A Bayesian approach to estimating the regression coefficients of a multinomial logit model

A Bayesian approach to estimation of the regression coefficients of a multinominal logit model with ordinal scale response categories is presented. A Monte Carlo method is used to construct the posterior distribution of the link function. The link function is treated as an arbitrary scalar function. Then the Gauss-Markov theorem is used to determine a function of the link which produces a random vector of coefficients. The posterior distribution of the random vector of coefficients is used to estimate the regression coefficients. The method described is referred to as a Bayesian generalized least square (BGLS) analysis. Two cases involving multinominal logit models are described. Case I involves a cumulative logit model and Case II involves a proportional-odds model. All inferences about the coefficients for both cases are described in terms of the posterior distribution of the regression coefficients. The results from the BGLS method are compared to maximum likelihood estimates of the regression coefficients. The BGLS method avoids the nonlinear problems encountered when estimating the regression coefficients of a generalized linear model. The method is not complex or computationally intensive. The BGLS method offers several advantages over Bayesian approaches. ^

Aplicación de Métodos Meshless al Análisis de Problemas de Autovalores

La presente Tesis Doctoral aborda la aplicación de métodos meshless, o métodos sin malla, a problemas de autovalores, fundamentalmente vibraciones libres y pandeo. En particular, el estudio se centra en aspectos tales como los procedimientos para la resolución numérica del problema de autovalores con estos métodos, el coste computacional y la viabilidad de la utilización de matrices de masa o matrices de rigidez geométrica no consistentes. Además, se acomete en detalle el análisis del error, con el objetivo de determinar sus principales fuentes y obtener claves que permitan la aceleración de la convergencia. Aunque en la actualidad existe una amplia variedad de métodos meshless en apariencia independientes entre sí, se han analizado las diferentes relaciones entre ellos, deduciéndose que el método Element-Free Galerkin Method [Método Galerkin Sin Elementos] (EFGM) es representativo de un amplio grupo de los mismos. Por ello se ha empleado como referencia en este análisis. Muchas de las fuentes de error de un método sin malla provienen de su algoritmo de interpolación o aproximación. En el caso del EFGM ese algoritmo es conocido como Moving Least Squares [Mínimos Cuadrados Móviles] (MLS), caso particular del Generalized Moving Least Squares [Mínimos Cuadrados Móviles Generalizados] (GMLS). La formulación de estos algoritmos indica que la precisión de los mismos se basa en los siguientes factores: orden de la base polinómica p(x), características de la función de peso w(x) y forma y tamaño del soporte de definición de esa función. Se ha analizado la contribución individual de cada factor mediante su reducción a un único parámetro cuantificable, así como las interacciones entre ellos tanto en distribuciones regulares de nodos como en irregulares. El estudio se extiende a una serie de problemas estructurales uni y bidimensionales de referencia, y tiene en cuenta el error no sólo en el cálculo de autovalores (frecuencias propias o carga de pandeo, según el caso), sino también en términos de autovectores. This Doctoral Thesis deals with the application of meshless methods to eigenvalue problems, particularly free vibrations and buckling. The analysis is focused on aspects such as the numerical solving of the problem, computational cost and the feasibility of the use of non-consistent mass or geometric stiffness matrices. Furthermore, the analysis of the error is also considered, with the aim of identifying its main sources and obtaining the key factors that enable a faster convergence of a given problem. Although currently a wide variety of apparently independent meshless methods can be found in the literature, the relationships among them have been analyzed. The outcome of this assessment is that all those methods can be grouped in only a limited amount of categories, and that the Element-Free Galerkin Method (EFGM) is representative of the most important one. Therefore, the EFGM has been selected as a reference for the numerical analyses. Many of the error sources of a meshless method are contributed by its interpolation/approximation algorithm. In the EFGM, such algorithm is known as Moving Least Squares (MLS), a particular case of the Generalized Moving Least Squares (GMLS). The accuracy of the MLS is based on the following factors: order of the polynomial basis p(x), features of the weight function w(x), and shape and size of the support domain of this weight function. The individual contribution of each of these factors, along with the interactions among them, has been studied in both regular and irregular arrangement of nodes, by means of a reduction of each contribution to a one single quantifiable parameter. This assessment is applied to a range of both one- and two-dimensional benchmarking cases, and includes not only the error in terms of eigenvalues (natural frequencies or buckling load), but also of eigenvectors

Theoretical Transition Probabilities, Oscillator Strengths and Radiative Lifetimes Of Levels In Pb IV

Transitionprobabilities and oscillatorstrengths of 176 spectral lines with astrophysical interest arising from 5d10ns (n = 7,8), 5d10np (n = 6,7), 5d10nd (n = 6,7), 5d105f, 5d105g, 5d10nh (n = 6,7,8), 5d96s2, and 5d96s6p configurations, and radiativelifetimes for 43 levels of PbIV, have been calculated. These values were obtained in intermediate coupling (IC) and using relativistic Hartree–Fock calculations including core-polarization effects. For the IC calculations, we use the standard method of least-square fitting from experimental energy levels by means of the Cowan computer code. The inclusion in these calculations of the 5d107p and 5d105f configurations has facilitated a complete assignment of the energy levels in the PbIV. Transitionprobabilities, oscillatorstrengths, and radiativelifetimes obtained are generally in good agreement with the experimental data.

A proposal for the metrological characterization of circular features with digital optical machines

This paper aims to analyze the different adjustment methods commonly used to characterize indirect metrology circular features: least square circle, minimum zone circle, maximum inscribed circle and minimum circumscribed circle. The analysis was performed from images obtained by digital optical machines. The calculation algorithms, self-developed, have been implemented in Matlab® and take into consideration as study variables: the amplitude of angular sector of the circular feature, its nominal radio and the magnification used by the optical machine. Under different conditions, it was determined the radius and circularity error of different circular standards. The comparison of the results, obtained by the different methods of adjustments used, with certified values for the standards, has allowed us to determine the accuracy of each method and its scope.

Bernstein polynomials in element-free Galerkin method

In the recent decades, meshless methods (MMs), like the element-free Galerkin method (EFGM), have been widely studied and interesting results have been reached when solving partial differential equations. However, such solutions show a problem around boundary conditions, where the accuracy is not adequately achieved. This is caused by the use of moving least squares or residual kernel particle method methods to obtain the shape functions needed in MM, since such methods are good enough in the inner of the integration domains, but not so accurate in boundaries. This way, Bernstein curves, which are a partition of unity themselves,can solve this problem with the same accuracy in the inner area of the domain and at their boundaries.

Discriminant Analysis of Geographical Origin of Cork Planks and Stoppers by Near Infrared Spectroscopy

The objective of this study was to assess the potential of visible and near infrared spectroscopy (VIS+NIRS) combined with multivariate analysis for identifying the geographical origin of cork. The study was carried out on cork planks and natural cork stoppers from the most representative cork-producing areas in the world. Two training sets of international and national cork planks were studied. The first set comprised a total of 479 samples from Morocco, Portugal, and Spain, while the second set comprised a total of 179 samples from the Spanish regions of Andalusia, Catalonia, and Extremadura. A training set of 90 cork stoppers from Andalusia and Catalonia was also studied. Original spectroscopic data were obtained for the transverse sections of the cork planks and for the body and top of the cork stoppers by means of a 6500 Foss-NIRSystems SY II spectrophotometer using a fiber optic probe. Remote reflectance was employed in the wavelength range of 400 to 2500 nm. After analyzing the spectroscopic data, discriminant models were obtained by means of partial least square (PLS) with 70% of the samples. The best models were then validated using 30% of the remaining samples. At least 98% of the international cork plank samples and 95% of the national samples were correctly classified in the calibration and validation stage. The best model for the cork stoppers was obtained for the top of the stoppers, with at least 90% of the samples being correctly classified. The results demonstrate the potential of VIS + NIRS technology as a rapid and accurate method for predicting the geographical origin of cork plank and stoppers

Un método de diferencias finitas generalizadas para simular la actividad eléctrica de un tejido cardiaco

Una evolución del método de diferencias finitas ha sido el desarrollo del método de diferencias finitas generalizadas (MDFG) que se puede aplicar a mallas irregulares o nubes de puntos. En este método se emplea una expansión en serie de Taylor junto con una aproximación por mínimos cuadrados móviles (MCM). De ese modo, las fórmulas explícitas de diferencias para nubes irregulares de puntos se pueden obtener fácilmente usando el método de Cholesky. El MDFG-MCM es un método sin malla que emplea únicamente puntos. Una contribución de esta Tesis es la aplicación del MDFG-MCM al caso de la modelización de problemas anisótropos elípticos de conductividad eléctrica incluyendo el caso de tejidos reales cuando la dirección de las fibras no es fija, sino que varía a lo largo del tejido. En esta Tesis también se muestra la extensión del método de diferencias finitas generalizadas a la solución explícita de ecuaciones parabólicas anisótropas. El método explícito incluye la formulación de un límite de estabilidad para el caso de nubes irregulares de nodos que es fácilmente calculable. Además se presenta una nueva solución analítica para una ecuación parabólica anisótropa y el MDFG-MCM explícito se aplica al caso de problemas parabólicos anisótropos de conductividad eléctrica. La evidente dificultad de realizar mediciones directas en electrocardiología ha motivado un gran interés en la simulación numérica de modelos cardiacos. La contribución más importante de esta Tesis es la aplicación de un esquema explícito con el MDFG-MCM al caso de la modelización monodominio de problemas de conductividad eléctrica. En esta Tesis presentamos un algoritmo altamente eficiente, exacto y condicionalmente estable para resolver el modelo monodominio, que describe la actividad eléctrica del corazón. El modelo consiste en una ecuación en derivadas parciales parabólica anisótropa (EDP) que está acoplada con un sistema de ecuaciones diferenciales ordinarias (EDOs) que describen las reacciones electroquímicas en las células cardiacas. El sistema resultante es difícil de resolver numéricamente debido a su complejidad. Proponemos un método basado en una separación de operadores y un método sin malla para resolver la EDP junto a un método de Runge-Kutta para resolver el sistema de EDOs de la membrana y las corrientes iónicas. ABSTRACT An evolution of the method of finite differences has been the development of generalized finite difference (GFD) method that can be applied to irregular grids or clouds of points. In this method a Taylor series expansion is used together with a moving least squares (MLS) approximation. Then, the explicit difference formulae for irregular clouds of points can be easily obtained using a simple Cholesky method. The MLS-GFD is a mesh-free method using only points. A contribution of this Thesis is the application of the MLS-GFDM to the case of modelling elliptic anisotropic electrical conductivity problems including the case of real tissues when the fiber direction is not fixed, but varies throughout the tissue. In this Thesis the extension of the generalized finite difference method to the explicit solution of parabolic anisotropic equations is also given. The explicit method includes a stability limit formulated for the case of irregular clouds of nodes that can be easily calculated. Also a new analytical solution for homogeneous parabolic anisotropic equation has been presented and an explicit MLS- GFDM has been applied to the case of parabolic anisotropic electrical conductivity problems. The obvious difficulty of performing direct measurements in electrocardiology has motivated wide interest in the numerical simulation of cardiac models. The main contribution of this Thesis is the application of an explicit scheme based in the MLS-GFDM to the case of modelling monodomain electrical conductivity problems using operator splitting including the case of anisotropic real tissues. In this Thesis we present a highly efficient, accurate and conditionally stable algorithm to solve a monodomain model, which describes the electrical activity in the heart. The model consists of a parabolic anisotropic partial differential equation (PDE), which is coupled to systems of ordinary differential equations (ODEs) describing electrochemical reactions in the cardiac cells. The resulting system is challenging to solve numerically, because of its complexity. We propose a method based on operator splitting and a meshless method for solving the PDE together with a Runge-Kutta method for solving the system of ODE’s for the membrane and ionic currents.

Determinación de un modelo de geoide gravimétrico para Puerto Rico como sistema de referencia para las altitudes ortométricas

El geoide, definido como la superficie equipotencial que mejor se ajusta (en el sentido de los mínimos cuadrados) al nivel medio del mar en una determinada época, es la superficie que utilizamos como referencia para determinar las altitudes ortométricas. Si disponemos de una superficie equipotencial de referencia como dátum altimétrico preciso o geoide local, podemos entonces determinar las altitudes ortométricas de forma eficiente a partir de las altitudes elipsoidales proporcionadas por el Sistema Global de Navegación por Satélite (Global Navigation Satellite System, GNSS ). Como es sabido uno de los problemas no resueltos de la geodesia (quizás el más importante de los mismos en la actualidad) es la carencia de un dátum altimétrico global (Sjoberg, 2011) con las precisiones adecuadas. Al no existir un dátum altimétrico global que nos permita obtener los valores absolutos de la ondulación del geoide con la precisión requerida, es necesario emplear modelos geopotenciales como alternativa. Recientemente fue publicado el modelo EGM2008 en el que ha habido una notable mejoría de sus tres fuentes de datos, por lo que este modelo contiene coeficientes adicionales hasta el grado 2190 y orden 2159 y supone una sustancial mejora en la precisión (Pavlis et al., 2008). Cuando en una región determinada se dispone de valores de gravedad y Modelos Digitales del Terreno (MDT) de calidad, es posible obtener modelos de superficies geopotenciales más precisos y de mayor resolución que los modelos globales. Si bien es cierto que el Servicio Nacional Geodésico de los Estados Unidos de América (National Geodetic Survey, NGS) ha estado desarrollando modelos del geoide para la región de los Estados Unidos de América continentales y todos sus territorios desde la década de los noventa, también es cierto que las zonas de Puerto Rico y las Islas Vírgenes Estadounidenses han quedado un poco rezagadas al momento de poder aplicar y obtener resultados de mayor precisión con estos modelos regionales del geoide. En la actualidad, el modelo geopotencial regional vigente para la zona de Puerto Rico y las Islas Vírgenes Estadounidenses es el GEOID12A (Roman y Weston, 2012). Dada la necesidad y ante la incertidumbre de saber cuál sería el comportamiento de un modelo del geoide desarrollado única y exclusivamente con datos de gravedad locales, nos hemos dado a la tarea de desarrollar un modelo de geoide gravimétrico como sistema de referencia para las altitudes ortométricas. Para desarrollar un modelo del geoide gravimétrico en la isla de Puerto Rico, fue necesario implementar una metodología que nos permitiera analizar y validar los datos de gravedad terrestre existentes. Utilizando validación por altimetría con sistemas de información geográfica y validación matemática por colocación con el programa Gravsoft (Tscherning et al., 1994) en su modalidad en Python (Nielsen et al., 2012), fue posible validar 1673 datos de anomalías aire libre de un total de 1894 observaciones obtenidas de la base de datos del Bureau Gravimétrico Internacional (BGI). El aplicar estas metodologías nos permitió obtener una base de datos anomalías de la gravedad fiable la cual puede ser utilizada para una gran cantidad de aplicaciones en ciencia e ingeniería. Ante la poca densidad de datos de gravedad existentes, fue necesario emplear un método alternativo para densificar los valores de anomalías aire libre existentes. Empleando una metodología propuesta por Jekeli et al. (2009b) se procedió a determinar anomalías aire libre a partir de los datos de un MDT. Estas anomalías fueron ajustadas utilizando las anomalías aire libre validadas y tras aplicar un ajuste de mínimos cuadrados por zonas geográficas, fue posible obtener una malla de datos de anomalías aire libre uniforme a partir de un MDT. Tras realizar las correcciones topográficas, determinar el efecto indirecto de la topografía del terreno y la contribución del modelo geopotencial EGM2008, se obtuvo una malla de anomalías residuales. Estas anomalías residuales fueron utilizadas para determinar el geoide gravimétrico utilizando varias técnicas entre las que se encuentran la aproximación plana de la función de Stokes y las modificaciones al núcleo de Stokes, propuestas por Wong y Gore (1969), Vanicek y Kleusberg (1987) y Featherstone et al. (1998). Ya determinados los distintos modelos del geoide gravimétrico, fue necesario validar los mismos y para eso se utilizaron una serie de estaciones permanentes de la red de nivelación del Datum Vertical de Puerto Rico de 2002 (Puerto Rico Vertical Datum 2002, PRVD02 ), las cuales tenían publicados sus valores de altitud elipsoidal y elevación. Ante la ausencia de altitudes ortométricas en las estaciones permanentes de la red de nivelación, se utilizaron las elevaciones obtenidas a partir de nivelación de primer orden para determinar los valores de la ondulación del geoide geométrico (Roman et al., 2013). Tras establecer un total de 990 líneas base, se realizaron dos análisis para determinar la 'precisión' de los modelos del geoide. En el primer análisis, que consistió en analizar las diferencias entre los incrementos de la ondulación del geoide geométrico y los incrementos de la ondulación del geoide de los distintos modelos (modelos gravimétricos, EGM2008 y GEOID12A) en función de las distancias entre las estaciones de validación, se encontró que el modelo con la modificación del núcleo de Stokes propuesta por Wong y Gore presentó la mejor 'precisión' en un 91,1% de los tramos analizados. En un segundo análisis, en el que se consideraron las 990 líneas base, se determinaron las diferencias entre los incrementos de la ondulación del geoide geométrico y los incrementos de la ondulación del geoide de los distintos modelos (modelos gravimétricos, EGM2008 y GEOID12A), encontrando que el modelo que presenta la mayor 'precisión' también era el geoide con la modificación del núcleo de Stokes propuesta por Wong y Gore. En este análisis, el modelo del geoide gravimétrico de Wong y Gore presento una 'precisión' de 0,027 metros en comparación con la 'precisión' del modelo EGM2008 que fue de 0,031 metros mientras que la 'precisión' del modelo regional GEOID12A fue de 0,057 metros. Finalmente podemos decir que la metodología aquí presentada es una adecuada ya que fue posible obtener un modelo del geoide gravimétrico que presenta una mayor 'precisión' que los modelos geopotenciales disponibles, incluso superando la precisión del modelo geopotencial global EGM2008. ABSTRACT The geoid, defined as the equipotential surface that best fits (in the least squares sense) to the mean sea level at a particular time, is the surface used as a reference to determine the orthometric heights. If we have an equipotential reference surface or a precise local geoid, we can then determine the orthometric heights efficiently from the ellipsoidal heights, provided by the Global Navigation Satellite System (GNSS). One of the most common and important an unsolved problem in geodesy is the lack of a global altimetric datum (Sjoberg, 2011)) with the appropriate precision. In the absence of one which allows us to obtain the absolute values of the geoid undulation with the required precision, it is necessary to use alternative geopotential models. The EGM2008 was recently published, in which there has been a marked improvement of its three data sources, so this model contains additional coefficients of degree up to 2190 and order 2159, and there is a substantial improvement in accuracy (Pavlis et al., 2008). When a given region has gravity values and high quality digital terrain models (DTM), it is possible to obtain more accurate regional geopotential models, with a higher resolution and precision, than global geopotential models. It is true that the National Geodetic Survey of the United States of America (NGS) has been developing geoid models for the region of the continental United States of America and its territories from the nineties, but which is also true is that areas such as Puerto Rico and the U.S. Virgin Islands have lagged behind when to apply and get more accurate results with these regional geopotential models. Right now, the available geopotential model for Puerto Rico and the U.S. Virgin Islands is the GEOID12A (Roman y Weston, 2012). Given this need and given the uncertainty of knowing the behavior of a regional geoid model developed exclusively with data from local gravity, we have taken on the task of developing a gravimetric geoid model to use as a reference system for orthometric heights. To develop a gravimetric geoid model in the island of Puerto Rico, implementing a methodology that allows us to analyze and validate the existing terrestrial gravity data is a must. Using altimetry validation with GIS and mathematical validation by collocation with the Gravsoft suite programs (Tscherning et al., 1994) in its Python version (Nielsen et al., 2012), it was possible to validate 1673 observations with gravity anomalies values out of a total of 1894 observations obtained from the International Bureau Gravimetric (BGI ) database. Applying these methodologies allowed us to obtain a database of reliable gravity anomalies, which can be used for many applications in science and engineering. Given the low density of existing gravity data, it was necessary to employ an alternative method for densifying the existing gravity anomalies set. Employing the methodology proposed by Jekeli et al. (2009b) we proceeded to determine gravity anomaly data from a DTM. These anomalies were adjusted by using the validated free-air gravity anomalies and, after that, applying the best fit in the least-square sense by geographical area, it was possible to obtain a uniform grid of free-air anomalies obtained from a DTM. After applying the topographic corrections, determining the indirect effect of topography and the contribution of the global geopotential model EGM2008, a grid of residual anomalies was obtained. These residual anomalies were used to determine the gravimetric geoid by using various techniques, among which are the planar approximation of the Stokes function and the modifications of the Stokes kernel, proposed by Wong y Gore (1969), Vanicek y Kleusberg (1987) and Featherstone et al. (1998). After determining the different gravimetric geoid models, it was necessary to validate them by using a series of stations of the Puerto Rico Vertical Datum of 2002 (PRVD02) leveling network. These stations had published its values of ellipsoidal height and elevation, and in the absence of orthometric heights, we use the elevations obtained from first - order leveling to determine the geometric geoid undulation (Roman et al., 2013). After determine a total of 990 baselines, two analyzes were performed to determine the ' accuracy ' of the geoid models. The first analysis was to analyze the differences between the increments of the geometric geoid undulation with the increments of the geoid undulation of the different geoid models (gravimetric models, EGM2008 and GEOID12A) in function of the distance between the validation stations. Through this analysis, it was determined that the model with the modified Stokes kernel given by Wong and Gore had the best 'accuracy' in 91,1% for the analyzed baselines. In the second analysis, in which we considered the 990 baselines, we analyze the differences between the increments of the geometric geoid undulation with the increments of the geoid undulation of the different geoid models (gravimetric models, EGM2008 and GEOID12A) finding that the model with the highest 'accuracy' was also the model with modifying Stokes kernel given by Wong and Gore. In this analysis, the Wong and Gore gravimetric geoid model presented an 'accuracy' of 0,027 meters in comparison with the 'accuracy' of global geopotential model EGM2008, which gave us an 'accuracy' of 0,031 meters, while the 'accuracy ' of the GEOID12A regional model was 0,057 meters. Finally we can say that the methodology presented here is adequate as it was possible to obtain a gravimetric geoid model that has a greater 'accuracy' than the geopotential models available, even surpassing the accuracy of global geopotential model EGM2008.

Development of a methodology for nuclear data uncertainty propagation on isotopic evolution calculations for advanced nuclear systems

Una apropiada evaluación de los márgenes de seguridad de una instalación nuclear, por ejemplo, una central nuclear, tiene en cuenta todas las incertidumbres que afectan a los cálculos de diseño, funcionanmiento y respuesta ante accidentes de dicha instalación. Una fuente de incertidumbre son los datos nucleares, que afectan a los cálculos neutrónicos, de quemado de combustible o activación de materiales. Estos cálculos permiten la evaluación de las funciones respuesta esenciales para el funcionamiento correcto durante operación, y también durante accidente. Ejemplos de esas respuestas son el factor de multiplicación neutrónica o el calor residual después del disparo del reactor. Por tanto, es necesario evaluar el impacto de dichas incertidumbres en estos cálculos. Para poder realizar los cálculos de propagación de incertidumbres, es necesario implementar metodologías que sean capaces de evaluar el impacto de las incertidumbres de estos datos nucleares. Pero también es necesario conocer los datos de incertidumbres disponibles para ser capaces de manejarlos. Actualmente, se están invirtiendo grandes esfuerzos en mejorar la capacidad de analizar, manejar y producir datos de incertidumbres, en especial para isótopos importantes en reactores avanzados. A su vez, nuevos programas/códigos están siendo desarrollados e implementados para poder usar dichos datos y analizar su impacto. Todos estos puntos son parte de los objetivos del proyecto europeo ANDES, el cual ha dado el marco de trabajo para el desarrollo de esta tesis doctoral. Por tanto, primero se ha llevado a cabo una revisión del estado del arte de los datos nucleares y sus incertidumbres, centrándose en los tres tipos de datos: de decaimiento, de rendimientos de fisión y de secciones eficaces. A su vez, se ha realizado una revisión del estado del arte de las metodologías para la propagación de incertidumbre de estos datos nucleares. Dentro del Departamento de Ingeniería Nuclear (DIN) se propuso una metodología para la propagación de incertidumbres en cálculos de evolución isotópica, el Método Híbrido. Esta metodología se ha tomado como punto de partida para esta tesis, implementando y desarrollando dicha metodología, así como extendiendo sus capacidades. Se han analizado sus ventajas, inconvenientes y limitaciones. El Método Híbrido se utiliza en conjunto con el código de evolución isotópica ACAB, y se basa en el muestreo por Monte Carlo de los datos nucleares con incertidumbre. En esta metodología, se presentan diferentes aproximaciones según la estructura de grupos de energía de las secciones eficaces: en un grupo, en un grupo con muestreo correlacionado y en multigrupos. Se han desarrollado diferentes secuencias para usar distintas librerías de datos nucleares almacenadas en diferentes formatos: ENDF-6 (para las librerías evaluadas), COVERX (para las librerías en multigrupos de SCALE) y EAF (para las librerías de activación). Gracias a la revisión del estado del arte de los datos nucleares de los rendimientos de fisión se ha identificado la falta de una información sobre sus incertidumbres, en concreto, de matrices de covarianza completas. Además, visto el renovado interés por parte de la comunidad internacional, a través del grupo de trabajo internacional de cooperación para evaluación de datos nucleares (WPEC) dedicado a la evaluación de las necesidades de mejora de datos nucleares mediante el subgrupo 37 (SG37), se ha llevado a cabo una revisión de las metodologías para generar datos de covarianza. Se ha seleccionando la actualización Bayesiana/GLS para su implementación, y de esta forma, dar una respuesta a dicha falta de matrices completas para rendimientos de fisión. Una vez que el Método Híbrido ha sido implementado, desarrollado y extendido, junto con la capacidad de generar matrices de covarianza completas para los rendimientos de fisión, se han estudiado diferentes aplicaciones nucleares. Primero, se estudia el calor residual tras un pulso de fisión, debido a su importancia para cualquier evento después de la parada/disparo del reactor. Además, se trata de un ejercicio claro para ver la importancia de las incertidumbres de datos de decaimiento y de rendimientos de fisión junto con las nuevas matrices completas de covarianza. Se han estudiado dos ciclos de combustible de reactores avanzados: el de la instalación europea para transmutación industrial (EFIT) y el del reactor rápido de sodio europeo (ESFR), en los cuales se han analizado el impacto de las incertidumbres de los datos nucleares en la composición isotópica, calor residual y radiotoxicidad. Se han utilizado diferentes librerías de datos nucleares en los estudios antreriores, comparando de esta forma el impacto de sus incertidumbres. A su vez, mediante dichos estudios, se han comparando las distintas aproximaciones del Método Híbrido y otras metodologías para la porpagación de incertidumbres de datos nucleares: Total Monte Carlo (TMC), desarrollada en NRG por A.J. Koning y D. Rochman, y NUDUNA, desarrollada en AREVA GmbH por O. Buss y A. Hoefer. Estas comparaciones demostrarán las ventajas del Método Híbrido, además de revelar sus limitaciones y su rango de aplicación. ABSTRACT For an adequate assessment of safety margins of nuclear facilities, e.g. nuclear power plants, it is necessary to consider all possible uncertainties that affect their design, performance and possible accidents. Nuclear data are a source of uncertainty that are involved in neutronics, fuel depletion and activation calculations. These calculations can predict critical response functions during operation and in the event of accident, such as decay heat and neutron multiplication factor. Thus, the impact of nuclear data uncertainties on these response functions needs to be addressed for a proper evaluation of the safety margins. Methodologies for performing uncertainty propagation calculations need to be implemented in order to analyse the impact of nuclear data uncertainties. Nevertheless, it is necessary to understand the current status of nuclear data and their uncertainties, in order to be able to handle this type of data. Great eórts are underway to enhance the European capability to analyse/process/produce covariance data, especially for isotopes which are of importance for advanced reactors. At the same time, new methodologies/codes are being developed and implemented for using and evaluating the impact of uncertainty data. These were the objectives of the European ANDES (Accurate Nuclear Data for nuclear Energy Sustainability) project, which provided a framework for the development of this PhD Thesis. Accordingly, first a review of the state-of-the-art of nuclear data and their uncertainties is conducted, focusing on the three kinds of data: decay, fission yields and cross sections. A review of the current methodologies for propagating nuclear data uncertainties is also performed. The Nuclear Engineering Department of UPM has proposed a methodology for propagating uncertainties in depletion calculations, the Hybrid Method, which has been taken as the starting point of this thesis. This methodology has been implemented, developed and extended, and its advantages, drawbacks and limitations have been analysed. It is used in conjunction with the ACAB depletion code, and is based on Monte Carlo sampling of variables with uncertainties. Different approaches are presented depending on cross section energy-structure: one-group, one-group with correlated sampling and multi-group. Differences and applicability criteria are presented. Sequences have been developed for using different nuclear data libraries in different storing-formats: ENDF-6 (for evaluated libraries) and COVERX (for multi-group libraries of SCALE), as well as EAF format (for activation libraries). A revision of the state-of-the-art of fission yield data shows inconsistencies in uncertainty data, specifically with regard to complete covariance matrices. Furthermore, the international community has expressed a renewed interest in the issue through the Working Party on International Nuclear Data Evaluation Co-operation (WPEC) with the Subgroup (SG37), which is dedicated to assessing the need to have complete nuclear data. This gives rise to this review of the state-of-the-art of methodologies for generating covariance data for fission yields. Bayesian/generalised least square (GLS) updating sequence has been selected and implemented to answer to this need. Once the Hybrid Method has been implemented, developed and extended, along with fission yield covariance generation capability, different applications are studied. The Fission Pulse Decay Heat problem is tackled first because of its importance during events after shutdown and because it is a clean exercise for showing the impact and importance of decay and fission yield data uncertainties in conjunction with the new covariance data. Two fuel cycles of advanced reactors are studied: the European Facility for Industrial Transmutation (EFIT) and the European Sodium Fast Reactor (ESFR), and response function uncertainties such as isotopic composition, decay heat and radiotoxicity are addressed. Different nuclear data libraries are used and compared. These applications serve as frameworks for comparing the different approaches of the Hybrid Method, and also for comparing with other methodologies: Total Monte Carlo (TMC), developed at NRG by A.J. Koning and D. Rochman, and NUDUNA, developed at AREVA GmbH by O. Buss and A. Hoefer. These comparisons reveal the advantages, limitations and the range of application of the Hybrid Method.

On the application of meshfree methods to the nonlinear dynamics of multibody systems

Esta tesis propone una completa formulación termo-mecánica para la simulación no-lineal de mecanismos flexibles basada en métodos libres de malla. El enfoque se basa en tres pilares principales: la formulación de Lagrangiano total para medios continuos, la discretización de Bubnov-Galerkin, y las funciones de forma libres de malla. Los métodos sin malla se caracterizan por la definición de un conjunto de funciones de forma en dominios solapados, junto con una malla de integración de las ecuaciones discretas de balance. Dos tipos de funciones de forma se han seleccionado como representación de las familias interpolantes (Funciones de Base Radial) y aproximantes (Mínimos Cuadrados Móviles). Su formulación se ha adaptado haciendo sus parámetros compatibles, y su ausencia de conectividad predefinida se ha aprovechado para interconectar múltiples dominios de manera automática, permitiendo el uso de mallas de fondo no conformes. Se propone una formulación generalizada de restricciones, juntas y contactos, válida para sólidos rígidos y flexibles, siendo estos últimos discretizados mediante elementos finitos (MEF) o libres de malla. La mayor ventaja de este enfoque reside en que independiza completamente el dominio con respecto de las uniones y acciones externas a cada sólido, permitiendo su definición incluso fuera del contorno. Al mismo tiempo, también se minimiza el número de ecuaciones de restricción necesarias para la definición de uniones realistas. Las diversas validaciones, ejemplos y comparaciones detalladas muestran como el enfoque propuesto es genérico y extensible a un gran número de sistemas. En concreto, las comparaciones con el MEF indican una importante reducción del error para igual número de nodos, tanto en simulaciones mecánicas, como térmicas y termo-mecánicas acopladas. A igualdad de error, la eficiencia numérica de los métodos libres de malla es mayor que la del MEF cuanto más grosera es la discretización. Finalmente, la formulación se aplica a un problema de diseño real sobre el mantenimiento de estructuras masivas en el interior de un reactor de fusión, demostrando su viabilidad en análisis de problemas reales, y a su vez mostrando su potencial para su uso en simulación en tiempo real de sistemas no-lineales. A new complete formulation is proposed for the simulation of nonlinear dynamic of multibody systems with thermo-mechanical behaviour. The approach is founded in three main pillars: total Lagrangian formulation, Bubnov-Galerkin discretization, and meshfree shape functions. Meshfree methods are characterized by the definition of a set of shape functions in overlapping domains, and a background grid for integration of the Galerkin discrete equations. Two different types of shape functions have been chosen as representatives of interpolation (Radial Basis Functions), and approximation (Moving Least Squares) families. Their formulation has been adapted to use compatible parameters, and their lack of predefined connectivity is used to interconnect different domains seamlessly, allowing the use of non-conforming meshes. A generalized formulation for constraints, joints, and contacts is proposed, which is valid for rigid and flexible solids, being the later discretized using either finite elements (FEM) or meshfree methods. The greatest advantage of this approach is that makes the domain completely independent of the external links and actions, allowing to even define them outside of the boundary. At the same time, the number of constraint equations needed for defining realistic joints is minimized. Validation, examples, and benchmarks are provided for the proposed formulation, demonstrating that the approach is generic and extensible to further problems. Comparisons with FEM show a much lower error for the same number of nodes, both for mechanical and thermal analyses. The numerical efficiency is also better when coarse discretizations are used. A final demonstration to a real problem for handling massive structures inside of a fusion reactor is presented. It demonstrates that the application of meshfree methods is feasible and can provide an advantage towards the definition of nonlinear real-time simulation models.

Determination of chromite composition from multispectral reflectance measurements (400-1000 nm)

The relationship between the chemical composition and the multispectral reflectance values of chromite in the VNIR (Visible and Near-Infra-Red) realm is tested and mathematically analysed. Statisticaltools as Pearson's correlation coefficients, linear stepwise regression analysis and least-square adjustments are applied to two populations of data obtained from 14 selected samples 01 chromite multielemental microprobe analysis and multispectral reflectance values (400-1 000 nm). Results show that both data sets correlate, and suggest that the VNIR reflectance spectra can be used as a tool to determine the chemical composition of chromites.

GESTÃO DO CONHECIMENTO: UM ESTUDO SOBRE A RELAÇÃO ENTRE A LIDERANÇA TRANSFORMACIONAL, A CONVERSÃO DO CONHECIMENTO E A EFICÁCIA ORGANIZACIONAL

Este estudo teve como objetivo principal analisar a relação entre a Liderança Transformacional, a Conversão do Conhecimento e a Eficácia Organizacional. Foram considerados como pressupostos teóricos conceitos consolidados sobre os temas desta relação, além de recentes pesquisas já realizadas em outros países e contextos organizacionais. Com base nisto identificou-se potencial estudo de um modelo que relacionasse estes três conceitos. Para tal considera-se que as organizações que buscam atingir Vantagem Competitiva e incorporam a Knowledge-Based View possam conquistar diferenciação frente a seus concorrentes. Nesse contexto o conhecimento ganha maior destaque e papel protagonista nestas organizações. Dessa forma criar conhecimento através de seus colaboradores, passa a ser um dos desafios dessas organizações ao passo que sugere melhoria de seus indicadores Econômicos, Sociais, Sistêmicos e Políticos, o que se define por Eficácia Organizacional. Portanto os modos de conversão do conhecimento nas organizações, demonstram relevância, uma vez que se cria e se converte conhecimentos através da interação entre o conhecimento existente de seus colaboradores. Essa conversão do conhecimento ou modelo SECI possui quatro modos que são a Socialização, Externalização, Combinação e Internalização. Nessa perspectiva a liderança nas organizações apresenta-se como um elemento capaz de influenciar seus colaboradores, propiciando maior dinâmica ao modelo SECI de conversão do conhecimento. Se identifica então na liderança do tipo Transformacional, características que possam influenciar colaboradores e entende-se que esta relação entre a Liderança Transformacional e a Conversão do Conhecimento possa ter influência positiva nos indicadores da Eficácia Organizacional. Dessa forma esta pesquisa buscou analisar um modelo que explorasse essa relação entre a liderança do tipo Transformacional, a Conversão do Conhecimento (SECI) e a Eficácia Organizacional. Esta pesquisa teve o caráter quantitativo com coleta de dados através do método survey, obtendo um total de 230 respondentes válidos de diferentes organizações. O instrumento de coleta de dados foi composto por afirmativas relativas ao modelo de relação pesquisado com um total de 44 itens. O perfil de respondentes concentrou-se entre 30 e 39 anos de idade, com a predominância de organizações privadas e de departamentos de TI/Telecom, Docência e Recursos Humanos respectivamente. O tratamento dos dados foi através da Análise Fatorial Exploratória e Modelagem de Equações Estruturais via Partial Least Square Path Modeling (PLS-PM). Como resultado da análise desta pesquisa, as hipóteses puderam ser confirmadas, concluindo que a Liderança Transformacional apresenta influência positiva nos modos de Conversão do Conhecimento e que; a Conversão do Conhecimento influencia positivamente na Eficácia Organizacional. Ainda, concluiu-se que a percepção entre os respondentes não apresenta resultado diferente sobre o modelo desta pesquisa entre quem possui ou não função de liderança.

Otimização termodinâmica do sistema binário Ti-Si.

A otimização de sistemas do tipo Ti-Si-X requer que os sistemas binários estejam constantemente atualizados. O sistema Ti-Si foi investigado experimentalmente desde a década de 50 e poucos estudos usaram os dados experimentais para calcular o diagrama de fases Ti-Si usando modelamento termodinâmico. A otimização mais recente do sistema Ti-Si foi realizada em 1998, descrevendo a fase Ti5Si3 como um intermetálico não estequiométrico contendo três sub-redes e mostrando a presença da fase intermetálica estequiométrica Ti3Si. Dada a recente disputa sobre a cinética de precipitação e a estabilidade das fases Ti3Si e Ti5Si3 nos sistemas Ti-Si e Ti-Si-X, o canto rico em titânio do sistema Ti-Si (estável e metaestável) foi otimizado no presente trabalho. Os limites de estabilidade de fases, os valores dos erros pelo método dos mínimos quadrados do procedimento de otimização e os desvios padrões relativos das variáveis calculadas foram discutidos para inspirar a realização de mais trabalhos experimentais para investigar as reações eutetóides estáveis e/ou metaestáveis, ?->? + Ti3Si e ?->? + + Ti5Si3; e para melhorar cada vez mais as otimizações termodinâmicas do diagrama de fases do sistema Ti-Si.

Real time optimization in chemical process: evaluation of strategies, improvements and industrial application.

The increasing economic competition drives the industry to implement tools that improve their processes efficiencies. The process automation is one of these tools, and the Real Time Optimization (RTO) is an automation methodology that considers economic aspects to update the process control in accordance with market prices and disturbances. Basically, RTO uses a steady-state phenomenological model to predict the process behavior, and then, optimizes an economic objective function subject to this model. Although largely implemented in industry, there is not a general agreement about the benefits of implementing RTO due to some limitations discussed in the present work: structural plant/model mismatch, identifiability issues and low frequency of set points update. Some alternative RTO approaches have been proposed in literature to handle the problem of structural plant/model mismatch. However, there is not a sensible comparison evaluating the scope and limitations of these RTO approaches under different aspects. For this reason, the classical two-step method is compared to more recently derivative-based methods (Modifier Adaptation, Integrated System Optimization and Parameter estimation, and Sufficient Conditions of Feasibility and Optimality) using a Monte Carlo methodology. The results of this comparison show that the classical RTO method is consistent, providing a model flexible enough to represent the process topology, a parameter estimation method appropriate to handle measurement noise characteristics and a method to improve the sample information quality. At each iteration, the RTO methodology updates some key parameter of the model, where it is possible to observe identifiability issues caused by lack of measurements and measurement noise, resulting in bad prediction ability. Therefore, four different parameter estimation approaches (Rotational Discrimination, Automatic Selection and Parameter estimation, Reparametrization via Differential Geometry and classical nonlinear Least Square) are evaluated with respect to their prediction accuracy, robustness and speed. The results show that the Rotational Discrimination method is the most suitable to be implemented in a RTO framework, since it requires less a priori information, it is simple to be implemented and avoid the overfitting caused by the Least Square method. The third RTO drawback discussed in the present thesis is the low frequency of set points update, this problem increases the period in which the process operates at suboptimum conditions. An alternative to handle this problem is proposed in this thesis, by integrating the classic RTO and Self-Optimizing control (SOC) using a new Model Predictive Control strategy. The new approach demonstrates that it is possible to reduce the problem of low frequency of set points updates, improving the economic performance. Finally, the practical aspects of the RTO implementation are carried out in an industrial case study, a Vapor Recompression Distillation (VRD) process located in Paulínea refinery from Petrobras. The conclusions of this study suggest that the model parameters are successfully estimated by the Rotational Discrimination method; the RTO is able to improve the process profit in about 3%, equivalent to 2 million dollars per year; and the integration of SOC and RTO may be an interesting control alternative for the VRD process.

Dissolved organic carbon in sediments of the central Arctic Ocean collected during POLARSTERN cruise ARK-XXVII/3 from August-September 2012

Marine organic matter (OM) sinks from surface waters to the seafloor via the biological pump. Benthic communities, which use this sedimented OM as energy and carbon source, produce dissolved organic matter (DOM) in the process of remineralization, enriching the sediment porewater with fresh DOM compounds. We hypothesized that in the oligotrophic deep Arctic basin the molecular signal of freshly deposited primary produced OM is restricted to the surface sediment pore waters which should differ from bottom water and deeper sediment pore water in DOM composition. This study focused on: 1) the molecular composition of the DOM in sediment pore waters of the deep Eurasian Arctic basins, 2) whether the signal of marine vs. terrigenous DOM is represented by different compounds preserved in the sediment pore waters and 3) whether there is any relation between Arctic Ocean ice cover and DOM composition. Molecular data, obtained via 15 Tesla Fourier transform ion cyclotron resonance mass spectrometer, were correlated with environmental parameters by partial least square analysis. The fresher marine detrital OM signal from surface waters was limited to pore waters from < 5 cm sediment depth. The productive ice margin stations showed higher abundances of peptides, unsaturated aliphatics and saturated fatty acids formulae, indicative of fresh OM/pigments deposition, compared to northernmost stations which had stronger aromatic signals. This study contributes to the understanding of the coupling between the Arctic Ocean productivity and its depositional regime, and how it will be altered in response to sea ice retreat and increasing river runoff.