Analogues aux cyclotrivératrilènes et aux calix[n]arènes, les pillar[n]arènes sont composés de n unités hydroquinoliques et reliés entre elles par un pont méthylénique en position para. Ces macrocycles ont été utilisés en tant que supports fonctionnalisables afin de préparer divers nanomatériaux. Dans ce contexte, la modification chimique du pont méthylénique a été réalisée sur le pillar[5]arène afin d’obtenir un nouveau site de fonctionnalisation, à ce jour jamais exploité. L’oxydation de cette position a permis dans un premier temps de réaliser une extension de cycle par une réaction de Colvin, afin d’obtenir un macrocycle portant une triple liaison tendue. Cette particularité a permis la réalisation de cycloaddition 1,3-dipolaire de Huisgen ou chimie click sans utilisation de cuivre(I), mais également l’obtention de produits de cycloadditions [2+2] par voie thermique normalement interdites. L’introduction d’un fullerène C60 sur ce pont méthylénique a également été réalisée sans déformation de la cavité. C’est pourquoi dans un deuxième temps des [2]rotaxanes photoactifs ont pu être élaborés à partir de ce fulléropillar[5]arène. Dans un dernier temps, une nouvelle méthode de préparation des [2]rotaxanes a été développée. Par échange de bouchons activés, divers [2]rotaxanes ont pu être synthétisés, sans être limités par la nature des bouchons souhaités. A partir de cette méthode de préparation, des cristaux liquides ont pu être obtenus en substituant ces bouchons activés par des bouchons portants des groupements post-fonctionnalisables, puis en greffant des groupements cyanobiphényles. / Analogues of cyclotriveratrylenes and calix[n]arenes, pillar[n]arenes are composed of 1,4-disubstituted hydroquinone subunits linked by methylene bridges in their para positions. This macrocyclic core has been used as a compact scaffold for the preparation of nanomaterials. In this context, the chemical modification of the methylene bridge has been achieved to further functionalize the core in a way never explored so far. Firstly, oxidation of this position followed by Colvin reaction generated a strained triple bond in the macrocyclic scaffold. This particularity allowed the introduction of functional groups under copper free Huisgen 1,3-dipolar cycloadditions as well as by thermal [2+2] cycloadditions normally prohibited. Insertion of [60]fullerene on the methylene bridge has been also carried out. In a second time, photoactive [2]rotaxanes have been obtained from this fulleropillar[5]arene. Finally, a new methodology for the preparation of [2]rotaxanes has been developed. By exchange of activated stoppers, various [2]rotaxanes were thus obtained and this method is not limited by the nature of the stopper. This methodology has been used to prepare new liquid crystalline rotaxane derivatives by introduction of clickable stoppers followed by the grafting of dendritic mesogenic subunits.

Master thesis provides an overview of demographic development and its relations to the sustainability of the pension systems. The theoretical part of the thesis focuses on the description of demographical processes and its main characteristics since the year 1989 and prognoses of its future development in Czech Republic. Later on, the theoretical knowledge gained in the first part is interconnected with the description of the pension system, as defined in Czech Republic and as valid since 1st of January, 2013. In practical part of the thesis the main focus is given to the calculations of sustainability of the pension system. The calculations are performed at the model situation, based at the pension system as defined in Czech Republic, but adjusted for some simplifying facts and premises. The calculations are provided for few different situations, when the revenues and expenses of the first pillar of the pension system are calculated. Based on the development of revenues and expenses, the percentage of people, that are supposed to enter the second, fully funded, pillar is calculated. The percentage is calculated in situation when the revenues are equal to the expenses and therefore the PAYG part of the pension system is sustainable in the long run.

Can a multilateral negotiating process—that is, cooperation between many states in a single forum—successfully reform the network of bilateral tax treaties that currently makes up the bulk of international tax law? The BEPS Project aims to be the first major push for a multilateral tax process since the creation of the OECD’s Model Tax Convention in the 1960s. Through BEPS, the OECD and 130-plus countries are in final negotiations to implement Pillar One and Two, which will: (1) create a new taxing right for “market jurisdiction” countries on the profit of international companies that do business there without a physical presence; and (2) implement a top-up tax levied against companies that offshore profits from intangible assets in low-tax jurisdictions. To predict whether the multilateral reform effort will be successful, it is important to examine the nature of the multilateral negotiating process itself, because every negotiation is shaped by its context.  But this context is not static—rather, the nature of tax multilateralism varies depending on certain global conditions. Sometimes, it is a hierarchical process, dominated by powerful countries operating in a closed-club of developed states spearheading the effort, while weaker countries must tag along and accept the eventual outcome. Alternatively, multilateralism may be egalitarian and inclusive, with many countries—strong and weak alike—contributing to the debate, accepting tradeoffs, and endorsing the outcome. In this thesis, I demonstrate that the nature of tax multilateralism has changed from the former model to the latter by comparing the negotiation of the OECD Model Tax Conventions with the Pillars Negotiation. I begin by identifying several factors that influence the nature of tax multilateralism: first, the distribution of global power among states; and second, the level of integration of the global economy. In an international system where power is concentrated in a few states, and the international economy is fragmented (i.e., the conditions of the 20th Century), multilateralism tends to be hierarchical and exclusive. However, when power is diffused and the global economy is integrated, (the conditions of the 21st Century), then multilateralism is egalitarian and inclusive. In such a context, international tax issues—like base erosion and profit-shifting—are so vast and complex that no state, acting alone or in a small group, could deal with them. The thesis thus concludes that the nature of tax multilateralism has changed, because in modern negotiations, powerful states are both less capable of dominating other states in the negotiating process and are highly dependent on a successful outcome that creates global consensus.

When two parallel tunnels are excavated under high to moderate horizontal in-situ stresses combined with minor deformations in the pillar between the tunnels, the in-situ stresses can be redistributed over the tunnels in form of two compressive arches and are transferred from the roof to the abutments of the two tunnels. At additional deformations in the pillar, a new redistribution of the stresses can occur creating one compressive arch over both of the tunnels. This leads to lower vertical stresses in the pillar between the two tunnels. Today, this effect is normally not accounted for in the design of rock support. By accounting for this arching effect, it is possible to design the pillars for a lower load. The aim of this thesis is to analyze how to optimize the rock support (rock bolts) in the pillar by accounting for this potential arching effect in the rock mass. To study this, a sensitivity analyses is performed where the rock mass is represented by three different qualities (very good, good and fair). The geometry of the rock pillar is defined by a height of 6 m and two width dimensions of 3 m and 6 m are used. The in-situ stresses are categorized in three levels: minimal, typical and maximal according to typical conditions in the Stockholm region. Numerical models are analyzed in PLAXIS based on these different conditions. Stress redistribution in the rock is simulated by reducing the modulus of elasticity of the pillar in five stages. Based on the results from the numerical simulations and comparisons against analytical solutions it can be concluded that it is possible to design the pillar for a lower load, which accounts for this secondary arching effect over the two tunnels. The number of bolts could be reduced with at least 1-5 units per meter tunnel for the analyzed cases; thereby reducing the costs and also contribute to a more sustainable use of natural resources. / När parallella tunnlar tas ut i en bergmassa under höga eller måttliga horisontella in-situ spänningar omfördelas de över de båda tunnlarna i form av två tryckbågar och överförs från taket till stöden. Vid ytterligare deformationer i pelaren kan istället ytterligare en omfördelning ske och en tryckbåge över båda tunnlarna skapas. Detta leder till en minskning av de vertikala spänningarna i pelaren mellan de båda tunnlarna. Idag beaktas normalt inte denna effekt vid dimensioneringen av pelarens förstärkning. Genom att beakta denna valveffekt är det möjligt att dimensionera pelarens förstärkning för en lägre last. Syftet med detta arbete är att analysera hur förstärkningen kan optimeras i pelaren genom att beakta denna valveffekt i bergmassan. För att studera detta har en känslighetsanalys genomförts där bergmassan representeras av tre olika kvaliteter (mycket bra, bra och acceptabel). Geometrin för bergpelaren definieras av en höjd på 6 m och två olika bredder på 3 m och 6 m har analyserats. In-situ spänningarna kategoriseras i tre nivåer: minimala, typiska och maximala enligt typiska förhållanden för Stockholmsregionen. Olika numeriska modeller har analyserats i PLAXIS utifrån dessa olika förutsättningar. Spänningsfördelningen i berget simulerades genom att pelarens elasticitetsmodul reducerades i fem steg. Baserat på resultaten från de numeriska analyserna och jämförelser mot analytiska lösningar kan slutsatsen dras att det är möjligt att dimensionera förstärkningen för en lägre last genom att beakta den sekundära valvverkan som kan uppstå i bergmassan över de båda tunnlarna. I de utförda analyserna kunde antalet bergbultar reduceras med mellan 1-5 stycken per meter tunnel; vilket därmed kan bidra till läge kostnader och en mer hållbar användning av naturresurser.

This thesis presents an analytical and experimental investigation into the capillary wicking limitation of an array of pillars. Commercial and nanopillar wicks are examined experimentally to assess the effects of micro and nanoscale capillary forces. By exerting a progressively higher heat flux on the wick, a maximum achievable mass flow was observed at the capillary limit. Through the balance of capillary and viscous forces, an ab initio analytical model is also presented to support the experimental data. Comparison of the capillary limit predicted by the analytical model and actual limit observed in experimental results are presented for three baseline wicks and two nanowicks. / text

This thesis presents numerical and analytical investigation of the geomechanics underlying longwall mining. It was tried out to study the disturbances induced by longwall mining in nearby rocks and their influence on the stability of the gates, pillars and main tunnels of longwall mines. The thesis consists of two major parts: numerical and analytical investigations. The study site is the Svea Nord coalmine, Svalbard, Norway. A novel algorithm was proposed for numerical simulation of the longwall mining process. In the proposed algorithm progressive cave-in and fracturing of the roof strata, consolidation of the cave-in materials and stress changes are simulated in detail. In order to outline the caved-in roof rocks a criterion based on maximum principal strain (in tension) was used. The critical tensile strain of roof cave-in was determined through back-calculation of the surface subsidence above a longwall panel at the mine. The results of the simulations were then used to analyse stress changes induced by longwall mining and the stability of gates. The simulations revealed that the stability of the gates and the loading to the rock bolts are closely related to the width of the chain pillars. With slender pillars, shear displacements along weak interlayers and bedding planes result in heavy loading to the rock bolts. Therefore, the locations of weakness zones should be taken into account in rock bolt design. The developed algorithm was implemented to study the loading and stability of the barrier pillar of the mine. The barrier pillars protect the main tunnels and border area of the mine from disturbances induced by longwall mining in the panels. The simulations show that the stresses in the barrier pillars fluctuate up and down during mining because of periodic cave-in events behind the longwall face. A failure zone of about 12 m exists in the wall of the barrier pillars. A large portion of the barrier pillar is still intact and is, thus, capable of protecting the border area. The results of the detailed simulations of longwall mining via the developed algorithm were, also, implemented in a large-scale numerical model. The model consists of all of the longwall panels and the border area of the mine. It is intended that the coal in the border area on the other side of the longwall panels will be mined after completion of the longwall mining. There is concern about how the longwall mining affects the stress state in the border area and how stress changes would affect future mining in the border area. A failure zone of about 20 m developed in the wall of the main tunnels on the side of the border area after all the longwall panels were mined out. The stress state in the remaining portion of the border area remains unchanged. Therefore, it will be possible to mine the border area in the future. In order to investigate the roof strata cave-in mechanism in detail a discontinuous numerical simulation of roof cave-in process was conducted by UDEC code. The block size in the roof strata and the mechanical parameters of the discontinuities were obtained through back-calculations. The back-calculations were conducted with a statistical method, Design of Experiment (DOE). Numerical simulations revealed that jointed voussoir beams formed in the roof strata before the first cave-in. Beam bending results in stress fluctuations in the roof strata. The maximum deflection of a roof stratum at the study site before the first cave-in is about 70% of the stratum thickness. The simulations and field measurements show no periodic weighting on the longwall shields in this mine. Numerical sensitivity analyses show, however, that periodic weighting may occur in strong roof strata. Roof strata with a high Young’s modulus and large joint spacing are not suitable for longwall mining. The maximum sustainable deflection of the roof strata before cave-in depends upon the horizontal in-situ stress state. It slightly increases with the in-situ horizontal stress in the stratum beams, but the horizontal stress would increase the possibility of rock-crushing in deflected roof beams. The implemented numerical method would be useful in assessment of the cavability of the roof strata and in selection of longwall shields with adequate load capacity. As shown through discontinuous numerical simulations, the roof strata above the underground opening constructed in the stratified rocks form voussoir beams. The stability of those beams is the major concern in the study of the gate stability and roof cave-in assessment in the longwall panels. Two different analytical methods were developed for cases with and without the in-situ horizontal stress acting along the beams. In the analytical model for the beams without horizontal stress a bilinear shape was assumed for the compression arch generated within the voussoir beams. The stability of the compression arch is governed by the energy method. The model requires an iterative procedure for convergence, and an algorithm was proposed for it. The analytical method was verified with numerical simulations by means of a discrete element code, UDEC. For the beams subjected to in-situ horizontal stress, the classic beam theory was employed to drive the analytical solution for it. The superposition method was used to obtain bending/deflection equations of the beam. The validity of both the assumptions and the developed method were, also, investigated by numerical simulations. The developed analytical method revealed that high Young’s modulus of a beam rock increases the stability of the beams against buckling but it causes higher stress within the compression arch which increases the probability of crushing failures in the beam abutments and midspan. In-situ horizontal stress along beams increases their stability against buckling and abutment sliding failure, but it raises the possibility of crushing failure at the abutments and the midspan.

A wind tunnel based investigation into the effects of unsteady yaw angles on the aerodynamics of a simple automotive body has been carried out to increase the understanding of the effects of unsteady onset conditions similar to those experienced in normal driving conditions. Detailed flow field measurements have been made using surface pressure tappings and PIV around a simple automotive model in steady state conditions and these have been compared to measurements made whilst the model was oscillating in the yaw plane. The oscillating motion was created by a motored crank which was used to produce consistent and repeated motion which produced a reduced frequency that indicated that a quasi-static response should be expected. The PIV data are used to compare the wake flow structures and the surface pressures are used to infer aerodynamic loads and investigate the development of the flow structures across the surfaces of the model. This includes a comprehensive comparison of the surface pressures on the sides of the model during a transient and quasi-static yaw angel oscillation. These results show differences between the two test conditions with the oscillating model results containing hysteresis and the greatest differences in the flow field occurring on the leeside of the model. Two configurations of the same model with different rear pillar geometries were used to isolate model specific effects. Square rear pillars create strong and stable trailing vortices which are less affected by the model motion whereas radiused rear pillars created weaker and less steady vortices that mixed with the quasi-2D wake behind the model base and were affected to a greater extent by the model motion. The unsteadiness in the trailing vortex separation feeds upstream into the A-pillar vortex demonstrating that small geometry changes at the rear can affect the entire flow field around the model.

Ausgewählte Fragen der dritten Phase der Rentenreform in der Tschechische Republik Das Ziel meiner Diplomarbeit ist die Beschreibung, die Analyse und die Auswertung der dritten Phase der Rentenreform mit dem Hinweis an die Probleme, mit dennen auch die letzte Entscheidung der Regierung über die Aufhebung des zweiten Pfeilers des Rentensparens verbunden wurde. Die Arbeit wird systematisch an die 5 Kapitel geteilt. In der ersten Kapitel werden die universale Prinzipen und Möglichkeiten der Konstruktion der Rentensysteme zusammen mit der Aufnahme des tschechischen Rentensystems in dem System der Sozialversicherung detailisiert. Die zweite Kapitel detailisiert die Gültigrechtsausgestaltung des tschechischen Rentensystems.In der dritten Kapiltel wird auf die Probleme verbundene mit der Einführung der Groβrentenreform hingewiesen und auf diese Problematik knüpft die letzte Kapitel an, die genau das nächste Prozess der Aufhebung des zweiten Pfeilers der Rentensparung analysiert. Am Ende meiner Arbeit werden die gewonnene Kentnisse allgemein gemacht und die Überlegung über die Erfolgsamkeit der Einführung einer Fondfinanzierung in das tschechische Rentensystem. Powered by TCPDF (www.tcpdf.org)

O método de lavra câmaras e pilares é muito utilizado em minas de carvão subterrâneo, principalmente nos estados de Santa Catarina e Paraná, onde todas as minas subterrâneas utilizam este método. Vale ressaltar, porém, que o método apresenta recuperações de lavra abaixo de 50%, dependendo do tamanho dos pilares, e a produtividade é altamente dependente de uma boa concatenação das operações unitárias. Entre os aspectos relacionados à eficiência produtiva, a distância de transporte é um item preponderante no desempenho do sistema. Devido à profundidade da lavra, há um aumento do tamanho dos pilares de sustentação da mina, e assim, surgem problemas relacionados ao incremento no tempo de ciclo de transporte dos equipamentos. O aumento da distância de transporte entre uma frente de lavra com material desmontado e o alimentador/britador primário, reduz o resultado da produção de um conjunto de equipamentos. Em mineração a céu aberto, este tipo de problema é resolvido com o aumento da frota de transporte, todavia, na mineração de carvão subterrânea, não é possível aumentar de forma irrestrita a quantia de máquinas em subsolo, pois impactaria diretamente na necessidade de incremento da vazão de ar, assim como, limitação de espaço para o tráfego de equipamentos. A aproximação da distância do ponto de descarga para um local adjacente às frentes de serviço é uma alternativa para solucionar a necessidade de incremento da frota de produção. No entanto, o ponto de mudança deve ser avaliado de forma consistente para determinar o momento mais adequado para que essa reaproximação proporcione um resultado ótimo. Este estudo buscou compreender esta etapa necessária ao processo produtivo, utilizando técnicas de regressão para analisar o impacto da distância de transporte na capacidade produtiva. O problema foi modelado e foram propostas alternativas que forneçam um sequenciamento de lavra capaz de amenizar os problemas decorrentes do aumento da distância de transporte das frentes de lavra aos respectivos pontos de descarga. Os resultados demonstraram que a distância de transporte tem influência direta na produção, mas não somente a distância máxima, mas também, uma distância mínima que deve ser respeitada para obter maior produtividade quando se tem a associação de equipamentos de produção. É possível concluir com este estudo que a distância de transporte tem impacto relevante e deve ser considerada, não tão somente no sequenciamento, mas também no dimensionamento da frota e consequente capacidade produtiva. / The room and pillar mining method is widely used in underground coal mines. Santa Catarina and Paraná where all underground mines use this method. Indeed, the method has mining recoveries below 50% and the productivity is highly dependent on a good concatenation of unit operations. Among the aspects related to production efficiency, the transport distance is an important item on system performance. Due to the depth of the mine, there is an increment in the size of the underground supporting pillars, and consequently, problems related to the increase in equipment cycle times. The increase of the transportation distance between mining faces and the primary crusher reduces the result of a set of production equipment. In open pit mining, this problem is solved by increasing the haulage fleet, however, in the underground coal mining, the number of machines cannot be increased indefinitely because it would impact directly on the need of increased air flow. Therefore, the approximation of the distance from the discharge point to an adjacent location from the mining faces is an alternative to address the need of increased production fleet. However, the relocation point must be evaluated consistently to determine the most appropriate time to get the most from this approach. The goal of the study was to understand this imperative step for the production process, using regression techniques to analyze the impact of transport distance in productive capacity. Based on the experimental design used in this study, alternative proposals provide a mining sequence able to mitigate the problems from increasing transportation distance from mining faces to their discharge points. The results show that the transport distance has directly influence on the production, and it is not limited to the maximum distance. Likewise, a minimum distance must be respected for higher productivity when you have the combination of production equipment. So, it is possible to conclude that the transport distance has a significant impact and must be considered not only during the sequencing, but also when determining the fleet size and consequent production capacity.

Since the discovery of X-rays over a century ago the techniques applied to the engineering of X-ray sources have remained relatively unchanged. From the inception of thermionic electron sources, which, due to simplicity of fabrication, remain central to almost all X-ray applications at this time, there have been few fundamental technological advances. The emergence of new materials and manufacturing techniques has created an opportunity to replace the traditional thermionic devices with those that incorporate Field Emission electron sources. One of the most important attributes of Field Emission X-ray sources is their controllability, and in particular the fast response time, which opens the door to applying techniques which have formerly been the preserve of optical systems. The work in this thesis attempts to bridge the gap between the fabrication and optimisation of the vacuum electronic devices and image processing aspects of a new approach to high speed radiographic imaging, particularly with a view to addressing practical real-world problems. Off the back of a specific targeted application, the project has involved the design of a viable field emission X-ray source, together with the development of an understanding of the failure modes in such devices, both by analysis and by simulation. This thesis reviews the capabilities and the requirements of X-ray sources, the methods by which nano-materials may be applied to the design of those devices and the improvements and attributes that can be foreseen. I study the image processing methods that can exploit these attributes, and investigate the performance of X-ray sources based upon electron emitters using carbon nanotubes. Modelling of the field emission and electron trajectories of the cathode assemblies has led me to the design of equipment to evaluate and optimise the parameters of an X-ray tube, which I have used to understand the performance that is achievable. Finally, I draw conclusions from this work and outline the next steps to provide the basis for a commercial solution.