Inherent safety is claimed for gas-cooled pebble bed reactors, such as the South African Pebble Bed Modular Reactor (PBMR), as a result of its design characteristics, materials used, fuel type and physics involved. Therefore, a proper understanding of the mechanisms of heat transfer, fluid flow and pressure drop through a packed bed of spheres is of utmost importance in the design of a high temperature Pebble Bed Reactor (PBR). In this study, correlations describing the effective thermal conductivity through packed pebble beds are examined. The effective thermal conductivity is a term defined as representative of the overall radial heat transfer through such a packed bed of spheres, and is a summation of various components of the overall heat transfer. This phenomenon is of importance because it forms an intricate part of the self-acting decay heat removal chain, which is directly related to the PBR safety case. In this study standard correlations generally employed by the thermal fluid design community for PBRs are investigated, giving particular attention to the applicability of the correlations when simulating the effective thermal conductivity in the near-wall region. Seven distinct components of heat transfer are examined namely: conduction through the solid, conduction through the contact area between spheres, conduction through the gas phase, radiation between solid surfaces, conduction between pebble and wall, conduction through the gas phase in the wall region, and radiation between the pebble and wall surface. The effective thermal conductivity models are typically a function of porosity in order to account for the pebble bed packing structure. However, it is demonstrated in this study that porosity alone is insufficient to quantify the porous structure in a randomly packed bed. A new Multi-sphere Unit Cell Model is therefore developed, which accounts more accurately for the porous structure, especially in the near-wall region. Conclusions on the applicability of the model are derived by comparing the simulation results with measurements obtained from various experimental test facilities. This includes the PBMRs High Temperature Test Unit (HTTU) situated on the campus of the North-West University in Potchefstroom in South Africa. The Multi-sphere Unit Cell Model proves to encapsulate the impact of the packing structure in a more fundamental way and can therefore serve as the basis for further refinement of models to simulate the effective thermal conductivity. / Thesis (PhD (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2010

Inherent safety is claimed for gas-cooled pebble bed reactors, such as the South African Pebble Bed Modular Reactor (PBMR), as a result of its design characteristics, materials used, fuel type and physics involved. Therefore, a proper understanding of the mechanisms of heat transfer, fluid flow and pressure drop through a packed bed of spheres is of utmost importance in the design of a high temperature Pebble Bed Reactor (PBR). In this study, correlations describing the effective thermal conductivity through packed pebble beds are examined. The effective thermal conductivity is a term defined as representative of the overall radial heat transfer through such a packed bed of spheres, and is a summation of various components of the overall heat transfer. This phenomenon is of importance because it forms an intricate part of the self-acting decay heat removal chain, which is directly related to the PBR safety case. In this study standard correlations generally employed by the thermal fluid design community for PBRs are investigated, giving particular attention to the applicability of the correlations when simulating the effective thermal conductivity in the near-wall region. Seven distinct components of heat transfer are examined namely: conduction through the solid, conduction through the contact area between spheres, conduction through the gas phase, radiation between solid surfaces, conduction between pebble and wall, conduction through the gas phase in the wall region, and radiation between the pebble and wall surface. The effective thermal conductivity models are typically a function of porosity in order to account for the pebble bed packing structure. However, it is demonstrated in this study that porosity alone is insufficient to quantify the porous structure in a randomly packed bed. A new Multi-sphere Unit Cell Model is therefore developed, which accounts more accurately for the porous structure, especially in the near-wall region. Conclusions on the applicability of the model are derived by comparing the simulation results with measurements obtained from various experimental test facilities. This includes the PBMRs High Temperature Test Unit (HTTU) situated on the campus of the North-West University in Potchefstroom in South Africa. The Multi-sphere Unit Cell Model proves to encapsulate the impact of the packing structure in a more fundamental way and can therefore serve as the basis for further refinement of models to simulate the effective thermal conductivity. / Thesis (PhD (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2010

Thesis (M.S. in Chemical Engineering)--University of California, Berkeley, June 1955. / "Unclassified Chemistry." Errata sheet at end. Includes bibliographical references (p. 88). 12

A ciclodextrina glicosiltransferase (CGTase, EC 2.4.1.19) faz parte da família das α-amilases e se destaca por ser a única enzima capaz de produzir ciclodextrinas (CDs). Esses oligossacarídeos cíclicos possuem a capacidade de formar complexos de inclusão com uma variedade de moléculas, alterando suas características como, por exemplo, solubilidade, volatilidade e estabilidade. Desta forma, CDs tem encontrado aplicação nas mais diversas áreas. Na indústria de alimentos, se destacam por serem potenciais estabilizantes naturais. Buscando alternativas viáveis para produção destas ciclodextrinas, neste trabalho, a enzima CGTase foi imobilizada covalentemente em esferas de quitosana e posteriormente utilizada em um reator enzimático para uso contínuo. O rendimento da imobilização foi de aproximadamente 100 %, com uma carga de 20 mg de enzima por grama de suporte seco. O processo de imobilização foi capaz de manter o comportamento da enzima frente à variação de pH e temperatura de reação, apresentando pH ótimo em 5,0 e a faixa de temperatura ótima de 70 a 95 ºC, para ambos. A estabilidade conferida ao catalisador imobilizado possibilitou sua reutilização, 61 % da sua atividade inicial foi mantida após 100 ciclos de reação. Durante utilização contínua, realizada em um reator de leito fixo, analisou-se a influência da taxa de fluxo e da concentração do substrato na geração de β-CD. A máxima produção (1,32 g / L) foi alcançada utilizando-se 4 % de amido solúvel em uma taxa de fluxo de 3 mL / min. Além disso, o biocatalisador apresentou uma ótima estabilidade operacional a 60 °C, mantendo 100 % da atividade inicial após 100 h de uso contínuo. Estes resultados demonstram que o desempenho do reator é diretamente afetado pelos parâmetros analisados e que a produção pode ser otimizada por regulação simples na velocidade de fluxo, ou pela concentração do substrato; e sugerem a possibilidade de utilizar este biocatalisador imobilizado na produção contínua de CDs. / Cyclodextrin glycosyltransferase (CGTase, EC 2.4.1.19) is member of the family α-amylase and is known for being the only enzyme able to produce cyclodextrins (CDs). These cyclic oligosaccharides have the ability to form inclusion complexes with a variety of molecules, changing its characteristics, for example, solubility, volatility and stability. Therefore, CDs have found application in several fields. In the food industry stand out for being potential natural stabilizers. Seeking to alternatives for producing these cyclodextrins, in this work, the CGTase enzyme was immobilized covalently on chitosan beads and subsequently used in enzymatic reactor for continuous use. The immobilization yield was high, reaching about 100 %, representing a load of 20 mg enzyme per gram of dry support. The immobilization process was capable of maintaining the behavior of the enzyme to the variation of pH and temperature of reaction, with pH optimum at 5.0 and the optimal temperature range of 70 - 95 ° C, for both. The stability afforded to the immobilized catalyst made possible its reuse, maintaining 61 % of its initial activity after 100 cycles of reaction. During its continuous use, in a packed bed reactor, we analyzed the influence of flow rate and concentration of the substrate in the generation of β-CD. The maximum yield (1.32 g / L) was achieved using 4 % soluble starch at a flow rate of 3 mL / min. In addition, the biocatalyst showed a great operational stability at 60 ° C, maintaining 100 % of initial activity after 100 h of continuous use. These results demonstrate that the performance is directly affected by the parameters analyzed and that the production can be optimized by simple adjustment in flow rate through the reactor, or the substrate concentration used and suggests the possibility of using this biocatalyst immobilized to the continuous production of CDs.

A ciclodextrina glicosiltransferase (CGTase, EC 2.4.1.19) faz parte da família das α-amilases e se destaca por ser a única enzima capaz de produzir ciclodextrinas (CDs). Esses oligossacarídeos cíclicos possuem a capacidade de formar complexos de inclusão com uma variedade de moléculas, alterando suas características como, por exemplo, solubilidade, volatilidade e estabilidade. Desta forma, CDs tem encontrado aplicação nas mais diversas áreas. Na indústria de alimentos, se destacam por serem potenciais estabilizantes naturais. Buscando alternativas viáveis para produção destas ciclodextrinas, neste trabalho, a enzima CGTase foi imobilizada covalentemente em esferas de quitosana e posteriormente utilizada em um reator enzimático para uso contínuo. O rendimento da imobilização foi de aproximadamente 100 %, com uma carga de 20 mg de enzima por grama de suporte seco. O processo de imobilização foi capaz de manter o comportamento da enzima frente à variação de pH e temperatura de reação, apresentando pH ótimo em 5,0 e a faixa de temperatura ótima de 70 a 95 ºC, para ambos. A estabilidade conferida ao catalisador imobilizado possibilitou sua reutilização, 61 % da sua atividade inicial foi mantida após 100 ciclos de reação. Durante utilização contínua, realizada em um reator de leito fixo, analisou-se a influência da taxa de fluxo e da concentração do substrato na geração de β-CD. A máxima produção (1,32 g / L) foi alcançada utilizando-se 4 % de amido solúvel em uma taxa de fluxo de 3 mL / min. Além disso, o biocatalisador apresentou uma ótima estabilidade operacional a 60 °C, mantendo 100 % da atividade inicial após 100 h de uso contínuo. Estes resultados demonstram que o desempenho do reator é diretamente afetado pelos parâmetros analisados e que a produção pode ser otimizada por regulação simples na velocidade de fluxo, ou pela concentração do substrato; e sugerem a possibilidade de utilizar este biocatalisador imobilizado na produção contínua de CDs. / Cyclodextrin glycosyltransferase (CGTase, EC 2.4.1.19) is member of the family α-amylase and is known for being the only enzyme able to produce cyclodextrins (CDs). These cyclic oligosaccharides have the ability to form inclusion complexes with a variety of molecules, changing its characteristics, for example, solubility, volatility and stability. Therefore, CDs have found application in several fields. In the food industry stand out for being potential natural stabilizers. Seeking to alternatives for producing these cyclodextrins, in this work, the CGTase enzyme was immobilized covalently on chitosan beads and subsequently used in enzymatic reactor for continuous use. The immobilization yield was high, reaching about 100 %, representing a load of 20 mg enzyme per gram of dry support. The immobilization process was capable of maintaining the behavior of the enzyme to the variation of pH and temperature of reaction, with pH optimum at 5.0 and the optimal temperature range of 70 - 95 ° C, for both. The stability afforded to the immobilized catalyst made possible its reuse, maintaining 61 % of its initial activity after 100 cycles of reaction. During its continuous use, in a packed bed reactor, we analyzed the influence of flow rate and concentration of the substrate in the generation of β-CD. The maximum yield (1.32 g / L) was achieved using 4 % soluble starch at a flow rate of 3 mL / min. In addition, the biocatalyst showed a great operational stability at 60 ° C, maintaining 100 % of initial activity after 100 h of continuous use. These results demonstrate that the performance is directly affected by the parameters analyzed and that the production can be optimized by simple adjustment in flow rate through the reactor, or the substrate concentration used and suggests the possibility of using this biocatalyst immobilized to the continuous production of CDs.

A ciclodextrina glicosiltransferase (CGTase, EC 2.4.1.19) faz parte da família das α-amilases e se destaca por ser a única enzima capaz de produzir ciclodextrinas (CDs). Esses oligossacarídeos cíclicos possuem a capacidade de formar complexos de inclusão com uma variedade de moléculas, alterando suas características como, por exemplo, solubilidade, volatilidade e estabilidade. Desta forma, CDs tem encontrado aplicação nas mais diversas áreas. Na indústria de alimentos, se destacam por serem potenciais estabilizantes naturais. Buscando alternativas viáveis para produção destas ciclodextrinas, neste trabalho, a enzima CGTase foi imobilizada covalentemente em esferas de quitosana e posteriormente utilizada em um reator enzimático para uso contínuo. O rendimento da imobilização foi de aproximadamente 100 %, com uma carga de 20 mg de enzima por grama de suporte seco. O processo de imobilização foi capaz de manter o comportamento da enzima frente à variação de pH e temperatura de reação, apresentando pH ótimo em 5,0 e a faixa de temperatura ótima de 70 a 95 ºC, para ambos. A estabilidade conferida ao catalisador imobilizado possibilitou sua reutilização, 61 % da sua atividade inicial foi mantida após 100 ciclos de reação. Durante utilização contínua, realizada em um reator de leito fixo, analisou-se a influência da taxa de fluxo e da concentração do substrato na geração de β-CD. A máxima produção (1,32 g / L) foi alcançada utilizando-se 4 % de amido solúvel em uma taxa de fluxo de 3 mL / min. Além disso, o biocatalisador apresentou uma ótima estabilidade operacional a 60 °C, mantendo 100 % da atividade inicial após 100 h de uso contínuo. Estes resultados demonstram que o desempenho do reator é diretamente afetado pelos parâmetros analisados e que a produção pode ser otimizada por regulação simples na velocidade de fluxo, ou pela concentração do substrato; e sugerem a possibilidade de utilizar este biocatalisador imobilizado na produção contínua de CDs. / Cyclodextrin glycosyltransferase (CGTase, EC 2.4.1.19) is member of the family α-amylase and is known for being the only enzyme able to produce cyclodextrins (CDs). These cyclic oligosaccharides have the ability to form inclusion complexes with a variety of molecules, changing its characteristics, for example, solubility, volatility and stability. Therefore, CDs have found application in several fields. In the food industry stand out for being potential natural stabilizers. Seeking to alternatives for producing these cyclodextrins, in this work, the CGTase enzyme was immobilized covalently on chitosan beads and subsequently used in enzymatic reactor for continuous use. The immobilization yield was high, reaching about 100 %, representing a load of 20 mg enzyme per gram of dry support. The immobilization process was capable of maintaining the behavior of the enzyme to the variation of pH and temperature of reaction, with pH optimum at 5.0 and the optimal temperature range of 70 - 95 ° C, for both. The stability afforded to the immobilized catalyst made possible its reuse, maintaining 61 % of its initial activity after 100 cycles of reaction. During its continuous use, in a packed bed reactor, we analyzed the influence of flow rate and concentration of the substrate in the generation of β-CD. The maximum yield (1.32 g / L) was achieved using 4 % soluble starch at a flow rate of 3 mL / min. In addition, the biocatalyst showed a great operational stability at 60 ° C, maintaining 100 % of initial activity after 100 h of continuous use. These results demonstrate that the performance is directly affected by the parameters analyzed and that the production can be optimized by simple adjustment in flow rate through the reactor, or the substrate concentration used and suggests the possibility of using this biocatalyst immobilized to the continuous production of CDs.

Ditiocarbamatos (DTC) tem uma vasta gama de aplicação. Na indústria são usados como ativos para vulcanização da borracha; lubrificantes e anticorrosivos para trabalhos em alta pressão. Na medicina são estudados como potenciais inibidores do fator nuclear kappa β (NF-KB) e da protease do HIV-1; além da aplicação como indutores da apoptose em vários tipos de células carcinogênicas e como agentes antimicrobianos e antifúngicos. Derivados cíclicos de ditiocarbamatos são capazes de formar extensos arranjos no estado sólido mantidos por ligações de hidrogênio, interações do tipo π - π, interações metal - π e interações de van der Waals. No presente trabalho, determinou-se a natureza dessas interações em ditiocarbamatos derivados da própria amina substituinte e de metais alcalinos. Foram calculados mapas de potencial eletrostático molecular e momentos dipolo, a fim de entender quais fatores regem o empacotamento cristalino. Os átomos de enxofre nessas moléculas apresentam ligações mono ou bidentadas e ligações hidrogênio intramoleculares, que formam arranjos poliméricos. Essas interações são fracas, com distâncias da ordem da soma de seus raios de van der Waals, semelhante ao grafite. / Dithiocarbamates (DTC) are applied in several areas such as agricultural products, pesticides and repellents; industry, as additives for vulcanization of rubber; organic synthesis as precursors; chelating agents; lubricants and antiwear at high pressure. In medical fields, they have also been applied as a potential nuclear factor kappa B (NF - κB) inhinitor; transcription factor heat shock factor 1 (HSF1); HIV-1 protease inhibitor; co-adjuvant agent in the treatment of opportunistic infections in AIDS patients; inducer of apoptosis activity in several types of cancer cells, e.g. renal cell carcinoma, breast cancer; besides being great antimicrobicial and antifungal agents. Cyclic dithiocarbamate derivates are capable of forming extended hydrogen bonded arrays in the solid state. They are kept in the solid state by hydrogen bonds, π - π interactions stacking, π - metal interactions and van der Waals interactions. This work presents eight ditihiocarbamates derivates, their syntheses and recrystallization. The analysis of the dithiocarbamates salts was performed by X-ray diffraction which has gave the influence of the ligand in the crystalline arrangement, and molecular electrostatic potential maps, by DFT calculations. The sulphur atoms in these molecules have mono or bidentate bonds and intramolecular hydrogen bonds, forming polymeric arrangements. These interactions are weak, with distances of the order of the sum of their van der Waals radii, similar to graphite.

Packed bed combustors burn fairly large solid fuel particles within confining walls, with air supplied from below the grate. As combustion occurs and particles are consumed, fresh particles are fed onto the bed so the level is kept roughly constant. Packed bed combustion is used for wood and biomass combustion in small-scale power plants, wood waste combustion in pulp and paper plants, and trash incineration. The structure of a packed bed is very important to the combustion process and can be defined by particle shape and size, sphericity, particle overlap (decreasing area availability) and chiefly by void fraction. Void fraction has already been proven of great influence in packed beds – it is raised to the third power in the pressure loss equation, and it can also affect heat and mass transfer and surface reaction rates. This thesis presents results of several experimental combustion tests that were performed in a packed bed combustor, using commercial spruce lumber particles of parallelepipedal geometry as fuel. At the end of each test the bed contents were removed, taking care to preserve their structure, and fixed with liquefied wax. The solidified bed was then cut into circular cross sections at different heights of the bed, and photographs of the cross sections were taken so the local void fraction could be estimated using image analysis. The bed sampling led to the discovery that, surprisingly, the actual bulk void fraction in the combustor, which is the average of local void fraction measurements, is less than that of the unburnt particles, varying from 19% to 30% in decrease in void fraction depending on the particle type used. Local measurements allowed the development of an empirical linear equation model to represent the variation of void fraction with height above the grate. Each combustion test had measurements of gas volume fractions and temperatures at different heights above the bed grate to be compared with the results of a numerical model simulation. The numerical model used in this work is an existing numerical model of all the relevant processes in packed bed combustion. Previously, the numerical model had assumed the void fraction to be constant and equal to that of the unburnt fuel, since no information on local variation was available, and the packing geometry remained self-similar as particles are consumed. Three models for void fraction were then compared in the combustion model: a constant void equal to that of the unburnt particles, the empirical linear fit of void fraction with height, and a constant void equal to the measured bulk void fraction. Maximum temperatures were higher using the unburnt fuel void fraction because of a thicker oxidation zone, whereas the void fraction model iii based on experiments generated a thicker reduction zone and therefore higher CO concentrations. CO concentrations were experimentally measured and agreed quite well with the CO concentration from the model. Local void fraction differences had the most impact in the diffusion-controlled zone, as shown by comparing the empirical void model and the measured bulk void fraction. How lowering the void fraction can increase gas velocities, heat and mass transfer coefficients, and burning rates is also discussed in this work.

Ask a computer to store a decimal whole number in binary and it will do it without any fuss. A decimal fraction, however, that’s another thing. In this episode, we will present a method called Packed BCD that is used to accurately represent decimal values in binary by storing each digit in its own nibble.

<p> A unified approach, employing effective phonon frequency distributions, is used to investigate effects of phonon anisotropy in the hcp metals.</p> <p> Phonon information is included by means of empirical force constant models, and pseudopotentials are used to describe the electron-ion interaction.</p> <p> Zinc and thallium superconducting gaps are determined as a function of position on the Fermi surface. The gap anisotropy is used to calculate thermodynamic properties.</p> <p> The normal state electron-phonon mass enhancement and the imaginary part of the electron self-energy are calculated as a function of temperature and Fermi surface position. Anisotropic transport scattering times are defined, calculated and used to obtain the polycrystalline and single crystal resistivities. Comparison is made with resistivities obtained by the variational approach.</p> / Thesis / Doctor of Philosophy (PhD)