analysis • Microstructure-macroscopic relationship analysis This study begins with an introduction regarding the systems where these materials could be applied, in order to establish and understand their service conditions. In this case, the component that defines the conditions is the Divertor of magnetic-confinement fusion reactors. It seems obvious that their use as fusion reactor components, more exactly as plasma facing components (PFCs), makes these alloys work under conditions of neutron irradiation. In addition to this, the fact that they are novel materials demands a preliminary study of the basic characteristics which will guarantee their minimum requirements prior to a more complex study. This constitutes the motivation of the present research. The current energy crisis has driven to join forces so as to develop new materials, techniques and devices for their application in the nuclear energy industry. The development of production techniques for tungsten-based alloys, with a very high melting point, requires the use of precursors for sintering to achieve higher densifications and, accordingly, better mechanical properties. This is the purpose of the addition of titanium and vanadium to these alloys. Nevertheless, one of the main problems of using tungsten as structural material is its high ductile-brittle transition temperature. This temperature is characteristic of metallic materials with body centered cubic structure and depends on several metallurgical factors. The recrystallization process increases their transition temperature. Since PFCs have a very high service temperature, this facilitates the metal recrystallization. In order to inhibit this process, insoluble particles are dispersed in the material allowing higher service temperatures. So far, oxides of thorium, lanthanum and yttrium have been used as dispersed particles. Tungsten binary alloys are studied in comparison with pure tungsten to understand how the contents of some elements and oxide particles affect tungsten properties. In turn, these binary alloys are used as reference materials to understand the behavior of ternary alloys. Given the close relationship between the material properties, structure and manufacturing process, this research is completed with a fractographical and micrographic analysis. The fractographical analysis is aimed to show the mechanisms that are involved in the process of the material fracture. Besides, the micrographic study will help to understand this behavior through the identification of present phases. The grain size measurement is a crucial part of the microstructural characterization. In this work, the measurement of grain size was carried out by chemical selective etching to reveal the boundary grain on prepared samples. Afterwards, micrographs were subjected to both treatment and image analysis. The dissertation ends with a discussion of results and the compilation of the most important conclusions reached through this work. The development of new materials for plasma facing components application is still under study. The analysis of these materials will help to complete a database of the features that will allow a more reliable materials selection.

Influencia de las restricciones medioambientales en el sector eléctrico

El objetivo de esta tesis es la caracterización de la generación térmica representativa de la existente en la realidad, para posteriormente proceder a su modelización y simulación integrándolas en una red eléctrica tipo y llevar a cabo estudios de optimización multiobjetivo económico medioambiental. Para ello, en primera instancia se analiza el contexto energético y eléctrico actual, y más concretamente el peninsular, en el que habiendo desaparecido las centrales de fuelóleo, sólo quedan ciclos combinados y centrales de carbón de distinto rango. Seguidamente se lleva a cabo un análisis de los principales impactos medioambientales de las centrales eléctricas basadas en combustión, representados sobre todo por sus emisiones de CO2, SO2 y NOx, de las medidas de control y mitigación de las mismas y de la normativa que les aplica. A continuación, a partir de las características de los combustibles y de la información de los consumos específicos, se caracterizan los grupos térmicos frente a las funciones relevantes que definen su comportamiento energético, económico y medioambiental, en términos de funciones de salida horarias dependiendo de la carga. Se tiene en cuenta la posibilidad de desnitrificación y desulfuración. Dado que las funciones objetivo son múltiples, y que están en conflicto unas con otras, se ha optado por usar métodos multiobjetivo que son capaces de identificar el contorno de puntos óptimos o frente de Pareto, en los que tomando una solución no existe otra que lo mejore en alguna de las funciones objetivo sin empeorarlo en otra. Se analizaron varios métodos de optimización multiobjetivo y se seleccionó el de las ε constraint, capaz de encontrar frentes no convexos y cuya optimalidad estricta se puede comprobar. Se integró una representación equilibrada de centrales de antracita, hulla nacional e importada, lignito y ciclos combinados en la red tipo IEEE-57, en la que se puede trabajar con siete centrales sin distorsionar demasiado las potencias nominales reales de los grupos, y se programó en Matlab la resolución de flujos óptimos de carga en alterna con el método multiobjetivo integrado. Se identifican los frentes de Pareto de las combinaciones de coste y cada uno de los tres tipos de emisión, y también el de los cuatro objetivos juntos, obteniendo los resultados de costes óptimos del sistema para todo el rango de emisiones. Se valora cuánto le cuesta al sistema reducir una tonelada adicional de cualquier tipo de emisión a base de desplazarse a combinaciones de generación más limpias. Los puntos encontrados aseguran que bajo unas determinadas emisiones no pueden ser mejorados económicamente, o que atendiendo a ese coste no se puede reducir más allá el sistema en lo relativo a emisiones. También se indica cómo usar los frentes de Pareto para trazar estrategias óptimas de producción ante cambios horarios de carga. ABSTRACT The aim of this thesis is the characterization of electrical generation based on combustion processes representative of the actual power plants, for the latter modelling and simulation of an electrical grid and the development of economic- environmental multiobjective optimization studies. In this line, the first step taken is the analysis of the current energetic and electrical framework, focused on the peninsular one, where the fuel power plants have been shut down, and the only ones remaining are coal units of different types and combined cycle. Then it is carried out an analysis of the main environmental impacts of the thermal power plants, represented basically by the emissions of CO2, SO2 y NOx, their control and reduction measures and the applicable regulations. Next, based on the combustibles properties and the information about the units heat rates, the different power plants are characterized in relation to the outstanding functions that define their energy, economic and environmental behaviour, in terms of hourly output functions depending on their load. Optional denitrification and desulfurization is considered. Given that there are multiple objectives, and that they go in conflictive directions, it has been decided the use of multiobjective techniques, that have the ability of identifying the optimal points set, which is called the Pareto front, where taken a solution there will be no other point that can beat the former in an objective without worsening it in another objective. Several multiobjective optimization methods were analysed and pondered, selecting the ε constraint technique, which is able to find no convex fronts and it is opened to be tested to prove the strict Pareto optimality of the obtained solutions. A balanced representation of the thermal power plants, formed by anthracite, lignite, bituminous national and imported coals and combined cycle, was integrated in the IEEE-57 network case. This system was selected because it deals with a total power that will admit seven units without distorting significantly the actual size of the power plants. Next, an AC optimal power flow with the multiobjective method implemented in the routines was programmed. The Pareto fronts of the combination of operative costs with each of the three emissions functions were found, and also the front of all of them together. The optimal production costs of the system for all the emissions range were obtained. It is also evaluated the cost of reducing an additional emission ton of any of the emissions when the optimal production mix is displaced towards cleaner points. The obtained solutions assure that under a determined level of emissions they cannot be improved economically or, in the other way, at a determined cost it cannot be found points of lesser emissions. The Pareto fronts are also applied for the search of optimal strategic paths to follow the hourly load changes.

Synthesis Report on the Impact of Capital Use. Factor Markets Working Document No. 57, August 2013

This paper examines the drivers of productivity in EU agriculture from a factor markets perspective. Using econometrically estimated production elasticities and shadow prices of factors for a set of eight EU member states, we focus on field crop farms represented in the FADN database for the years 2002-08. As it turned out that output reacts most elastically to materials input, we investigate this factor further and find different rationing regimes represented in different member states. Marginal return on materials is low in Denmark and West Germany, but significantly above typical market interest rates in East Germany, Italy and Spain. In the latter countries and in Denmark it also increased towards the end of the observed period. This finding is consistent with a perception of tightening funding access, possibly induced or reinforced by the unfolding financial crisis. Marginal returns to land, labour and fixed capital are generally low. We conclude that the functioning of factor markets plays a crucial role for productivity growth, but that factor market operations display considerable heterogeneity across EU member states.

Rare earth element geochemistry of Late Devonian reefal carbonates, canning basin, Western Australia: Confirmation of a seawater REE proxy in ancient limestones

Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd-SN/Yb-SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd-SN/Yb-SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modem seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans. Copyright (C) 2004 Elsevier Ltd.

Effect of body position on transient evoked accoustic emissions: The clinical perspective

The present study investigated body position effects on transient evoked otoacoustic emission (TEOAE) recordings of clinical significance. Sixty adults (30 males, 30 females) were assessed using the Otodynamics ILO88 Analyzer in three positions (sitting, supine, and side-lying). Results indicated significant positional effects on the TEOAE parameters of A-B difference, noise, whole wave reproducibility, and response levels. These differences included higher noise levels in supine and side-lying positions in comparison to the upright sitting position. Lower whole wave reproducibility measurements, and higher response amplitudes, in the side-lying position compared with supine and seated positions were also observed. No significant effects were evident for signal-to-noise ratio or band reproducibility. Given the lack of significant body position effects on these latter parameters and the infrequent clinical use of the other parameters in isolation, there was no evidence to suggest the future need for major review of current pass/fail criteria or of the standard test protocol.

Direct quantification of rare earth element concentrations in natural waters by ICP-MS

A direct quadrupole ICP-MS technique has been developed for the analysis of the rare earth elements and yttrium in natural waters. The method has been validated by comparison of the results obtained for the river water reference material SLRS-4 with literature values. The detection limit of the technique was investigated by analysis of serial dilutions of SLRS-4 and revealed that single elements can be quantified at single-digit fg/g concentrations. A coherent normalised rare earth pattern was retained at concentrations two orders of magnitude below natural concentrations for SLRS-4, demonstrating the excellent inter-element accuracy and precision of the method. The technique was applied to the analysis of a diluted mid-salinity estuarine sample, which also displayed a coherent normalised rare earth element pattern, yielding the expected distinctive marine characteristics. (c) 2006 Published by Elsevier Ltd.