This thesis is largely a study of the ADOR process (assembly-disassembly-organisation-reassembly) when applied to zeolite UTL. The final chapter of this thesis deals with the adsorption of the medical gases NO and CO onto the metal organic framework NiNaSIP. Chapter 4 is devoted to the disassembly and organisation steps of the ADOR process. Calcined UTL was hydrolysed using 0.1 – 12 M HCl solutions from 75 – 95 °C run over 10 mins to 72 hrs. A three step mechanism is proposed, which is comprised of an initial rapid hydrolysis that removes the majority of the interlayer constituents of UTL, causing the silica-rich layers to largely collapse. This is followed by a slow, temperature and molarity dependent, deintercalation process that sees the remainder of the interlayer material removed resulting in the full collapse of the layers to form IPC-1P. The third step is a temperature and molarity dependent rebuilding process, whereby the interlayer region is slowly rebuilt, eventually forming a precursor which upon calcination becomes IPC-2 (OKO). Chapter 5 uses the pair distribution function (PDF) technique to structurally confirm the intermediate of the ADORable zeolite UTL. The intermediate, IPC-1P, is a disordered layered compound formed by the hydrolysis of UTL in 0.1 M HCl. Its structure is unsolvable by traditional X-ray diffraction techniques. The PDF technique was first benchmarked against high-quality synchrotron Rietveld refinements of IPC-2 (OKO) and IPC-4 (PCR) – two end products of IPC-1P condensation that share very similar structural features. An IPC-1P starting model derived from density functional theory was used for the PDF refinement, which yielded a final fit of Rw = 18% and a geometrically reasonable structure. This confirms that the layers do stay intact throughout the ADOR process, and shows that PDF is a viable technique for layered zeolite structure determination. Chapter 6 examines the reassembly stage by following the in-situ calcination of a variety of hydrolysed intermediates into their three-dimensional counterparts. Beamline I11 at Diamond Light Source provided high-quality PXRD patterns as a function of temperature, which were refined against using sequential Pawley refinements to track the unit cell changes. 0.1, 1.75, 2.5 and 12 M hydrolysed lamellar precursor phases were calcined. The largest unit cell changes were observed for 0.1 M, and the smallest for 12 M. This shows that increasing the molarity must prebuild most of the interlayer connections, such that upon calcination, only minimal condensation occurs to fully connect the layers. Chapter 7 probes the uptake of the medical gases CO and NO into the metal organic framework NiNaSIP. An in-situ single-crystal XRD study was undertaken using an environmental gas cell at beamline 11.3.1 at the Advanced Light Source. NiNaSIP was first dehydrated to reveal an open nickel site, which acted as the main site of adsorption for the inputted gases. NO was observed in a bent geometry at an occupancy of 40 % and a Ni – N bond length of 2.166(16) Å. The oxygen was modelled to be disordered over two sites. CO was not fully observed, as only the carbon was able to be modelled with an occupancy of 31.2 % and a Ni – C bond length of 2.27(3) Å.

Os controladores eletrônicos de pulverização visam minimizar a variação das taxas de insumos aplicadas no campo. Eles fazem parte de um sistema de controle, e permitem a compensação da variação de velocidade de deslocamento do pulverizador durante a operação. Há vários tipos de controladores eletrônicos de pulverização disponíveis no mercado e uma das formas de selecionar qual o mais eficiente nas mesmas condições, ou seja, em um mesmo sistema de controle, é quantificar o tempo de resposta do sistema para cada controlador específico. O objetivo desse trabalho foi estimar os tempos de resposta para mudanças de velocidade de um sistema eletrônico de pulverização via modelos de regressão não lineares, estes, resultantes da soma de regressões lineares ponderadas por funções distribuição acumulada. Os dados foram obtidos no Laboratório de Tecnologia de Aplicação, localizado no Departamento de Engenharia de Biossistemas da Escola Superior de Agricultura \"Luiz de Queiroz\", Universidade de São Paulo, no município de Piracicaba, São Paulo, Brasil. Os modelos utilizados foram o logístico e de Gompertz, que resultam de uma soma ponderada de duas regressões lineares constantes com peso dado pela função distribuição acumulada logística e Gumbell, respectivamente. Reparametrizações foram propostas para inclusão do tempo de resposta do sistema de controle nos modelos, com o objetivo de melhorar a interpretação e inferência estatística dos mesmos. Foi proposto também um modelo de regressão não linear difásico que resulta da soma ponderada de regressões lineares constantes com peso dado pela função distribuição acumulada Cauchy seno hiperbólico exponencial. Um estudo de simulação foi feito, utilizando a metodologia de Monte Carlo, para avaliar as estimativas de máxima verossimilhança dos parâmetros do modelo. / The electronic controllers spray aimed at minimizing the variation of inputs rates applied in the field. They are part of a control system, and allow for compensation for variation spray travel speed during operation. There are several types of electronic spray controllers on the market and one way to select which more efficient under the same conditions, ie in the same system of control, is to quantify the system response time for each specific driver. The objective of this study was to estimate the response times for changes in speed of an electronic spraying system via nonlinear regression models, these resulting from the sum of weighted linear regressions for cumulative distribution functions. Data were obtained on the Application Technology Laboratory, located in the Department of Biosystems Engineering from College of Agriculture \"Luiz de Queiroz\", University of Sao Paulo, in Piracicaba, Sao Paulo, Brazil. The models used were the logistic and Gompertz, resulting from a weighted sum of two constant linear regressions with weight given by the cumulative distribution function logistics and Gumbell respectively. Reparametrization been proposed for inclusion in the control system response time models, in order to improve the statistical interpretation and inference of the same. It has also been proposed a non-linear regression model two-phase which is the weighted sum of constant linear regressions weight given by a cumulative distribution function exponential hyperbolic sine Cauchy in which a simulation study was conducted using the methodology of Monte Carlo to evaluating the maximum likelihood estimates of the model parameters.

The magnetic properties of materials are primarily dictated by its ion ordering which occurs by means of electrostatic exchange interaction. Many other factors are also involved such as the lattice geometry, non-magnetic ions, anisotropy, external fields, and so forth. In this work, we investigate the ferromagnetic spin 1=2 Heisenberg model within the mean field approximation as well as in the effective field framework in two distinct structures, namely, the kagome and simple cubic lattices. For the kagome structure, we applied the mean field approximation including Dzyaloshinkii-Moriya (DM) anisotropy and an external field. Then, we worked out its phase diagram on the temperature-interaction manifold and analyzed some fundamental thermodynamics properties such as magnetization and magnetic susceptibility for varying (exchange interaction parameter), anisotropy (DM), and temperature. For the simple cubic lattice, we rely on the effective-field approximation by means of the differential operator technique. In this case, we assumed the external field to follow a trimodal distribution and also added a term that accounts for the bond distribution. We then explored the resulting behavior of the phase diagrams. Our findings provide an accurate description of the magnetic behavior of real systems featuring anisotropy and similar topologies. / O magnetismo exibido pelos materiais tem como um dos requisitos físicos o ordenamento dos seus íons magnéticos que ocorre por meio de uma interação denominada de interação de troca de origem eletrostática. Muitos outros fatores influenciam fortemente no surgimento do magnetismo como a geometria da rede, presença de íons não magnéticos no cristal, presença de anisotropia, fatores externos ao material, como campos aplicados ao mesmo. Neste trabalho, obtivemos propriedades magnéticas do modelo de Heisenberg ferromagnético de spin 1=2 nas aproximações de campo médio, e de campo efetivo via operador diferencial em duas redes distintas: kagomé e cúbica simples. Para a rede tipo kagomé, a aproximação utilizada foi a de campo médio e adicionamos os termos de anisotropia de Dzyaloshinkii-Moriya (DM) e de campo externo. Nessa parte foi analisado o diagrama de fases no plano Temperatura versus interação (DM) e o comportamento das grandezas termodinâmicas como magnetização e susceptibilidade magnética sob a flutuação dos parâmetros (definido como parâmetro de troca), do termo de anisotropia (DM) e da temperatura. Para a rede cúbica simples, a abordagem foi realizada na aproximação de campo efetivo por meio da técnica do operador diferencial. Nesse contexto, adicionamos ao formalismo um termo de distribuição das ligações e uma distribuição trimodal para o campo externo e estudamos os efeitos dessas distribuições nos diagramas de fases temperatura versus campo externo e temperatura versus ligação. Com isso, obtivemos resultados que podemos considerá-los como uma boa estimativa do comportamento magnético de sistemas reais, ao quais possuem os tipos de redes considerados e que estão sob a influência dos parâmetros anisotrópicos e das distribuições consideradas.

A resistência à ruptura de materiais frágeis como o concreto de granulometria fina é fortemente dependente de sua heterogeneidade, do tamanho da amostra e da heterogeneidade das tensões. A partir de uma abordagem probabilista, fundamentada no modelo de Weibull, este trabalho trata da influência de tais efeitos sobre a resistência à tração de painéis compósitos formados por concreto de granulometria fina e telas soldadas. Desde que as armaduras se mantenham em regime elástico, mostra-se que o modelo de Weibull de dois parâmetros pode ser empregado com sucesso na previsão da ruptura dos painéis compósitos em estudo. Os parâmetros foram então identificados com medidas de ensaios de flexão em três e em quatro pontos de barras de concreto de granulometria fina de dois tamanhos diferentes. A utilização do modelo de Weibull confirmou, por outro lado, a validade da teoria de misturas como ferramenta para estimar as resistências de rupturas locais correspondentes a diferentes níveis de formação de fissuras / The rupture strength of brittle materials such as the microconcrete is strongly dependent on the microstructural heterogeneity, the sample size and the stress heterogeneity. Using a probabilistic approach, based on the Weibull distribution, this work deals with the influence of such effects on the tensile strength of composite panels formed by microconcrete and welded wire grids. Provide the reinforcements behaves in elastic regime, it is shown that the model of Weibull of two parameters can be used with success to predict the failure of the composite panels studied. The parameters were then identified from measurements of flexural tests in three and in four points of two different sizes of microconcrete samples. The feasibility of the Weibull model validates, as well, the rule of mixture as a satisfactory tool to estimate local failure strengths of related to different levels of cracking

Au cours des dernières années, des changements importants dans le domaine des assurances et des finances attirent de plus en plus l’attention sur la nécessité d’élaborer un cadre normalisé pour la mesure des risques. Récemment, il y a eu un intérêt croissant de la part des experts en assurance sur l’utilisation de l’espérance conditionnelle des pertes (CTE) parce qu’elle partage des propriétés considérées comme souhaitables et applicables dans diverses situations. En particulier, il répond aux exigences d’une mesure de risque “cohérente”, selon Artzner [2]. Cette thèse représente des contributions à l’inférence statistique en développant des outils, basés sur la convergence des intégrales fonctionnelles, pour l’estimation de la CTE qui présentent un intérêt considérable pour la science actuarielle. Tout d’abord, nous développons un outil permettant l’estimation de la moyenne conditionnelle E[X|X > x], ensuite nous construisons des estimateurs de la CTE, développons la théorie asymptotique nécessaire pour ces estimateurs, puis utilisons la théorie pour construire des intervalles de confiance. Pour la première fois, l’approche de bootstrap non paramétrique est explorée dans cette thèse en développant des nouveaux résultats applicables à la valeur à risque (VaR) et à la CTE. Des études de simulation illustrent la performance de la technique de bootstrap.

In the present paper, we identify several distributions from Physics and study their applicability to phenomena such as distribution of income, wealth, and expenditure. Firstly, we apply logistic distribution to these data and we find that it fits very well the annual data for the entire income interval including for upper income segment of population. Secondly, we apply Fermi-Dirac distribution to these data. We seek to explain possible correlations and analogies between economic systems and statistical thermodynamics systems. We try to explain their behaviour and properties when we correlate physical variables with macroeconomic aggregates and indicators. Then we draw some analogies between parameters of the Fermi-Dirac distribution and macroeconomic variables. Thirdly, as complex systems are modelled using polynomial distributions, we apply polynomials to the annual sets of data and we find that it fits very well also the entire income interval. Fourthly, we develop a new methodology to approach dynamically the income, wealth, and expenditure distribution similarly with dynamical complex systems. This methodology was applied to different time intervals consisting of consecutive years up to 35 years. Finally, we develop a mathematical model based on a Hamiltonian that maximises utility function applied to Ramsey model using Fermi-Dirac and polynomial utility functions. We find some theoretical connections with time preference theory. We apply these distributions to a large pool of data from countries with different levels of development, using different methods for calculation of income, wealth, and expenditure.

Aim of this thesis is provide basic information about characteristic function used in statistic and compare its properties with the Fourier transform used in engineering applications. First part of this thesis is theoretical, there are discussed basic concepts, their properties and mutual relations. The second part is devoted to some possible applications, for example normality testing of data or utilization of the characteristic function in independent component analysis. The first chapter describes the introduction to probability theory for the unification of terminology and mentioned concepts will be used to demonstrate the interesting properties of characteristic function. The second chapter describes the Fourier transform, definition of characteristic function and their comparison. The second part of this text is devoted to applications the empirical characteristic function is analyzed as an estimate of the characteristic function of examined data. As an example of application is describe a simple test of normality. The last part deals with more advanced applications of characteristic function for methods such as independent component analysis.

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Masters of Science / The multivariate two-sample tests provide a means to test the match between two multivariate distributions. Although many tests exist in the literature, relatively little is known about the relative power of these procedures. The studies reported in the thesis contrasts the effectiveness, in terms of power, of seven such tests with a Monte Carlo study. The relative power of the tests was investigated against location, scale, and correlation alternatives. Samples were drawn from bivariate exponential, normal and uniform populations. Results from the power studies show that there is no single test which is the most powerful in all situations. The use of particular test statistics is recommended for specific alternatives. A possible supplementary non-parametric graphical procedure, such as the Depth-Depth plot, can be recommended for diagnosing possible differences between the multivariate samples, if the null hypothesis is rejected. As an example of the utility of the procedures for real data, the multivariate two-sample tests were applied to photometric data of twenty galactic globular clusters. The results from the analyses support the recommendations associated with specific test statistics.

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