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.

Le RXP470.1 est l’un des premiers inhibiteurs puissants de la MMP-12, une métalloprotéase à zinc impliquée dans de nombreuses pathologies comme l’athéroclérose et la bronchopneumopathie obstructive chronique (BPCO). Pour comprendre les bases moléculaires contrôlant l’interaction de cet inhibiteur avec sa cible, des approches pluridisciplinaires associant des relations structure-activité, avec des études de cristallographie de complexes enzymes inhibiteurs et d’études de microcalorimétrie, décrivant les contributions enthalpiques et entropiques impliquées dans la formation des complexes, ont été réalisées dans ce travail de thèse. Les affinités de trois analogues du RXP470.1 ont été tout d’abord déterminées. Puis quatre structures cristallographiques de complexes enzyme/inhibiteur décrivant le mode d’interaction duRXP470.1 et de ces trois analogues ont été obtenues avec des résolutions de 1.15 Å, 1.50 Å, 1.50Å et 1.30 Å, respectivement. Parallèlement les études de microcalorimétrie ont été menées pour étudier les facteurs énergétiques contrôlant l’interaction du RXP470.1 avec la MMP-12. Les résultats indiquent que la présence d’une chaîne latérale très longue et hydrophobe en position P1’de l’inhibiteur s’insérant dans la cavité S1’ de la MMP-12 est essentielle à la très bonne affinité de cet inhibiteur pour la MMP-12. Cette interaction met essentiellement en jeu un effet entropique très important de - 4 kcal/mol. L’interaction du RXP470.1 est aussi essentiellement dirigée par une forte augmentation d’entropie (-TDS= -10 kal/mol) et une composante enthalpique beaucoup plus faible (DH= -2.5 kcal/mol), et ce malgré l’observation dans le cristal de nombreuses interactions entre l’inhibiteur et le site actif de la MMP-12. L’étude de microcalorimétrie met aussi en lumière la prise d’un proton au cours de la formation du complexe enzyme inhibiteur impliquant deux résidus chargés négativement en solution, le résidu catalytique Glu219 et le groupe phosphoryle chélatant du zinc dans l’inhibiteur. Cette étude révèle aussi que si le groupe phosphoryle est considéré comme un chélatant faible de l’atome de zinc, il impose néanmoins des contraintes directionnelles très importantes qui ont un impact sur le positionnement des autres parties de l’inhibiteur dans le site actif de l’enzyme. Ce dernier effet pourrait expliquer pourquoi un certain nombre d’interactions entre l’inhibiteur et l’enzyme ne sont pas optimisées et pourquoi la variation d’enthalpie pour former le complexe reste relativement faible. Cette étude ouvre maintenant la voie à d’autres études en plaçant au centre des futurs travaux le rôle du groupe chélatant dans la conception des inhibiteurs de MMP, ainsi de nouveaux inhibiteurs puissants et sélectifs d’autres MMP devraient voir le jour grâce à ce travail et aux résultats obtenus. / RXP470.1 is one of the first highly potent and selective inhibitor of MMP-12, a zinc protease involved in several human diseases such as atherosclerosis and chronic obstructive pulmonary disease (COPD). To understand the molecular determinants controlling the interaction of RXP470.1 with MMP-12 active site, a multidisciplinary approach combining structure-activity data, crystallography and microcalorimetry have been performed on RXP470.1 and its three analogues. The affinities of the three RXP470.1 analogues have been determined. Then, fourcrystal structures of MMP-12 in interaction with these inhibitors have beendetermined at high resolution, 1.15 Å, 1.50 Å, 1.50 Å et 1.30 Å, respectively. These data have indicated that the presence of a long hydrophobic side chain in the P1’ position of the RXP470.1, which enters deeply inside the S1’ cavity of MMP-12, is playing a key role in the inhibitor affinity. The contribution of this side chain is mostly entropic (-TDS - 4 kcal/mol). The interaction of RXP470.1 with MMP-12 is also mostly driven by a sizeable entropy increase (-TDS= -10 kal/mol) and a more modest enthalpy contribution (DH= -2.5 kcal/mol), despite the observation in the crystal structure of several contacts between inhibitor and MMP-12 active site. Furthermore, this study reveals that the binding of RXP470.1 to MMP-12 is linked to a proton uptake involving two negatively charged residues, the catalytic Glu219 and the phosphoryl group of the inhibitor. Furthermore, despite that the phosphoryl group is considered as a weak zincbinding group, this study highlights that the interactions of this group with the active site zinc atom involved strong directionality between these two groups. This effect has strong impact on the positioning of the other parts of the inhibitor in the MMP-12 active site. This last effect could be responsible for the modest enthalpy increase associated with the binding of RXP470.1 to MMP-12, by preventing the optimization of several interactions between the inhibitor and the enzyme. The results indicate that the role of the zinc-binding group should be better consider in the future. Finally this study opens a new vision in this field and should allow the design of new selective inhibitors of other MMPs.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-08T19:05:31Z No. of bitstreams: 1 TACIANO PESSOA – TESE (PPGEP) 2015.pdf: 1372058 bytes, checksum: e953b936619e36c851136deb1ffc76af (MD5) / Made available in DSpace on 2018-06-08T19:05:31Z (GMT). No. of bitstreams: 1 TACIANO PESSOA – TESE (PPGEP) 2015.pdf: 1372058 bytes, checksum: e953b936619e36c851136deb1ffc76af (MD5) Previous issue date: 2015-08 / Realizou-se esta pesquisa com o objetivo de produzir palitos de inhame fritos em óleos de coco e de soja, estabelecendo parâmetros comparativos de qualidade nutricional e sensorial. Para obtenção do óleo de coco, foi realizada uma prensagem a frio, após estudo de secagem das tiras de coco em estufa a 60 e 70°C, que foram ajustadas as equações matemáticas de Cavalcanti Mata, Handerson & Pabis, Page, Verma e modelo difusional de Fick 4 termos. A caracterização dos óleos utilizados, avaliados antes e após as frituras quanto ao teor de água, índices de acidez, peróxido, refração, iodo, saponificação e calorimetria diferencial de varredura (DSC). Os palitos de inhame foram pré tratados em soluçõ es osmóticas salinas, contendo 5, 10 e 15% de sal (NaCl), onde realizou-se a cinética de desidratação osmotica, que pode-se calcular as perdas de massa e ganho de sólidos das amostras, em seguida foram fritos em óleo de coco e de soja, nas temperaturas de 150, 170 e 190°C, em que foram avaliados as características químicas e físico-químicas dos palitos de inhame In natura, após DO e frituras, quanto aos parâmetros: acidez, pH, atividade de água, teor de água, lipídeos, teor de sódio, teor de amido, absorção de gordura, remoção de água, razão de absorção de gordura. Para a cor (L, a e b) e textura instrumental os parâmetros: firmeza, coesividade, elasticidade e mastigabilidade . Para verificar a aceitação do produto, as amostras foram fritas a 190°C em seguida submetidas a análise sensorial. Concluiu-se que: A equação matemática de secagem proposta Cavalcanti Mata é, dentre aqueles testados, o que apresenta melhor ajuste sendo o selecionado para a representação da cinética dos palitos de coco; As características de identidades do óleo de soja analisado, apresentaram-se dentro dos padrões exigidos para os índices de acidez, peróxido, iodo, refração e saponificação; As caraterísticas de identidade do óleo de coco, apresentou-se dentro dos padrões estabelecidos para os índices de acidez, peróxido e refração; O DSC permitiu verificar o seu desempenho térmico de oxidação com evento exotérmico em pico a 238,3 e 237,8°C, para o óleo de coco e de soja respectivamente; O índice de peróxido dos óleos utilizados nas frituras de 150°C ocorre um aumento do índice avaliado, com o aumento do número de frituras, o óleo de soja apresenta valores superiores a 8,494 (meq/1000 de óleo) quanto aos observados no óleo de coco valores menores que 4,244 (meq/1000 de óleo), que o torna indesejado para o consumo, quando se compara a legislação brasileira; O aumento da concentração de sal nas soluções favoreceu para uma maior perda de peso e ganho de sólidos dos palitos de inhame; Para a razão de absorção de gordura (RAG) amostras fritas com óleo de coco apresentaram menores valores de RAG. O aumento das temperaturas de fritura das amostras, tenderam apresentar menores valores de RAG; A textura instrumental dos palitos de inhame fritos, obtiveram influencias direta do tratamentos osmóticos, óleo e temperatura utilizados na fritura; Com base no perfil de atitude dos consumidores, pode-se concluir que as amostras que apresentaram maior aceitação foram: os palitos de inhame fritos em óleo de coco pré tratados com desidrat ação osmótica a 15% de solução salina, para os palitos de inhame fritos em óleo de soja, foram as amostras tratadas com desidratação osmótica a 10 e 15% de solução salina. Considerando os resultados obtidos na pesquisa para a produção de palitos de inhame frito, conclui-se que a união de matérias primas permitiu originar um produto com quam lidade sensorial e acessibilidade para o mercado consumidor. / Carried out this search in order to produce fried yams sticks coconut and soy oils, establishing comparative parameters of nutritional and sensory quality. To obtain coconut oil a cold pressing was performed after drying study of coconut strips in a greenhouse at 60 to 70 ° C, which were adjusted mathematical equations Cavalcanti Woods, Handerson & Pabis, Page Verma and model diffusive Fick 4 terms. The characterization of the oils used, evaluated before and after frying as the water content, acidity index, peroxide, refraction, iodine, saponification and differential scanning calorimetry (DSC). Yam sticks were pretreated with saline osmotic solutions containing 5, 10 and 15% salt (NaCl), which was he ld osmotic dehydration kinetics, which can calculate the mass loss and solid gain of sample then they were fried in coconut oil and soybean oil at temperatures of 150, 170 and 190°C, which evaluated the chemical and physicochemical characteristics of yam sticks in natura after DO and fried foods, as the parameters : acidity, pH, water activity, water content, lipids, sodium content, starch content, fat absorption, water removal rate of fat absorption. For color (L, a and b) and instrumental texture parameters: firmness, cohesiveness, springiness and chewiness. To verify acceptance of the product, samples were fried at 190°C and then subjected to sensory analysis. It was concluded that: The mathematical equation drying proposal Cavalcanti Mata is among thos e tested, which fits better being selected to represent the kinetics of coconut sticks; The characteristics of soybean oil identities analyzed were within the standards required for the acid values, peroxide, iodine, refraction and saponification The ident ity characteristics of coconut oil, was within the standards established for the acidity index, peroxide and refraction; The DSC has shown this thermal oxidation performance with peak exothermic event at 238.3 and 237.8 ° C for coconut oil and soybean oil, respectively; The peroxide value of the oils used in the frying of 150 ° C an increase of the estimated index, with increase of fried foods, soybean oil exhibited superior values 8.494 (meq / 1000 oil) as those observed in the oil coconut values less than 4,244 (mEq / 1000 oil) which makes it undesirable for consumption, when comparing the Brazilian legislation; Increasing the salt concentration in the solution favored for greater weight loss and gain the yams solid sticks; For the reason of fat absorption (RAG) chips with coconut oil samples showed lower values RAG. The increase in frying temperatures of the samples tended RAG have lower values; The instrumental texture of fried yam sticks, obtained direct influence of osmotic treatments, oil and temperature used for frying; Based on consumer attitude profile, it can be concluded that the samples had higher acceptance were fried yams sticks pre coconut oil treated with osmotic dehydration at 15% saline to fried yams sticks in soybean oil samples were treated with osmotic dehydration at 10 and 15% saline. Considering the results obtained in the research for the production of fried yam sticks, concluded that the union of raw materials allowed yield a product with sensory quality and affordability for the consumer market.

L’industrie de métallurgie est demandeuse de propriétés thermophysiques essentielles pour la modélisation et l’optimisation des procédés d’élaborations.Les propriétés thermophysiques des métaux et des alliages métalliques à l’état liquide sont mal connues. Ces propriétés dépendent de la température et sont difficiles à mesurer surtout à haute température. A l’état liquide, le métal est réactif et facilement polluable. Dans les années 1980, Egry a développé un lévitateur électromagnétique TEMPUS pour mesurer en apesanteur sans contact matériel les propriétés thermophysiques des métaux et alliages en fusion. Dans l’espace, les effets du brassage électromagnétique et de la déformation des échantillons fondus sont beaucoup plus faibles que sur terre.L’emploi de cet outil spatial est coûteux. C’est pour, à terme, diminuer les coûts tout en maintenant voire améliorant la qualité des mesures, que nous avons souhaité remplacer la microgravité par un champ magnétique continu.Les travaux réalisés dans cette thèse consistent à mesurer les propriétés thermiques des métaux par procédé électromagnétique en utilisant une méthode de calorimétrie modulée.Elle comporte deux parties.-Une partie numérique dans laquelle nous avons simulé d’une part le lévitateur spatial TEMPUS et d’autre part le lévitateur terrestre AEXAM.La simulation du lévitateur spatial TEMPUS a pour but de déterminer l’effet de la superposition de courants inducteurs de fréquences différentes (courants de chauffage et de centrage) sur les comportements hydrodynamique et thermique de la goutte. Les résultats des calculs nous ont montré que le courant de centrage est susceptible d’agir sur les mesures.La simulation du lévitateur terrestre AEXAM consiste à déterminer la fréquence d’oscillation verticale de la goutte, la puissance Joule dissipée dans celle-ci, les champs de vitesse et de température. La goutte prend la forme d’une poire et elle oscille à une fréquence de 7 Hz. La puissance Joule dissipée dans la charge est maximale vers le bas de la charge dans les premiers millimètres à mi-hauteur entre l’équateur et le pôle. Elle diminue en pénétrant dans la charge et est nul sur l’axe de symétrie. La convection dans la goutte crée un brassage électromagnétique et homogénéise le champ de température.-Une partie expérimentale dans laquelle le lévitateur AEXAM a été placé dans un champ magnétique continu horizontal pour amortir l’oscillation verticale et le brassage électro-magnétique de la goutte mentionnée dans les calculs. Ceci nous a permis la mise en œuvre d’un protocole de mesure original sur un métal liquide. Ce protocole est un programme de traitement des donnés basé sur le comportement du champ de température lorsque les sources thermiques internes à l’échantillon sont instationnaires. Dans ce programme, nous avons utilisé une fonction d’identification qui permet d’obtenir un modèle mathématique à partir de mesures. Pour obtenir un modèle mathématique consistant, il est important d'exciter le système avec toutes les fréquences de sa plage de fonctionnement. C’est ce que nous faisons quand nous appliquons un bruit blanc sur la consigne d’entrée du générateur. Nous avons précédemment validé le protocole sur du solide en remontant aux valeurs de la capacité calorifique et de la conductivité thermique.Pour optimiser les pertes de masse, les instabilités sur les mesures du courant inducteur et la bonne reproductivité des mesures sur une goutte, nous avons choisi une masse initiale de 3,5 g pour faire les mesures avec modulation du courant inducteur dans un champ magnétique continu de 1 Tesla. Nous avons obtenu les valeurs de la capacité calorifique et de la conductivité thermique de la goutte. Celles-ci sont voisines des valeurs données par la littérature. Ce qui nous a permis de valider en partie le protocole de traitement des mesures.Dans le futur, ce protocole peut être appliqué sur des alliages métalliques. / The metal industry is requesting essential thermophysical properties for modeling and optimizing elaboration processes.Thermophysical properties of metals and metal alloys in liquid state are well known. These properties depend on the temperature and are difficult to measure especially at high temperature. In the liquid state, the metal is reactive and easily contaminated .In the 1980s, Egry developed an electromagnetic levitator TEMPUS developed an electromagnetic levitator TEMPUS to measure thermophysical properties of molten metals and alloys using a contactless technique under microgravity conditions. In space, the effects of electromagnetic stirring and deformation in molten samples are much lower than on Earth.The use of this space tool is expensive. In order to reduce the cost while maintaining or even improving the quality of measurements, we wanted to replace microgravity by a continuous magnetic field.The work in this thesis includes measuring the thermal properties of metals by electromagnetic method using a modulated calorimetry technique.The work has been divided in two parts:-The first consisted in the numerical simulation of space levitator TEMPUS and a terrestrial levitator AEXAM.The numerical simulation of space levitator TEMPUS aims to determine the effect of the superposition currents of different induction frequencies (heating currents and centering) on the hydrodynamic and thermal behavior of the drop. Calculation results showed that in some cases the centering current is likely to act on the measures and therefore it should be taking into account.The numerical simulation of terrestrial levitator AEXAM was destined to determine the vertical oscillation frequency of the drop, the power dissipated, the velocity fields developed inside and temperature. The drop takes the form of a pear and oscillates at a frequency of 7 Hz. The Joule power dissipated in the load is maximum on the lower part of the drop and decreases towards the interior of the drop vanishing at the center. Convection in the drop creates an electromagnetic stirring and homogenizing the temperature field.-The second part present the experiments performed using the levitator AEXAM placed in a horizontal continuous magnetic field for dampening the vertical oscillation and the turbulence produced by the effect of the electromagnetic stirring as it was mentioned in the calculations.This allowed us the implementation of a new protocol for measuring thermal properties in liquid metals.The protocol is a post processing program based on the temperature field variation resulting from unsteady joule power dissipation in the charge. An implemented identification function provides a mathematical model based on performed measurements. The use of a wide range of system frequencies was required to obtain a robust mathematical model. This was achieved by using pseudo-white noise perturbation at the generator inlet. The program has been validated successfully on solid matter by reverse determination of thermal conductivity and heat capacity.The preliminary studies under continuous magnetic field without modulation have mounted for a maximum initial weight of 3.5, we have less mass loss and improved measurement stability of the inductor current, as well as the reproductivity of the measurements.The protocol was validated successfully on the liquid charge using modulated perturbation under a continuous magnetic field of 1 Tesla. The obtained values of the heat capacity and thermal conductivity were comparable to the values given by the literature which partially validates the protocol.As a perspective, this protocol can be applied to a wide range of metal alloys.

Ce travail porte sur le développement d’une technique de calorimétrie sans contact pour des écoulements diphasiques. Ces derniers sont réalisés sur la forme d’un train gouttes dans des tubes de taille millimétriques dans des supports isopériboliques. L’idée principale est de coupler la Thermographie Infrarouge et les outils microfluidiques pour proposer une technique adapté de mesure. L’utilisation de la microfluidique rend possible l’utilisation de très faibles volumes réactionnels limitant ainsi tout risque lié à la dangerosité des réactions réalisées au sein des gouttes, l’outil Infrarouge permet de suivre ces écoulements avec grande précision. Les résultats de ces travaux de thèse montrent que l’outil est capable d’estimer des propriétés thermo-physiques des écoulements non réactifs. Ainsi, que de caractériser de réactions chimiques en termes d’enthalpie et cinétique. Finalement cette dernière caractérisation a été comparée aux techniques classiques pour mettre en évidence la précision et les avantages de l’outil développé / This work concerns the development of a non-contact calorimeter for two-phase flow characterization. The biphasic flow is performed under a droplet configuration inside millimetric tubings which are inserted into the isoperibolic chip. The main idea is to combine the Infrared Thermography and microfluidic tools to propose a suitable technique for accurate measurements. Microfluidics enables the use of small reaction volumes thus limiting any risk of dangerous reactions inside droplets, the Infrared tool enables to monitor the thermal signature of these flows with high accuracy. The results of this thesis show that this tool is able to estimate the thermophysical properties of non-reactive flows. Also , it is possible to characterize chemical reactions in terms of enthalpy and kinetics . Finally the latter characterization was compared to conventional techniques to demonstrate the benefits and the precision of the tool.

This thesis describes the optimisation of the calorimeter design for collider experiments at the future Compact Linear Collider (CLIC) and the International Linear Collider (ILC). The detector design of these experiments is built around high-granularity Particle Flow Calorimetry that, in contrast to traditional calorimetry, uses the energy measurements for charged particles from the tracking detectors. This can only be realised if calorimetric energy deposits from charged particles can be separated from those of neutral particles. This is made possible with fine granularity calorimeters and sophisticated pattern recognition software, which is provided by the PandoraPFA algorithm. This thesis presents results on Particle Flow calorimetry performance for a number of detector configurations. To obtain these results a new calibration procedure was developed and applied to the detector simulation and reconstruction to ensure optimal performance was achieved for each detector configuration considered. This thesis also describes the development of a software compensation technique that vastly improves the intrinsic energy resolution of a Particle Flow Calorimetry detector. This technique is implemented within the PandoraPFA framework and demonstrates the gains that can be made by fully exploiting the information provided by the fine granularity calorimeters envisaged at a future linear collider. A study of the sensitivity of the CLIC experiment to anomalous gauge couplings that {affect} vector boson scattering processes is presented. These anomalous couplings provide insight into possible beyond standard model physics. This study, which utilises the excellent jet energy resolution from Particle Flow Calorimetry, was performed at centre-of-mass energies of 1.4 TeV and 3 TeV with integrated luminosities of 1.5$\text{ab}^{-1}$ and 2$\text{ab}^{-1}$ respectively. The precision achievable at CLIC is shown to be approximately one to two orders of magnitude better than that currently offered by the LHC. In addition, a study into various technology options for the CLIC vertex detector is described.

Made available in DSpace on 2016-08-15T20:31:12Z (GMT). No. of bitstreams: 1 HericaGTD_DISSERT.pdf: 597617 bytes, checksum: 59784d911ca59573a589df402958dde5 (MD5) Previous issue date: 2012-05-21 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study aimed to assess the daily variation of metabolic heat production in goats based on oxygen consumption and carbon dioxide production in association with meteorological variables and physiological responses. 10 SPRD goats were used, four with predominantly white fur and six with predominantly black. The observations were made with the protected and exposed animals to direct sunlight, in a period of 12 days during the months of August and September, 2010 in Mossoró-RN. The metabolic heat production (M, Wm-2), the latent heat flow from the respiratory system (ER, Wm-2) and from the cutaneous surface (ESC Wm-2) were determined simultaneously through a face mask and a ventilated capsule, respectively. We also measured the rectal temperature, surface temperature and respiratory rate and measured the environmental variables, air temperature, black globe temperature, wind speed, air humidity, partial vapor pressure and solar radiation. Analysis of variance was based on least-squares method and comparison of means was done by Tukey's test at 5% level of significance. The results showed that the semi-arid goats maintained stable to metabolic heat production during the day, however, when exposed to direct sunlight, significantly increased the latent heat loss in the cutaneous surface and reduced metabolic heat production approximately 24% in an attempt to maintain constant internal temperature / Este estudo objetivou avaliar a variação diária da produção de calor metabólico em caprinos baseada no consumo de oxigênio e produção de dióxido de carbono em associação com variáveis meteorológicas e respostas fisiológicas. Foram utilizados 10 caprinos SPRD, sendo quatro com pelame predominantemente branco e seis com pelame predominantemente preto. As observações foram feitas com os animais protegidos e expostos à radiação solar direta, em um período de 12 dias, durante os meses de agosto e setembro de 2012, em Mossoró-RN. A produção de calor metabólico (M, Wm-2), o fluxo de calor latente a partir do sistema respiratório (ER, Wm-2 ) e a partir da superfície cutânea (ESC, Wm-2) foram determinados, ao mesmo tempo, por meio de uma máscara facial e uma cápsula ventilada, respectivamente. Foram também aferidas a temperatura retal, temperatura de superfície e a freqüência respiratória e medidas as variáveis ambientais, temperatura do ar, temperatura do globo negro, e velocidade do vento, pressão parcial de vapor, e radiação solar. A análise de variância foi baseada no método dos quadrados mínimos e a comparação de médias foi feita pelo teste de Tukey com nível de 5% de significância. Os resultados mostraram que as cabras do semi-árido brasileiro mantiveram estável a produção de calor metabólico ao longo do dia, no entanto, quando expostas a radiação solar direta, aumentaram consideravelmente a perda de calor latente na superfície cutânea e reduziram a produção de calor metabólico em aproximadamente 24%, numa tentativa de manter a temperatura interna constante

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.