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M.S.

M.S.

M.S.

Microwave heating is implemented in various fields such as drying, material processing, and chemical reactors. Microwaves offer several advantages over conventional heating methods: 1) microwaves deposit heat directly in the material without convection or radiation, 2) microwave heating is easy and efficient to implement, and 3) microwave processes can be controlled.In order to understand how to use microwaves more efficiently, we must understand how they affect the material with which they interact.This requires the ability to predict the temperature distribution that is achieved within the material.In recent years packed and fluidized beds have been used as chemical reactors to achieve various tasks in industry.Recent studies have shown that microwave heating offers the potential to heat the bed particles to a higher temperature than that of the fluid.This results in enhanced reaction rates and improves the overall efficiency of the reactor.T he focus of this work is to determine the temperature distributions within the packed and fluidized beds, and to determine whether the catalyst particles can be heated to a higher temperature than the gas in catalytic reactions. The beds are modeled with multiphase flow equations.The gas velocity profiles along with the solid and gas temperature profiles for packed and fluidized beds are provided. F or the fluidized beds, the hydrodynamics is modeled using FLUENT and the solid velocity profiles are also determined. / Ph. D.

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When a disordered packed bed, or any heterogeneous media is studied using computational fluid dynamics, the tortuous task of generating a domain and creating a workable mesh presents a challenging issue to Engineers and Scientists. In this Thesis these challenges are addressed in the form of three studies in which both traditional and novel techniques are used to generate packed beds of spheres and cylinders for analysis using computational fluid dynamics, more specifically, the finite volume method. The first study uses a Monte-Carlo method to generate random particle locations for use with a traditional CADbased meshing approach. Computational studies are performed and compared in detail with experimental equivalent beds. In the second study, where there is a need for actual, physical beds to be studied, magnetic-resonance-imaging is used coupled with a novel approach known as image based meshing. In parallel experimental studies are performed on the experimental bed and compared with computational data. In the third study, to overcome fidelity issues with the previous approaches, a physical packed bed is manufactured which is 100% geometrically faithful to its computational counterpart to provide a direct comparison. All three computational studies have shown promising results in comparison with the experimental data described in this Thesis, with the data of Reichelt (1972) and the semi-empirical correlation of Eisfeld & Schnitzlein (2001). All experiments and computational models were carried out by the author unless otherwise stated.

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.

Requirements for increased operating efficiencies mean that future generations of aero-engines will need to operate at temperatures beyond the capabilities of current nickel-base superalloys. As a result, new alloy compositions for turbine disc applications are being developed. Optimising these alloy compositions requires balancing directly competing requirements. Increased Cr contents are needed to provide environmental resistance and increased concentrations of other refractory metals to improve solid solution strengthening. However, these elements compromise the alloyâs long-term microstructural stability by promoting the formation of topologically close-packed (TCP) phases, which are deleterious to alloy performance. High $\gamma^\prime$ volume fractions, which are needed to provide high-temperature strength, exacerbate the problem by increasing the concentration of these elements in the $\gamma$ phase. Therefore, an understanding of TCP formation and the compositional limits of stability is vital in the design of new alloys. This thesis presents a combination of fundamental studies of TCP phase formation in model alloys and microstructural assessment of the thermal stability of developmental alloy compositions. Knowledge of the effect of individual elements on thermal stability is important to enable the development of optimised alloy compositions. As a result, the first fundamental study investigated the effect of Co content on thermal stability. An unexpected transition in $\sigma$ precipitation behaviour after 500 hours at 800°C was observed between 12 and 16 at.\% Co. It is proposed that this behaviour may be due to the effect of Co on the $\gamma$/$\gamma^\prime$ partitioning behaviour of other elements. Preliminary results from further fundamental studies investigating the effect of the Mo/W ratio and B content on thermal stability are also presented. Decreasing the Mo/W ratio was found to reduce the quantity of $\sigma$ precipitation and promote the precipitation of a W-rich phase. B additions were found to promote the precipitation of the M$_3$B$_2$ phase. Thermodynamic predictions are frequently used to inform alloy design as an alternative to time-consuming and costly experiments. However, the accuracy of solvus temperature predictions for TCP phases has not been thoroughly considered. In this work, it was found that differential scanning calorimetry could be used as a means of measuring $\sigma$ solvus temperature in a series of alloys designed to be sufficiently unstable with respect to $\sigma$ precipitation. Comparison of experimental results with thermodynamic solvus temperature predictions revealed a significant underprediction of the $\sigma$ solvus temperatures for all of the studied alloys. This can inform our use of such predictions during alloy design. The ability to quantify the amount of TCP precipitation that occurs is extremely important when assessing the thermal stability of alloys. A new method was applied to the problem of TCP quantification, involving synchrotron X-ray diffraction of solid aged samples. This was an attempt to avoid some of the problems identified with the commonly used quantification method, which involves electrolytic extraction of minor phases, and assess the accuracy of the results produced by this method. Samples of a currently used commercial alloy, RR1000, were investigated following ageing for up to 5000 hours at 800°C, revealing the evolution of phases at this temperature. The presence of extremely low quantities of minor phases was successfully detected in the solid samples using this method. However, these quantities were too low for this to be a reliable method of quantification for commercial alloys. In parallel with these fundamental and technique-based studies, the thermal stability of a number of candidate alloys, which were developed during the design of a next-generation disc alloy by Rolls-Royce, was assessed. The alloys were characterised following a variety of thermal exposure temperatures and durations, which were determined by industrial needs at the time. Various minor phases were identified depending on the alloy compositions, including the TCP phases, $\sigma$ and $\mu$, as well as MC and M$_{23}$C$_6$ carbides and M$_3$B$_2$ borides.

Pressure drops over a packed bed of pebble bed reactor type are investigated. Measurement of porosity and pressure drop over the bed were carried out in a cylindrical packed bed facility. Air and water were used for working fluids. There are several parameters of the pressure drop in packed beds. One of the most important factors is wall effect. The inhomogeneous porosity distribution in the bed and the additional wetted surface introduced by the wall cause the variation of pressure drop. The importance of the wall effects and porosity can be explained by using different bed-to-particle diameter ratios. Four different bed-to-particle ratios were used in these experiments (D/dp = 19, 9.5, 6.33 and 3.65). A comparison is made between the predictions by a number of empirical correlations including the Ergun equation (1952) and KTA (by the Nuclear Safety Commission of Germany) (1981) in the literature. Analysis of the data indicated the importance of the bed-to-particle size ratios on the pressure drop. The comparison between the present and the existing correlations showed that the pressure drop of large bed-to-particle diameter ratios (D/dp = 19, 9.5and 6.33) matched very well with the original KTA correlation. However the published correlations cannot be expected to predict accurate pressure drop for certain conditions, especially for pebble bed with D/dp (bed-to-particle diameter ratio) </= 5. An improved correlation was obtained for a small bed-to-particle diameter ratio by fitting the coefficients of that equation to experimental database.