Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Non-metallic inclusions in steels are generally considered to be detrimental for mechanical properties. However, it has been recognized that certain inclusions, such as Ti-oxide and TiN, can serve as potent nucleation sites for the formation of intragranular ferrite (IGF) in low-alloy steels. The formation of IGF could improve the toughness of the coarse grained heat affected zone (CGHAZ) of weld metals. Thus, the present thesis mainly focuses on the effect of size of nucleation sites on the IGF formation. Quantitative studies on the composition, size distribution and nucleation probability for each size of the inclusions as well as the area fraction, starting temperature and morphology of an IGF have been carried out. In the present work, the Ti-oxide and TiN powders were mixed with metallic powders. The mixed powders were heated up to the liquid state and cooled with a slow cooling rate of 3.6 ºC/min. These as-cast steels with Ti-oxide and TiN additions were used to simulate the IGF formation in the CGHAZ of weld metals. Specifically, the inclusion and microstructure characteristics in as-cast steels have been investigated. The results show that the nucleant inclusion was identified as a TiOx+MnS phase in steels with Ti2O3 additions and as a TiN+Mn-Al-Si-Ti-O+MnS phase in steels with TiN additions. In addition, the TiOx and TiN phases are detected to be the effective nucleation sites for IGF formation. It is clearly shown that an increased inclusion size leads to an increased probability of IGF nucleation. This probability of IGF nucleation for each inclusion size of the TiOx+MnS inclusions is clearly higher than that of the complex TiN+Mn-Al-Si-Ti-O+MnS inclusions. In addition, the area fraction of IGF in the steels with Ti2O3 additions is larger than that of the steels with TiN additions. This result agrees with the predicted tendency of the probability of IGF nucleation for each inclusion size in the steels with Ti2O3 and TiN additions. In order to predict the effective inclusion size for IGF formation, the critical diameters of the TiO, TiN and VN inclusions, which acted as the nucleation sites of IGF formation, were also calculated based on the classical nucleation theory. The critical diameters of TiO, TiN and VN inclusions for IGF formation were found to be 0.192, 0.355 and 0.810 μm in the present steels. The calculation results were found to be in agreement with the experiment data of an effective inclusion size. Moreover, the effects of the S, Mn and C contents on the critical diameters of inclusions were also calculated. It was found that the critical diameter of the TiO, TiN and VN inclusions increases with an increased content of Mn or C. However, the S content doesn’t have a direct effect on the critical diameter of the inclusions for IGF formation. The probability of IGF nucleation for each inclusion size slightly decreases in the steel containing a higher S content. This fact is due to that an increased amount of MnS precipitation covers the nucleant inclusion surface. In the as-cast experiment, it was noted that an IGF can be formed in steels with Ti2O3 and TiN additions with a cooling rate of 3.6 ºC/min. In order to control the microstructure characteristics, such as the area fraction and the morphology of an IGF, and to investigate the starting temperature of IGF and grain boundary ferrite (GBF) formation, the dynamic transformation behavior of IGF and GBF was studied in-situ by a high temperature confocal laser scanning microscope (CLSM). Furthermore, the chemical compositions of the inclusions and the morphology of IGF after the in-situ observations were investigated by using scanning electron microscopy (SEM), electron backscatter diffraction (EBSD) and electron probe microanalysis (EPMA) which equipped wavelength dispersive spectrometer (WDS). The results show that the area fraction of IGF is larger in the steels with Ti2O3 additions compared to the steels with TiN additions, after the same thermal cycle has been imposed. This is due to that the TiOx phase provides more potent nucleation sites for IGF than the TiN phase does. Also, the area fraction of IGF in the steels is highest after at an intermediate cooling rate of 70 ºC/min, since the competing phase transformations are avoided. This fact has been detected by using a hybrid methodology in combination with CLSM and differential scanning calorimetry (DSC). In addition, it is noted that the morphology of an IGF is refined with an increased cooling rate. / <p>QC 20150325</p>

Processing of Bolu-Himmetoglu (Type I Kerogen) and Ankara-Beypazari (Type II Kerogen) oil shales by flotation techniques were investigated for achieving clean solid fuel substitutes. Materials characterization was done through mineralogical, XRD and FTIR analyses. Flotation responses of the samples were tested with non-ionizing and ionizing collectors of cationic and anionic types. The effects of the collector dosage and pulp pH on cleaning were determined. Other important flotation parameters, conditioning time, flotation time, pulp density, particle size and frother dosage were encountered using a statistical approach, through a full two level factorial experimental design. An advanced flotation procedure, assisted by ultrasonic application, was developed for further improvement in flotation performance. The effects of cleaning on thermal characterstics and combustion kinetics were evaluated with Differential Scanning Calorimetry and ASTM methods while the changes in the emission profiles were assessed using Effluent Gas Analysis. Himmetoglu sample was characterized as a carbonate and organic rich humic oil shale with XRD and FTIR analyses while Beypazari oil shale involved significant carbonate and clay minerals and exhibited a fulvic character with a poor organics content. Reverse flotation with amine acetates provided the most effective means of cleaning with Himmetoglu oil shale. Ash was decreased from 34.76 % to 23.52 % with a combustible recovery of 83.57 % using 800 g/ton Flotigam CA at natural pH and the calorific value increased from 4312 kcal/kg to 5010 kcal/kg. Direct flotation with amines was most effective for Beypazari oil shale cleaning. Using Armoflote 17, ash was reduced from 69.88 % to 53.10 % with 58.64 % combustible recovery using 800 g/ton Armoflote 17 at natural pulp pH and the calorific value of the sample increased from 876 kcal/kg to 2046 kcal/kg. Following optimization, ash of Himmetoglu oil shale decreased to 16.81 % with 84.10 % combustible recovery and calorific value increased to 5564 kcal/kg. For Beypazari oil shale ash decreased to % 48.42 with 59.17 % combustible recovery and the calorific value increased to 2364 kcal/kg. Ultrasonic pre-treatment before flotation further decreased the ash of Himmetoglu sample to 11.82 % with 82.66 % combustible recovery at 15 minutes pre-conditioning time and 50 % power level. For Beypazari oil shale, ash decreased to 34.76 % with 64.78 % combustible recovery after 15 minutes pre-treatment time at 70 % power level. Comparative XRD spectra and SEM analyses revealed that the extent of mineral matter removal relied on the flotation performance. The thermal indicators considerably improved after cleaning and the extent of improvement increased with a decrease in the ash of the concentrates. Kinetic analysis showed the favorable effect of inorganics removal on the effectiveness and easiness of combustion and activation energies decreased after cleaning for both oil shales. The contributions of cleaning on the effectiveness of combustion were also revealed by the increases in the emission rates and total CO2 and CO emission amounts. CO2 emissions due to mineral matter decomposition and harmful SO2 emissions apparently decreased as a consequence of the cleaning of the undesired inorganic contituents and potentially cleaning components. Results of the cleaning and thermal analysis sudies revealed that it was possible to achieve a clean energy source alternative from oil shales through flotation and a significant potential can be anticipated for future use of oil shales as a cost effective and environmental friendly solid fuel substitute in view of Turkey&amp / #8217 / s great oil shale reserves.

Les mécanismes de formation de phases dans des films minces du système ternaire Al-Cu-Fe et des systèmes binaires Al-Cu, Al-Fe et Cu-Fe ont été étudiés. Dans chacun des systèmes, plusieurs échantillons avec des compositions distinctes ont été préparés par pulvérisation cathodique. Des couches d’aluminium, de cuivre et de fer ont été déposées séquentiellement sur des substrats de silicium oxydé et ont été traités thermiquement par différentes méthodes puis caractérisés. Des mesures de diffraction de rayons X et de résistivité in-situ ont été effectuées pour suivre la formation des phases. Des recuits thermiques suivis de trempe ont été réalisés et les échantillons ont été caractérisés par diffraction des rayons X. L’analyse enthalpique différentielle a également été utilisée ainsi que des mesures simultanées in-situ de résistivité et de diffraction des rayons X. L’ensemble des résultats obtenus nous a permis de proposer des mécanismes de formation de phases pour chacun des échantillons étudiés et en utilisant des modèles théoriques de croissance de phases nous avons pu déterminer des données cinétiques sur la formation de phases dans ces films. / The mechanisms of phase formation in thin films have been studied in the Al-Cu, Al-Fe, Fe-Cu and Al-Cu-Fe systems. Several samples with different compositions have been prepared by sputtering. Aluminium, copper and iron layers were deposited onto oxidized silicon substrates, they were heat treated and characterized by using several techniques. In situ X-ray diffraction and resistivity measurements were used to follow the phase formation. Thermal annealings followed by quenching have also been carried out to get additional information.Differential Scanning Calorimetry and coupled in-situ resistivity and X-ray diffractionmeasurements were performed. The whole results allowed us to suggest a mechanism of phase formation for each sample and by using theoretical models of growth we determined kinetic data on the phase formation.

Des études antérieures ont mis en évidence que le transfert de solutés neutres à travers des membranes est influencé par la présence d'ions en solution. Ainsi, la connaissance des interactions multiples à l'échelle nanométrique, entre le polymère, l'eau et les solutés (ions, espèces organiques) constituent un verrou pour l'amélioration des performances des procédés membranaires. Dans cette étude une approche multi-échelle fondamentale est proposée, combinant des outils théoriques et expérimentaux, afin d'obtenir les paramètres microscopiques et macroscopiques caractérisant les interactions étudiées pour différentes compositions ioniques. Plus précisément, il s'agit de comprendre comment les ions affectent le transfert d'un soluté organique. Dans un premier temps, certaines propriétés caractérisant l'hydratation des ions sont calculées et comparées aux flux de diffusions de sucres à travers des membranes de Nanofiltration et échangeuses d'ions obtenus pour différentes compositions ioniques. Dans un deuxième temps, des systèmes constitués d'une membrane échangeuse de cations (CMX) équilibrée avec différents cations ainsi que le glucose hydraté sont modélisés en utilisant une approche combinée Mécanique Quantique/ Mécanique Moléculaire. Cette approche a permis d'étudier la solubilité du sucre dans la matrice polymère ainsi que les interactions polymère-polymère comme l'énergie de cohésion. Enfin, l'influence des ions sur les caractéristiques physiques de la membrane CMX est étudiée en utilisant diverses méthodes expérimentales comme la détermination des angles de contacts et des spectres IR ou la mesure de la température de solidification par DSC. Les propriétés vibrationnelles sont également calculées dans le cadre de la théorie de la fonctionnelle de la densité (DFT). L'ensemble de ces données sont comparées avec les grandeurs de transport afin de valider les mécanismes moléculaires proposés. Ce travail montre que la nature des contre-ions de la membrane modifie l'énergie de cohésion entre les fragments de la membrane. Ainsi, l'énergie de cohésion influe sur la diffusion des composés organiques neutres à travers les membranes. / Previous works have shown that the transfer of neutral solutes through membranes is influenced by the presence of ions in solution. In the framework of process intensification, the knowledge of the molecular mechanisms involved is of fundamental importance to increase and predict the process performances. The aim of this Thesis is to use a combined quantum/molecular computational approach and experimental methodologies to better understand how ions can affect the solute flux. In the first part of the work, some properties of ions in solution are computed and compared with sugar fluxes through membranes for nanofiltration and electrodialysis. In the following, systems composed of Cation-exchange membrane equilibrated by different counter-ion and hydrated glucose are examined by Quantum Mechanics/Molecular Mechanics. This is done mainly to investigate the sugar solubility in the polymer matrix and diffusion related interactions like polymer chain-chain cohesion energy. In the last part, contact angle, differential scanning calorimetry and Infra-Red spectra are measured to characterize the physical properties of the membrane and possible influence of the counter-ion on cation exchange membrane. This work shows that the nature of the counter-ions modifies the cohesion energy between the membrane polymer fragments. In its turn, the cohesion energy affects the diffusion of neutral organic compounds through the membranes.

Objetivou-se nessa pesquisa comparar oito tipos de fios de NiTi superelásticos e termoativos, de seis empresas comerciais (GAC, TP, ORMCO, MASEL, MORELLI e UNITEK) àqueles com adição de cobre (CuNiTi 27 e 35OC, ORMCO), observando se as propriedades mecânicas dos dois últimos justificariam sua escolha clínica. Para tal foram realizados ensaios de tração e microscopia eletrônica de varredura. Os ensaios de tração foram realizados em máquina de ensaios mecânicos da marca EMIC, modelo DL10000, de 10 toneladas de capacidade, no Instituto Militar de Engenharia (IME). A composição química e a topografia superficial dos fios foram determinadas através da microscopia eletrônica de varredura em microscópio da marca JEOL, modelo JSM-5800 LV com sistema de microanálise EDS (energy dispersive spectroscopy). Os resultados mostraram que, de forma geral, os fios de NiTi termoativados apresentaram cargas mais suaves de desativação em relação aos superelásticos. Entre os fios que apresentaram as cargas biologicamente mais adequadas de desativação estão os termoativados da GAC e da UNITEK. Entre os fios de NiTi superelásticos, os de CuNiTi 27C da ORMCO foram os que apresentaram as cargas mais suaves de desativação, sendo semelhantes, estatisticamente (ANOVA), às apresentadas pelos fios de NiTi termoativados da UNITEK para a deformação de 4%. Quando comparados os fios de CuNiTi a 27 e a 35C, observou-se que os primeiros apresentaram forças de desativação de, aproximadamente, 1/3 das apresentadas pelos últimos, para a deformação de 4%. Quando analisada a microscopia eletrônica de varredura de superfície, os fios de NiTi superelásticos que apresentaram melhores acabamentos foram os da MASEL e MORELLI e os que apresentaram os piores acabamentos foram os de NiTi e CuNiTi 27C da ORMCO. Entre os termoativados, todos apresentaram marcas e ranhuras de trefilação bastante visíveis, com características inadequadas em termos de topografia de superfície, sendo que os de CuNiTi 35C da ORMCO e os da UNITEK apresentaram os piores acabamentos de superfície graças à presença de microcavidades formadas devido aos arrancamento de partículas, possivelmente de NiTi4. Quando analisada a morfologia da região de fratura observou-se a presença de deformação plástica, e de microcavidades, características de fratura do tipo dúctil com redução macroscópica do diâmetro, para todos os grupos de fios NiTi e CuNiTi ensaiados, sendo que os de CuNiTi 27 C e os termoativados da UNITEK apresentaram as menores microcavidades e os melhores acabamentos à fratura. Concluiu-se que os fios de CuNiTi 35C, além de terem apresentado as maiores cargas de desativação entre os fios de NiTi termoativados, apresentaram os piores acabamentos das superfícies, o que não justificaria sua escolha como os primeiros fios para utilização clínica. / Leveling and aligning orthodontic wires must be able to generate light and continuous forces. Thus need to have high springback and flexibility. For this purpose it was suggested a variety of supereslatic and termoactivated Nickel-Titanium (NiTi) wires that may offer a load-deformation curve, in a constant plataform. Copper NiTi wires are presented as exhibiting better thermoactivating properties for optimum-forces system with better dental movement control. The aim of this study was to compare 8 NiTi superelastic and thermoactivated wires of six different brands (GAC, TP, ORMCO, MASEL, MORELLI and UNITEK) to Copper addicted wires (CuNiTi 270C and 350C, ORMCO) to verify if the mechanical properties of Copper NiTi would support its clinical use. Stress-strain tests were done in Engeneering Military Institute (IME-Brazil), through test machine (EMIC- DL 10000 model). Scanning electronic microscope with energy dispersive spectroscopy (JOEL, JSM-5800 LV model) was used to determine chemical composition and superficial topography of the wires. Results showed that, in general, thermoactivated NiTi wires exhibited lower deactivation loads when compared to NiTi superelastics. Among the thermoactivated, the GAC and UNITEK ones are the lighter ones. Among the superelastics, the Copper NiTi 270C (ORMCO) were the lighter ones, statistically similar (ANOVA) to thermoactivated NiTi from UNITEK, for 4% strain. Once Copper NiTi 270C showed deactivated loads 62% lower than Copper NiTi 350C , under 4% strain. As regard to Scanning Electronic Microscopy results for superelastic NiTi wires, better superficial burnishing were found for MASEL and MORELLI ones. On the other hand, the worst were ORMCO Superelastic NiTi and CuNiTi 270C. The thermoactivated ones were superficially visibly marked with inadequate superficial topography. Copper NiTi 350 C and UNITEK showed the worst burnishing among the thermoactivated wires, linked to microtags. It was concluded that CuNiTi 350 C showed the greatest deactivation loads and not favorable superficial burning.

L’acier inoxydable martensitique durci par précipitation 15-5PH est utilisé dans le domaine del’aéronautique comme matériau constitutif des pièces liant les réacteurs aux ailes, il est ainsi soumisen utilisation à des températures de l’ordre de 300°C, ce qui entraine sa fragilisation. Cettefragilisation des aciers inoxydables dans ce domaine de températures est causée par la démixtion dufer et du chrome, principaux constituants de la matrice, par décomposition spinodale. De plus, lamicrostructure complexe du 15-5PH contient également des précipités de cuivre assurant ledurcissement initial de l’alliage, de l’austénite de réversion, connue dans ce type d’aciers pourapporter un regain de ductilité, apparaissant lors du traitement de précipitation du cuivre et de laphase G apparaissant au cours du vieillissement. L’évolution de ces phases pourrait égalemententrainer une modification des propriétés mécaniques de l’alliage. Pour observer les différentesévolutions de la microstructure nous avons utilisé une combinaison de techniques apportant desinformations complémentaires afin d’en obtenir une caractérisation la plus complète possible. Nousavons ainsi pu montrer que les modifications de propriétés sont causées par la décompositionspinodale de la matrice. L’évolution de ses caractéristiques microstructurales a pu être décrite pardes lois phénoménologiques, fonctions de la durée et de la température de vieillissement. Nousavons également pu fournir une méthode permettant la mesure indirecte de l’avancée duvieillissement du 15-5PH, validée par les observations microstructurales, ainsi qu’un modèlephénoménologique permettant de prévoir la dureté de l’alliage.Mots clés : acier martensitique, décomposition spinodale, vieillissement, diffusion aux petits angles,sonde atomique tomographique, calorimétrie différentielle à balayage. / The precipitation hardened martensitic stainless steel grade 15-5PH is used in the airplane industryas constitutive material of parts joining reactors to wings. Due to its application it is subjected totemperatures around 300°C leading to its embrittlement. Stainless steels embrittlement in thistemperature range is due to iron-chromium unmixing by spinodal decomposition. In addition, the 15-5PH grade has a complex microstructure comprising copper precipitates responsible for the initialhardening of the alloy, reversed austenite, known in this kind of steels to improve the toughness,which appears during the precipitation thermal treatment and G phase that precipitates duringaging. The evolutions of these microstructure components could also lead to some modifications ofthe material mechanical properties. In order to study the microstructure evolutions we use acombination of characterization techniques aiming at their most complete description. We show thatthe mechanical properties evolution is controlled by the spinodal decomposition of the matrix whoseevolution we are able to depict by simple phenomenological laws. We propose an indirect methodfor the measurement of aging kinetics of the 15-5PH steel, which we have correlated to directmeasurements, and a phenomenological law allowing the prediction of the alloy hardness based onits thermal history.

O composto SbxCoSb3-x foi produzido em altas pressões e altas temperaturas em uma reação de auto-inserção a partir da escuterudita binária CoSb3. A reação de auto-inserção é caracterizada pelo colapso de átomos de Sb para o sítio 2a, no interior das cavidades formadas pelos átomos de Co e Sb na estrutura da escuterudita. A reação inversa, de desinserção de Sb, ocorre quando o composto SbxCoSb3-x é aquecido à pressão ambiente. O acompanhamento desta reação de desinserção por meio de medidas de calorimetria exploratória diferencial (DSC), difração de raios X (DRX) e de resistividade elétrica constitui o objetivo principal deste trabalho. A amostra de CoSb3 foi sintetizada conforme rota proposta pela literatura. A síntese foi confirmada por meio de DRX, e não foi observada a presença de fases contaminantes. Amostras cilíndricas da fase SbxCoSb3-x foram obtidas submetendo CoSb3 a pressões de 7,7 GPa e temperaturas de até 550ºC, com o auxílio de prensas hidráulicas e câmaras toroidais disponíveis no Laboratório de Altas Pressões e Materiais Avançados LAPMA no Instituto de Física da Universidade Federal do Rio Grande do Sul IF/UFRGS. A presença da fase SbxCoSb3-x foi comprovada por meio de análises de DRX. Para determinação da resistividade elétrica de amostras ricas de fase SbxCoSb3-x foi desenvolvido um sistema DC, aplicável a amostras cilíndricas de pequeno volume tal como as obtidas em altas pressões e altas temperaturas. A aferição do sistema foi feita através de medidas de resistividade elétrica de materiais de referência (NIST-SRM 1461 e NIST-SRM 8426). As medidas de DSC revelaram a presença de dois eventos térmicos. Um pico endotérmico foi observado em 118ºC e não está associado a alterações estruturais e nem a variações significativas na resistividade elétrica. O evento exotérmico, que inicia em 180ºC, constitui a assinatura da desinserção dos átomos de Sb do interior da escuterudita, como verificado por análises de DRX e medidas elétricas. Após aquecimento até 350ºC, a amostra rica na fase SbxCoSb3-x retorna à fase estável, CoSb3. A reação de desinserção obedece a uma cinética de primeira ordem, cuja entalpia de transição é de aproximadamente 50 J /g e uma energia de ativação de 83 kJ/mol. A resistividade elétrica à temperatura ambiente de amostras ricas em SbxCoSb3-x é cerca de dez vezes inferior à do CoSb3. Este resultado, aliado possivelmente a uma baixa condutividade térmica, sugere que a fase de auto-inserção SbxCoSb3-x pode constituir um material termoelétrico de alto desempenho. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-03T19:52:12Z No. of bitstreams: 1 Dissertacao Fernanda Miotto.pdf: 1202367 bytes, checksum: b66708b3e1d417eab6ba5104702a3458 (MD5) / Made available in DSpace on 2014-06-03T19:52:12Z (GMT). No. of bitstreams: 1 Dissertacao Fernanda Miotto.pdf: 1202367 bytes, checksum: b66708b3e1d417eab6ba5104702a3458 (MD5) / The compound SbxCoSb3-x was produced at high pressures and high temperatures in a self-insertion reaction from the binary skutterudite CoSb3. The self-insertion reaction is characterized by the collapse of Sb atoms to the 2a site, into the cage formed by the Co and Sb atoms in the skutterudite structure. The opposite reaction, i.e., Sb desinsertion, occurs when the SbxCoSb3-x compound is heated at room pressure. This desinsertion reaction was followed by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD) and electrical resistivity measurements, and its study constitutes the main objective of this work. The CoSb3 sample was synthesized as described in the literature. The synthesis was confirmed by XRD, and the presence of contaminant phases was not observed. Cylindrical samples of the SbxCoSb3-x phase were obtained by submitting CoSb3 at pressures of 7.7 GPa and temperatures up to 550ºC, with the aid of a toroidal high pressure cell available at the Laboratório de Altas Pressões e Materiais Avançados - LAPMA in the Instituto de Física of the Universidade Federal do Rio Grande do Sul - IF/UFRGS. The presence of the SbxCoSb3-x phase was confirmed by XRD analysis. In order to determine the electrical resistivity of samples rich in SbxCoSb3-x phase, a DC system was developed which is applicable to small volume cylindrical samples such as those obtained at high pressures and high temperatures. The calibration of the DC system was made by measurements of the electrical resistivity of reference materials (NIST-SRM 1461 and NIST-SRM 8426). The DSC measurements revealed the presence of two thermal events. An endothermic peak was observed at 118ºC which is not associated to structural changes neither significant variation in the electrical resistivity. The exothermic event that starts at 180ºC is the signature of the desinsertion of Sb atoms from the skutterudite cage, as verified by XRD analysis and electrical measurements. After heating to 350°C, the sample rich in the SbxCoSb3-x phase converts back to the stable phase, CoSb3. The desinsertion reaction follows a first-order kinetics, with a transition enthalpy of approximately 50 J/g and an activation energy of 83 kJ/mol. The electrical resistivity at room temperature of samples rich in SbxCoSb3-x is about ten times smaller than that of CoSb3. This result, along with a possible low thermal conductivity, suggests that SbxCoSb3-x may constitute a high performance thermoelectric material.

Objetivou-se nessa pesquisa comparar oito tipos de fios de NiTi superelásticos e termoativos, de seis empresas comerciais (GAC, TP, ORMCO, MASEL, MORELLI e UNITEK) àqueles com adição de cobre (CuNiTi 27 e 35OC, ORMCO), observando se as propriedades mecânicas dos dois últimos justificariam sua escolha clínica. Para tal foram realizados ensaios de tração e microscopia eletrônica de varredura. Os ensaios de tração foram realizados em máquina de ensaios mecânicos da marca EMIC, modelo DL10000, de 10 toneladas de capacidade, no Instituto Militar de Engenharia (IME). A composição química e a topografia superficial dos fios foram determinadas através da microscopia eletrônica de varredura em microscópio da marca JEOL, modelo JSM-5800 LV com sistema de microanálise EDS (energy dispersive spectroscopy). Os resultados mostraram que, de forma geral, os fios de NiTi termoativados apresentaram cargas mais suaves de desativação em relação aos superelásticos. Entre os fios que apresentaram as cargas biologicamente mais adequadas de desativação estão os termoativados da GAC e da UNITEK. Entre os fios de NiTi superelásticos, os de CuNiTi 27C da ORMCO foram os que apresentaram as cargas mais suaves de desativação, sendo semelhantes, estatisticamente (ANOVA), às apresentadas pelos fios de NiTi termoativados da UNITEK para a deformação de 4%. Quando comparados os fios de CuNiTi a 27 e a 35C, observou-se que os primeiros apresentaram forças de desativação de, aproximadamente, 1/3 das apresentadas pelos últimos, para a deformação de 4%. Quando analisada a microscopia eletrônica de varredura de superfície, os fios de NiTi superelásticos que apresentaram melhores acabamentos foram os da MASEL e MORELLI e os que apresentaram os piores acabamentos foram os de NiTi e CuNiTi 27C da ORMCO. Entre os termoativados, todos apresentaram marcas e ranhuras de trefilação bastante visíveis, com características inadequadas em termos de topografia de superfície, sendo que os de CuNiTi 35C da ORMCO e os da UNITEK apresentaram os piores acabamentos de superfície graças à presença de microcavidades formadas devido aos arrancamento de partículas, possivelmente de NiTi4. Quando analisada a morfologia da região de fratura observou-se a presença de deformação plástica, e de microcavidades, características de fratura do tipo dúctil com redução macroscópica do diâmetro, para todos os grupos de fios NiTi e CuNiTi ensaiados, sendo que os de CuNiTi 27 C e os termoativados da UNITEK apresentaram as menores microcavidades e os melhores acabamentos à fratura. Concluiu-se que os fios de CuNiTi 35C, além de terem apresentado as maiores cargas de desativação entre os fios de NiTi termoativados, apresentaram os piores acabamentos das superfícies, o que não justificaria sua escolha como os primeiros fios para utilização clínica. / Leveling and aligning orthodontic wires must be able to generate light and continuous forces. Thus need to have high springback and flexibility. For this purpose it was suggested a variety of supereslatic and termoactivated Nickel-Titanium (NiTi) wires that may offer a load-deformation curve, in a constant plataform. Copper NiTi wires are presented as exhibiting better thermoactivating properties for optimum-forces system with better dental movement control. The aim of this study was to compare 8 NiTi superelastic and thermoactivated wires of six different brands (GAC, TP, ORMCO, MASEL, MORELLI and UNITEK) to Copper addicted wires (CuNiTi 270C and 350C, ORMCO) to verify if the mechanical properties of Copper NiTi would support its clinical use. Stress-strain tests were done in Engeneering Military Institute (IME-Brazil), through test machine (EMIC- DL 10000 model). Scanning electronic microscope with energy dispersive spectroscopy (JOEL, JSM-5800 LV model) was used to determine chemical composition and superficial topography of the wires. Results showed that, in general, thermoactivated NiTi wires exhibited lower deactivation loads when compared to NiTi superelastics. Among the thermoactivated, the GAC and UNITEK ones are the lighter ones. Among the superelastics, the Copper NiTi 270C (ORMCO) were the lighter ones, statistically similar (ANOVA) to thermoactivated NiTi from UNITEK, for 4% strain. Once Copper NiTi 270C showed deactivated loads 62% lower than Copper NiTi 350C , under 4% strain. As regard to Scanning Electronic Microscopy results for superelastic NiTi wires, better superficial burnishing were found for MASEL and MORELLI ones. On the other hand, the worst were ORMCO Superelastic NiTi and CuNiTi 270C. The thermoactivated ones were superficially visibly marked with inadequate superficial topography. Copper NiTi 350 C and UNITEK showed the worst burnishing among the thermoactivated wires, linked to microtags. It was concluded that CuNiTi 350 C showed the greatest deactivation loads and not favorable superficial burning.

Made available in DSpace on 2015-05-14T13:21:45Z (GMT). No. of bitstreams: 1 parte1.pdf: 2326464 bytes, checksum: edf040b92b5fdf343007a3626c02e26b (MD5) Previous issue date: 2009-02-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The present work aimed at investigating the biodiesel issuing from the transesterification of used frying oil with ethanol, via alkaline catalysis. Such investigation covers its thermo-oxidative stability during heating (thermal analysis and rheological properties) as well the kinetic profiles of the samples in the best oxidative induction time by the technique of Pressurized Differential Scanning Calorimetry (PDSC). The behavior of such biodiesel, as part of binary blends with fossil diesel at the proportions of 3, 5, 10, 25, 50, 75 and 100%, was also studied. The biodiesel synthesis used the ethanol route and was carried out under the following conditions: oil/alcohol molar ratio of 1:6 (m/m), 1 % de KOH, temperature of 32 °C, washing with 0.1M HCl and hot water. The reaction yield, determined by means of a mass balance aided by the technique of gas chromatography coupled to mass spectrometry, was of 90.56% and the ester content was of 99.56%. According to the physicochemical analyses, all the specifications for the biodiesel and blends met the requirements from Technical Regulation # 7 from the Brazilian National Agency of Petroleum, Natural Gas and Biofuels, with the exceptions of the odixative induction time (1.72 h) and kinematic viscosity (6.10 mm2s-1), which displayed values outside the limits established by the standard. In the thermal study, the thermogravimetric curves showed that the biodiesel blends in diesel are more volatile than the biodiesel derived from used frying oil (B100), whereas at lower concentrations (3, 5, 10 and 25%) are similar to fossil diesel. At higher concentrations (50 and 75%) the blends presented lower volatility and higher thermal stability in relation to fossil diesel and thus, biodiesel and its more concentrated blends showed higher safety in relation to transport, storage, handling and utilization. The study of the fluid dynamic properties of biodiesel and its blends showed that all the samples behave as Newtonian fluids at the studied (10, 25 and 40 ºC) temperatures. Also the results of cloud point, pour point and cold filter plugging point showed that the behavior of the blends with 3, 5 and 10% are similar to fossil diesel, therefore at these concentrations biodiesel acts as a lubricity additive to fossil diesel. The study by Pressurized Differential Scanning Calorimetry (PDSC) in the dynamic mode and the Rancimat technique revealed that the best antioxidant for the storage of biodiesel is BHT at the concentration of 2500 ppm. The determination of the kinetic parameters by the isothermal PDSC technique allowed determining the theoretical value of the shelf life of used frying oil biodiesel with 2500 ppm of the antioxidant BHT. Therefore, used frying oil biodiesel and its blends B3, B5, B10, B25, B50 and B75 may be used as an alternative source of biofuels. / O presente trabalho buscou investigar o biodiesel proveniente da transesterificação do óleo de fritura usado com álcool etílico, via catálise básica, e elucidar a sua estabilidade termo-oxidativa durante o aquecimento (análise térmica e propriedade reologicas) e estudar o perfil cinético da amostra com o melhor tempo de indução oxidativa pela técnica de calorimetria exploratória diferencial pressurizada (PDSC). Também, foi observado o comportamento do referido biodiesel, inserido em misturas binárias com o diesel fóssil nas proporções de 3, 5, 10, 25, 50, 75 e 100% também foi estudada. A síntese do biodiesel na rota etanólica processou-se sob condições de: razão molar óleo-álcool de 1:6 (m/m), 1 % de KOH, temperatura de 32 °C, lavagem com HCl 0,1 M e água quente. O rendimento reacional determinado por balanço de massa com auxilio da técnica de cromatografia gasosa acoplada a espectrometria de massa, foi de 90,56 %, com teor de esteres de 99,56 %. Nas análises físicoquímicas, todos as especificações para ambos biodiesel e blendas satisfizeram as exigências dos limites permitidos pelo Regulamento Técnico nº 7 da Agência Nacional do Petróleo, Gás Natural e Biocombustíveis. Com exceção do tempo de indução oxidativa (1,72 h) e a viscosidade cinemática (6,10 mm2s-1) que apresentaram valores fora dos limites estabelecidos pela norma. No estudo térmico, as curvas termogravimétricas evidenciaram que as blendas de biodiesel em diesel são mais voláteis em relação ao biodiesel derivado de óleo de fritura usado (B100) e em baixas concentrações (3, 5, 10 e 25%) se assemelham ao diesel fóssil. Em concentrações mais elevadas (50 e 75%) as blendas apresentam menor volatilidade e maior estabilidade térmica em relação ao diesel fóssil, e, portanto, o biodiesel e suas blendas mais concentradas apresentam maior segurança em relação ao transporte, armazenagem, manuseio e utilização. O estudo das propriedades fluído-dinâmicas do biodiesel e suas blendas, demostraram que todas as amostras comportam como fluídos newtonianos a temperatura (10, 25 e 40 ºC) e que tanto os resultados de ponto de nevoa, fluidez e ponto de entupimento de filtro a frio, apresentaram comportamento para as blendas 3, 5 e 10% semelhantes ao observado para o diesel fossil, e, portanto nestas concentrações o biodiesel atua como um aditivo de lubricidade do óleo diesel fossil. O estudo por calorimetria exploratória diferencial pressurizada no modo dinâmico e a técnica de rancimat revelou que o melhor antioxidante para o armazenamento do biodiesel é o BHT com concentração de 2500 ppm. A determinação dos parâmetros cinéticos pela técnica de PDSC isotérmica foi possível determinar teoricamente o tempo de vida de prateleira do biodiesel derivado de óleo de fritura usado com 2500 ppm do antioxidante BHT. Então, o biodiesel de fritura usado e blendas B3, B5, B10, B25, B50 e B75 podem ser utilizados como uma fonte alternativa de biocombustíveis.