Spin polarised Heusler compounds

In der vorliegenden Dissertation dient ein einfaches Konzept zur Systematisierung der Suche nach neuen Materialien mit hoher Spinpolarisation. Dieses Konzept basiert auf zwei semi-empirischen Modellen. Zum einen kann die Slater-Pauling Regel zur Abschätzung magnetischer Momente verwendet werden. Dieses Modell wird dabei durch Rechnungen zur elektronischen Struktur unterstützt. Das zweites Modell kann insbesondere für die Co2YZ Heusler Verbindungen beim Vergleich ihrer magnetischen Eigenschaften gefunden werden. Für diese Verbindungen ergibt sich eine scheinbare lineare Abhängigkeit der Curie-Temperatur beim Auftragen als Funktion des magnetischen Momentes. Angeregt durch diese Modelle wurde die Heusler Verbindung Co2FeSi nochmals detailliert im Hinblick auf ihre geometrische und magnetische Struktur hin untersucht. Als Methoden dienten dabei die Pulver-Röntgenbeugung, die EXAFS Spektroskopie, Röntgen Absorptions- and Mößbauer Spektroskopie sowie Hoch- und Tieftemperatur Magnetometrie, XMCD and DSC. Die Messungen zeigten, dass es sich bei Co2FeSi um das Material mit dem höchsten magnetischen Moment (6 B) und der höchsten Curie Temperatur (1100 K) sowohl in der Klasse der Heusler Verbindungen als auch in der Klasse der halbmetallischen Ferromagnete handelt. Zusätzlich werden alle experimentellen Ergebnisse durch detaillierte Rechnungen zur elektronischen Struktur unterstützt. Die gleichen Konzepte wurden verwendet, um die Eigenschaften der Heusler Verbindung Co2Cr1-xFexAl vorherzusagen. Die elektronische Struktur und die spektroskopischen Eigenschaften wurden mit der voll-relativistischen Korringa-Kohn-Rostocker Methode berechnet, unter Verwendung kohärenter Potentialnäherungen um der zufälligen Verteilung von Cr und Fe Atomen sowie zufälliger Unordnung Rechnung zu tragen. Magnetische Effekte wurden durch die Verwendung Spin-abhängiger Potentiale im Rahmen der lokalen Spin-Dichte-Näherung mit eingeschlossen. Die strukturellen und chemischen Eigenschaften der quaternären Heusler Verbindung Co2Cr1-xFexAl wurden an Pulver und Bulkproben gemessen. Die Fernordnung wurde mit der Pulver Röntgenbeugung und Neutronenbeugung untersucht, während die Nahordnung mit der EXAFS Spektroskopie aufgeklärt wurde. Die magnetische Struktur von Pulver und Bulkproben wurde mitttels 57Fe-Mößbauer Spektroskopie gemessen. Die chemische Zusammensetzung wurde durch XPS analysiert. Die Ergebnisse dieser Methoden wurden verglichen, um eine Einsicht in die Unterschiede zwischen Oberflächen und Volumeneigenschaften zu erlangen sowie in das Auftreten von Fehlordnung in solchen Verbindungen. Zusätzlich wurde XMCD an den L3,2 Kanten von Co, Fe, and Cr gemessen, um die elementspezifischen magnetischen Momente zu bestimmen. Rechnungen und Messungen zeigen dabei eine Zunahme des magnetischen Momentes bei steigendem Fe-Anteil. Resonante Photoemission mit weicher Röntgenstrahlung sowie Hochenergie Photoemission mit harter Röntgenstrahlung wurden verwendet, um die Zustandsdichte der besetzten Zustände in Co2Cr0.6Fe0.4Al zu untersuchen. Diese Arbeit stellt außerdem eine weitere, neue Verbindung aus der Klasse der Heusler Verbindungen vor. Co2CrIn ist L21 geordnet, wie Messungen mittels Pulver Röntgenbeugung zeigen. Die magnetischen Eigenschaften wurden mit magnetometrisch bestimmt. Co2CrIn ist weichmagnetisch mit einer Sättigungsmagnetisierung von 1.2B bei 5 K. Im Gegensatz zu den bereits oben erwähnten Co2YZ Heusler Verbindungen ist Co2CrIn kein halbmetallischer Ferromagnet. Im Rahmen dieser Arbeit wird weiterhin eine Regel zur Vorhersage von halbmetallischen komplett kompensierten Ferrimagneten in der Klasse der Heusler Verbindungen vorgestellt. Dieses Konzept resultiert aus der Kombination der Slater-Pauling Regel mit der Kübler-Regel. Die Kübler Regel besagt, dass Mn auf der Y Position zu einem hoch lokalisierten magnetischen Moment tendiert. Unter Verwendung dieses neuen Konzeptes werden für einige Kandidaten in der Klasse der Heusler Verbindungen die Eigenschaft des halbmetallischen komplett kompensierten Ferrimagnetismus vorhergesagt. Die Anwendung dieses Konzeptes wird anhand von Rechnungen zur elektronischen Struktur bestätigt.

Ab initio quantum mechanical investigation of structural and chemical-physical properties of selected minerals for minero-petrological, structural ceramic and biomaterial applications

The purpose of this thesis is the atomic-scale simulation of the crystal-chemical and physical (phonon, energetic) properties of some strategically important minerals for structural ceramics, biomedical and petrological applications. These properties affect the thermodynamic stability and rule the mineral-environment interface phenomena, with important economical, (bio)technological, petrological and environmental implications. The minerals of interest belong to the family of phyllosilicates (talc, pyrophyllite and muscovite) and apatite (OHAp), chosen for their importance in industrial and biomedical applications (structural ceramics) and petrophysics. In this thesis work we have applicated quantum mechanics methods, formulas and knowledge to the resolution of mineralogical problems ("Quantum Mineralogy”). The chosen theoretical approach is the Density Functional Theory (DFT), along with periodic boundary conditions to limit the portion of the mineral in analysis to the crystallographic cell and the hybrid functional B3LYP. The crystalline orbitals were simulated by linear combination of Gaussian functions (GTO). The dispersive forces, which are important for the structural determination of phyllosilicates and not properly con-sidered in pure DFT method, have been included by means of a semi-empirical correction. The phonon and the mechanical properties were also calculated. The equation of state, both in athermal conditions and in a wide temperature range, has been obtained by means of variations in the volume of the cell and quasi-harmonic approximation. Some thermo-chemical properties of the minerals (isochoric and isobaric thermal capacity) were calculated, because of their considerable applicative importance. For the first time three-dimensional charts related to these properties at different pressures and temperatures were provided. The hydroxylapatite has been studied from the standpoint of structural and phonon properties for its biotechnological role. In fact, biological apatite represents the inorganic phase of vertebrate hard tissues. Numerous carbonated (hydroxyl)apatite structures were modelled by QM to cover the broadest spectrum of possible biological structural variations to fulfil bioceramics applications.

Anwendungen von Rezeptoren auf Triphenylenketal-Basis

Im Rahmen dieser Arbeit wurde die Bindung von Koffein und verwandten Oxopurinen in C¬3-symmetrischen Rezeptoren auf der Basis von Triphenylenketalen untersucht. Dabei stand vor allem die Evaluierung für eine spätere Anwendung im Vordergrund. Für die Anwendung als Chemosensor wurden mehrere optische Verfahren getestet. Die Verwendung von UV/Vis-Spektroskopie gelingt nur unter Einsatz eines elektronenarmen Konkurrenzgastes, welcher durch das stärker bindende Koffein unter Entfärbung verdrängt wird. Obwohl dieser Effekt sogar mit bloßem Auge zu erkennen ist und somit eine einfache Untersuchung ermöglichen würde, machen die besondere Reaktivität des Konkurrenzgastes und dessen geringe Affinität zum Rezeptor eine weitere Anwendung als Chemosensor für Koffein unwahrscheinlich. Den entscheidenden Durchbruch lieferte der Wechsel auf Fluoreszenzspektroskopie. Die Bindung von Gästen lässt sich mit dieser Methode direkt beobachten und für quantitative Studien nutzen. Die Signalzunahme bei Zugabe von Koffein liegt bei maximal 30%. Durch Verwendung eines vom Koffein abgeleiteten Konkurrenzgastes können weitere Verbesserungen erzielt werden. So konnte eine maximale Signaldynamik von fast 400% erzielt werden. Durch die Entwicklung eines geeigneten Probenvorbereitungsprotokolls war es möglich, mit dem fluoreszenzbasierten System einen Nachweis von Koffein an kommerziell verfügbaren Getränkeproben durchzuführen. Die Ergebnisse waren in guter Übereinstimmung mit HPLC-Kontrollexperimenten. Die Eignung von Rezeptoren auf Triphenylenketalbasis für die enantiofaciale Differenzierung an Heteroaromaten wurde durch Untersuchung verschiedener Wirt-Gast-Komplexe mittels CD-Spektroskopie und Tieftemperatur-NMR systematisch demonstriert. Rezeptoren mit Menthyl-Substituenten liefern laut NMR die stärkste Seitendifferenzierung. Anhand des CD wird ein vollständiges und schlüssiges Bild über den Zusammenhang zwischen dem Raumbedarf am Gast, der Ausrichtung der chiralen Gruppen am Wirt und dem erhaltenen CD hergestellt. Durch umfangreiche molekulardynamische Simulationen und nachfolgende semiempirische Berechnungen wurden Referenzspektren berechnet, welche die Zuordnung der Stereochemie anhand des CD eindeutig belegen. Die Ergebnisse sind zudem in guter Übereinstimmung mit den Ergebnissen aus röntgenkristallographischen Untersuchungen. (Diese Methode ließ sich erfolgreich auf die helicale Faltung von Alkanen in Kapseln von Rebek, jr. umsetzen.) Obwohl die Energieunterschiede zwischen den diastereomeren Komplexen klein sind, konnte anhand der CD-Spektroskopie somit erstmalig die enantiofaciale Differenzierung an einem heterocyclischen System bei Raumtemperatur beobachtet werden. Die beste enantiofaciale Differenzierung erzielen die Menthyl-abgeleiteten Rezeptoren. Diese sind hinsichtlich einer möglichen Anwendung als chirales „Auxiliar“ ungeeignet, da sie mit den sperrigen Cyclohexylgruppen auch den Raum oberhalb des gebundenen Gastes blockieren. Daher wird für die weitere Entwicklung auf die praktische Einführung chiraler Information in Form des Isocyanats verzichten werden müssen. Stattdessen zielen aktuelle Bemühungen auf den Aufbau chiraler Rückgrate, welche den Raum in der unteren Peripherie des Gastes beeinflussen.

Global and regional sea level variations in the recent past and future: insight from observations and modeling

This work is focused on the analysis of sea–level change (last century), based mainly on instrumental observations. During this period, individual components of sea–level change are investigated, both at global and regional scales. Some of the geophysical processes responsible for current sea-level change such as glacial isostatic adjustments and current melting terrestrial ice sources, have been modeled and compared with observations. A new value of global mean sea level change based of tide gauges observations has been independently assessed in 1.5 mm/year, using corrections for glacial isostatic adjustment obtained with different models as a criterion for the tide gauge selection. The long wavelength spatial variability of the main components of sea–level change has been investigated by means of traditional and new spectral methods. Complex non–linear trends and abrupt sea–level variations shown by tide gauges records have been addressed applying different approaches to regional case studies. The Ensemble Empirical Mode Decomposition technique has been used to analyse tide gauges records from the Adriatic Sea to ascertain the existence of cyclic sea-level variations. An Early Warning approach have been adopted to detect tipping points in sea–level records of North East Pacific and their relationship with oceanic modes. Global sea–level projections to year 2100 have been obtained by a semi-empirical approach based on the artificial neural network method. In addition, a model-based approach has been applied to the case of the Mediterranean Sea, obtaining sea-level projection to year 2050.

Car, parce que, puisque’ revisited: Three empirical studies on French causal connectives

In French, a causal relation is often conveyed by the connectives car, parce que or puisque. Since the seminal work of the Lambda-l Group (1975), it has generally been assumed that parce que, used to relate semantic content, contrasts with car and puisque, both used to connect either speech act or epistemic content. However, this analysis leaves a number of questions unanswered. In this paper, I present a reanalysis of this trio, using empirical methods such as corpus analysis and constrained elicitation. Results indicate that car and parce que are interchangeable in many contexts, even if they are still prototypically used in their respective domain in writing. As for puisque, its distribution does not overlap with car, despite their similar domains of use. I argue that the specificity of puisque with respect to the other two connectives is to introduce a cause with an echoic meaning.

A Semi-Lagrangian Particle Level Set Finite Element Method for Interface Problems

We present a quasi-monotone semi-Lagrangian particle level set (QMSL-PLS) method for moving interfaces. The QMSL method is a blend of first order monotone and second order semi-Lagrangian methods. The QMSL-PLS method is easy to implement, efficient, and well adapted for unstructured, either simplicial or hexahedral, meshes. We prove that it is unconditionally stable in the maximum discrete norm, � · �h,∞, and the error analysis shows that when the level set solution u(t) is in the Sobolev space Wr+1,∞(D), r ≥ 0, the convergence in the maximum norm is of the form (KT/Δt)min(1,Δt � v �h,∞ /h)((1 − α)hp + hq), p = min(2, r + 1), and q = min(3, r + 1),where v is a velocity. This means that at high CFL numbers, that is, when Δt > h, the error is O( (1−α)hp+hq) Δt ), whereas at CFL numbers less than 1, the error is O((1 − α)hp−1 + hq−1)). We have tested our method with satisfactory results in benchmark problems such as the Zalesak’s slotted disk, the single vortex flow, and the rising bubble.

Análisis comparativo y nuevas estimaciones de las tasas de rebase en obras marítimas en grandes profundidades

El rebase se define como el transporte de una cantidad importante de agua sobre la coronación de una estructura. Por tanto, es el fenómeno que, en general, determina la cota de coronación del dique dependiendo de la cantidad aceptable del mismo, a la vista de condicionantes funcionales y estructurales del dique. En general, la cantidad de rebase que puede tolerar un dique de abrigo desde el punto de vista de su integridad estructural es muy superior a la cantidad permisible desde el punto de vista de su funcionalidad. Por otro lado, el diseño de un dique con una probabilidad de rebase demasiado baja o nula conduciría a diseños incompatibles con consideraciones de otro tipo, como son las estéticas o las económicas. Existen distintas formas de estudiar el rebase producido por el oleaje sobre los espaldones de las obras marítimas. Las más habituales son los ensayos en modelo físico y las formulaciones empíricas o semi-empíricas. Las menos habituales son la instrumentación en prototipo, las redes neuronales y los modelos numéricos. Los ensayos en modelo físico son la herramienta más precisa y fiable para el estudio específico de cada caso, debido a la complejidad del proceso de rebase, con multitud de fenómenos físicos y parámetros involucrados. Los modelos físicos permiten conocer el comportamiento hidráulico y estructural del dique, identificando posibles fallos en el proyecto antes de su ejecución, evaluando diversas alternativas y todo esto con el consiguiente ahorro en costes de construcción mediante la aportación de mejoras al diseño inicial de la estructura. Sin embargo, presentan algunos inconvenientes derivados de los márgenes de error asociados a los ”efectos de escala y de modelo”. Las formulaciones empíricas o semi-empíricas presentan el inconveniente de que su uso está limitado por la aplicabilidad de las fórmulas, ya que éstas sólo son válidas para una casuística de condiciones ambientales y tipologías estructurales limitadas al rango de lo reproducido en los ensayos. El objetivo de la presente Tesis Doctoral es el contrate de las formulaciones desarrolladas por diferentes autores en materia de rebase en distintas tipologías de diques de abrigo. Para ello, se ha realizado en primer lugar la recopilación y el análisis de las formulaciones existentes para estimar la tasa de rebase sobre diques en talud y verticales. Posteriormente, se llevó a cabo el contraste de dichas formulaciones con los resultados obtenidos en una serie de ensayos realizados en el Centro de Estudios de Puertos y Costas. Para finalizar, se aplicó a los ensayos de diques en talud seleccionados la herramienta neuronal NN-OVERTOPPING2, desarrollada en el proyecto europeo de rebases CLASH (“Crest Level Assessment of Coastal Structures by Full Scale Monitoring, Neural Network Prediction and Hazard Analysis on Permissible Wave Overtopping”), contrastando de este modo la tasa de rebase obtenida en los ensayos con este otro método basado en la teoría de las redes neuronales. Posteriormente, se analizó la influencia del viento en el rebase. Para ello se han realizado una serie de ensayos en modelo físico a escala reducida, generando oleaje con y sin viento, sobre la sección vertical del Dique de Levante de Málaga. Finalmente, se presenta el análisis crítico del contraste de cada una de las formulaciones aplicadas a los ensayos seleccionados, que conduce a las conclusiones obtenidas en la presente Tesis Doctoral. Overtopping is defined as the volume of water surpassing the crest of a breakwater and reaching the sheltered area. This phenomenon determines the breakwater’s crest level, depending on the volume of water admissible at the rear because of the sheltered area’s functional and structural conditioning factors. The ways to assess overtopping processes range from those deemed to be most traditional, such as semi-empirical or empirical type equations and physical, reduced scale model tests, to others less usual such as the instrumentation of actual breakwaters (prototypes), artificial neural networks and numerical models. Determining overtopping in reduced scale physical model tests is simple but the values obtained are affected to a greater or lesser degree by the effects of a scale model-prototype such that it can only be considered as an approximation to what actually happens. Nevertheless, physical models are considered to be highly useful for estimating damage that may occur in the area sheltered by the breakwater. Therefore, although physical models present certain problems fundamentally deriving from scale effects, they are still the most accurate, reliable tool for the specific study of each case, especially when large sized models are adopted and wind is generated Empirical expressions obtained from laboratory tests have been developed for calculating the overtopping rate and, therefore, the formulas obtained obviously depend not only on environmental conditions – wave height, wave period and water level – but also on the model’s characteristics and are only applicable in a range of validity of the tests performed in each case. The purpose of this Thesis is to make a comparative analysis of methods for calculating overtopping rates developed by different authors for harbour breakwater overtopping. First, existing equations were compiled and analysed in order to estimate the overtopping rate on sloping and vertical breakwaters. These equations were then compared with the results obtained in a number of tests performed in the Centre for Port and Coastal Studies of the CEDEX. In addition, a neural network model developed in the European CLASH Project (“Crest Level Assessment of Coastal Structures by Full Scale Monitoring, Neural Network Prediction and Hazard Analysis on Permissible Wave Overtopping“) was also tested. Finally, the wind effects on overtopping are evaluated using tests performed with and without wind in the physical model of the Levante Breakwater (Málaga).

Modelo computacional para avaliação do desempenho hidrodinâmico de embarcações de planeio em águas calmas.

Em geral, uma embarcação de planeio é projetada para atingir elevados níveis de velocidade. Esse atributo de desempenho está diretamente relacionado ao porte da embarcação e à potência instalada em sua planta propulsiva. Tradicionalmente, durante o projeto de uma embarcação, as análises de desempenho são realizadas através de resultados de embarcações já existentes, retirados de séries sistemáticas ou de embarcações já desenvolvidas pelo estaleiro e/ou projetista. Além disso, a determinação dos atributos de desempenho pode ser feita através de métodos empíricos e/ou estatísticos, onde a embarcação é representada através de seus parâmetros geométricos principais; ou a partir de testes em modelos em escala reduzida ou protótipos. No caso específico de embarcações de planeio, o custo dos testes em escala reduzida é muito elevado em relação ao custo de projeto. Isso faz com que a maioria dos projetistas não opte por ensaios experimentais das novas embarcações em desenvolvimento. Ao longo dos últimos anos, o método de Savitsky foi largamente utilizado para se realizar estimativas de potência instalada de uma embarcação de planeio. Esse método utiliza um conjunto de equações semi-empíricas para determinar os esforços atuantes na embarcação, a partir dos quais é possível determinar a posição de equilíbrio de operação e a força propulsora necessária para navegar em uma dada velocidade. O método de Savitsky é muito utilizado nas fases iniciais de projeto, onde a geometria do casco ainda não foi totalmente definida, pois utiliza apenas as características geométricas principais da embarcação para realização das estimativas de esforços. À medida que se avança nas etapas de projeto, aumenta o detalhamento necessário das estimativas de desempenho. Para a realização, por exemplo, do projeto estrutural é necessária uma estimativa do campo de pressão atuante no fundo do casco, o qual não pode ser determinado pelo método de Savitsky. O método computacional implementado nesta dissertação, tem o objetivo de determinar as características do escoamento e o campo de pressão atuante no casco de uma embarcação de planeio navegando em águas calmas. O escoamento é determinado através de um problema de valor de contorno, no qual a superfície molhada no casco é considerada um corpo esbelto. Devido ao uso da teoria de corpo esbelto o problema pode ser tratado, separadamente, em cada seção, onde as condições de contorno são forçadamente respeitadas através de uma distribuição de vórtices.

Testing a new Free Core Nutation empirical model

The Free Core Nutation (FCN) is a free mode of the Earth's rotation caused by the different material characteristics of the Earth's core and mantle. This causes the rotational axes of those layers to slightly diverge from each other, resulting in a wobble of the Earth's rotation axis comparable to nutations. In this paper we focus on estimating empirical FCN models using the observed nutations derived from the VLBI sessions between 1993 and 2013. Assuming a fixed value for the oscillation period, the time-variable amplitudes and phases are estimated by means of multiple sliding window analyses. The effects of using different a priori Earth Rotation Parameters (ERP) in the derivation of models are also addressed. The optimal choice of the fundamental parameters of the model, namely the window width and step-size of its shift, is searched by performing a thorough experimental analysis using real data. The former analyses lead to the derivation of a model with a temporal resolution higher than the one used in the models currently available, with a sliding window reduced to 400 days and a day-by-day shift. It is shown that this new model increases the accuracy of the modeling of the observed Earth's rotation. Besides, empirical models determined from USNO Finals as a priori ERP present a slightly lower Weighted Root Mean Square (WRMS) of residuals than IERS 08 C04 along the whole period of VLBI observations, according to our computations. The model is also validated through comparisons with other recognized models. The level of agreement among them is satisfactory. Let us remark that our estimates give rise to the lowest residuals and seem to reproduce the FCN signal in more detail.

The use of maturity models in improving project management performance:an empirical investigation

Purpose – The purpose of the paper was to conduct an empirical investigation to explore the impact of project management maturity models (PMMMs) on improving project performance. Design/methodology/approach – The investigation used a cross-case analysis involving over 90 individuals in seven organisations. Findings – The findings of the empirical investigation indicate that PMMMs demonstrate very high levels of variability in individual's assessment of project management maturity. Furthermore, at higher levels of maturity, the type of performance improvement adopted following their application is related to the type of PMMM used in the assessment. The paradox of the unreliability of PMMMs and their widespread acceptance is resolved by calling upon the “wisdom of crowds” phenomenon which has implications for the use of maturity model assessments in other arena. Research limitations/implications – The investigation does have the usual issues associated with case research, but the steps that have been taken in the cross-case construction and analysis have improved the overall robustness and extendibility of the findings. Practical implications – The tendency for PMMMs to shape improvements based on their own inherent structure needs further understanding. Originality/value – The use of empirical methods to investigate the link between project maturity models and extant changes in project management performance is highly novel and the findings that result from this have added resonance.

An Overview of Modelling Bulgarian Wildland Fire Behaviour by Application of a Mathematical Game Method and WRF-Fire Models

This paper presents the main achievements of the author’s PhD dissertation. The work is dedicated to mathematical and semi-empirical approaches applied to the case of Bulgarian wildland fires. After the introductory explanations, short information from every chapter is extracted to cover the main parts of the obtained results. The methods used are described in brief and main outcomes are listed. ACM Computing Classification System (1998): D.1.3, D.2.0, K.5.1.

Az árfolyamsávok empirikus modelljei és a devizaárfolyam sávon belüli előrejelezhetetlensége = Empirical models of exchange rate target zones

A sávosan rögzített devizaárfolyamok elméleti és gyakorlati vizsgálatai a nemzetközi közgazdaságtan egyik legnépszerűbb témaköre volt a kilencvenes évek elején. A gyakorlati módszerek közül az alkalmazások és hivatkozások száma tekintetében az úgynevezett eltolódással igazítás módszere emelkedett ki. A módszert alkalmazó szerzők szerint amíg a lebegő árfolyamú devizák előrejelzése céltalan feladatnak tűnik, addig sávos árfolyam esetén az árfolyam sávon belüli helyzetének előrejelzése sikeresen végezhető. E tanulmány bemutatja, hogy az Európai Monetáris Rendszer és az északeurópai államok sávos árfolyamrendszereinél e módszer alkalmazásával adódott eredmények például a lebegő árfolyamú amerikai dollárra és az egységgyökfolyamatok többségére is érvényesek. A tanulmány feltárja e látszólagos ellentmondás okait, és bemutat egy olyan, a sávos árfolyamrendszerek főbb megfigyelt jellemzőire épülő modellt, amelynek keretei között a sávon belüli árfolyam előrejelzése nem feltétlenül lehetséges, mert a leértékelés előtti időszakban a sávon belüli árfolyam alakulása kaotikus lehet. / === / Following the development of the first exchange rate target zone model at the end of the eighties dozens of papers analyzed theoretical and empirical topics of currency bands. This paper reviews different empirical methods to analyze the credibility of the band and lays special emphasis on the most widely used method, the so-called drift-adjustment method. Papers applying that method claim that while forecasting a freely floating currency is hopeless, predicting an exchange rate within the future band is successful. This paper shows that the results achieved by applications to EMS and Nordic currencies are not specific to data of target zone currencies. For example, application to US dollar and even to most unit root processes leads qualitatively to the same. This paper explores the solutions of this puzzle and shows a model of target zones in which the exchange rate within the band is not necessarily predictable since the process might follow chaotic dynamics before devaluation.

Estudo da previsão da carga de ruptura de estacas pré-moldadas de concreto

The piles are one of the most important types of solution adopted for the foundation of buildings. They are responsible for transmitting to the soil in deepe r and resistant layers loads from structures. The interaction of the foundation element with the soil is a very important variable, making indispensable your domain in order to determine the strength of the assembly and establish design criteria for each c ase of application of the pile. In this research analyzes were performed f rom experiments load tests for precast concrete piles and inve stigations of soil of type SPT, a study was performed for obtaining the ultimate load capacity of the foundation through methods extrapolation of load - settlement curve , semi - empirical and theoretic . After that, were realized comparisons between the different methods used for two types of soil a granular behavior and other cohesive. For obtaining soil paramet ers to be used i n the methods were established empirical correlations with the standard penetration number (NSPT). The charge - settlement curves of the piles are also analyzed. In the face of established comparisons was indicated the most reliable semiempirical method Déco urt - Quaresma as the most reliable for estimating the tensile strength for granular and cohesive soils. Meanwhile, among the methods studied extrapolation is recommended method of Van der Veen as the most appropriate for predicting the tensile strength.

Dimensionamento de uma estrutura de contenção de terras flexível com vários níveis de apoio

O presente trabalho, no âmbito de projeto final de curso de metrado em Engenharia da Construção, teve como objetivo o estudo do comportamento de estruturas de suporte de terras flexíveis multi-apoiadas (com diferentes tipos de apoio) para dois tipos solos homogéneos. Recorreu-se às teorias clássicas, como a de Rankine, desenvolvidas para estruturas de suporte de terras rígidas. Às teorias semi-empíricas de Terzaghi & Peck que culminaram nos diagramas de Terzaghi & Peck. Apesar de os digramas de Terzaghi & Peck serem diagramas de pressões de terras a usar em estruturas de suporte de terras flexíveis, apresentam algumas limitações importantes, como a sua aplicação apenas em solos heterogéneos, com presença ou não de níveis freáticos, e sem fornecer distribuição das pressões de terras na zona passiva (zona enterrada). Como na atualidade os modelos de elementos finitos permitem simular de modo muito mais rigoroso os problemas da engenharia. O presente trabalho esteve focado em analisar um caso prático em diferentes solos e com diferentes tipos de apoios. Será estudado mediante os métodos analíticos usando as teorias clássicas e posteriormente métodos numéricos (com diferentes programas de cálculo). Finalmente serão comparados os resultados obtidos mediante os diferentes métodos usados. As estruturas foram inicialmente pré-dimensionadas usando os métodos clássicos. Assim foram usados os diagramas de pressões de terras de Terzaghi & Peck para a zona ativa (zona em escavação) e a teoria de Rankine para conhecer as pressões de terras na zona enterrada da cortina (parede moldada) e recorrendo ao software Ftool para a obtenção dos parâmetros de dimensionamento de estruturas de suporte de terras objeto de estudo. Posteriormente utilizaram-se os programas de cálculo automático CYPE 2015 k, e o programa de cálculo de elementos finitos PLAXIS Introductory 2010. Estes programas permitem simular o faseamento construtivo do muro. Para estudar a influência de algúns parâmetros no comportamento da Resumo IV cortina o estudo foi realizado com dois solos distintos, um solo argiloso mole e um solo arenoso denso. Assim como para dois tipos de apoios distintos, ancoragens ativas e escoras passivas. Foram analisados diferentes parâmetros na estrutura de suporte; pressões horizontais das terras, deslocamentos horizontais, esforço axial, transverso e momento fletor.

Estudo teórico da interação existente entre a artemisinina e o heme

The purpose of this work is to study theoretically stereoelectronic aspects of the interaction between heme and artemisinin in the transitional heme-artemisinin complex. Through semi-empirical calculations using the PM3 method, the potential energy barrier of artemisinin rotation relative to heme in the heme-artemisinin complex was studied in vacuum and in the partially solvated state. The minimum heat of formation obtained for the complex with and without water molecules is -702.39 and -100.86 kcal mol-1, respectively, which corresponds to the dihedral angle C-Fe-O1-O2 of 43.93º and 51.90º around the iron-oxygen O1 bond, respectively. The water molecules bind to heme via 13 hydrogen bonds and O-H O and 6 C-H O interactions, which accounts for -67.23 kcal mol-1. It is observed that the inclusion of water molecules does not affect significantly the stability of the heme-artemisinin complex.