The objective of this study is to explore the effects of various process parameters upon the tube formability. In the condition of no axial loads and free bulging, the process parameters that affect tube bulge pressure and formability are die corner radius, tube thickness, bulge length and tube diameter. To proceed the experiments of tube hydro forming, this paper has designed and constructed an experimental system of tube hydroforming comprised of a hard tooling set, hydraulic pressurization circuit, an intensifier and a half ton hoisting device, firstly. In experiments, annealed aluminum alloy tubes are used to carry out the experiments with different tube thickness, bulge length and die corner radius. Furthermore, FEM packages are applied to proceed the analyses of bulge height, forming pressure and tube thickness distribution with forming parameters above. Finally, the comparisons between the analytical and experimental results are discussed to explore the deform action mechanism of tube hydro-forming.

Cette étude se concentre sur l'influence des conditions hydrodynamiques et de mélange sur les caractéristiques de microcapsules obtenues par inversion/précipitation. Ce processus est classiquement exécuté dans une cuve agitée alors qu'il a été montré que l'exécution de procédés de fabrication de produits chimiques peut être améliorée en utilisant des microtechnologies en raison du meilleur contrôle hydrodynamique et de l'intensification des échanges de chaleur et de matières. Donc, afin d'évaluer l'avantage potentiel de ces nouvelles technologies, des microcapsules de parfum enrobé dans du PMMA ont été fabriquées par inversion de phase/précipitation (système THF/Eau) dans une cuve semi-fermé agitée standard, dans un mélangeur structuré et dans un micromélangeur de type V (FZK). Les trois procédés sont évalués en terme de propriétés de capsules (la distribution de taille, l'épaisseur de membrane, l'efficacité d'encapsulation et la cinétique de libération). Il a été montré que le micromélangeur offre une vaste gamme de conditions de fonctionnement / This study focuses on the influence of the hydrodynamic and mixing conditions on the characteristics of microcapsules obtained by inversion/precipitation. This process is classically run in semi-batch stirred tank while it has been shown that the performance of chemical product manufacturing processes can be improved by using microtechnologies due to better hydrodynamic control and intensification of mass and heat exchanges. Therefore, in order to evaluate the potential benefit of these new technologies, microcapsules of perfume in PMMA have been manufactured by phase inversion/precipitation (system THF/Water) in a classical semi-batch stirred tank, in a structured mixer and in a V-Type micromixer (FZK). The three process is evaluated in term of capsules properties (size distribution, membrane thickness, encapsulation efficiency and release rate). It is shown that micromixer offers a wide range of operating conditions

[pt] Esta tese de doutorado se propõe a estudar a reologia de pastas de hidratos composta por água e tetrahidrofurano (C4H8O - THF) em diversas conjunturas. Os hidratos de gás natural são sólidos cristalinos, análogos ao gelo, formados pela agregação de água e de gás numa determinada estrutura organizada. Sua preocupação para a Indústria de petróleo e gás deve-se ao risco potencial relacionada a área de garantia de escoamento. Assim sendo, amplos investimentos são feitos com o propósito de prevenir e avaliar os ricos da formação de hidratos. Neste contexto, a reologia é um elemento chave, pois permite detectar a formação dos hidratos a partir de variações das propriedades reológicas, sendo as mais comuns: viscosidade, módulos viscoso e elástico. Entretanto, duas condições fundamentais para o sucesso desta abordagem são relativamente difíceis de se conseguir em laboratório, a combinação de alta pressão e baixa temperatura. Inicialmente serão estudadas pastas de hidratos formadas à pressão atmosférica, ainda a temperaturas acima de 0 graus Celsius. Em outro momento, serão estudados os efeitos da adição de álcool nas pastas de hidratos e, finalmente, serão analisadas as pastas formadas em pressões acima da pressão atmosférica. Foram realizados ensaios reológicos para diferentes composições de fluidos. Alcançam-se resultados transientes e de estado estacionário, mostrando que a reologia é fortemente afetada pela aglomeração e desagregação de cristais de hidratos que ocorrem simultaneamente à medida que os hidratos se formam e as condições de contorno que cercam os experimentos. / [en] This doctoral thesis proposes to study the rheology of water hydrate and tetrahydrofuran slurries (C4H8O - THF) at different conditions. Natural gas hydrates are crystalline solids, analogous to ice, formed by the aggregation of water and gas in a given organized structure. Their concern for the oil and gas industry is due to the potential risk related to the area of flow assurance. Thus, extensive investments are made for the purpose of preventing and evaluating the risk of hydrate formation. In this context, rheology is a significant element, since it allows to detect the formation of hydrates from variations in rheological properties, the most common being: viscosity, viscous and elastic modules. However, two fundamental conditions for the success of this approach are relatively difficult to achieve in the laboratory, the combination of high pressure and low temperature. Initially will be studied hydrate pastes formed at atmospheric pressure, still at temperatures above 0 Celsius degrees. In another moment, the effects of the addition of alcohol in the hydrate pastes will be studied and, finally, the pastes formed at pressures encountered above atmospheric pressure will be analyzed. Rheological tests were performed for different fluid compositions. Transient and steady-state results are reached, showing that rheology is strongly affected by the agglomeration and disaggregation of hydrate crystals occurring simultaneously as hydrates form and the boundary conditions surrounding the experiments.

Cyclic peroxides are abundant in Nature and synthetic manipulation of the peroxide linkage and alkene portion of 1,2-dioxines has established 1,2-dioxines as important compounds as both chemical building blocks and bioactive compounds. Much of the chemistry performed thus far utilizing 1,2-dioxines involves the initial rearrangement of 1,2-dioxines to γ-hydroxyenones allowing for the generation of structural motifs such as cyclopropanes, THF’s, THP’s, 1,4-diketones and natural sugars. Herein describes the synthesis of novel 1,2-dioxines with a variety of tethered functionalities and their transformations to afford novel cyclic compounds whilst maintaining the peroxide linkage intact. Chapter two outlines the intramolecular cyclisations of tethered hydroxyl and carboxylic acid moieties onto the olefin of 1,2- dioxines to generate both tetrahydrofurans and dihydrofuran-2(3H)-ones, whilst maintaining the peroxide linkage. This work presents the first examples of syn fused cyclic peroxide furans through intramolecular cyclisation of tethered hydroxyl groups. Improved methods for the oxidation of hydroxyl tethered 1,2-dioxines to carboxylic acid moieties are also reported. In addition, improved methods for intramolecular cyclisation of carboxylic acid moieties where developed to afford syn fused cyclic peroxide lactones. Furthermore, reduction of the peroxide bond enabled generation of functionalized tetrahydrofurans and dihydrofuran-2(3H)-ones which have previously been utilized as synthetic building blocks for several natural products. Chapter three reports the first examples of carbenoid insertion into the peroxide linkage of 1,2-dioxines allowing for the generation of novel bicyclic hemiacetals. Alternatively novel tricyclic cyclopropyl peroxides where generated through insertion into the olefin whilst maintaining the peroxide linage intact. Additionally, the attempted intramolecular cyclisation of diazoketone tethered bicyclic 1,2-dioxines was also probed. Furthermore, the attempted intermolecular insertion of diazoketones onto 1,2-dioxines are presented within this chapter. Finally, Chapter four outlines the intramolecular cyclisations of bromo-alkyl tethered 1,2-dioxines to furnish novel cyclic cyclopentyl peroxides whilst maintaining the peroxide linkage intact. The work presented in this chapter represents the first examples of the synthesis of syn fused cyclic cyclopentyl peroxides. In summary, this thesis outlines methodology towards the synthesis of novel cyclic peroxides from 1,2-dioxines containing tethered functional groups. / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2009

Les amphidinolides C et F sont des macrocycles isolés de dinoflagellés Amphidinium sp. vivant en symbiose avec des plathelminthes Amphiscolops sp.. Ces amphidinolides ont montrés des activités cytotoxiques importantes sur des lignées de cellules KB et L1210. Au vu du potentiel thérapeutique intéressant et de l’architecture complexe de ces substances naturelles, un programme de synthèse totale a été initié. Dans ce manuscrit, différentes approches pour la construction de ces produits naturels sont détaillées, les principaux défis étant la création efficace de motifs 2,5-Trans THF, l’incorporation de motifs diénique par des méthodes catalytiques et le contrôle des centres asymétriques grâce à des époxydes chiraux. / Amphidinolides C and F are macrocyles isolated from dinoflagellates Amphidinium sp., which are living in symbiosis with marine flatworms Amphiscolops sp.. Those amphidinolides had shown an important cytotoxic activity against KB and L1210 cell lines. Due to promising therapeutical potential and complex framework of these natural products, a total synthesis program had been initiated. In this manuscript, different approaches for the construction of these natural targets are detailed. The main challenges were the efficient formation of 2,5-Trans THF, incorporation of dienic moieties by catalytic processes and the installation of chiral centers through chiral epoxyde chemistry.

The cobalt-catalysed oxidative cyclisation of 5-hydroxy alkenes has been demonstrated to be a powerful synthetic tool for the formation of trans-THFs with excellent diastereoselectivity. This thesis describes the utilisation of this methodology in the synthesis of the FG fragment of pectenotoxin-4, allowing the scope of the reaction to be further explored. Introduction: This section introduces the pectenotoxins, a family of structurally complex closed-chain polyether macrolides with promising biological activities. The isolation, structural elucidation, and biological properties of the pectenotoxins are reviewed, along with a summary of previous syntheses towards the FG fragment of pectenotoxin-4. In addition, the cobalt-catalysed oxidative cyclisation of 5-hydroxy alkenes and its application in synthesis is discussed. Results and Discussion: An outline of the synthetic strategy employed in this project and details of the novel retrosynthesis of the C31-C40 fragment of pectenotoxin-4 is described. The synthetic studies carried out towards the synthesis of the FG fragment of pectenotoxin-4 are discussed in detail, with the exploitation of a cobalt-catalysed oxidative cyclisation as the key step to form the trans-THF F-ring. Overall, the FG fragment, which contains six stereogenic centres, was achieved in 18 total synthetic steps (13 longest linear sequence).

O uso da simulação via método de elementos finitos (MEF) tem sido de suma importância para o desenvolvimento de processos de conformação hidrostática de tubos (CHT). Sua utilização reduz o método de tentativa e erro na definição do processo e grandes ganhos de produtividade são auferidos. Neste trabalho, a simulação via MEF em conjunto com o desenvolvimento analítico existente na literatura foi utilizada para o desenvolvimento de um método projeto de uma ferramenta simples para a CHT em matriz aberta e para uso em prensa comum. Obtida a ferramenta, foi possível a um baixo custo ser determinado experimentalmente os limites de conformação, o caminho de deformação e as dimensões do tubo expandido sendo possível compara-los com os resultados simulados via MEF. Esta comparação de resultados experimentais e simulados validou o procedimento de simulação e o método de projeto da ferramenta. Quanto ao carregamento, com a ferramenta obtida foram expandidos tubos por dois carregamentos distintos: só pressão e pressão e carga axial simultâneos permitindo assim comprovar a eficácia do segundo carregamento para a obtenção de razões de expansão maiores. Quanto às simulações, executadas em um programa comercial, elas foram desenvolvidas também para ambos os carregamentos. Ainda nestas simulações duas maneiras de aplicar-se a pressão foram avaliadas. Para a determinação dos limites de conformação do tubo fez-se uso da técnica denominada Circle Grid Analisys. Foi escolhido para estudo um tubo extrudado de aço inoxidável AISI 316 L submetido a tempera de solubilização. O método de projeto desenvolvido, numa primeira tentativa, utilizou como dado de entrada as propriedades do Aço AISI 316 L obtidos para chapas o que levou a diferenças entre os resultados simulados e experimentais. Assim foi necessário determinar-se as propriedades do aço AISI 316 L para a condição de tubo extrudado. Para a direção circunferencial utilizou-se o método de ensaios denominado Ring Hoop Tension Test, e para o sentido longitudinal o foi utilizado um ensaio de tração usual. Foram determinados inclusive os coeficientes de anisotropia. Com estes dados novas simulações, considerando a anisotropia do material, foram realizadas. Um aprimoramento do método de projeto foi realizado, sendo construída uma segunda versão da ferramenta para a CHT. Assim os novos resultados simulados foram obtidos e foram comparados com os resultados experimentais e os erros diminuíram significativamente. Como resultado final, para esta segunda versão de simulações, de projeto e ferramenta, os erros dos valores obtidos via simulação via MEF, no diâmetro e na espessura ficaram ao redor de 10%, assumindo o resultado experimental como padrão. Quanto ao limite de conformação os resultados simulados diferiram dos experimentais, porém o estado de deformação e os caminhos de deformação situaram-se no mesmo quadrante no plano das deformações (Curva CLC) para os dois carregamentos. Finalmente, quanto ao diâmetro externo do tubo para os dois carregamentos, o tubo em aço Inoxidável AISI 316 L atingiu diâmetros até 12,9% maiores para expansão por pressão e carga axial em relação àqueles expandidos somente por pressão, os quais foram assumidos como padrão. / The simulation using the finite elements method (FEM) has been of utmost importance for the tube hydroforming (THF) processes development. It reduces the try and error method in the process definition and great profits are gained. In this work, the FEM simulation together with the existing analytical THF theory in the literature was used to develop a process and a simple tool design for the THF, in open die arrangement and to be used in a common press. Gotten this tool, it was possible in a low cost, determine experimentally the forming limits, the strain paths and the evolution of geometry for a tube and then make it possible compares these experimental results with the simulated results obtained by FEM. This comparison of experimental and simulated results validated the simulation procedure and the tool design method. Relate the loads applied during the THF, two distinct load cases were possible: only pressure and simultaneous pressure and axial load, thus allowing proving the effectiveness of the second load case in obtain bigger expansion ratios. Relate to the simulations, they were run in commercial software and also the two load cases were simulated. Additionally in these simulations, two ways to apply the pressure had been evaluated. In the experiments, in the forming limits determination, the Circle Grid Analysis technique was used. A seamless stainless cold finished AISI 316 L solution annealed and quenched tube was chosen for evaluation. The tool design method, in a first attempt, uses the AISI 316 L steel properties obtained from sheets. Big differences between the FEM simulated and experimental results was gotten. Thus, it was necessary execute tensile tests in order to obtain the AISI 316 L steel properties for the seamless stainless cold finished, solution annealed condition. In such a way, a tensile tube test method called Ring Hoop Tension Test was used, to determined AISI 316 L steel properties in the transversal direction and a common tensile test was used for the longitudinal direction. Also, for both directions, anisotropy coefficients were also determined. With these new material properties set, new simulations including the anisotropy and a new improved tool design method were carried through, resulting in a new and improved tool version. Thus, new experiments were performed and compared with the new simulated results and the errors had diminished significantly. As final result, the errors in the diameter and in the thickness had been around of 10%, assuming the experimental result as standard. Relate the forming limits the results had differed, however the strain state and the strain path had been placed the same quadrant in a strain plane graphic (FLD diagram) for both load cases. Finally, relate to the tube expansion ratio, the tube external diameter increase 12,9% greater for tube expansion under pressure and axial load assuming the tube expansion under only pressure as standard.

Previously we have suggested the concept of tuning hydrate compositions which makes it possible to increase the gas storage capacity of binary hydrates. Herein, we report for the first time the existence of a critical guest concentration (CGC) and establish the complete tuning pattern that appears to exist in binary hydrates, including the water-soluble hydrate formers (promoters) and water insoluble guests,. The first attempt to verify the new features of clathrate hydrate compositions is executed on the binary hydrate of CH4 + THF and involves a detailed examination of the guest distribution by spectroscopic methods. THF molecules by themselves form sII hydrate from a completely miscible aqueous solution, and in this structure, because of their size, THF molecules occupy only the large 51264 cages. The CGC value appears to depend largely on the chemical nature of the liquid guest component participating in the binary hydrate formation. The present experimental findings on the existence of critical guest concentration and the complete tuning phenomenon can be expected to make a meaningful contribution to both inclusion chemistry and a variety of hydrate-based fields.

Raman spectroscopic measurements of various hydrogen bearing clathrate hydrates have been performed under high (< 1cm-1) and low resolution (>2 cm-1) conditions. Raman bands for hydrogen in most common clathrate hydrate cavities have been assigned. Unlike most clathrate hydrate guests, the general observation is no longer valid that the larger the clathrate cavity in which a guest resides, the lower the vibrational frequency. This is rationalized by the multiple hydrogen occupancies in larger clathrate cavities. Both the roton and vibron bands for hydrogen clathrates illuminate interesting quantum dynamics of the enclathrated hydrogen molecules. At 77K, the progression from ortho to para H2 occurs over a relatively slow time period (days). The para contribution to the roton region of the spectrum exhibits the triplet splitting also observed in solid para H2. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature and with isotopic substitution by deuterium. Raman spectra from H2 and D2 hydrates suggest that the occupancy patterns between the two hydrates are analogous. The Raman measurements demonstrate that this is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

The statistics of liquid-to-crystal nucleation are measured for clathrate-forming mixtures of tetrahydrofuran and water using an automatic lag time apparatus (ALTA). We measure the nucleation temperature where a single sample is repeatedly cooled, nucleated and thawed. This is done for a series of tetrahydrofuran concentrations and in several different sample tubes since the nucleation is heterogeneous and occurring on the tube wall. The measurements are also done at the same concentrations and tubes but with an added catalyst, a single crystal of silver iodide. We discuss the need for this type of measurement if the true nucleation temperature of the clathrate is to be found. Comparisons are also made with our high pressure data on real-world clathrate formers.