Este trabalho teve por objetivo aplicar a análise térmica e outras técnicas físico-químicas e analíticas ao desenvolvimento e controle de qualidade de fármacos e medicamentos para tratamento de tuberculose, em especial a rifampicina. A calorimetria exploratória diferencial (DSC), termogravimetria/termogravimetria derivada (TG/DTG), análise elementar, espectrometria de absorção na região do infravermelho (IV) e difratometria de raios X (DRX) foram as principais ferramentas utilizadas. Estas técnicas permitiram: avaliar a estabilidade térmica e o processo de decomposição térmica da rifampicina e dos excipientes, utilizados em formulações farmacêuticas; diferenciar os dois tipos de formas polimórficas; desenvolver estudos para determinação de parâmetros cinéticos e avaliar as possíveis interações entre a rifampicina e excipientes. Os estudos foram desenvolvidos empregando duas amostras de rifampicina, identificadas como polimorfos I e II. Os resultados de análise elementar evidenciaram que ambas as amostras têm a mesma composição e estequiometria (C43H58N4O12), característica do fármaco em questão. Os espectros no IV de ambas as amostras são muito similares, porém apresentam ligeiras diferenças devido às pequenas variações que existem na conformação molecular das formas polimórficas. Essas diferenças são nítidas quando se compara as bandas de absorção dos grupos ansa-OH, furanona e acetil, em ambos os espectros. Os difratogramas de raios X evidenciam que ambas as amostras são cristalinas, porém as distâncias interplanares não são coincidentes confirmando que se trata de duas estruturas distintas. As curvas TG/DTG evidenciaram que o polimorfo I é mais estável termicamente que o polimorfo II. As curvas DSC confirmam o resultado de TG/DTG e permitem diferenciar claramente uma forma polimórfica da outra. A curva DSC do polimorfo II mostra que inicialmente ocorre o processo de fusão seguido de cristalização com a formação do polimorfo I, que simultaneamente se decompõe termicamente. O espectro infravermelho do produto isolado após a recristalização do polimorfo II confirma a conversão ao polimorfo I. A partir dos estudos cinéticos não isotérmicos e isotérmicos por TG foi possível calcular a energia de ativação envolvida na decomposição térmica de cada um dos polimorfos. Os estudos de pré-formulação, empregando misturas físicas na proporção 1:1 fármaco/excipiente, indicaram que há interação entre o polimorfo II e os excipientes PEG 6000 e Lutrol F68. Durante a fusão dos excipientes ocorre à dissolução do fármaco e a conseqüente conversão ao polimorfo I. Os estudos de compatibilidade fármaco-fármaco de rifampicina e isoniazida mostraram que há interação com ambos os polimorfos. Tudo indica que a interação entre as espécies conduz a formação do composto 3-(isonicotinoilhidrazinometil)rifamicina. A avaliação dos perfis termoanalíticos dos produtos comerciais permitiu identificar qual dos polimorfos foi empregado na produção. Foi possível concluir que os ensaios de DSC permitem identificar o tipo de polimorfo de rifampicina utilizado em associações com isoniazida. / This work was aimed at implementing the thermal analysis and other physico-chemical and analytical techniques in the development and quality control of drugs and medicines for the treatment of tuberculosis, especially rifampicin. The differential scanning calorimetry (DSC), thermogravimetry/derivative thermogravimetry(TG/DTG), elemental analysis, X-ray diffraction (XRD) and infrared spectrometry (IR) were the main tools used. These techniques allowed to: evaluate thermal stability and the process of thermal decomposition of rifampicin and excipients used in pharmaceutical formulations; distinguish the two types of polymorphic forms; develop studies to establish kinetic parameters and evaluate the possible interactions between rifampicin and excipients. The studies were developed using two rifampicin samples, identified as polymorphs I and II. The elemental analysis results showed that both samples have the same composition and stoichiometry (C43H58N4O12), characteristic of the drug in question. IR spectra of both samples are very similar, but with little differences due to variations in the molecular conformation of polymorphic forms. These differences are clear when the absorption bands of ansa-OH, furanone and acetyl groups are compared in both spectra. XRD patterns showed that the two samples are crystalline and that they are two distinct structures. TG/DTG curves showed that polymorph I is more thermally stable than polymorph II. DSC curves confirm the TG/DTG results and allow to clearly differentiate a polymorphic form of the other. DSC curve of the polymorph II shows that initially occur the melting process, followed by crystallization and formation of polymorph I, which then is thermally decomposed. IR spectrum of the product isolated after recrystallization of polymorph II confirms the conversion to polymorph I. After Isothermal and non-isothermal kinetic studies by TG, it was possible to calculate, in both cases, the activation energy envolved in the thermal decomposition of each polymorph. The pre-formulation studies, using physical mixtures in the proportion 1:1 drug/excipient, indicated that there is interaction between the polymorph II and PEG 6000 and Lutrol F68. The excipients melt and dissolve the drug, which is converted to polymorph I. The drug-drug compatibility studies of rifampicin and isoniazid showed that there is interaction with both polymorphs. It appears that the interaction between the species leads to formation of the 3-(isonicotinylhydrazinmethyl) rifamycin compound. The evaluation of thermoanalytical profiles of commercial products allowed the identification of the polymorph was used in the formulation. It was possible to conclude that DSC tests identify the rifampicin polymorph used in association with isoniazid.

Orientador: Osvair Vidal Trevisan / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica e Instituto de Geociencias / Made available in DSpace on 2018-08-12T07:44:05Z (GMT). No. of bitstreams: 1 Pereira_AndersondoNascimento_M.pdf: 1764452 bytes, checksum: 44e9759a891f9db655bfe6ef14b37f3a (MD5) Previous issue date: 2008 / Resumo: Um dos maiores desafios nos estudos da Combustão In Situ é o desenvolvimento de um modelo cinético reacional de forma a representar a dinâmica das numerosas reações químicas que ocorrem em diferentes faixas de temperatura. O objetivo deste trabalho é desenvolver um estudo do comportamento oxidativo de um óleo pesado brasileiro e obter parâmetros cinéticos a partir dos dados experimentais gerados nas técnicas clássicas de análise térmica como TG, DTA e DSC. A análise térmica é sistematicamente desenvolvida em amostras de óleo e óleo com areia. Os dados experimentais nela obtidos são tratados para a realização de um estudo cinético global de acordo com diferentes modelos cinéticos não-isotérmicos convencionais e isoconversionais, gerados por método integral ou diferencial, todos baseados no modelo cinético de Arrhenius. Como resultado do estudo termoanalítico foram identificadas três regiões de oxidação: de baixa temperatura (OBT), de transição e de alta temperatura (OAT). Verificou-se uma maior intensidade na variação de massa e energia na faixa de OAT e um efeito de resistência de transferência de massa no final da OBT (efeito "skin"). Como resultado do estudo cinético, todos os modelos estudados forneceram valores de energia de ativação maiores na OAT do que na OBT. Observou-se que a presença de areia contribui para as reações OAT e dificulta o início da OAT por conta da acentuação do efeito "skin". / Abstract: One of the main challenges in studies on In Situ Combustion resides in developing a kinetic reaction model to represent the dynamics of the numerous chemical reactions that occur at different temperature ranges. The objective of the present research is to develop a study on the oxidation behavior of a crude Brazilian oil and obtain kinetic parameters from the experimental data generated through classical thermal analysis techniques, such as TG, DTA and DSC. Thermal analysis is systematically developed in samples of crude oil and oil mixed with sand, and the experimental data are treated in order to conduct a global kinetic study according to distinct conventional and iso-conversional non-isothermal models, developed using integral or differential methods, all based on Arrhenius's kinetic model. As a result of the thermo-analytical study addressed three oxidation regions have been identified: one at the low temperature (LTO) range, a transition zone and one at the high temperature (HTO) range. It has been verified that the highest variation of mass and energy generation occur at the HTO range. At the LTO range a mass transfer resistance (skin-effect) was evident. As a result of the kinetic study, all kinetic models studied provided higher activation energies in HTO than in LTO. It was noted that the presence of sand contributed to OBT and delayed HTO mode as a result of an increase in skineffect. / Mestrado / Reservatórios e Gestão / Mestre em Ciências e Engenharia de Petróleo

Orientador: Vivaldo Silveira Júnior / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T13:26:25Z (GMT). No. of bitstreams: 1 Silva_Karla_D.pdf: 5033012 bytes, checksum: 65b836ec14627b88ae3c341f00426fab (MD5) Previous issue date: 2012 / Resumo: Módulos termoelétricos ou Peltier podem funcionar como bombas de calor promovendo o fluxo térmico entre suas faces opostas à custa da inserção de potência elétrica. O efeito Peltier profere a linearidade entre transferência de calor e corrente elétrica inserida, tornando o módulo um aparato de características potencialmente ideais aos estudos dos efeitos das trocas térmicas. Nesse contexto, o presente trabalho traz o projeto, montagem e avaliação de um protótipo termoelétrico idealizado para congelamento unidirecional por contato direto de amostras consistentes em placa Peltier. A instrumentação do sistema possibilitou o monitoramento da potência elétrica inserida na placa e das temperaturas em diferentes pontos da superfície da placa bem como do espaço interno do sistema. Os testes de avaliação do protótipo comprovaram a adequada montagem com garantia das leituras dos sensores, bem como a boa repetibilidade dos resultados em nível de significância de 5%. Os resultados obtidos para congelamentos de gel de gelatina 2% confirmaram a viabilidade de uso do aparato para estudos dos efeitos de diferentes taxas de congelamento sobre a estruturação do gelo, com alto nível de monitoramento das condições de avanço da frente de congelamento. A precisão do protótipo em detectar pontos de alterações energéticas na amostra, nas proximidades de pontos de alterações estruturais, inferiu na utilização do aparato para estudos térmicos de materiais. Assim, o protótipo termoelétrico foi testado como ferramenta de estudos térmicos, evidenciando-se a possibilidade de seu uso para determinação da região de transição vítrea. A utilização desse aparato para análises térmicas viabiliza e torna mais eficiente o processo comparativamente aos métodos tradicionalmente empregados como o DSC / Abstract: Peltier modules or thermoelectric modules can operate as a heat pump promoting the heat flow in its opposite faces from inserting electric power. The Peltier effect gives the linearity between heat transfer and inserted electrical current, making the characteristics of an apparatus module potentially ideal for studies of the effects of heat exchange. In this context, this paper presents the design, assembly and evaluation of a thermoelectric prototype designed for unidirectional freezing of samples by direct contact semi-solid thermal plate. The instrumentation system allowed the monitoring of electrical power inserted into the card and temperatures in different parts of the plaque and the internal space of the system. The evaluation tests of the prototype proved to guarantee proper assembly of the sensor readings, as well as the good repeatability of results at a 5% significance level. The results for freezing of gelatin gel 2% confirmed the feasibility of using the apparatus for studies of the effects of different freezing rates on the structure of ice, with a high level of conditions monitoring the advancing of the cold freezing. The high accuracy of the prototype in detecting points of energy in the sample, inferred changes in the use of apparatus for thermal study of materials, so the thermoelectric prototype was tested as a tool for thermal studies, demonstrating the possibility of its use for determining the region vitreous transition. The use of this Peltier modules enable it to be more efficient compared to traditional processes such as DSC / Doutorado / Engenharia de Alimentos / Doutora em Engenharia de Alimentos

A study of the role of different oxidants with silicon as the fuel in simple binary pyrotechnic compositions is reported. Several oxidants were examined, but only three (Sb₂0₃, Fe₂0₃ and Sn0₂) satisfied the restrictions that the combustion temperatures should be below the melting point of platinum/rhodium thermocouples (1760°C), that burning rates should not exceed the response of the thermocouples, and that burning should occur without significant mass-transport. A fourth oxidant, KN0₃, was selected on account of its low melting point and general importance as a pyrotechnic oxidant. The oxidation of silicon in the presence of either Sb₂0₃ or KN0₃ could be identified from thermal analysis curves. No thermal events were noted when Si/Sn0₂ and SiFe₂0₃ compositions were heated under similar conditions. The oxidation of Si powder in oxygen was also studied. All four binary systems sustained burning over a reasonably wide range of compositions. The range of burning rates measured (2 to 35 mm s⁻¹) depended on the oxidant used. Fe₂0₃ and Sb₂0₃ gave slow burning mixtures compared to Sn0₂ and to KN0₃ compositions with a high Si content. Burning rates generally increased with increasing specific surface area of silicon, but decreased in the presence of inert diluents and moisture. The burning rates of the Si/Fe₂0₃ and Si/Sn0₂ systems increased with increasing compaction of the samples. Kinetic parameters derived from the temperature proftles recorded during combustion were generally low (6 to 37 kJ mol⁻¹). This is in keeping with proposals that burning is diffusion controlled. The values of kinetic parameters derived from thermal analysis curves were considerably greater ( > 250 kJ mol⁻¹). Two other fuels, FeSi₇ and CaSi₂, gave similar thermal analysis curves when used instead of silicon. There were considerable differences in the burning rates for binary mixtures of these fuels compared to silicon. Ternary systems with two fuels or two oxidants showed that only limited interaction occurs during thermal analysis. The use of a second fuel or oxidant did, however, modify the burning behaviour considerably. Other techniques used in this study to probe the details of the reaction processes included bomb calorimetry, measurement of thermal conductivities, infrared spectroscopy, X-ray diffraction and scanning electron micoscropy.

Barium peroxide was selected as oxidant in a fundamental physico-chemical study of binary pyrotechnic systems on account of its apparently simple decomposition stoichiometry. With this selection, the choice of fuel was governed by the requirements of a self-sustaining reaction at combustion temperatures below the melting point of the platinum/rhodium thermocouples (∼1760°C) used for recording temperature-time profiles during burning, and at burning rates not exceeding the response of the sensors used to monitor combustion. Both manganese and molybdenum metal powders satisfied the above requirements. Strontium peroxide was also available as an oxidant and so the combustion of binary metal/oxidant systems using both fuels and both BaO₂ and SrO₂ oxidants was investigated. The Mn/BaO₂, MoBaO₂ and Mn/SrO₂ systems burnt over a wide range of compositions, but the range of ignitable compositions for the Mo/SrO₂ system was very limited. The linear burning rates, for all these systems, ranged from 2 to 12 mm s⁻¹ and burning rates were increased by the use of smaller particle-sizes of fuel and greater loading pressures. Inert additives generally decreased the burning rate. Temperature-time profiles were recorded for all the compositions which sustained combustion. Kinetic parameters were estimated from the shapes of these profiles using procedures developed by Hill et al and Boddington and Laye. Activation energies derived from the profiles were low (3 to 40 kJ mol⁻¹) and support suggestions that reactions at high temperatures are controlled by diffusion processes. Thermal analysis was used to identify the processes occurring in the four systems. The main exothermic events were observed to correspond approximately with the onset of oxidant decomposition. A pre-ignition reaction was tentatively identified in the Mn/BaO₂ system. Oxidation of the metal fuels was generally incomplete, probably because of the formation of protective layers of product. Activation energies, derived from thermal analysis results, were in the range of from 70 to 720 kJ mol⁻¹. Ternary systems containing either mixed fuels or mixed oxidants were also examined. No interactions hetween the fuels or between the oxidants were observed. Other techniques used included bomb calorimetry, measurement of thermal conductivity, X-ray powder diffraction, infrared spectroscopy and scanning electron microscopy.

A two-dimensional constant heating rate thermoelastic model has been used to develop design and selection criteria for refractory components of linings of high-temperature furnaces and process vessels. The criteria are in the form of resistance to fracture initiation and resistance to damage parameters which account for the influence of thermal and mechanical properties, geometry, and temperature range, while distinguishing between the heating and cooling cases. The resistance to fracture initiation parameter ɸs is the maximum rate at which a shape can be heated or cooled through a specified temperature range without causing fracture. The damage resistance parameter Rd is expressed as the ratio of surface energy per unit area to the elastic strain energy available for crack propagation. Both parameters can be quickly estimated for arbitrary conditions with the aid of tabulated solutions for the maximum principal tensile stress and total strain energy Thermoelastic analyses were used to interpret published results of a variety of thermal shock experiments. Thermal conditions associated with water quenching, radiative furnace heating, gas burners, and controlled heating were simulated using appropriate analytical solutions. Finite element analysis was used to compute maximum principal tensile stresses and elastic strain energy. A simple procedure was developed to invert the stress solution and thereby determine the instant of fracture. Good agreement between thermoelastic predictions and published experimental results with regard to strength retained versus thermal shock relationships, location of fracture, and safe heating rates provided justification for a thermoelastic approach to the thermal shock. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

Hlavním cílem diplomové práce byla studie vlivu huminových kyselin a jejich solí na termooxidační stabilitu a degradabilitu polyvinylalkoholu (PVA). Pro tento účel byla využita metoda termogravimetrie. Bylo prokázáno, že nízké koncentrace huminových kyselin způsobily zvýšení stability zkoumaného PVA. Naopak, vyšší koncentrace měly pouze slabý stabilizační efekt a v některých případech přítomnost huminových kyselin vedla dokonce k destabilizaci PVA. V další části byla upravena životnost polymerního materiálu pomocí gama záření. Získané výsledky naznačovaly, že přítomnost amonných a sodných solí způsobila značnou stabilizaci polymeru ve srovnání s čistým PVA a dokonce ukazovaly stabilizační efekt i po dlouhodobé expozici gama záření. Posledním úkolem bylo zhodnotit efekt stárnutí na směsi PVA a huminových kyselin popřípadě jejich solí. Žádné další chemické reakce v těchto směsích nebyly zaznamenány, tudíž možno konstatovat, že připravený materiál vykazoval konstantní fyzikální vlastnosti během celého, několika měsíčního experimentu.

This diploma thesis deals with the applicability of thermal analysis in the influence of stress factors on microorganisms. The main aim of the presented work was to design and implement a series of experiments to thest the usability of advanced methods of thermal analysis in the characterization of microorganisms. Two bacterial strains were used as model organisms: Cupriavidus necator H16 and its mutant strain Cupriavidus necator PHB-4, which differs in the ability to produce polyhydroxyalkanoates. The basic technique used thermogravimetric analysis (TGA), which was optimized and applied in the study of water transport, behavior and determination of intracellular water content with respect to the influence of the presence of intracellular PHB granules. The results of this method were subsequently supported by TEM photos.

Orientador: Clovis Augusto Ribeiro / Coorientador: Leonardo Miziara Barbosa Ferreira / Banca: Marcos Antonio Correa / Banca: Patricia Roberta Dametto Levada / Resumo: A interface entre nanomateriais e a pele compreende uma série de interações não-covalentes dinâmicas entre as superfícies do sistema nanoestruturado e biológica. A modulação de respostas biológicas, tais como permeação e retenção de fármacos na pele, é dependente dessas interações. O estrato córneo é uma interface biológica complexa e considerado a principal barreira limitante a absorção percutânea de fármacos, dificultando a terapia localizada. O modo que o sistema de liberação interage com essa barreira culminará na sua eficácia ou não. Portanto, torna-se necessário o desenvolvimento de novas estratégias que sejam capazes de modular a interação do sistema de liberação com o estrato córneo visando-se o controle da permeação do fármaco em camadas específicas da pele. O objetivo foi avaliar a viabilidade da modulação da permeação de fármacos e partículas nanoestruturadas através da pele por meio do uso de diferentes géis liquido-cristalinos. Estes materiais são produzidos pela simples manipulação de forças não-covalentes entre fases oleosa e hidrofílica dirigidas pelos princípios da Química Supramolecular e a Nanoarquitetônica. Particularmente, este trabalho contempla o estudo da aplicação de géis líquido- cristalinos liotrópicos para permeação e liberação de fármacos/partículas nanoestruturadas no estrato córneo produzidos a partir de adutos supra-anfifílicos derivados de ácidos graxos análogos de cadeia longa (componente hidrofóbico) e meglumina (componente hidrofílico). Alé... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The interface between nanomaterials and skin comprises a series of dynamic non- covalent interactions between the surfaces of nanostructured and biological system. The modulation of biological responses, such as permeation and retention of drugs in the skin, is dependent on these interactions. The stratum corneum is a complex biological interface and it is considered the main barrier limiting the percutaneous absorption of drugs, being the principal difficult for localized therapy. The way the drug delivery system interacts with this barrier will culminate in its effectiveness or not. Therefore, it is necessary to develop new strategies that are capable of modulating the interaction of the drug delivery system with the stratum corneum aiming at controlling the permeation of the drug in specific layers of the skin. In this project, our objective is to evaluate the feasibility of modulating the permeation of drugs and nanostructured particles through the skin through the use of different liquid-crystalline gels. Liquids-crystal systems are functional supramolecular arrays which exhibit an intermediate ordering state between the order of a crystalline state and the disordered state of the isotropic liquid. These materials are produced by the manipulation of non-covalent forces between oily and hydrophilic phases driven by the principles of Supramolecular Chemistry and Nanoarquitetonics. Particularly, this work contemplates the study of the application of liotropic liquid- crysta... (Complete abstract click electronic access below) / Mestre

Lors de son fonctionnement, une machine tournante est le lieu de nombreux échanges thermiques et de sources de chaleur. Dans la littérature, les roulements font l'objet d'une attention toute particulière. En effet par leur fonctionnement les roulements ont tendance à produire de la chaleur en raison des frottements entre les différents éléments. Ces frottements se traduisent par de la fatigue qui peut entrainer un arrachement de matière sur les bagues ou les éléments roulants donnant naissance à un écaillage. L'écaillage, à son tour, produit un choc répétitif qui représente une nouvelle source d'énergie thermique. Ce travail propose un modèle physique pour l'étude du chauffage thermique d'un roulement à billes sain et d’un roulement endommagé en fonctionnement. Celui-ci s’appuie sur une théorie nodale considérant d’abord l'échauffement du roulement par friction et aussi par l'apport de chaleur dû à l'apparition d'un écaillage. La résolution du bilan énergétique est obtenue par la méthode nodale où l'échauffement dû au frottement et la chaleur induite par le passage des billes sur le défaut est pris en compte. Le modèle thermique proposé est validé par une analyse thermique expérimentale. Les résultats obtenus montrent que la température augmente dans les éléments où le défaut est localisé avec l'augmentation de la vitesse de rotation. Les mêmes résultats sont obtenus pour l'influence de la charge radiale.Le pronostic de défaillance des roulements peut être considéré comme une solution efficace. La prédiction précise de la durée de vie résiduelle (RUL) des roulements est indispensable pour des opérations sûres et optimisées dans le temps. Une nouvelle méthode met l'accent sur l'analyse des relations comme les corrélations entre l'indicateur de santé (IH) et la température est proposée. Nous développons une solution pour l'ensemble de données sur les roulements dans différentes conditions de fonctionnement et de sévérité des défauts. La performance de la méthode proposée est vérifiée par quatre ensembles de données sur les roulements recueillis dans le cadre d'une installation expérimentale. Les résultats montrent que l'indicateur de santé obtient des valeurs de monotonie et de corrélation assez élevées et qu'il est bénéfique pour la prédiction de la durée de vie du roulement. / Many sources of heat can emanate from the operation of a rotating machine, and one of which is the friction among the different parts of the ball bearings. Over time, these frictions may lead to a tearing of matter of the rings or on the rolling elements that cause some type of degradation by flaking. Flaking, in turn, produces a repetitive shock as a new source of thermal energy. This work proposes a physical model for the study of the thermal heating of a ball bearing during operation. The resolution of the energy balance is achieved by the Nodal method where both the heating due to friction and the heat induced by the passage of the balls on defect are taken into account. The proposed thermal model is validated through an experimental thermal analysis. The obtained results show that the temperature increases in the position of defect ball ring with increasing rotational speed. The same results are obtained for the influence of radial load.Bearings failure prognostics, which aims to achieve an effective way to handle the increasing requirements for higher reliability and in the same time reduce unnecessary costs, has been an area of extensive research. The accurate prediction of bearings Remaining Useful Life (RUL) is indispensable for safe and lifetime-optimized operations. A new method focuses on analysing the relationships such as correlations between the HI and temperature is proposed. We develop a solution for the Connectiomics contest dataset of bearings under different operating conditions and severity of defects. The performance of the proposed method is verified by four bearing data sets collected from experimental setup. The results show that the health indicator obtains fairly high monotonicity and correlation values and it is beneficial to bearing life prediction.