Abstract not available

The research addressed in this thesis focuses on monitoring and characterization of pharmaceutical compounds by laser backscattering. In particular, this study covers two topics: (1) the determination of naproxen sodium solubility in water, and its phase transition; and (2) comparisons of batch and laminar flow tubular crystallizers for the production of paracetamol (acetaminophen) and D-mannitol. Using a Lasentec™ Focused Beam Reflectance Measurement (FBRM) device, the solubility of naproxen sodium in aqueous solutions was determined over a temperature range from 15.2 to 39.7 ℃ With the determination of the solubilities of two pseudopolymorphs, anhydrous and dihydrated naproxen sodium, the phase transition point between these two forms of the pharmaceutical compound was determined to occur at 30.3 ℃ Enthalpy of solution and metastable zone widths were also determined for the experimental conditions. Crystallizations of paracetamol and D-mannitol were performed in a batch crystallizer and in a laminar flow tubular crystallizer (LFTC) system. In the latter system, supersaturation was generated rapidly in the solution being transported through a temperature-controlled tube and recovered in a batch vessel where product crystals were grown to equilibration. Because of the rapid rate at which supersaturation was generated in the LFTC, the resulting crystals were of smaller mean size than those obtained from batch crystallizations. The total time required for crystallization was significantly less with the LFTC than with the batch unit. Additionally, the rapid cooling in the LFTC led to the formation of two different polymorphs of paracetamol, Forms I and II.

In this thesis, performance of a heat pump aided by solar heating system with an evacuated tubular collector has been analyzed theoretically and experimentally. For this purpose, a domestic hot water heating system has been designed, constructed and tested. The evacuated tubular solar collector has been used to achieve higher collector efficiency in winter. The fraction of the solar energy utilized has been measured experimentally and estimated theoretically. Effects of various parameters have been investigated on the performance of the proposed system. A mathematical model was developed to investigate the effects of different environmental, design and operational parameters on the solar heating system. In order to compare the obtained theoretical results with experimental ones, an experimental study has been carried out. For that, a number of experiments have been made at the solar house of the Mechanical Engineering Department of METU. An air-to-air heat pump was integrated with an evacuated tubular solar water heater unit (closed water circulation) and the performance of it has been studied experimentally. As a result of the experimental study, the maximum value of the coefficient of performance of the solar assisted heat pump used in this study was obtained as 4.85. The second law efficiency of the system was between 4.8-27.4 %.

Capillary pumped loop (CPL) and loop heat pipe (LHP), are two-phase heat transport devices which rely on surface tension induced by a fine pore wick to drive a working fluid in a loop. These are based on a working principle similar to that of heat pipes -closed evaporation and condensation cycle being maintained by capillary pumping. CPLs and LHPs are gaining importance as a part of the thermal control system of modern high power spacecraft, electronic thermal management, cryogenics, etc. A mathematical model to simulate the thermo-hydraulic performance of CPLs and LHPs is developed to aid in the design of such a spacecraft thermal control system. In this study a unified mathematical model to estimate thermal and hydraulic performance of a CPL and an LHP -with a two-phase or a hard-filled reservoir is presented. The steady state model is based on conservation of energy and mass in the system. Heat exchanges between the loop and the surroundings and pressure drops in the loop are calculated. The constant conductance regime in a CPL or an LHP occurs when the reservoir is hard-filled. It also occurs in an LHP if the condenser is fully utilised. The heat leak across the wick becomes significant in a hard-filled LHP since the core is no longer saturated and hence the mass flow rate must be calculated using an energy balance on the outer surface of the wick. Theoretical studies indicate that the core of a hard-filled CPL and LHP is always sub-cooled. Hard-filled LHPs (with a bayonet) cannot be operated under all conditions. If the heat exchange between the compensation chamber (of an LHP with bayonet) and the ambient is small then such an LHP will not deprime if the hard-filling occurs before the condenser opens. Deprime due to hard-filling is not expected if it occurs after the condenser opens. A laboratory model is built to demonstrate the operation of these two devices and to correlate the theoretical predictions with the experimental observations. The CPL/LHP laboratory model is fabricated and designed so that different evaporator and reservoir designs can be integrated into the test-rig and tested with different working fluids. Experiments are conducted on a three-port CPL with a tubular axially grooved (TAG) evaporator. This CPL is operated with three different fluids -namely -Ammonia, Acetone and R134a. The CPL is operated for heat loads in the range of 75W to 400W with sink temperatures of -10◦C and 0◦C. The influence of reservoir temperature (35◦C and 43◦C) is also studied. The TAG evaporator is modified to operate in an LHP mode with R134a as the working fluid with heat loads in the range of 75W to 150W. This LHP does not exhibit typical “√” shaped operating characteristic due to large liquid inventory in the compensation chamber (CC). The R134a based LHP results suggest that large liquid inventory (in the CC) and absence of secondary wick significantly influence the thermal coupling between the core and the compensation chamber. Experiments are also conducted with a flat plate (FP) evaporator, in LHP operating mode, with Ammonia as the working fluid. This LHP can transport heat loads from 25W to 300W with a sink temperature at -15◦C. The experimental results indicate that ammonia is the best working fluid (moderate temperature regime) among all the working fluids tested, and that evaporation heat transfer coefficients in sintered Ni-wick are better. The correlation of the predicted temperatures on the transport lines and the saturation temperature (in LHPs) with the observations is good. Some of the salient conclusions from these experiments are that mass of charge can significantly influence the operating characteristics of a TAG LHP, even though the fluid in the CC is in two-phase condition. Theoretical predictions can be significantly affected when thermal and hydraulic development lengths in the condenser are comparable with the length of the sub-cooling section.

Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 198-201). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 198-201). Also available on the Internet.

[pt] A deposição de parafinas em dutos traduz-se em perdas econômicas relevantes para a indústria. Dentre as formas de mitigação do fenômeno, encontram-se os inibidores de parafina, produtos químicos injetados continuamente e em baixas concentrações, cujo objetivo é eliminar ou reduzir a deposição. Tradicionalmente, a eficiência de inibição destes produtos para uma dada amostra de petróleo é avaliada em laboratório em equipamento denominado dedo-frio. No entanto, não há uma padronização para o projeto e uso destes equipamentos e procedimentos experimentais de teste. Também, ainda não há consenso entre fabricantes dos inibidores e operadoras de petróleo sobre a correlação entre a eficiência de inibição apresentada nos testes de dedo frio e aquela observada no campo. O presente trabalho teve como objetivo comparar resultados de deposição de parafina obtidos em dedo frio do tipo dinâmico com aqueles obtidos em duto circular em loop de teste, utilizando solução de teste com propriedades controladas, com e sem a presença de inibidor de parafina. No dedofrio do tipo dinâmico, um cilindro refrigerado imerso no óleo gira com velocidade angular constante, promovendo um escoamento do tipo Taylor-Couette, caracterizado por padrões de escoamento complexos e diferentes daqueles encontrados em dutos de transporte de petróleo. O trabalho teve como foco o estudo da influência de parâmetros hidrodinâmicos na deposição de parafinas, representados pelo número de Reynolds e tensão cisalhante adimensional sobre a superfície do depósito. Testes realizados com os fluidos modelo em regime laminar e turbulento mostraram boa correlação entre os resultados de inibição obtidos no dedo frio e no loop de teste, a despeito da diferença nos padrões de escoamento. Testes em regime turbulento resultaram em depósitos menores e menos porosos, tanto no dedo-frio quanto no loop. Foi também observada a redução da porosidade dos depósitos com a adição do inibidor,independentemente do tipo de equipamento e da condição operacional. Experimentos no dedo-frio com um segundo fluido, mais viscoso, foram conduzidos com o objetivo de avaliar a influência da viscosidade no processo de deposição, tendo como premissa a diminuição do coeficiente de difusão esperada para o fluido mais viscoso. Ao contrário do esperado, não foi observada variação sensível na deposição com a mudança da viscosidade do fluido. Efeitos positivos e negativos de inibição foram observados nos testes para o inibidor avaliado. Observou-se uma maior atuação do inibidor, seja positiva ou negativa, para experimentos em regime laminar. O presente estudo mostrou que o inibidor pode diminuir a massa total depositada aumentando, no entanto, a massa de parafina depositada. / [en] Wax deposition in pipelines is associated with relevant economic losses for the industry. Wax deposition inhibitors are among the options available to mitigate the problem, being continuously injected in the flow at low concentrations. Traditionally, the inhibition efficiency of these products for a particular oil sample is assessed in a laboratory equipment know as cold finger. However, a standard is still not available for the design and operation of cold fingers. Also, there is no consensus among operators and inhibitor suppliers as to the level of correlation between the inhibition efficiency found in the laboratory and that in the field. The objective of the present work was to compare wax deposition results obtained in a dynamic cold finger apparatus to those obtained in a pipe flow loop, employing a test solution with controlled properties, with and without inhibitor, In the dynamic cold finger, a cylinder immersed in the oil sample rotates at constant angular velocity producing a Taylor-Couette flow in the cylindrical oil container, which is characterized by complex flow patterns, that are distinct from those found in an oil pipeline. The investigation focused on the influence of the flow hydrodynamic parameters on the wax deposition, represented by the Reynolds number and the dimensionless shear stress imposed at the deposit surface. Tests conducted with model fluids in laminar and turbulent regimes displayed good correlation between the inhibition results obtained in the cold finger apparatus and in the test loop, despite the differences in flow patterns. Turbulent flow testes produced smaller and less porous deposits both, in the cold finger and in test loop. Also observed was a reduction in the deposit porosity in the presence of the inhibitor, independently of the equipment type and operational conditions. Experiments in the cold finger for a second more viscous fluid were conducted to assesses the influence of viscosity on the deposition process, and the expected decrease in the diffusion coefficient for the higher viscosity fluid. Contrary to what was expected, no significant variation was observed on the deposits with the viscosity change. Positive and negative inhibition effects were observed in the tests for the particular inhibitor tested. A more significant influence of the inhibitor, either positive or negative, was observed for tests in laminar flow conditions. The present study revealed that the inhibitor could decrease the total deposited mass while increasing the paraffin deposited mass.

Sepsis and septic shock remain major cause of mortality in non-coronary intenisve care units. Prognosis of septic patiens worsens further in case of concomitant acute kidney injury. Pathophysiological pathways leading to renal dysfunction in sepsis remain unclear despite of enormous experimental and clinical research. Similarly, the role of extracorporeal blood purification techniques as an adjunctive treatment in sepsis is highly controversial. The aim of our study was to dynamically assess renal haemodynamic, microvascular and metabolic responses in a porcine clinically relevant model of septic shock. The same experimental model was used in experiments elucidating potential benefit effects of two distinct haemopurification methods on different biological responses to infectious insult.

Le glycérol est un coproduit de la filière des biocarburants obtenu par transestérification destriglycérides. Avec le développement des biocarburants, la production de glycérol est en pleine croissance.La consommation de glycérol comme additif dans les industries cosmétique, pharmaceutique et agroalimentairen’augmentant pas de manière aussi significative, l’excédent doit être valorisé. L’une des voies devalorisation est la synthèse du carbonate de glycérol qui est un intermédiaire intéressant pour la chimie fine.La méthode de synthèse utilisée au sein de l’industrie Novance est la carbonylation du glycérol par l’urée enprocédé discontinu. Cette réaction produit, en plus du carbonate de glycérol, une grande quantitéd’ammoniac gazeux extrait du milieu réactionnel par dépression. L’ampleur de ce dégagement gazeux ainsique son irrégularité au cours du temps représente la limitation de production du procédé discontinu. Le sujetde cette étude est de développer le procédé continu de cette synthèse afin de pallier ce problème. Pourréaliser le suivi de la réaction, des méthodes analytiques ont été développées dans un premier temps. Avecces outils, les connaissances du système discontinu ont été approfondies pour déterminer les critères dechoix du procédé continu. Une unité de désorption réactive a été ensuite conçue pour créer un systèmebiphasique gaz-liquide à contre-courant. Une série d’essais préliminaires a permis le développement duprocédé qui a été optimisé par un plan de Doehlert. / Glycerol is a by-product of biofuels obtained by transesterification of triglycerides. With developmentof biofuel, glycerol production is growing. The use of glycerol in cosmetic, pharmaceutical and food industriesis not increasing in the same way, so the surplus should be preferable to market. One way of development isthe synthesis of glycerol carbonate which is an interesting intermediate for fine chemistry. The synthesisused by Novance is carbonylation of glycerol by urea with a batch process. This reaction produces, as wellas glycerol carbonate, a high quantity of gaseous ammonia extracted from reactive mixture in a vacuum. Thescale of this gaseous emission and its irregularity during synthesis show the limits of production using abatch process. The aim of this study is to develop the continuous process of the synthesis to solve thisproblem. To carry out the monitoring of the reaction, at first, analytical methods were used. With suchmethods, knowledge of the batch process was improved in order to determine the best criteria for acontinuous process. A unit of reactive desorption was then elaborated to create a liquid-gas biphasic systemin a counter-flow configuration. A series of preliminary experiments were performed to develop the processwhich was optimised by a Doehlert plan.

Este trabalho objetiva fornecer subsídios para uma maior compreensão dos elementos estruturais da Suíte para Órgão do Oratório “Sete Palavras de Cristo na Cruz”, opus 257 (1991) do compositor brasileiro Amaral Vieira e sua relação com o Oratório, do mesmo nome, opus 255a, através da análise relacionada com o texto e contexto do Oratório. A metodologia consiste no levantamento de informações a cerca da obra, questionário destinado ao compositor sobre o Oratório e Suíte para Órgão, identificação de aspectos retóricos e análise musical da obra observando a relação texto/música. Este trabalho poderá contribuir para uma melhor compreensão da Suíte para Órgão de Amaral Vieira através do aprofundamento de seu conteúdo musical aqui apresentado. / This study investigates the context and relationship of the Suite for Organ from the Oratory “The Seven Last Words of Christ on the Cross”, opus 257 (1991) and the Oratory itself (opus 255a), both by the Brazilian composer Amaral Vieira, for a better understanding of its structural elements. The methodology includes the context of both works, a questionnaire directed to the composer, analysis of the Suite, and identification of rhetorical aspects as they pertain to the Oratory. This work may contribute to a better understanding of the Suite for Organ by Amaral Vieira through the musical content presented here.